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Asaf Kleopas Sugih
The author thanks the University of Groningen for the financial support through an Ubbo Emmius Scholarship.
Synthesis and Properties of Starch Based Biomaterials
Proefschrift ter verkrijging van het doctoraat in de Wiskunde en Natuurwetenschappen aan de Rijksuniversiteit Groningen op gezag van de Rector Magnificus, dr. F. Zwarts in het openbaar te verdedigen op vrijdag 12 december 2008 om 13.15 uur door Asaf Kleopas Sugih geboren op 4 juli 1975 te Bandung, Indonesië
F. Broekhuis Prof.P. dr. Promotores : Prof.M. A.J.A. ir. H. A.J. Minnaard Prof.B. Moscicki ISBN : 978‐90‐367‐3592‐6 ISBN : 978‐90‐367‐3593‐3 (electronic version) . dr. L. dr. Heeres Prof. dr. dr. ir. dr. Janssen Prof. L. Picchioni Beoordelingscommissie : Prof.
to: Tresna. my parents. and my sister .
1. Starch 1. Thesis Outline 1.1.3. Materials 2. The potential of biodegradable plastics 184.108.40.206. References 2 3 4 5 5 7 9 9 10 11 11 13 14 16 16 17 Chapter 2: Experimental Studies on the Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐ Monosaccharide Initiator System 2.3.2. Starch production processes 220.127.116.11. Starch Esters 18.104.22.168.1.1. Product analyses .2. Starch modifications to improve product properties 1.3.4‐di‐O‐isopropylidene‐α‐D‐galactopyranose (2) 27 28 26 27 27 27 22.214.171.124.2.2.4. Introduction 2. Starch‐based blends by melt mixing 1. Structure and properties of starch 126.96.36.199. Starch‐based blends by in situ polymerization 1. Methods 188.8.131.52.5. Plastic applications and waste issues 1.3.1. Biodegradable plastics from starch 184.108.40.206.2. Biomaterials from starch 1.Table of Contents Chapter 1: Introduction 1.2. Thermoplasticized starch 220.127.116.11. Typical example for the synthesis of polydioxanone end‐capped with 1.4. Starch ‐ biopolymer blends and graft co‐polymers 1. Cross‐linked starch 1. Materials and Methods 2.
18.104.22.168.1. Introduction 22.214.171.124.126.96.36.199.2. Results and Discussions 2.4.2. References Chapter 3: Synthesis of Poly‐(ε)‐caprolactone Grafted Starch Co‐polymers by Ring Opening Polymerisation using Silylated Starch Precursors 3.3. Materials 188.8.131.52.3.2. Effects of process conditions on the average chain length ( X n exp ) and end group distribution 28 29 29 30 36 38 39 40 42 43 44 184.108.40.206. Results and Discussions 3.3. Nuclear Magnetic Resonance (NMR) 3.2. Peracetylation of silylated starch 3. Methods 3. De‐silylation of poly‐(ε)‐caprolactone grafted silylated starch co‐polymers 51 51 52 52 52 53 54 48 49 49 50 50 3. Calculation of average degree of polymerization 2. Product analyses 220.127.116.11. Product yield 2.2. Screening experiments 18.104.22.168. Typical example of the starch silylation procedure 3. Conclusions 2.3. Calculations 3. Analytical methods 22.214.171.124.3.2.1. Typical example of in situ polymerization of ε‐CL with silylated starch 50 3.2. Mechanistic aspects 2.1.3. Materials and Methods 3.2.2. Nomenclature 2.3. Systematic studies 2.1. 126.96.36.199. Synthesis of silylated starch viii .
2. Effect of the addition of toluene as a co‐solvent 4.3.2. 1H‐ and 13C‐NMR analyses 188.8.131.52.3. Materials and Methods 184.108.40.206.3. Exploratory experiments 4.3.1. Product characterisation 4. Methods 220.127.116.11.3. Systematic studies 4. Deprotection of silylated‐starch‐g‐PCL 3.3. Determination of the Degree of Substitution (DS) 4.2.2. Nomenclature 18.104.22.168.5.3.1. Conclusions 4.3. Typical example of the synthesis of laurate and stearate esters of corn starch 72 73 74 75 75 76 76 78 79 80 81 81 82 83 84 70 71 71 71 72 4.3.2. FT‐IR measurements 4.5.1. Effect of vinyl ester to AHG ratio on the product DS 4. Materials 4. References Chapter 4: Synthesis of Higher Fatty Acid Starch Esters using Vinyl Laurate and Stearate as Reactants 4.2.3. Peracetylation procedure 4.3. Nomenclature 4. In situ ring opening polymerization of ε‐caprolactone with silylated starch 57 63 64 64 65 3. Catalysts screening 4. Introduction 4.3.3. Conclusions 3.2. References ix .2.6.2. Results and Discussion 22.214.171.124.1. 126.96.36.199.1. Analytical equipment 4.3.
2.3. Mathematical modelling 188.8.131.52. Materials and Methods 184.108.40.206.2. Typical example of the preparation of laurate and stearate starch Esters 88 86 87 87 87 88 220.127.116.11. Materials 5. Experimental Design 5.2.3. Compatibilizer synthesis 6. Introduction 6. Analytical Methods 110 x . Methods 6.2.3. Peracetylation procedure and Degree of Substitution (DS) determination 88 88 89 92 96 102 102 103 5. Product properties 5.6. Materials and Methods 18.104.22.168.1. References Chapter 6: Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends 22.214.171.124.3.2.2. Materials 6. Work‐up of PCL‐g‐DEM 108 109 109 109 109 110 110 6. Conclusions 5.3. Results and Discussion 5.2. Introduction 5. Methods 5.4.2.Chapter 5: Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch 5.2.2. Nomenclature 126.96.36.199.2.1. Analytical Equipment 5.3. Preparation of PCL‐starch blends with the reactive compatibilisers 110 188.8.131.52.4.2. Work‐up of PCL‐g‐GMA products 6.
Preparation of the ractive compatibilizers 6. Ternary blends compatibilized with PCL‐g‐DEM 6. Statistical mdeling 6.2.2. Thermal properties of the compatibilizers 6.1.3. Nomenclature 184.108.40.206.3. Synthesis and Properties of Starch‐ PCL Blends 6. Effect of the BPO intake on the product FD 6.4. Binary blends of starch and PCL 6. References Summary Samenvatting (Dutch Summary) Acknowledgements List of Publications 133 137 141 143 xi .220.127.116.11. Modeling of the combined effects of the GMA/ DEM and BPO intakes on the FD 111 111 111 116 117 118 120 121 122 123 125 128 128 129 6.3. Results and Discussions 6.1. Effect of substrate (GMA/DEM) to PCL Ratio on the FD 18.104.22.168.22.214.171.124.2. Conclusions 126.96.36.199.1.4. 6. Ternary blends compatibilized with PCL‐g‐GMA 188.8.131.52.5.3. Calculation of the Degree of Functionalization (FD) of the reactive compatibilizers 6.3.
Finally.Chapter 1 Introduction Abstract A general overview of starch properties will be given and the potential use of starch as a starting material for a wide range of green biomaterials will be reviewed and discussed. . an outline of this thesis is given. Different routes to modify starch to improve the product properties and to extend the application range will be provided.
1. barley. current and future estimations of worldwide starch production are given in Figure 1. Plants synthesise and store starch in their structure as an energy reserve. Starch is found in seeds (i.1. potato.e.1. Most of the starch produced worldwide is derived from corn. wheat. 80 70 60 50 40 30 20 10 0 Starch Production (Million Tons) 1995 2000 Year 2005 2010 Figure 1. The worldwide production of starch in 2008 is estimated to be around 66 million tons . sweet potato. while corn seeds consist of 65‐80% starch by weight. Potato accumulates starch to approximately 75 % of the dry weight in the tubers with a yield up to 21 ton starch per hectare.e. maize. Past.9 ton starch per hectare . The second and third starch producer regions are Europe and Asia [4‐5]. rice. Past. with an average yield of 4. An important polysaccharide is starch. or peas) and in tubers or roots (i. .45 (estimated from the total volume and value of the US corn starch export ). present and a forecast of starch production  o : Europe □ : USA : Total ∆ : the Rest of the World 2 . Starch 75% of all organic material on earth is present in the form of polysaccharides. The current price of corn starch is around $0. sorghum.Chapter 1 1. corn. and wheat starch are also produced in large amounts [2. 4‐5]. Most starch crops are very productive. . It is generally deposited in the form of small granules or cells with diameters between 1‐100 µm . but other types of starch such as cassava. Most of the starch is produced in the USA. potato or cassava) of the plants [2‐3].
which is again fed to a second milling process. The resulting starch is further washed in a cyclone and finally dried. The low density gluten is separated from the starch suspension by centrifugation. As an example. After a coarse milling. b. and is embedded in a proteinaceous cellular matrix as is shown in Figure 1.1. and other foreign materials.2. and starch.2.b. the mixture is fed to a hydrocyclone to separate the germ and the rest of the kernel. Figure 1.a. a. The starch is present in the endosperms (floury and horny).1. Introduction 1. and starch granules are obtained after centrifugation from the suspension. the debris is filtered from the slurry. The plant material is grounded in water. gluten. After initial cleaning to remove cob. Corn starch production  a.2. Typical corn‐milling operation b. The resulting suspension from the mills contains fiber. Cross‐sectional view of a corn kernel 3 . Starch production processes Starch is generally extracted from the plant by wet milling processes [9‐10]. the corn kernel is softened by steeping in warm water containing SO2 until the volume of the kernel increases with 55‐65%. a typical corn starch production process is given in Figure 1. The fiber is removed using washing screens. sand.
a. Two types of AHG polymers are usually present in starch: amylose and amylopectin [2‐3. 6].6)‐ glucosidic bonds . The content of amylose and amylopectine in starch varies and largely depends on the starch source..Chapter 1 1..4)‐glucosidic bonds.. The molecular weight of amylopectin is higher than that of amylose and is typically 4‐5 x 108 Da . but it is very hygroscopic and binds water reversibly. H OH H2COH H2COH H . Amylopectin Starch is insoluble in cold water.1. The linear 4 . Amylose c. The molecular weight of amylose is a function of the plant source and processing method. Anhydroglucose (AHG) unit b. Amylose is essentially a linear polymer in which AHG units are predominantly connected through α‐D‐(1.3. H . Structure and properties of starch Starch is a polymer consisting of anhydroglucose (AHG) units (see Figure 1. H2COH H H OH H O H OH O H OH O CH2 H O H H OH H O H OH H O . Amylopectin is a branched polymer. Figure 1.2..3. the amylose content is between 18‐28% .1.. H OH H O H OH H O H H OH H c. but usually in the range of 1.. H2COH H . The starch granules will swell rapidly to many times of its original volume.) . . Heating a starch solution leads to loss of hydrogen bonding in the interior of the starch granule and the starch will start to gelatinize.6‐7 x 105 Da .. Each branch contains about 20‐30 anhydroglucose units. Chemical Structure of Starch a. H O H OH H OH H O H OH O H OH H O ...a.. containing periodic branches linked with the backbones through α‐D‐(1. H2COH H OH H O H H O b. H OH H H2COH H2COH H O H H OH H H2COH H O H H OH H O H OH H O .... The amylose content of several common starches is given in Table 1. . Typically..
Biomaterials from starch 1. Table 1.5‐70 62‐72 63‐72 58‐64 1. Plastics are used in a wide range of applications and the demand is still increasing every year .8 16.1. Cellulose nitrate was first prepared by A.2. Amylose content of common starches  Starch Arrowroot Corn Hybrid amylomaize Class V Hybrid amylomaize Class VII Oat Manioc Potato Rice Sago Sweet potato Tapioca Wheat Amylose (%) 20. depending on the amount of water present. The gelatinization temperature range of various starch sources is given in Table 1. Starch gelatinization temperature range  Starch Potato Tapioca Corn Waxy corn Wheat Gelatinization Temperature Range [o C] 59‐68 58. The first generation of commercial plastics was derived from cellulose nitrate and is known as celluloid [12‐14].5 25.7 26 Table 184.108.40.206. The resulting suspension contains a mixture of linear amylose molecules.8 17.5 28 52 70‐75 27 15. and celluloid was 5 . Parker in 1838. The gelatinization temperature range can be defined as the temperature at which granular swelling begins until the temperature when nearly 100% of the granules are gelatinized .7 20 18. will form a thick paste or gel. Plastic Applications and Waste Issues Plastic is the general term for a wide range of synthetic or semisynthetic polymerisation products. Introduction amylose molecules leach out of the granules into the solution.2. and granule fragments. and. swollen granules.
Adhesives. and PolyAcryl. when polyethylene (PE) was invented. Plastics are also used for building materials and automotive.) 250 Included: Thermoplastics. 15].Chapter 1 patented by J. the worldwide plastics production has reached 245 million ton per annum  (see Figure 1. polypropylene (PP). and 37% of the total plastics demand in EU  is used as packaging materials. PE is a very versatile plastic because it can be shaped easily into various forms. About 29% of the total plastics produced in the USA . Plastics have lower melting temperatures compared to glass and metals. Hyatt in 1870 . space. for instance to be used in packaging and paper coatings . A dramatic increase in demand for plastics began after World War II. and therefore need less energy to shape it into useful materials .4. Thermosets. and PP-Fibers 2006: 245 2002: 200 200 Plastics Production (Million Tons) Not Included: PET-. They have a low density and can be shaped in thin films while maintaining good properties. electrical. the oldest purely synthetic plastic is Bakelite. Elastomers. Plastics are very attractive materials. In 2006. and energy during transportation of goods. Worldwide Plastics Production (1950‐2006)  6 .5. and consumer products (see Figure 1. While celluloid is derived from a natural polymer (cellulose). polyvinyl chloride (PVC).Fibers 150 1989: 100 100 1976: 50 50 1950: 1. Coatings. and polycarbonates (PC). Polyurethanes. The latter is important when using the material for packaging purposes to save weight. polystyrene (PS). The largest application of plastics is for packaging purposes. The production and consumption of plastics has increased significantly with a rate of almost 10% every year since 1950. Important polymers used for packaging are polyethylene (HDPE and LDPE). PA-. discovered by Baekeland in 1907 [12. polyethylene terephtalate (PET).5 0 1950 1960 1970 1980 Year 1990 2000 2010 Figure 1.4. Sealants.).
threatening fishery. is causing serious environmental problems. Figure 1. only 20% of the plastic is recycled. Most of the waste is still disposed (50%) by landfill or incinerated to recover the energy (30%) . In the USA. ship navigation. It is not applicable for thermoset resins . however. In Europe (2006). In 1996. irrigation. soil. Recycling (part of) the plastics to reduce the amount of MSW also has limitations. are not easy to recycle . Plastic applications and waste treatment in Europe  1. Plastic litter is hazardous to wildlife [1. and is only effective for single plastic sources or simple plastic formulations. and accumulation of its residues in soil cause significant reductions in agricultural yields.5. consisting of 25%‐v of the total waste . the amount of plastics in MSW increased from less than 1% in the 1960 to 11. rivers. and may be more than twice the weight fraction . 6]. Co‐mingled plastics. The disposal of plastics materials in municipal solid waste (MSW) is a serious issue in many parts in the world. Plastics have been polluting sea [1. Introduction Plastic waste. The potential of biodegradable plastics The application of biodegradable plastics could be an attractive solution for the problems related to the use of conventional plastics (vide infra).7% in 2006 . and lakes. plastics waste was ranked as the second major source of MSW after paper and paperboard. 16]. It has a high volume to weight ratio and is resistant to degradation. hydropower plants operation.2.2. and other public works . which are usually found in waste streams. Biodegradable plastics are polymeric materials capable of decomposing when given an 7 . The volume fraction of plastic in MSW is much larger due to the low density of plastics.
biological and/or physical forces in the environment at a rate which leads to fragmentation or disintegration of the plastics. proteins (present abundantly in plants and animals). Biodegradable plastics may be classified into two general groups. biopolymers from nature (from plants. Several authorities have provided definitions for biodegradable plastics . The considerable growth of interest in composting as a means to replace landfill due to the decreasing disposal spaces (especially in Europe) may also help the progress of biodegradable plastics development . Biodegradable plastic waste may be treated in composting facilities.Chapter 1 appropriate environment and sufficient amount of time . It may also be treated in sewage sludge water treatment plants or buried in the soil [20‐21].2 working group on biodegradable polymers ‐ Biodegradation of a plastic material is a process leading to naturally occurring metabolic end products. together with food and yard waste as well as paper. animals. and microorganisms) and biodegradable synthetic polymers . because they take part in nature’s cycle of renewal. and polyesters from micro‐organisms . DIN 103. The change in chemical structure results from the action of naturally occurring micro‐ organisms. the price of PLA based plastics in 2010 is estimated to be around € 1. Common natural biopolymers are carbohydrates. The price of these biodegradable plastics is expected to be reduced considerably in the next decade . Biopolymers are inherently biodegradable. Nowadays new types of biodegradable plastics with improved properties and lower costs have been developed .5/ 8 .96 proposal ‐ Degradable plastics are plastic materials that undergo bond scission in the backbone of a polymer through chemical. ASTM sub‐committee D20. and these are shown below: ISO 472: 1998 ‐ A plastic designed to undergo a significant change in its chemical structure under specific environmental conditions resulting in a loss of some properties that may vary as measured by standard test methods appropriate to the plastics and application in a period of time that determines its classification. For instance. The market price of biodegradable plastics (mainly from starch and PLA) has decreased the last years. Biodegradable plastics have gained considerable interest since the 1980s. Japanese Biodegradable Plastic Society draft proposal ‐ Biodegradable plastics are polymeric materials which are changed into lower molecular weight compounds where at least one step in the degradation process is through metabolism in the presence of naturally occurring organisms. and since 2000 they have become competitive with traditional materials in some applications [20‐21].
The price of starch‐based biodegradable plastics (€ 1. Introduction kg. Biodegradable plastics are also used for food servicewares .3.8‐ 2. when recycling is not practical or uneconomical [20‐21]. € 1. consumer products and food products. 1. either from starch‐based materials (slightly modified starch.45 per kg . 9 .4 per kg in 2007‐2008 ). blending with other materials.2. These are summarized briefly in the next sections. Consequently. This price is much lower than conventional plastics derived from oil. half of its price in 2003 (around 3 Euro/kg). and chewable items for pets [1. because the price of oil based polymers may still increase due to the rise in the crude oil prices . Starch may become an attractive raw material for plastics in the future.50‐4. Biodegradable Plastics from Starch Starch is a very attractive source for the development of biodegradable plastics. before they can be applied as biodegradable plastics. 1. agricultural products (mulch films. It cannot be shaped in films with adequate mechanical properties (high percentage elongation. chemical modification or combinations of them . napkins) . Virgin starch is not suitable as a packaging material. Starch modifications to improve product properties Several techniques may be applied to develop starch based biomaterials with improved properties. such as polyethylene (PE. Biodegradable plastics are especially very useful for single‐use applications. towels. utensils . hygienic materials (diapers. . The global production capacity of starch‐based bioplastics in 2010 is estimated to increase to 200‐300 kiloton per year from 77‐200 kiloton in 2003 . breathable fabrics. Bastioli [20‐21] showed that nearly all biodegradable plastics available in the market are derived from starch.3. The price of starch in 2007 was about $ 0. starch must be modified.4 or $ 1. or when environmental impacts have to be minimized. either by plasticization. pots). biofillers for tires. alone or complexed with natural or synthetic biodegradable polymers) or from polylactic acid which originates from the fermentation of a starch feedstock. 20].2‐ 1.50/ kg in 2005) is also expected to be lower in the future due to considerable reduction in modification costs . Examples are the use as packaging material for carrier bags. tensile and flexural strength) and is too sensitive to water [26‐27].
As the result. Starch can be modified to obtain materials which melt below the decomposition temperature . At intermediate water levels. The use of water as a plasticizer is not preferable. 32. sorbitol. There are several substances used as plasticizer for the preparation of thermoplastic starch (TPS). 40]. The brittleness is known to increase in time due to free volume relaxation and retrogradation. the thermal properties of glycerol‐plasticized starch are a function of water content [31. 30]. Yu. approximately 230 oC) . plasticized. 37]. and blow moulding [28. 32‐ 36]. which is even above the thermal degradation temperature. glycol.1.Chapter 1 1. The thermoplasticization process will decrease the interactions of the molecular chain and destruct the structure of the starch . Although thermoplasticization seems to be a promising method. the semicrystalline structure of starch and its granular form are lost and the starch polymers are partially depolymerized. because the resulting product will be brittle when equilibrated with ambient humidity . .3. extrusion. sugars) [30. The use of other plasticizers (for example glycerol) results in a rubbery material. and the properties and amount of plasticizers. 30. Another issue is the poor water resistance and low strength. glycerol. 40]. 35. and therefore are processable by conventional polymer processing techniques such as injection. 39]. Thermoplasticized starch Virgin starch is brittle and difficult to be processed into articles due to its relatively high glass transition temperature (Tg. A biodegradation study according to ISO/CEN 14852 and ASTM D5209‐92 standards  on films made from starch–glycerol–water mixtures confirmed that the films are easily biodegradable. which still limits their use. such as water and polyols (glycerol. and hexylene glycol. which will result in a continuous phase in the form of a viscous melt [29‐30. which results in embrittlement. This problem is mainly caused by the presence of strong inter‐ and intra‐molecular hydrogen bonds between the starch macromolecules [28. or melted starch [29. TPS synthesized from polyol and sugar plasticizers have the tendency to re‐crystallize (retrogradation) after being stored for a period of time. with better properties than virgin starch in various applications. phase separation may still occur. For instance. et al  discovered that the elongation of break of the thermoplastic starch is significantly improved by plasticization with glycol. The modified products are known as thermoplastic. resulted in the formation of an amorphous mass [35. 33]. The plasticizers are also usually hydrophilic and can be 10 . The plasticized starch properties may be tuned by changing the temperature of processing. destructed. The modification involves break down of the starch granular structure by the use of plasticizers at high temperatures (90‐180 oC) and shear. water content.
textile. As a result. Chemicals of these classes having two or more of the reactive groups may react with two or more hydroxyls of the starch molecules. 39]. 1. These hydroxyls can react easily with a wide range of compounds such as acid anhydrides. Most studies dealt with the synthesis of starch esters of C1‐C4 carboxylic acids. Already in 1865. The esterification reaction is catalyzed by H+ and proceeds with the formation of water . especially in the food. The products are called cross‐linked starches. The cross‐linked starches have found many applications.3. Schuetzenberger acetylated starch with acetic anhydride . Low DS products (0. The simplest starch ester is starch formate (C1). Medium DS starch acetates (0. aldehydes.3‐1) are still soluble in water. epoxy. synthesized by direct addition of formic acid to starch at room temperature. paper. and adhesive industry. Introduction washed out by water . resulting in an increase of the Young’s modulus and tensile strength of the products and a decrease in elongation at break. Solutions to improve the properties of TPS are blending. The most popular starch ester is starch acetate . Cross‐linking results in a reduction of the solubility in water and to thickening. Higher processing temperatures generally led to higher cross‐linking levels.3. Substitution of the hydroxyl groups of starch with acetate groups makes the esters more hydrophobic than native starch. The cross‐linked products are therefore more rigid (and less elastic) materials than virgin starch . Three different types of starch acetates may be distinguished. differing in Degree of Substitution (DS). High DS starch acetate can be easily casted 11 . organic chloro‐compounds. the use of formyl esters of starch is much lower than that of acetate esters. Starch Esters The development of starch esters started in the mid 19th century [44.2. and particularly with acetic acid . Cross‐linked starch An anhydroglucose molecule of starch contains two secondary and one primary hydroxyl group. et al  studied the mechanical properties of films from maize starch cross‐linked by sodium trimetaphosphate (SMTP).2) are commercially available and used as food additives and in the textile industry. or coating with hydrophobic polymers [33. 46]. Breakdown of the starch and the formation of low molecular weight products occur to a significant extent .01‐0.3. leading to higher viscosities [42‐43]. The DS is defined as the moles of substituents per mole of AHG units . 1. Silva. while highly substituted starch acetate (DS of 2‐3) are soluble in organic solvents. and ethylenic compounds.
High DS starch acetates are thermoplastic materials suitable to be used as biodegradable plastics . The kinetics of the reaction between gelatinized aqueous potato starch and vinyl acetate was studied by De Graaf. Several synthetic routes have been developed for starch esters. xylene. and is shown in Scheme 1. DMSO. but also C‐6 and C‐ 3 substitution .1. The degree of acetylation of starch acetates can be easily controlled. Starch OH + OH - Starch O - + H2O O - O Starch O - + H3C C O CH O H3C C O CH2 H3C C O CH O Starch CH2 H2O O Starch + H3C C H + OH - O H3C C O Starch O - + OH - H3C C O OH Starch H2O O H3C C OH + Starch O - Scheme 1. Starch triacetate has been successfully synthesized using acetic anhydride in combination with pyridine‐gelatinized starch . acetate. Esterification may be performed using acid anhydrides in aqueous media or organic solvents (pyridine. or isopropanol) with acidic (hydrochloric or sulfuric acid) or alkaline (NaOH or triethylamine) catalysts . Acetylation of starch in water and DMSO using vinyl acetate has been studied lately by Mormann and Al‐Higari  as well as Dicke . Another attractive route involves the use of vinyl esters as reagents . and phosphate) will result in C‐2. Mechanism of starch acetylation using vinyl acetate 12 . allowing the polymer to be produced with a range of hydrophobicities . Neutral and weak acid/ alkaline catalysts result in regioselective substitution at the C2 hydroxyl groups of starch. Starch esters have also been synthesized using alkanoyl chlorides [49‐53]. DMF. et al [55‐56].Chapter 1 into films using organic solvents.1. hydrogencarbonate. while alkaline catalysts (such as carbonate.
i. Starch ‐ Biopolymer Blends and Graft Co‐Polymers Blending of different polymers is an established method to obtain products with improved properties. in order to achieve also a good molecular adhesion between the phases by melt mixing.e. in the simplest case of a binary blend. The second methodology for producing polymer blends involves the in situ polymerization of one component (thus originally present in the blend in monomeric form) in the presence of the second one. Fatty‐acid starch esters have been synthesized using fatty acid (octanoyl. they locate themselves at the interface between the 13 . but only relatively low‐DS (0. the latter are mixed together. interfacial agents (e. However. However.61) products could be obtained using this approach. it is frequently used in order to chemically graft the polymerized component on the other one (polystyrene on polybutadiene in our example above ). a chemical reaction might take place upon processing (reactive extrusion). The use of methyl and glyceryl esters of fatty acid (in the absence of solvent) to synthesize starch fatty acid esters has also been studied . The introduction of longer acid chain is expected to reduce the brittleness of virgin starch and to increase its hydrophobicity . As a result. If the right combination of chemical groups on the two components is present along the polymers backbone. which in turn provide a very strong adhesion at the molecular level between the dispersed phase and the matrix.g. relatively expensive and rather corrosive. Their role is comparable to the one of a surfactant in emulsion formation . Although the in situ polymerization process is not as technologically straightforward and economically convenient as melt‐mixing. 1. one component will be dispersed into the other. octadecanoyl) chlorides [49‐53]. The classical example of such process is represented by the production of High Impact Poystyrene (HIPS) obtained by styrene polymerization in the presence of polybutadiene . availability of mixing equipment and no necessity to use any organic solvent (often employed for the in situ polymerization). Two main methodologies are applied for the production of polymer blends. melt‐mixing remains the preferred route to polymer blends mainly because of very practical reasons: low costs. compatibilizers) might be used. The fatty acid chloride reactants are. The degree of adhesion (binding) between the dispersed phase and the matrix is dependent on the molcular interactions between the two components and represents a crucial factor in determining the morphology of the blends and eventually the product performance . Despite this advantage.4.3. By working at temperatures above the melting point or glass transition temperature of the two components.34‐0. dodecanoyl. polymers are rarely miscible with each other  so that. Introduction The synthesis of long chain fatty acid ester of starch has attracted much interest lately. the two components are chemically linked to each other. The first involves simple melt mixing of the two components for example by extrusion. however.
39. The uncompatibilized blends of starch and 14 . The products have been synthesized in the lab as well as on industrial scale [32. The blending and grafting of starch with synthetic polymers is usually performed to achieve higher hydrophobicity and to improve the mechanical and thermal properties as well as to obtain cheaper and more biodegradable products. Starch‐based blends by melt mixing Starch‐synthetic polymer blending has been studied as early as in 1973 [64‐65].4.). Matrix Dispersed Phase Figure 1. The most often used synthetic polymer for blending with starch is polyethylene [27. The synthesis of compatibilizer and its use for starch/ synthetic polymer blending has also been studied. there have been efforts to blend as well as to graft synthetic polymers onto starch. 66‐81]. A suitable interfacial agent for the blends of two polymeric materials is a block copolymer for which the chemical structure of every block is the same (or very similar) to the one of the individual components to be blended  (illustrated in Figure 1.6.3. In the past. Illustration of the role of interfacial agent in compatibilizing blends 1.Chapter 1 two components stabilizing the dispersion (most probably by a steric repulsion mechanism ) and providing an improved adhesion at the interface. 80‐ 81] or food packaging . Interfacial agents already available on the market can be used as such or can be produced upon mixing (in situ) by chemical reaction of the two components. 64‐98].1.6. The starch/polyethylene blends are used for agricultural mulch [27.
The mechanical properties of the blend are also improved. Polycaprolactone (PCL) is a well‐known synthetic biodegradable polyester. among which synthetic polyesters are considered very promising materials . while the tensile strength of the compatibilized ones decreases only slightly with the starch content. the uncompatibilized blends of starch with PCL give coarse phase separation and a reduction in the mechanical properties when the starch content is increased. poly‐dioxanone. 72‐73]. dextran‐g‐PCL . Some of these polyesters also have very good mechanical. while PE‐g‐GMA posseses epoxide groups. poly‐valerolactone. and of a premade starch‐g‐PCL  for starch/PCL blends resulted in a better dispersion between the phases and in turn in improved mechanical properties compared to the uncompatibilized blends. PCL‐g‐pyromellitic anhydride [94‐95]. 96]. Examples of these biodegradable polyesters are poly‐glycolide. To obtain completely biodegradable products. Polyethylene‐g‐maleic anhydride (PE‐g‐MA) and polyethylene‐g‐glycidyl methacrylate (PE‐g‐GMA) have been used as reactive compatibilizer for starch/PE blends. These biodegradable polyesters will finally decompose into non‐toxic products . which both can react in situ with the hydroxyl groups of starch [70. The use of conventional synthetic polymer such as PE for blending with starch will only result in a partially biodegradable material.e. which combines excellent biodegradability with acceptable mechanical properties. poly‐lactides. and EVOH . PCL‐g‐maleic anhydride (PCL‐g‐MA) [91. Despite these good results. The use of reactive compatibilizer precursors PCL‐g‐glycidyl methacrylate (PCL‐g‐GMA) [89‐90]. 39. i. and poly‐lactones (such as poly‐butyrolactone. The tensile strength of the uncompatibilized blends is drastically reduced when starch content is increased. As is the case of blends with PE. Introduction polyethylene show a coarse phase separation due to differences in polarity of starch (hydrophilic) and polyethylene (hydrophobic). thus improving the dispersion of starch in the PE matrix. 15 . 84‐98]. and poly‐caprolactone). thermal and water/gas permeability properties that are even comparable to bulk non‐biodegradable polymers such as PE and PP. As a result a graft copolymer (PE‐g‐Starch). The mechanical properties of these blends (tensile strength and elongation at break) decrease at higher starch content. is formed upon mixing. synthetic biodegradable polymers have been applied. Studies on the blending of starch with PCL have been already described [32. the compatibilizer. since the conventional synthetic polymers are usually poorly or non‐biodegradable. PE‐g‐MA contains reactive anhydride sites. systematic studies on the compatibilizer precursor synthesis as well as on the influence of the chain topology and chemical reactivity (for the in situ compatibilizer formation) have not yet been reported. The ester bonds of these polymers are susceptible to attack by water and this leads to enhanced biodegradability.
Chapter 2 describes the ROP of p‐dioxanone initiated by a protected monosaccharide (1. and the presence of liquid‐solid reaction system leads to reduced reaction rates between starch and ε−caprolactone. Starch is insoluble in the typical organic solvents used for ROP (such as toluene or THF). A new strategy for the in situ ROP of ε−caprolactone on starch with the use of common ROP catalyst is therefore highly desirable. and difficult to handle since it releases ethane. The method applied basically consists of three steps (temporary partial protection of starch‐hydroxyl 16 .3. during the reaction.2.4. the synthesis of starch‐g‐PCL is reported. defined as the percentage of grafted polyester to starch compared to the total amount of homopolymer and grafted polyester) . thus resulting eventually in low GE values . and starch‐g‐ biopolymer formation. The highest GE value (up to 90%) has been achieved when using triethylaluminium as catalyst [97‐98]. Thesis Outline The objective of this thesis is to study synthetic pathways to obtain starch derivatives with the potential to be used as bioplastic. Starch is a very hydrophilic material that always contains moisture. starch‐g‐PCL has been synthesized using toxic materials such as isocyanates . Another possible cause for the low GE values is the heterogenous nature of the reaction. but it can also provide an efficient synthetic methodology for the production of a compatibilizer to be used for melt blending of starch with a biopolymer . The results of this study have been used as input for the synthesis of the starch‐g‐PCL. In this reaction. The water in starch granules competes with the hydroxyl groups of starch in the initiation step of the polymerization reaction.3. a very flammable by‐product. Another approach consists of the Ring Opening Polymerization (ROP) of ε‐caprolactone monomer in the presence of starch.4. In Chapter 3. which however is extremely air‐ and water‐sensitive.4‐di‐O‐isopropylidene‐α‐D‐galactopyranose) using i Al(O Pr)3 as the catalyst. Starch‐based blends by in situ polymerization The synthesis of starch based graft copolymers by in situ polymerization represents not only an alternative route to melt blending (vide supra) for the production of novel biomaterials. Previous studies showed that common ROP catalysts such as tin octoate or aluminium isopropoxide gave low (0‐14%) grafting efficiencies (GE. 1. starch/ biopolymer blending.Chapter 1 1.2. Three routes have been studied in detail: starch esterification. the hydroxyl groups of starch are supposed to function as initiating sites. In the past. leading to formation of PCL homopolymers rather that starch‐g‐PCL.
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also polydioxanone with an OiPr end‐group was formed (20‐30 %). A statistical model has been developed that successfully describes the experimentally observed relation between the average chain length of the functionalized polymer and reaction parameters. The average chain length of the polymers is between 7 and 58 repeating units and may be tuned by the monomer to monosaccharide ratio (at constant Al(OiPr)3 intake).4‐di‐O‐isopropylidene‐α‐D‐galactopyranose)/Al(OiPr)3 initiator system to yield polydioxanone with a protected monosaccharide end‐ group is described. Keywords: biodegradable.2. polyesters. ring‐opening polymerization .Chapter 2 Experimental Studies on the Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐Monosaccharide Initiator System Abstract The ring opening polymerization (ROP) of p‐dioxanone using a protected monosaccharide (1. Systematic studies showed that the polymer yield is a function of the reaction temperature and the reaction time.3. The products were synthesized at 60‐100°C and characterized by 1H‐ and 13C‐NMR. with higher temperatures (100°C) leading to lower yields. and MALDI‐TOF mass spectrometry. Besides the desired polydioxanone functionalised with a monosaccharide end‐group.
2. only limited information about the synthesis and properties of polydioxanone is available in the open literature. This chapter describes experimental studies on the catalytic ROP of p‐ dioxanone in the presence of a protected glucose molecule (1.4‐di‐O‐ isopropylidene‐α‐D‐galactopyranose. stannous octoate [Sn(Oct)2]. probably because the p‐dioxanone monomer has become commercially available only recently .3 MPa and an elongation at break of 500‐600%. are interesting polymers because of their good product performance and biodegradability . The synthesis of protected monosaccharide end‐capped biodegradable polymers is usually performed via Ring Opening Polymerization (ROP). which to the best of our knowledge is the first study to functionalise polydioxanone with a monosaccharide. and polylactides.4‐dioxan‐2‐ one)). Biodegradable aliphatic polyesters end‐capped with sugar molecules have been studied extensively for use in biomedical applications. 9]. Despite its good properties. Besides 26 . whereas the high temperature for polylactides results in thermal degradation and undesirable transfer reactions during synthesis and processing steps .1. has interesting product properties compared to other aliphatic polyesters. The ring‐opening polymerization (ROP) of p‐dioxanone using metal catalysts such as aluminum isopropoxide [Al(OiPr)3]. This melting point is considerably higher than typically found for polycaprolactone (60 oC) and lower than that of polylactides (at least 175°C). Exchange of the alkoxide group by e. stigmasterol and ergocalciferol)  and also with protected monosaccharides (galactopyranose/ glucofuranose) [6‐7]. Polydioxanone (poly(p‐dioxanone) or poly(1. The catalysts are metal alkoxides with Lewis acidic character [8. pregnenolone. such as polycaprolactone. 2). or zinc lactate has been reported. From a biodegradability point of view. Introduction Aliphatic polyesters. polyglycolide. testosterone.g. particularly for nano‐ encapsulation systems for drug delivery . tocopherol. The relatively low melting point of polycaprolactone limits its applicability. and is tougher than polylactides and even HDPE . It is fully degraded in the body within a period of 180 days .3. quinine. Nishida et al  reported that polydioxanone decomposes to non‐toxic gases (CO2 and H2O) by microorganisms.Chapter 2 2. Polydioxanone has a tensile strength close to 48. polydioxanone also shows good performance. Its melting temperature is close to 110 oC. The alkoxide group will end up as an ester end‐group in the polymer and in this way at least one of the end‐groups may be easily controlled and varied. reaction of the metal‐alkoxide with an appropriate alcohol allows the synthesis of end‐capped poly‐lactones. accessible by the polymerization of p‐dioxanone (1). Several polymers with bioactive alcoholic and phenolic end‐groups of interest for drug‐related applications were synthesized (for example geraniol. which is a unique compromise between application and processing temperature.
NMR) due to the poor solubility of the products in standard organic solvents.4‐di‐O‐ isopropylidene‐α‐D‐galactopyranose (2).2. 2.5 mmol) was dissolved in toluene (1 ml) at 50 oC. Analytical grade dichloroethane (Labscan). 2. The polymerization was allowed to proceed for 16 h at 100 oC.07 g. relatively low molecular weight compounds reported in this study may be viewed as model systems for more complex.8 ml of a solution of an aluminum isopropoxide stock solution was added. The hot solution was 27 . Particularly interesting in this field are starch polymers grafted with polydioxanone.8 g. Subsequently.2. Toluene (Labscan) was dried and stored on molecular sieves 3 Å (Labscan) under nitrogen. 0. 8 mmol).4‐di‐O‐ isopropylidene‐α‐D‐galactopyranose (2) 2 (1. which was pre‐heated till about 60°C to obtain it in a liquid state. Methods All polymerization experiments were carried out under a protective nitrogen atmosphere using standard Schlenk‐ and glovebox techniques. part of this solution (350 µl. As such. 3]. 97% (Sigma) and aluminum isopropoxide. Boehringer Ingelheim. The resulting clear solution was stirred for 2 h at 50 oC. 2. Typical example for the synthesis of polydioxanone end‐capped with 1. After the pre‐determined reaction time. hot dichloroethane (20‐25 ml) was added to completely dissolve the partly solid polymer at room temperature. and diethylether (Labscan) were used as received.g.1. the results of this study are also of interest for the preparation of starch/polydioxanone polymers using ROP. the synthetic pathways and the soluble.2. To this solution.1. containing 0. However.44 g.2.08 mmol aluminum isopropoxide) was added to pure 1 (0. CDCl3 was obtained from Sigma and was used as received. The reaction mixture was clear and colorless during the reaction. (20 mmol) of aluminum isopropoxide to 20 ml of toluene.55 mmol of 2 and 0.2. Germany) was purified according to the procedure described by Raquez et al [2. Next. Materials and Methods 2. 5. 1.3. heptane (Acros). Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐Monosaccharide Initiator System potential applications in biomedical products.2.2. 98+% (Aldrich) were used as received. poorly soluble heterogeneous systems. the mixture was brought to room temperature and several drops of HCl (1 N) were added to stop the reaction. grafting efficiencies are difficult to determine in this system by standard analytical techniques (e.2. Materials p‐Dioxanone monomer (1. This stock solution was prepared by adding 4.3.
1. 1H‐ and 13C‐NMR spectra were recorded on a Varian AMX 400 NMR. 40 oC) until constant weight.2. 4:1 by volume) at 4‐8 oC. Product Analyses NMR analyses were performed in CDCl3. The white solid was finally separated from the liquid by decantation and dried in a vacuum oven (5 mbar. If the amount of sugar is in excess with respect to the aluminum catalyst.Chapter 2 precipitated in a heptane/ ether mixture (300‐400 ml. This leads to the following equation: Xn exp X n exp is = A A H-repeating unit H-galactopyranose end group +A (2. 2. it is assumed that all available initiator is used effectively.) H-isopropoxide end group 28 . MALDI‐TOF spectra were recorded on an Applied Biosystems Voyager DE‐PRO machine using dithranol/ NaI as the matrix (linear mode). two polymers with different end‐groups are present. the above equation simplifies to Xn theo = monomer conversion × [monomer ]0 [ sugar ]0 (2.) Here. X n exp of the product. Calculation of Average Degree of Polymerization The Theoretical Average Degree of Polymerization. The isolated yield at this condition was 68%. As will be shown later. 1 calculated by comparing the peak area of characteristic end‐group protons with that of a proton of the repeating unit in the polymer (A H‐polymer). X n theo in terms of number of monomer units is calculated as follows : Xn theo = monomer conversion × [monomer ]0 [total initiator ] [monomer ]0 = monomer conversion × 3[ Al (O i Pr) 3 ] + [ sugar ]0 (2.3.2.) H‐NMR was applied to determine the experimental average degree of polymerization.4.2. Processing of the raw data was performed using VNMR software.3. 2. 2D‐NMR spectra were recorded on a Varian Unity 500 NMR. one initiated on a galactopyranose molecule and the other on an isopropoxide group.
R gp . an Al ‐ monosaccharide 2 ‐ monomer 1 mol ratio of 1: 6. Typically. in term of the NMR resonances : R gp = A 5. The polymerization reaction was performed as a two step process.2. is calculated using: R gp = A H − galactopyranose end group H − isopropoxide end group A (2.7 ppm − 6 × A 5.3. To compensate for this effect.6: 96 was applied.1 ppm (2. To avoid the formation of isopropoxide end groups.1 ppm (2.6 ppm ] / 6 A 5.6. 2.3.1. is rewritten as: Xn exp = [ A 3. Results and Discussions 2.) or. Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐Monosaccharide Initiator System The NMR peaks of the repeating unit overlap partially with those of the galactopyranose end group. 2.1.) 2. In the first step. eq.6 ppm + A 5. The exchange reaction typically takes place at 50°C for 2 h. an excess of monosaccharide 2 on Al was used (see eq. the protected mono‐saccharide 2 reacts with Al(OiPr)3 to form the actual catalyst for the polymerization reaction.7.) The ratio of the two different types of polymers (either end‐capped with galactopyranose or an isopropoxide group).5.4‐di‐O‐isopropylidene‐α‐D‐ galactopyranose (2) and Al(OiPr)3 as the catalyst precursor (Scheme 2. Schematic representation of the polymerization reaction including atom numbering scheme 29 .1.).6 ppm A 5.4.3.).4− 4. CH2OH 6 O 4 H H5 O 3 H O O H 2 O H O 1 α O β O γ Al(OiPr)3 catalyst O O α γ γ' β' β α' H2C O [ C CH2 O CH2 CH2 O ]n C CH2 O CH2 CH2 OH 6 O H O H5 1 4 O H O H 2 3 H O + n+1 (2) (1) (3) Scheme 2. Screening Experiments Initial experiments to synthesize protected galactopyranose end‐capped polydioxanone (3) were performed using 1.3.
respectively.15‐1. Typical 1 H‐ and 13C‐NMR spectra of 3 are shown in Figure 2. the in‐situ formed catalyst was reacted with p‐dioxanone monomer 1 at 100 oC for 16 h. It confirms that polymer initiation not only occurs with the monosaccharide but also with the remaining isopropoxide group of the catalyst precursor (vide infra). This multiplet is characteristic for the CH proton of an isopropoxide end‐group. Although the spectra clearly indicate the presence of the monosaccharide 2. Product analyses The products were analyzed using 1H‐ and 13C‐ NMR and MALDI‐TOF.1. The off‐white solid reaction product was collected after a dissolution‐reprecipitation process using dichloroethane and a heptane/ diethyl ether mixture.) are not particularly informative.67.1 ppm compared to the monomer.3.1 and 2. 2.2.) In the next step.Chapter 2 H H CH2OH iPr O Al O iPr iPr O O O H O H H O H O O H O H O O H O Al O CH2 O O H O H H O O H O H H O + O 3 H H2C H2C O H H O H + H O 3 iPr OH O (2. However. together with the CH3 groups from the protecting groups of the sugar appear in the range 1. although it is evident that p‐dioxanone polymerisation occurred. Proton resonances of the CH3 group of the isopropoxide end‐group.1 ppm.. H‐NMR spectra (Figure 2. Typical isolated product yields are 68% at these conditions.7.51 ppm.78 to 4.1. it is not possible to determine whether this is truly an end‐group due to overlapping peaks with protons from the poly(p‐ dioxanone) backbone. It is difficult to determine the end‐groups of the polymer on the basis of 1H‐NMR. 1 30 .40 ppm) unit are broadened and shifted up to 0.1. of interest is the presence of a small multiplet at about 5. The typical proton resonances of the p‐dioxanone (3. The OiPr : 2 end‐group ratio for the standard experiment was 1: 2.
2‐70. C‐6 is shifted from δ = 62.4‐di‐O‐isopropylidene‐α‐D‐galactopyranose‐end‐capped polydioxanone.2 ppm. Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐Monosaccharide Initiator System Figure 2.28 ppm in 2 to δ 66. 3 1 C‐NMR (Figure 2. H‐NMR Spectra of: (a).2.) is more informative and clearly shows the presence of a polydioxanone polymer backbone and a monosaccharide end group.2 ppm. characteristic resonances of an ‐O‐C(=O)‐CH2‐O‐CH2‐CH2‐OH end group are present at δ = 61.2.3. 2 (b).61 (γ’) and 73.2.52 ppm (β’). Particularly the C2‐C6 carbons in the range δ = 66. 1 (c).17 and 69. 13 31 .1.3.2 ppm in product 3. 68. 1. Carbon resonances arising from the monosaccharide end‐group are present between δ = 66.3 ppm are shifted considerably. The carbon resonances of the polydioxanone backbone are present at δ = 63.2 and 96. In addition to the mono‐saccharide end‐ group. For instance.8.4‐di‐O‐isopropylidene‐α‐D‐galactopyranose. p‐dioxanone monomer. 1.
1 (c).3. A typical example of a part of the 2D‐NMR spectra is given in Figure 2. p‐dioxanone monomer.76‐25.2.97 (>C‐(CH3)2).2. D‐NMR (HSQC) was applied for complete peak assignment of the product. C‐ NMR Spectra of: (a)..76‐25.2. the numbering scheme of carbons and protons is given in Scheme 2. and 2. The resonances of the protecting group of the sugar appears at δ = 108.73 and 109. An overview of the data is given in Tables 2. 2 32 . 1.3.48 ppm (‐CH‐ (CH3)2) and between δ = 21.3.4‐di‐O‐isopropylidene‐α‐D‐galactopyranose.Chapter 2 Figure 2.4‐di‐O‐isopropylidene‐α‐D‐galactopyranose‐end‐capped polydioxanone. 2 (b).2.1. 3 13 Carbon resonances of the isopropoxide groups from the by‐product (isopropoxide end‐capped polydioxanone) are present at δ = 68.1.70 (>C‐(CH3)2) and between δ = 21. 1.97 ppm (‐CH‐(CH3)2).
around 1.59 4.09 4. HSQC 13C‐1H spectra of 3 Table 2.26 3.8 Reactant peaks (ppm) Galactopyranose (2) H‐1 H‐2 H‐3 H‐4 H‐5 H‐6 5.74 3. 33 .68 4. 1 H‐NMR peak assignments a Product peaks (ppm) Poly(p‐dioxanone) end‐capped with protected galactopyranose (3) H‐1 H‐2 H‐3 H‐4 H‐5 H‐6 H‐α H‐β H‐β’ H‐γ H‐γ’ H‐OH 5.16* 4. Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐Monosaccharide Initiator System Figure 2.50 4.3.83 p‐dioxanone Monomer (1) H‐α H‐β H‐γ a 4.54 4.78 4.32 * 4.31 4. except values with *.25 3.1.301 3.60 4. which were determined from HSQC spectrum due to overlapping resonances.40 all values were determined using 1H NMR.732 broad.00 4.17 3.77 3.
17 69.61 170.21 NMR analyses also allow calculation of the molecular weight of the products. MALDI‐TOF was also applied to characterize the products.52 63. A detailed procedure is given in the experimental section. 34 .63 68.10 71.28 70.75 70.54 166.4. A typical molecular weight distribution is observed. For this purpose.80 61.11/ 170.2 73. The latter likely stems from the matrix used to ionize the sample.) This series represents a dioxanone polymer end capped with 2 and an additional Na ion.Chapter 2 Table 2.28 p‐dioxanone monomer (1) C‐α C‐β C‐γ C‐carbonyl 61.57 62.21 70.33 70.00 171.31 70. the ratio of the intensity of the end groups and the polymer backbone peaks is determined. The difference in molecular weight between the main peaks is 102 g/mol.09 65. corresponding with an average number molecular weight (Mn) of about 1600. The product obtained at screening conditions (16 h reaction time at 100°C) contains on average 13 monomer units. which is the molecular weight of a repeating dioxanone unit.2 68.07 Reactant Peaks (ppm) Galactopyranose (2) C‐1 C‐2 C‐3 C‐4 C‐5 C‐6 96. 13 C‐NMR peak assignments Product Peaks (ppm) Poly(p‐dioxanone) end‐capped with protected galactopyranose (3) C‐1 C‐2 C‐3 C‐4 C‐5 C‐6 C‐α C‐β C‐β’ C‐γ C‐γ’ C‐carbonyl C‐carbonyl‐iPr/gal 96.58 68. An example of a MALDI‐TOF spectrum of 3 recorded in a dithranol/NaI matrix is given in Figure 2.2.92 66.8.92 68. The molecular weight distribution of the major peaks may be represented by the following relation: m / z = 23 + 260 + 102n (2.
11. see Figure 2. m / z = 23 + 18 + 102n m / z = 1 + 18 + 102n 35 (2.5. ionized with either Na+ or H+.11.5 +102 1400 1600 1800 2000 2200 2400 Mass (m/z) Figure 2. Furthermore.10.10. two other distributions are present.) and imply the presence of dioxanone polymers with carboxylic end groups. Typical MALDI‐TOF spectra of 3 A second molecular weight distribution is also clearly visible when enlarging the spectra.) (2.4.5. for details. This series may be described by the following relation: m / z = 23 + 60 + 102n (2. Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐Monosaccharide Initiator System 100 90 80 70 60 %-Intensity 50 40 30 20 10 0 600 800 1000 1200 1098. although both with a very low intensity (Figure 2.) .) This relation is indicative for the presence of a polydioxanone polymer containing an isopropoxide end‐group. in line with the NMR data.9.). These distributions may be represented by equation (2.) and (2.
different molecular weights were analysed.3. according to NMR. [6.Chapter 2 50 40 792. Most likely the matrix (dithranol/NaI). it proved not suitable to determine the average molecular weight of the products.1 0 600 700 800 900 Mass (m/z) 1000 1100 1200 Figure 2.7 796. A mechanistic proposal for the ROP of p‐dioxanone with Al(OiPr)3 as the catalyst precursor leading to the desired monosaccharide end‐ capped polydioxanone is given in Figure 2.7 %-Intensity 30 20 858. 2. although successfully applied for galactopyranose‐end‐capped polycaprolactone . The observed differences in the molecular weight distributions of the various samples were only marginal.3 10 836. Enlarged MALDI‐TOF spectra for 3 Although MALDI‐TOF clearly demonstrated the presence of various types of end‐groups in the product. Various samples with.2. low resolution spectra were obtained. is not particularly suitable for polydioxanone. small but significant amounts (20‐30%‐mol) of polydioxanone chains with an OiPr end group are present. 2‐(4′‐ hydroxybenzeneazo)benzoic acid (HABA)). Various other matrices were tested (e.5. In addition.g.6. but in all cases poor quality.13]. Mechanistic aspects Both NMR and MALDI‐TOF measurements imply that the main product is indeed the desired monosaccharide end‐capped polydioxanone. In the first step. the catalyst precursor is treated with monosaccharide 2 resulting in an alcohol exchange 36 .1.
Subsequent coordination and insertion of dioxanone molecules leads to the formation of a polymer chain with a monosaccharide end‐group. The termination reactions lead to the formation of ‐O‐C(=O)‐CH2‐O‐CH2‐CH2‐OH end groups. (R = monosaccharide 2) 37 . Simplified reaction scheme for the ROP of p‐dioxanone catalyzed by Al(OiPr)3. During the reaction. Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐Monosaccharide Initiator System reaction and the formation of the desired active catalyst with preferentially all three OiPr exchanged with 2. termination of the chain growth may occur by reaction with an alcohol. Next. Irreversible termination of the polymerisation is performed at the end of reaction period by adding dilute acid to the polymerisation mixture. a p‐dioxanone molecule will coordinate to the Lewis acidic aluminium center followed by an insertion step.6. iPr iPr O Al O iPr + R OH (in excess) O O Al O R + O iPr OH O Al O O iPr + O + O O O O n O l O O O Al [O CH2 CH2 O CH2 C ] n OR O O O O Al [O CH2 CH2 O CH2 C ] O n+m OR + m R-OH O + HX (termination) O Al O R O O Al X O O + + O O H [O CH2 CH2 O CH2 C ] l by-product O iPr H [O CH2 CH2 O CH2 C ]n OR H [O CH2 CH2 O CH2 C ] n+m OR product Figure 2. The termination reaction is known to be reversible and the formed polymer may again react with an aluminum center and continue to grow . The resulting Al‐alkoxide may again initiate a polymerisation reaction.
6 6.3 3.93 8.4 2. 2.6 89. two different reaction times (1.4 2. Chain Length (Xn exp ) Yieldb (%) 30.0 87.5 1.22 57.36 17.3.5 1.8 2. A total of 15 experiments were performed at two polymerization temperatures (60 and 100 oC).45 19. will be formed when the polymerization starts with an aluminum alkoxide with a remaining Al‐OiPr group (eq.74 52.6 96.49 13.3 6.7. degree of polymerisation of the product and the end group distribution was determined.3 81. formed in the first step of the polymerisation reaction (eq.6 81. An overview of the experiments and the results are given in Table 2.50 25.6 t (h) 16 16 16 16 16 16 16 16 16 16 1.5 hrs and 16 hrs) and a p‐dioxanone to monosaccharide 2 molar ratio ranging between 3. However.5 1.11 22.7 2.3 and 62.12 42.6 2.5.28 33.93 37.1 2.70 58.6 6.6 86.04 19.6 6.50 35. OiPr‐end‐capped poly(p‐dioxanone).6 6.1 3.74 18.08 30.53 59.3 6.2 91.6 6.81 16.85 14.). Set Sample S111 S112 S113 S114 S115 S211 S212 S213 S214 S215 S221 S222 S223 S224 S225 Overview of experiments a Processing Condition 2/Al ratio (mol/mol) 6.5 T (°C) 100 100 100 100 100 60 60 60 60 60 60 60 60 60 60 dioxanone/ 2 ratio (mol/mol) 3.6 6.74 23.5 2.2. the exchange reaction between the catalyst and the protected sugar was performed for 2 hours at 50°C The yield is the isolated yield of product 3 b 38 .16 46.3 6.5 67.Chapter 2 The minor product.5 92.96 2 3 a For each experiment.3‐6.22 13.4 3.7.21 54.6 80.10 15.6 91. 2. These may be present in the reaction mixture because the exchange reaction between Al(OiPr)3 and 2 was incomplete.5 1.3.4 2/OiPr ratio Rgp (mol/mol) 2.8 2.1 86. despite the excess of 2. time and the mol ratio of monomer to monosaccharide) on the yield.29 14.55 Product Properties Avg. In all cases. a (nearly) fixed Al(OiPr)3 : monosaccharide ratio of 1 : 6.9 2.9 1 7. 2.).22 16.3 6.6 6.5 84. the end group may also be formed by a termination reaction with free isopropanol. Systematic Studies The effect of important process variables (temperature. Table 2.8 3.3 6.30 62.6 was applied.3 6.6 6.1 2.78 10.3.5 81.
the yields are higher when performing the reaction at 16 h reaction times. leading to a low average chain length of the dioxanone polymer (7.5 and 16 h reaction time). the yields for reactions conducted at 60 oC are always higher than those performed at 100 oC.3. Similar observations were made by Raquez et al  and Kricheldorf et al  for dioxanone polymerisations using Al(OiPr)3 in the absence of a external alcohol or using benzyl alcohol.3. will be required. It was shown that at lower monomer to catalyst ratios. 1. The latter is due to the slight exothermicity of the reaction . Evidently.2. which reduced to 75% when increasing the temperature to 120oC.5 h is higher than the yield at 16 h. and particularly when comparing the data in set 2 and 3 (60oC. no detailed explanation has been put forward to explain this anomalous behaviour.). equilibrium conversion is not yet achieved within 1. Clearly. One of the experiments (S111) resulted in a very low yield (31%) compared to the other reaction. the monomer conversion reaches a maximum value before going down to the equilibrium monomer conversion.3. Product yield The isolated yields of the reactions are all but one between 67 and 96% (see Table 2. Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐Monosaccharide Initiator System 2.).5 h. a low dioxanone: monosaccharide 2 ratio was applied. A more detailed analysis on the actual nature and composition of the polymerization products.2. The effect of temperature on the yield of the bulk polymerization of dioxanone using Sn(Oct)2 and Al(OiPr)3 as catalysts (without the use of a second alcohol) has been studied by Nishida et al  and Esteves. For the two experiments with a dioxanone: 2 ratio higher than 16 (≅ 23 and 60). To the best of our knowledge. et al . the equilibrium conversion of dioxanone at 80oC was about 80%.1. However. On the basis of our experimental data and in line with literature data. Another possibility is the occurrence of polymer crystallization. The effect of the reaction temperature (60 and 100°C) on the product yield at three different dioxanone: 2 ratios is given in Table 2. see Table 2. as suggested by Raquez et al . when the reaction is performed at a low dioxanone: 2 ratio (≅ 16). we conclude that equilibrium conversion is achieved after 16 h and that the lower polymer yields at higher temperatures are due to the slight exothermicity of the reaction. These results were explained by assuming that the reaction is an equilibrium polymerisation and that the equilibrium is shifted to the monomer side at higher temperatures. For this particular experiment. Higher polymerisation yields were obtained at lower temperatures.3. with an enthalpy of polymerization of approximately ‐15 kJ/ mol . the yield at 1. which is expected to be more pronounced at lower temperatures. For instance. It is likely that this relatively low molecular weight compound dissolves partly during isolation/ purification procedure leading to lower isolated yields.3. 39 . The effect of the reaction time on the product yield may be derived from the data provided in Table 2.
time: 16 hr Temperature: 60oC. The X n exp increases linearly with respect to the dioxanone : 2 ratio.). Most experimental points are scattered along these lines. Effects of process conditions on the average chain length ( X n exp ) and end group distribution The effects of the p‐dioxanone: 2 ratio.3.2. time: 1.3. 2.7.) for all experiments are scattered randomly between 2. The R gp values (Table 2.) as a function of the dioxanone : 2 ratio at 90% and 100% monomer conversion is also provided. time: 16 hr 50 Temperature: 60oC. Average Chain Length ( X n exp ) of the product as a function of the dioxanone : 2 mol ratio The end group distribution was determined using NMR and is expressed in terms of R gp (eq. the X n theo (eq.6.Chapter 2 2.7.4 and 3.5. and 2.3. 2. A clear trend between R gp and the process conditions (temperature. and dioxanone/ 2 mol ratio) is absent.2.7. to reduce the number of OiPr endgroups in the product may be the removal of isopropyl alcohol formed in step 40 ..5 hr Xn theo theo (90%-conversion) (100%-conversion) 40 Xn exp Xn 30 20 10 0 0 10 20 30 40 50 dioxanone : 2 ratio (mol/mol) 60 70 Figure 2. in line with the theoretical predictions. In Figure 2.2. time. reaction time and temperature on the X n exp of the products is shown in Figure 2. 60 Temperature: 100oC. A possible strategy to increase the Rgp values i. as expected for a typical ring opening polymerisation .e.
7.854 × (dioxanone : 2 ratio) + 0. Analysis of variance (ANOVA) for linear model of X n function of experimental parameters SS 4103 93 4010 DF 3 12 15 MS 1337 7.459*10‐7 41 .) where t and T are respectively the polymerization time and temperature. A linear model proved adequate to describe the effects of the independent variables on the X n exp : Xn exp = 8.977 (with an adjusted R2 value of 0.543 exp as a Model Error Total P‐value 3.12.097 × (T ) (2.177 × (t ) − 0.3‐6.) from the reaction mixture by e.49 + 0. The low P‐value clearly indicates that the model is statistically significant.3.g.703 F 173.4. vacuum distillation before adding the dioxanone monomer .8. indicating that the model describes the experimental data reasonably well. time and dioxanone/ 2 ratio) on the X n exp has been performed by multivariable linear regression  on the data given in Table 2.974). 2. A parity plot of the modeled versus experimental values of the average chain length Xn confirms this statement (Figure 2. Statistical Data Analysis Quantification of the influence of the experimental factors (temperature.).3. 2. The R2 value for the model is 0.4. Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐Monosaccharide Initiator System 1 of the polymerisation process (eq.6) was too limited to draw sound conclusions.3. Table 2. The 2/ Al ratio was not included in the model as the experimental range (6. The analysis of variance for the model is given in Table 2.2.
Chapter 2 60 50 40 Xn model 30 20 10 0 0 10 20 30 Xn exp 40 50 60 Figure 2. This is in line with literature data [5. Within the experimental ranges. the model predicts that the X n exp is positively influenced by the polymerization time.4‐di‐O‐ isopropylidene‐α‐D‐galactopyranose. with higher ratios leading to higher molecular weights. 16. Furthermore.3. Modeled versus experimental values for the average chain length Xn The model predicts that the X n is a clear function of the p‐dioxanone : 2 mol ratio. 17]. Molecular weights (NMR) of the product were between 970 and 6200 and are a clear function of the p‐dioxanone/2 ratio (at constant Al(OiPr)3 intake). 11] and due to the fact that the reaction is an equilibrium polymerization with a slight exothermic effect. The isolated yields of the off‐white solid products were between 30 and 96%. Conclusions The ROP of p‐dioxanone in the presence of a monosaccharide (1.2.8. the model allows determination of the process variables to obtain a product with the desired degree of polymerization. Both NMR and MALDI‐TOF measurements indicate that the products are mixtures of polymers and significant 42 . 2) with Al(OiPr)3 as the catalyst is reported. In addition. which is in agreement with the available data on ring opening polymerization [15. 2. the X n exp is negatively influenced by temperature. with high ratios leading to a higher average chain length.4.
Kricheldorf.M. starch). . Chem.4‐dioxan‐2‐one. 1063‐1071. and mechanistic aspects of the ring‐opening polymerization of 1. P. Degee. 21. P.4‐dioxan‐2‐one and controlled synthesis of diblock copolymers with epsilon‐caprolactone. Rapid Commun. Raquez.L. Mater.O. .J. 1993. H. Moreover. kinetic. 1089‐ 1097. Macromolecules 2001. Macromol.M. 8419‐8425.g. P. 34. 199. C. 2. R. D. 153‐166. D. A statistical model has been developed to quantify the effects of process variables (time. Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐Monosaccharide Initiator System amounts of p‐dioxanone polymers with an isopropoxide end group (20‐30%) were present. J. Phys. 43 . Res.4‐dioxan‐2‐ one initiated by Al((OPr)‐Pr‐i)(3) in bulk. P. 27. Narayan.C. Degee. Lin. Grubb: Hydrolytic degradation and morphologic study of poly‐p‐dioxanone.6. Biomed. 1998. H.5. Narayan. Chu. 42. These studies will be reported in the next chapter. Macromol. Nomenclature AH A x − y ppm : peak area of certain proton in 1H‐NMR spectra [‐] : peak area of certain peak at x until y ppm in 1H‐NMR spectra [‐] : mol ratio of galactopyranose end‐capped polydioxanone and isopropoxide‐end‐capped polydioxanone [‐] : number of monomer unit in the polymer products [‐] : time [hour] : temperature [oC] : experimental average degree of polymerization the polymer products [monomer units] : theoretical average degree of polymerization of the polymer products [monomer units] R gp n t T X n exp X n theo 2. R. Dubois: ʺCoordination‐insertionʺ ring‐ opening polymerization of 1. Raquez. J. Zn‐lactate‐catalyzed polymerizations of 1. References . 2000. the findings of this study have proven to be valuable input for synthetic studies on the preparation of novel biodegradable polymers consisting of polydioxanones and polycaprolactones grafted on oligo‐ and polysaccharides (e.R. temperature and monomer: monosaccharide ratio) on the X n exp . . Damrau: Polylactones. Dubois: Some thermodynamic.
. H. Nishida, M. Yamashita, T. Endo, Y. Tokiwa: Equilibrium polymerization behavior of 1,4‐dioxan‐2‐one in bulk. Macromolecules 2000, 33, 6982‐6986. . T. Hamaide, M. Pantiru, H. Fessi, P. Boullanger: Ring‐opening polymerisation of epsilon‐caprolactone with monosaccharides as transfer agents. A novel route to functionalised nanoparticles. Macromol. Rapid Commun. 2001, 22, 659‐663. . K. Bernard, P. Degee, P. Dubois: Regioselective end‐functionalization of polylactide oligomers with D‐glucose and D‐galactose. Polym. Int. 2003, 52, 406‐411. . H.R. Kricheldorf: Syntheses and application of polylactides. Chemosphere 2001, 43, 49‐54. . H.R. Kricheldorf, M. Berl, N. Scharnagl: Poly(lactones). 9. Polymerization mechanism of metal alkoxide initiated polymerizations of lactide and various lactones. Macromolecules 1988, 21, 286‐293. . H.R. Kricheldorf, I. Kreisersaunders: Polylactones. 30. Vitamins, hormones and drugs as co‐Initiators of AlEt3‐initiated polymerizations of lactide. Polymer 1994, 35, 4175‐4180. . L.M. Esteves, L. Marquez, A.J. Muller: Optimization of the coordination‐ insertion ring‐opening polymerization of poly(p‐dioxanone) by programmed decrease in reaction temperatures. J. Appl. Polym. Sci. 2005, 97, 659‐665. . D.C. Montgomery: Design and Analysis of Experiments, 5th Edition, John Wiley & Sons Inc., New York, USA, 2001. . P. Dubois, R. Jerome, P. Teyssie: Aluminum alkoxides ‐ A family of versatile initiators for the ring‐opening polymerization of lactones and lactides. Makromol. Chem. Macromol. Symp. 1991, 42/43, 103‐116. . A. Duda, A. Kowalski, J. Libiszowski, S. Penczek: Thermodynamic and kinetic polymerizability of cyclic esters. Macromol. Symp. 2005, 224, 71‐84. . A. Kowalski, A. Duda, S. Penczek: Polymerization of L,L‐lactide initiated by aluminum isopropoxide trimer or tetramer. Macromolecules 1998, 31, 2114‐ 2122. . A. Duda, A. Kowalski, S. Penczek, H. Uyama, S. Kobayashi: Kinetics of the ring‐opening polymerization of 6‐, 7‐, 9‐, 12‐, 13‐, 16‐, and 17‐membered lactones. Comparison of chemical and enzymatic polymerizations. Macromolecules 2002, 35, 4266‐4270. . A. Duda: Polymerization of epsilon‐caprolactone initiated by aluminum isopropoxide carried out in the presence of alcohols and diols. Kinetics and mechanism. Macromolecules 1996, 29, 1399‐1406.
Ring Opening Polymerization of p‐dioxanone using an Al(OiPr)3‐Monosaccharide Initiator System
. S. Penczek, T. Biela, A. Duda: Living polymerization with reversible chain transfer and reversible deactivation: The case of cyclic esters. Macromol. Rapid Commun. 2000, 21, 941‐950.
Chapter 3 Synthesis of Poly‐(ε)‐caprolactone Grafted Starch Co‐polymers by Ring Opening Polymerisation using Silylated Starch Precursors Abstract Poly‐(ε)‐caprolactone grafted corn starch co‐polymers were synthesized using a hydrophobised silylated starch precursor.45‐0. grafting. The poly‐(ε)‐caprolactone side chains consist of 40‐55 monomer units and is a function of the reagent intakes. Keywords: starch. silylation . Silylated starch with a degree of substitution (DS) between 0. The grafting efficiency varies between 28 and 58%. the remainder being homopolymers of ε‐caprolactone. The silylation reaction was performed using hexamethyl disilazane (HMDS) as the reagent in DMSO at 70°C.7 was obtained. ε‐ Caprolactone is grafted to silylated starch by a ring‐opening polymerisation catalysed by Al(OiPr)3 in THF at 50oC. polycaprolactone.21 and 0. biodegradable polymers. The DS of the polycaprolactone graft is between 0. Removal of the silyl groups of the poly‐(ε)‐ caprolactone grafted starch co‐polymers is possible using a mild acid treatment with diluted hydrochloric acid in THF at room temperature. Experiments with native starch under similar conditions do not result in the desired poly‐(ε)‐caprolactone grafted corn starch co‐polymers and unreacted starch was recovered after work‐up.72.
and this value increases with about 10% per year . A wide variety of synthetic biodegradable polymers have been prepared.1. 5]. and the mechanical properties of starch‐based films are generally inferior to those derived from synthetic polymers [4. These plastics are mainly synthetic polymers from fossil resources. Well known examples are polyesters derived from cyclic lactones (polycaprolactone. as starch is highly hydrophilic. for instance grafting of monomers (like styrene and methyl methacrylate) to the starch backbone [6. Chapter 3 3. the future generation of packaging materials is highly desirable. amylose (a linear polymer of anhydroglucoses with α‐D‐1. the product properties are in most cases still not up to standards and blending with other polymers is required . roots) as granules or cells with typical particle sizes between 1‐100 µm. PCL has gained much interest for possible applications in the medical field as well as in the area of packaging materials [12‐ 13] Several studies to combine the properties of starch and PCL have been performed to obtain fully biodegradable materials with improved product properties. The development of green biodegradable polymers for e. The amylose‐amylopectin ratio in native as well as modified starches has a strong impact on the product properties. polyvalerolactone. a natural biopolymer. Blends of thermoplastic starch and PCL are not fully miscible. and polybutyrolactone). However. The content of amylose in starches depends on the plant and typically varies between 18‐28%. However.6‐glucosidic bonds besides α‐D‐1. Aerobic soil‐burial experiments showed that the mechanical properties of PCL films decreased rapidly in time and were fully degraded after 4 weeks .4‐ glucosidic bonds). 245 million tons of plastics are produced per year. Starch is present in the body of many plants (tubers. the used monomers and the corresponding grafted chains are not easily biodegradable. Starch has also been thermoplasticized with the help of plasticizers such as glycerol and other polyalcohols . Global production of starch is 60 million ton per year in 2004 . resulting 48 . There are two types of biopolymer in starch. Starch. Introduction Worldwide.4‐glucosidic bonds) and amylopectin (a branched polymer with α‐D‐1. is one of the potential candidates for future biodegradable polymer products. Polycaprolactone (PCL) is easily degraded by micro‐organisms . Starch modification is therefore needed to meet the product properties in a number of application areas. The polymeric structure of starch consists of repeating anhydroglucose units. However. it is water sensitive. 7]. in almost all cases. Starch is abundantly available. which are known to degrade with difficulty and cause serious environmental problems . Starch films are known to have good oxygen barrier properties. Various modification strategies have been explored.g.
The starch source is made less hydrophilic and thus more soluble in organic solvents by substituting part of the OH groups of starch by a bulky silyl group [16‐18]. ε‐Caprolactone monomer (Fluka) was dried over Calcium Hydride (CaH2) for 48 h. Aluminium triisopropoxide [Al(OiPr)3] (Acros) was used without further purification. The highest GE (90%) was achieved using triethylaluminium as catalyst . 49 . This approach has also been applied successfully to graft PCL and polylactide on dextran [19‐20]. To increase the miscibility of starch and polycaprolactone. therefore difficult to handle and releases ethane.67 gram (8 mmol) Al(OiPr)3 in 50 ml of dry toluene in a glove box. This catalyst is extremely air and water sensitive. Acros) and methanol (Labscan) were used as received. Common Ring Opening Polymerization (ROP) catalysts such as tin octoate or aluminium isopropoxide gave low grafting efficiencies (GE. A stock solution was prepared by dissolving 1. Another possible cause for the low grafting efficiencies is the heterogenous nature of the reaction. an alternative method to synthesize poly‐(ε)‐caprolactone grafted starch co‐polymers (starch‐g‐PCL) is reported. during the reaction. In this chapter. This is rationalised by assuming that water competes with the hydroxyl groups of starch in the initiation step of the polymerization reaction.2. Synthesis of Poly‐(ε)‐caprolactone Grafted Starch Co‐polymers using Silylated Starch Precursors in undesirable phase separation . Hexamethyldisilazane (HMDS. DMSO (Acros) and toluene (Labscan) were dried overnight over molecular sieves 3 Å (Merck) and stored under a protective nitrogen atmosphere. thus leading to the formation of PCL homopolymers rather that starch‐g‐PCL . distilled under reduced pressure at 100 oC and stored under a protective nitrogen atmosphere. Hydrochloric acid (HCl) 1 N was prepared from Titrisol concentrated hydrochloric acid solution (Merck) and distilled (Milipore) water. All available data indicate that the presence of water reduces the GE. it has been proposed to chemically graft caprolactone onto the hydroxyl groups of starch using ring‐opening polymerisation . leading to a liquid‐solid system. a very flammable by‐product. Materials Corn starch (Sigma) was dried at high vacuum (~1 mbar) at 100 oC for one day before use. thus to a reduction in the GE. Starch is insoluble in the typical organic solvents used for ROP (such as toluene or THF). the ring opening polymerisation occurs solely in the liquid phase and this is expected to lead to higher GE values. 3.2.1. In this way. 0‐14%). This is expected to lead to reduced reaction rates between starch and CL compared to CL homopolymerisation. Dry tetrahydrofuran (THF) and toluene for polymerization experiments were obtained in closed vessels from Aldrich and were used as received. Materials and Methods 3.
Typical example of in situ polymerization of ε‐CL with silylated starch The silylated product from the first step was dissolved in THF (0.2.111 mol) was added to the gelatinized mixture to initiate the silylation reaction.60): H‐NMR (CDCl3.1. After 24 h. After 2 and 4 h reaction time. Sample SN‐3.2. before peracetylation. Methods All reactions and manipulations with air‐sensitive materials were carried out under a protective nitrogen atmosphere either using standard Schlenk techniques or in a glove box.2.12 (m. A mol ratio of ‐OH groups to catalyst of 10:1 was used. Chapter 3 3.5 (m. 1. acetate‐CH3). another portion of toluene (20 ml) was added. Subsequently. After removal of the solvents under reduced pressure (0. Sample SN‐3.2. 3‐6 ppm (m. silyl‐CH3). Typical example of the starch silylation procedure The procedure for corn starch silylation was adapted from that published for dextran [19‐23].2. broad peaks. 80 oC). After 6 h. The pre‐determined amount of HMDS (typically 24 ml. starch). This procedure was repeated three times.5 ml) and a predetermined amount of the stock solution of Al(OiPr)3 in toluene were added. the silylated starch (1) product was dried in a vacuum oven (~5 mbar. 1 3.12 (m. DS = 0. pre‐dried corn starch (6 g) and dry DMSO (75 ml) were stirred at 70oC for about 3 h until a clear solution was formed. To this homogenous solution. The samples were characterized by 1H‐NMR. 3‐6 ppm (m. the solvents were removed from the silylated starch product under reduced pressure (~ 20 mbar) at 70 oC.1 mbar.60): 1 H‐NMR (CDCl3. Silylated Starch (1. For each experiment. toluene (40 ml) was added to solubilize the precipitated (partially silylated) starch. 0. silyl‐CH3). The reaction was carried out at 70 oC. starch). after peracetylation. broad peaks. 3. 50 oC): δ 0.6 mL) at 50 oC (1‐2 h).2.2. Silylated Starch (1. The mixture was stirred at 50 oC for 4 h to promote the exchange reaction between the isopropoxide groups of Al(OiPr)3 and the free ‐OH groups of starch. The white‐to‐transparent solid products were stored under vacuum in a desiccator at 6‐8 oC. THF (4. DS = 0. 50 oC): δ 0. The intake of 1 depended on its DS and was adjusted to obtain a solution with 5 x 10‐5 mol free‐OH groups/ml of THF. 40 oC) until constant weight. a predetermined amount of ε‐caprolactone monomer (molar ratio of monomer to 50 . Traces of DMSO trapped in the product were removed by dissolving the product in a small amount of toluene and re‐precipitation in methanol.7‐2.
broad peaks. α‐PCL). 1 3. iPr). 60 oC): δ 1. 3.88 ppm (m.5.88 ppm (m.34): H‐NMR (DMSO. The solid precipitate was filtered and dried under vacuum (~ 5 mbar) at 40 oC for 48 h.98 (t.12 (s.5‐ 3. silyl‐CH3). and 5‐5. 1 (0. Deprotection product of Sample SN1CL220.127.116.11‐4.54 (m. 2.5‐3. The product was collected as a white solid and characterised by 1H‐NMR. 4.16 (d. The silylated starch‐g‐PCL (2) product was precipitated from the solution by the addition of heptane (about 250 ml) at ‐18 o C. 1. 1. 1. starch).54 (m. iPr).68. α‐PCL).) was >99 %. The total isolated yield at this condition (see Table 3.4 (m.2. Starch‐g‐PCL (3.3‐4.2. ε’‐PCL). γ‐PCL).2. ‐CH3 .31 (m.16 (d.75.37 (t. The peracetylation procedure applied in this study was adapted from the literature [24. and 5‐5. starch). ε’‐PCL).2. ‐CH3. filtrated.25 (t. 4. broad peaks. After stirring for 2 h. The reaction was stopped by cooling down the mixture to room temperature and the addition of 2‐3 drops of 1 N HCl to deactivate the catalyst. 3. β and δ‐ PCL). and vacuum dried at 40 oC for 24 h. iPr). 1 3. ‐CH. Silylated Starch‐g‐PCL (2.68. the peracetylating reagents 51 . ε‐PCL).75. 4. the desilylated starch‐g‐polycaprolactone product (3) was precipitated using heptane. β and δ‐PCL). 1. The samples were characterized by 1H‐NMR. 60 oC): δ 0. Subsequently. Typically. 1. The silyl group was removed by adding a slight excess (with respect to the number of the silyl functionalities) of 1N HCl to a solution of ‐starch‐silylated‐g‐PCL in THF (10 % w/v). Synthesis of Poly‐(ε)‐caprolactone Grafted Starch Co‐polymers using Silylated Starch Precursors OH‐groups was 13 : 1 for a standard experiment) was added and the ring opening polymerization reaction was allowed to proceed for 24 h at 50 oC.25 (t. 25].1 g) was suspended in THF (4%‐w/v) and stirred at 55 oC until it was fully dissolved (typically 3 h).4 (m. γ‐ PCL).3. 2. DSPCL=0.5.98 (t.37 (t. 3. 3. iPr). ‐CH. ε‐PCL). Peracetylation of the remaining OH groups of modified starch is a well established procedure to improve characterisation of the products by NMR . The yield was measured gravimetrically and is based on the weight of the product and the total weight of reactants charged to the reactor. 4. Sample SN1CL1.31 (m.21): H‐NMR (DMSO d‐6. DSsilylation = 0. 3. DSPCL=0. De‐silylation of poly‐(ε)‐caprolactone grafted silylated starch co‐polymers Desilylation of the 2 was performed using a procedure described by Ydens et al  for desilylation of silylated dextran‐g‐PCL. DSsilylation = 0. Peracetylation of silylated starch Characterisation of the silylated starch by NMR proved very difficult due to the presence of very broad and overlapping resonances arising from starch. 3.
1. This leads to the following equation: ACL = ACH 2 −ε + ACH 2 −ε ' ACH 2 −ε ' = A18.104.22.168−0. The peracetylation reaction was conducted for 7 h at 50 oC.3−3.8 ppm (3.4 ppm + 1 (3.3.2. the DSPCL may be calculated using eq. The Average Chain Length (ACL) of the Poly‐(ε)‐caprolactone chain is defined as the average number of CL repeating units in a grafted polymer chain. Chapter 3 (DMAP. 1 3. it is assumed that the average length of the grafted chain is equal to the chain length of the homopolymer. 3.2. Calculations The DS of the silylated starch (DSsilylation) is defined as the average number of silyl groups present on an anhydroglucose unit (AHG) of starch. Nuclear Magnetic Resonance (NMR) H‐ NMR spectra were recorded in CDCl3 at 50oC or in DMSO d‐6 at 60 oC on a Varian AMX 400 NMR machine.) where Ax‐y stands for the 1H‐NMR peak area in the range δ x‐y ppm. 3.2. When assuming that all ε‐CL monomer is converted. ACH 3 silyl / 9 1 7 A−0.3.) 52 .1. It was finally dried overnight in a vacuum oven at 70 oC and 5 mbar until constant weight.3.1. DSsilylation may be calculated using 1H‐NMR spectra of the products after peracetylation using eq. Analytical Methods 3. 3. acetic anhydride and pyridine in a DMAP : acetic anhydride : pyridine : AHG molar ratio of 1: 10: 22 : 1) were added.) The degree of substitution of the PCL graft on 2 (DSPCL) is defined as the average number of PCL polymer chains present on an AHG unit of starch.4. In this calculation. The assumption of high conversions (>95%) was correct for all experiments (see Table 3.). The product was precipitated by the addition of methanol and washed several times with methanol.2.6 ppm DSsilylation = × = × 3 Astarch proton / 7 27 A3−5.8− 4.2 ppm A3. The ACL is calculated from 1H‐NMR spectra by comparing the peak area of protons attached to ε‐carbon atoms in a repeating CL unit with that of the characteristic ε’ protons of the last CL unit in a PCL chain  (see Figure 3.
Results and Discussions The overall procedure to synthesize poly‐(ε)‐caprolactone grafted starch co‐ polymers (3) consists of three steps and includes hydrophobization of starch by silylation of part of the hydroxyl groups of starch using hexamethyl disilazane (HMDS). It is calculated by comparing the area of protons related to the PCL grafted to starch with the area of the protons of all PCL chains present in the product.9 ⎟ × 100 % ⎜ ⎜ ⎟ ACH 2 −ε ' / 2 ⎠ A3. the focus of this chapter will be on the first two steps of the procedure.) The grafting efficiency (GE) is defined as the percentage of PCL grafted to starch compared to the total amount of polymerized CL (grafted and PCL homopolymer). Synthesis of Poly‐(ε)‐caprolactone Grafted Starch Co‐polymers using Silylated Starch Precursors DS PCL = 0.4 / 2 ⎟ ⎠ ⎝ ⎝ where Ax‐y stands for the peak area in the range δ x‐y ppm. followed by an in‐situ Ring Opening Polymerization (ROP) of ε‐ caprolactone monomer on the hydrophobized starch and subsequent silyl group removal by a mild acid treatment.CL/OH ratio ⎥ ⎣ ⎦ (3.3−3.5. 2007) 3.3.8− 4 .8− 4.3−3. This leads to the following equation: GE = ACH 2 −ε ' / 2 − ACH −iso ACH 2 −ε ' / 2 × 100 % (3.9 ⎡ 0.4 + A3. The values of ∆Hv and Vm were obtained from the SciFinder Scholar database (American Chemical Society.5.4. T stands for absolute temperature.8− 4 . The Hildebrand solubility parameter of HMDS and DMSO were calculated using the following equation : ⎛ ∆H v − RT ⎞ ⎟ δ =⎜ ⎟ ⎜ Vm ⎠ ⎝ 1/ 2 where ∆Hv stands for heat of vaporization. 53 .2 ) ⎤ 1 × ⎢ (3 − DSsilylation )⎥ ⎢ ε .4 − A4 .( A3. and Vm stands for molar volume. A3.) ⎛ ⎞ ⎞ ⎛ A A = ⎜1 − CH −iso ⎟ × 100 % = ⎜1 − 4.3−3.3. Although all steps have been investigated.
60 was obtained. However. 6 H2C OH 4H 3 H5 OH H 6 H2C O R 4H H5 OR 3 H O H 1 H H3C CH3 CH3 CH3 + H3C Si NH Si DMSO 50 deg. Chapter 3 3. as suggested by Einfeldt et al .3. The degree of substitution of the silyl groups (DSsilylation) was determined by 1H‐ NMR. 70 oC.1. The 1H‐ NMR spectrum of silylated starch (Figure 3.1. The silylated products were characterised by NMR. a homogeneous reaction mixture was maintained throughout the reaction. a product with a DS of 0.a. The 1H‐ NMR peaks from the AHG unit after peracetylation were indeed considerably sharper and allowed more accurate DS calculations (Figure 3. the starch peaks are very broad and this feature hampers accurate determination of the DSsilylation. The silylation procedure was adapted from that previously reported for dextran [19‐23].). Using standard conditions (HMDS: AHG molar ratio of 3. mixtures of toluene and DMSO were applied to avoid precipitation of the silylated starch during the reaction. Very broad peaks of starch protons at δ 3‐5 ppm and a sharp peak of the methyl substituents of the silyl group at about δ 0 ppm were observed (see Figure 3.) shows the presence of silyl groups at about δ 0 ppm. It is defined as the average number of silyl substituted OH groups on the anhydroglucose (AHG) unit of starch. In this way.). 3.5. 54 .a.b. Synthesis of Silylated Starch The silylation of corn starch was performed with HMDS as the silylating agent (eq. C O H 2OR H 1 + NH3 2 OH H3C [R = H or Si(CH3)3] Starch Hexamethyldisilazane Silylated Starch (1) (3.1.1.) Instead of using DMSO as solvent. An additional peracetylation procedure to substitute the free hydroxyl groups with acetate groups was performed to improve the quality of the NMR spectra.5. 24 h).).
not peracetylated (b).1. 50 oC): (a).5‐4. DSsilylation=0. 55 . Synthesis of Poly‐(ε)‐caprolactone Grafted Starch Co‐polymers using Silylated Starch Precursors Figure 3.60. and Figure 3.5) on the product DS was investigated by performing experiments with a constant starch and a variable HMDS intake. The results are given in Table 3.2.1. Typical 1H‐NMR Spectra of Silylated Starch (Sample SN3. peracetylated The effect of the HMDS to starch molar ratio (1. in CDCl3.
4 1. The silylation reaction 56 . Effect of HMDS: AHG mol ratio on DS of the silylation product a HMDS intake (ml.1. For all experiments.68 0. the volumetric HMDS intake is about half of the DMSO intake. a fixed starch intake of 6 g (37 mmol AHG) starch was applied.25 cal1/2cm‐3/2) due to the presence of the bulky apolar SiMe3 groups. At a mol ratio of HMDS to AHG of 4.5 Figure 3.36 cal1/2cm‐3/2) considerably.65 0.25 3 4. mmol) 12 (56) 18 (83) 24 (111) 36 (167) HMDS: AHG mol ratio 1.67 0.60 0.5 2 2.6 DSsilylation 0.2. For reactions with an order higher than zero.5 0. Its presence will reduce the polarity of the reaction medium (DMSO. HMDS is a rather apolar compound (Hildebrand solubility parameter of 6.55 0. Surprisingly.5 2.5 3 3.5 HMDS : AHG Ratio [mol/ mol] 4 4. The experimentally observed lowering at higher HMDS intakes is likely due to a decrease in the polarity of the reaction mixture. 70 oC) Table 3. solubility parameter = 11.5:1.5 Product DS (DSsilylation) 0.46 Experiment SN1 SN2 SN3 SN4 a Experiments were performed in DMSO at 70°C. a positive effect of higher reagent intake on the reaction rate and thus the DS is expected.45 0. Chapter 3 0. the DSsilylation decreases for higher intakes of HMDS. DS of the silylated products at different HMDS: AHG ratios (DMSO.
the silylation of starch in pure DMSO using HMDS as the reagent has not been reported to date. The products are soluble in DMSO as well as in less‐polar solvent such as chloroform and THF. Synthesis of Poly‐(ε)‐caprolactone Grafted Starch Co‐polymers using Silylated Starch Precursors involves charged‐ionic species  and a reduction in the polarity of the reaction medium is expected to lead to a lowering of the silylation reaction rates. pyridine. O O H2C O R H H OR H O O H OR H O Catalyst: Al(OiPr)3 Toluene. In situ Ring Opening Polymerization of ε‐Caprolactone with Silylated Starch A number of in situ ROP experiments with ε‐caprolactone (CL) were carried out using a typical silylated starch sample (DS=0. Similar reductions in the reaction rates when working at higher reactant intakes were observed for the esterification of starch with vinyl laurate and stearate . The much higher DS values obtained for dextran compared to starch may be related to differences in molecular weights between starch and dextran and the type of AHG linkages (mainly α‐1.25‐5.0) gave silylated dextran with DS values between 1.2.7‐3. 50 oC H CH2 H OR H C (CH2)5 O n H O H OR + H (R = H or Si(CH3)3 Silylated Starch (1) ε-Caprolactone Monomer [R = H or Si(CH3)3 ] Silylated Starch-g-Polycaprolactone (2) (3.0 [18. The DSsilylation (0.6‐glucosidic for dextran). To the best of our knowledge.) 57 . white solid products with isolated yield > 96% were obtained. A schematic representation of the reaction is provided in eq. sample SN‐1) in THF at 50 oC for 24 h using Al(OiPr)3 as catalyst. DMA/LiCl.3. 29].2. Petzold et al  reported that silylation of starch with trimethylsilylchloride (TMSCl) in pyridine yielded trimethyl‐silyl substituted starch with DS values between 0. and DMSO/pyridine mixtures yielded silylated starch with DS values ranging between 0.7) of the products is in the range of those published for other starch silylation systems.6. 3. liquid ammonia. 3.45‐0.1 and 3.0 .3‐2.68.6. DMF. After precipitation with heptane and vacuum drying. The use of HMDS to silylate dextran (Mw=6000‐40000) in DMSO (HMDS to OH molar ratio of 0. Silylation of starch with HMDS in formamide.
4‐3. A typical spectrum is shown in Figure 3. Figure 3. Apparently. (Sample SN1CL1. Further process optimization studies allowed the synthesis of products with less than 42% of homopolymers (vide infra).2‐4 ppm and imply that the ring‐opening polymerisation reaction of CL indeed occurred. The homopolymers are formed by direct polymerization of ε‐CL initiated on isoproproxide moieties attached to the Al catalyst. Chapter 3 The products were characterized using 1H‐NMR analysis in DMSO‐d‐6 as the solvent.4 ppm. Typical 1H‐NMR spectrum of a silylated starch‐g‐PCL sample. as is shown in Figure 3.2 ppm.0‐5.3. DSsilylation =0. broad peaks in the region δ 3. not all of the caprolactone is grafted to starch and large amounts of PCL homopolymers (72%) were formed. DSPCL=0.21) in DMSO‐d6 at 60 oC.4. The peaks from the polycaprolactone units are clearly present in the range of δ 1. the exchange reaction between Al(OiPr)3 and the OH groups of silylated starch is not quantitative under the conditions applied in this study. 26].68.4. Coding of the peaks is given in Figure 3. This is clearly indicated by resonances of the iPr end‐group of the PCL homopolymer at δ 4.3. The formation of CL homopolymers for this type of reactions has been observed before [15.8 and 5. 58 . However.9 and 1. Resonances from the starch peaks are observable as small.
peaks arising from a ‐COOH unit could not be detected in 13C‐ NMR spectra (δ 175‐180 ppm). Synthesis of Poly‐(ε)‐caprolactone Grafted Starch Co‐polymers using Silylated Starch Precursors 1. Exchange Reaction: iPr O Al O iPr iPr O + H2O iPr O iPr O Al OH + iPr OH 2. Product formation for the reaction between silylated starch and ε‐ caprolactone Besides the ‐OH group of starch. Exchange Reaction: iPr O Al O iPr H2C OH iPr O Al O iPr iPr O H2C O O O H O H OR H H OR [R = H or Si(CH3)3 ] H O + O H H OH H H OH H O + iPr OH Silylated Starch (1) 2. Polymerization Reaction: O iPr O Al OH iPr O PCL homopolymer with carboxylic end-group + O O α H β χ δ ε O α' β' χ' δ' ε' [O C CH2 CH2 CH2 CH2 CH2 ]n O C CH2 CH2 CH2 CH2 CH2 OH (3.7. However.). residual water may also initiate the polymerisation reaction.7.) 59 . This leads to the formation of carboxylic end groups (see eq. Polymerization Reaction: iPr O Al O iPr H2C O O H O H OR H H OR H O O O O α β χ δ ε α' β' χ' δ' ε' H2C [O C CH2 CH2 CH2 CH2 CH2 ]n O C CH2 CH2 CH2 CH2 CH2 OH O O H O H OR H H OR H O [R = H or Si(CH3)3 ] + n+1 Silylated Starch-g-PCL (2) O iPr O Al O iPr iPr O + O n+1 iPr O α β χ δ ε O α' β' χ' δ' ε' [O C CH2 CH2 CH2 CH2 CH2 ]n O C CH2 CH2 CH2 CH2 CH2 OH PCL homopolymer Figure 3. 3.4. 1.
The yield of the products was measured gravimetrically and varies between 96.5 Avg. However. and reaches 58% for a ε‐CL to starch–OH ratio of 29. The ACL of the polymer and the DSPCL increase almost linearly with the ε‐ caprolactone intake (Figure 3. The results are given in Table 3. Chapter 3 The ratio of homopolymerisation versus grafting on starch may be obtained by comparing the integrals of selected peaks in 1H‐NMR spectra.0 15.58 0.5 29.2.5 and 100%. (SN1CL1) is 28%. Chain Length [mon. Table 3. This indicates that higher ε‐CL concentrations during the reaction lead to longer PCL grafts as well as to higher levels of initiation of the grafting reaction on free hydroxyl group of silylated starch.34 0.2. Five experiments were performed to study the effect of different ε‐CL to silylated starch ratio.3. and Figure 3. the intensity of the resonance ε’ was considerably higher that that of the ‐CH‐ iPr peak.47 0.72 Grafting Efficiency [%] 28 43 48 55 58 All reactions were performed using the same intake of SN1 silylated starch (DS=0. b. The GE increases with higher ε‐CL intakes.5. Determined gravimetrically and defined as the total weight of the isolated product divided by the total intake of reactants (silylated starch and CL). Experiment SN1CL1 SN1CL2 SN1CL3 SN1CL4 SN1CL5 a.68) in THF at 50 oC with Al(OiPr)3 as the catalyst (1 mol Al(OiPr)3 per 10 mol‐starch‐OH groups).0 18.2. The grafting efficiency (GE) for the sample given in Figure 3. 60 .).9 ppm).5. units] 40 43 44 49 54 DSPCL 0.9 22. This implies that the ε‐CL conversion is essentially quantitative in all cases.21 0. This implies that grafting of caprolactone to starch also occurs to a significant extent. the intensity of the peak from the ‐CH2‐ end group of the homopolymer (ε’ at δ 3. Overview of results for the grafting of ε‐CL on silylated starch a ε‐CL/ OH [mol/ mol] 13.3 ppm) should be twice the intensity of the ‐CH‐ proton of the isopropoxide end group (δ 4. In the case of only homopolymerisation. in all samples.2 Total Yieldb [%] >99 >99 >99 99 96.
Synthesis of Poly‐(ε)‐caprolactone Grafted Starch Co‐polymers using Silylated Starch Precursors
Average Polymer Length [mon. units]
50 0.7 45 0.6 0.5 40 0.4 35 0.3 0.2 30 12 14 16 18 20 22 24 26 28 30 DSPCL
ε-CL : Starch-OH Ratio [mol/ mol]
Figure 3.5. Average Chain Length (ACL) and the DS for as a function of the CL‐ starch intake. ∆ : Average Chain Length (ACL); □ : DSPCL The mechanism of ROP of cyclic esters such as caprolactone in the presence of an alcohol (ROH, silylated starch in our case) is provided in Scheme 3.1. [30‐31]. Higher monomer intakes are expected to lead to higher polymerization rates as shown in Scheme 3.1.b. This will result in longer PCL chains in the final product, in line with the experimental observations (see Table 3.2. and Figure 3.5.). At higher ε‐caprolactone intakes not only the ACL of the grafted chain increases but also higher values for the DSPCL are observed. This finding may be rationalised by assuming that the rate of chain transfer (Scheme 3.1.c.) with starch is increased at higher ε‐caprolactone intakes. The rate of this reaction is expected to be a function of both the starch and the concentrations of Al‐species with a growing PCL chain. The starch intake for all experiments was equal, meaning that the concentration of Al‐species with a growing PCL chain should be higher at higher ε‐CL intakes. This is indeed predicted by the mechanism given in Scheme 3.1.b.; higher caprolactone intakes will increase the rate of this reaction and lead to higher concentration of Al‐species with a growing PCL chain.
Al O iPr
R OH O O kp kd
Al O R
O Al O [(CH2)5 C O]n R
Al O R
O Al O [(CH2)5 C O]n R + R OH
O Al O R
+ HO [(CH2)5 C O]n R
Scheme 3.1. The observation that a higher monomer to alcohol ratio leads to higher amounts of PCL chains with an alcohol end group and thus a higher DS was also reported for the polymerization of p‐dioxanone with Zn‐lactate as catalyst and α‐tocopherol as the alcohol . To show the potential of our approach to use hydrophobised starch instead of native starch for the ring opening polymerisation of cyclic esters, several ring openings polymerisations of native starch with ε‐CL monomer were performed either in pure ε‐CL or in a mixture of ε‐CL and toluene (80‐100oC, 24 hr). At the start of the reaction, the starch was always insoluble in the reaction medium. After reaction the product was isolated, washed thoroughly with toluene and dried. The weight of the product, however, was very close to the initial starch intake. Examination of the products by FT‐IR does not show the presence of caprolactone vibrations. Thus, it may be concluded that solubilisation of starch is of key importance to obtain poly‐(ε)‐caprolactone grafted starch co‐polymers. These findings are in line with earlier studies on the ROP of ε‐caprolactone on native granular starch using Al(OiPr)3 as catalyst . Here, caprolactone polymerization did not occur after 18‐24 h reaction time and only liquid ε‐CL was recovered. Only when performing the reaction with high concentrations of the aluminium catalyst, a product with a GE of about 13% was obtained. This low GE was explained by assuming that the reaction between starch and Al(OiPr)3 is slow and due to the heterogeneous nature of the reaction mixture. Our study, together with the result of Dubois et al  indicate that homogenous reaction conditions are required for the successful ROP of ε‐CL to obtain poly‐(ε)‐caprolactone grafted starch co‐polymers when using Al(OiPr)3 as the catalyst. When performing the reaction under heterogenous conditions, a high grafting efficiency is only achievable when using triethylaluminium as the catalyst .
Synthesis of Poly‐(ε)‐caprolactone Grafted Starch Co‐polymers using Silylated Starch Precursors
3.3.3. Deprotection of Silylated‐Starch‐g‐PCL A preliminary experiment was performed to remove the silylated groups of the silylated starch‐g‐PCL (eq. 3.8.) using a mild acid treatment with diluted hydrochloric acid in THF at room temperature. All silyl groups were removed successfully, as is clearly seen from an NMR spectrum given in Figure 3.6.
Figure 3.6. H‐ NMR Spectrum of Starch‐g‐PCL (reaction product after desilylation of sample SN1CL2, DSsilylation =0.68, DSPCL=0.34), in DMSO‐d6
O O H2C H H OR H C (CH2)5 O
O H O CH2 H H OH H C (CH2)5 O
O H OR
THF, 2 hr H
O H OH
[R = H or Si(CH3)3 ]
Silylated Starch-g-Polycaprolactone (2)
Silylated starch with a low‐medium DS (0. depending on the ε‐CL‐starch ratio. The ROP with ε‐CL was performed using Al(OiPr)3 as catalyst in THF as the solvent. The key feature is the use of a homogeneous reaction mixture for the ROP of starch with ε‐CL. Conclusions The successful synthesis of poly‐(ε)‐caprolactone grafted corn starch co‐ polymers using a three step approach is reported. This was achieved by making the starch more hydrophobic by partial substitution of the OH groups by trimethylsilyl groups.2. indicating that homogeneous reaction conditions are favorable for the grafting reaction. Chapter 3 3. The grafting efficiency varied between 28‐58%. average value of mole of substituted –OH per mole of anhydroglucose (AHG) units [‐] A x − y ppm ACL DS DSsilylation : DS of silyl group substituents [‐] DSPCL GE : DS of PCL chain substituents [‐] : Grafting Efficiency. Control ROP experiments of ε‐CL with native starch under similar conditions did not produce the desired poly‐(ε)‐caprolactone grafted corn starch co‐polymers. the highest value was obtained with a ε‐CL‐AHG ratio of 29.68) was obtained using a DMSO/toluene mixture as the solvent and HMDS as the silylating agent.46‐0.72. the percentage of PCL grafted to starch compared to the total amount (grafted and homopolymer) of polymerized CL [%] : gas constant.5. Poly‐(ε)‐caprolactone grafted silylated starch co‐polymers with average chain length of 40‐55 monomer units (polymer molecular weight of 4500‐6300) were obtained. 1. Nomenclature A : peak area of certain proton in 1H‐NMR spectra [‐] : peak area of certain peak at x until y ppm in 1H‐NMR spectra [‐] : average number of CL repeating units in a grafted polymer chain or homopolymer [monomer units] : Degree of Substitution.21‐0. The DS of the PCL chains was between 0.986 cal mol‐1 K‐1 : temperature [K] : R T Vm molar volume [cm3/ mol] 64 . Considerable amounts of ε‐CL hompolymers with isopropyl end‐groups were also formed. 3.4. The products may have interesting applications as compatibilizers for starch‐polymer blends.
R. Y.6. . Karlsson. Bagley. 3. Adv. 17.A. J. De Mulder‐Johnston: Edible and biodegradable polymer films: Challenges and opportunities. D. 385–409 . Fanta. . Polym. A. Denmark: http://www. .C. . Polym. Association of Plastics Manufacturers. . 61‐67. report of Food Biopack Project (Ed. Chiellini. F. H.F. 1977. 8. A.A. W. J. Yavuz. . status and perspectives. Eng. Frederiksberg C. 61‐74. Degrad. Website of International Starch Institute. Starch‐Starke 2004.Sci. Aly. X. Department of Dairy and Food Science. Wang: Properties of starch blends with biodegradable polymers. 1273‐1335. Solaro: Biodegradable polymeric materials. Polym. Sci. Russell: Graft copolymers of polysaccharides with thermoplastic polymers ‐ new type of filled plastic. 305‐313. Albertsson: Biodegradable polymers and environmental interaction. Macromol. Sci. Rustgi: Biodegradable polymers. 1998. Goldberg: Review of the biodegradability and utility of poly(caprolactone). C. .dk/isi/stat/rawmaterial. 2008. Yang. Belgium. Denmark. E.R. Environmen. References . J. Prog. R. 2003. Abdel‐Mohdy: Grafting of poly(methacrylic acid) on starch and poly(vinyl alcohol). R. Wang.A. C. M. 51. 53‐57.. 38. Babac: Preparation and biodegradation starch/polycaprolactone films. 1998. Tsiapouris. Biobased packaging materials for the food industry. R. .K. Krochta. Environ. Weber). accessed on August 01. Linke: Water vapor sorption determination of starch based porous packaging materials. Burr. Polym. 65 . 2008. Eng. Chandra.starch. Brussels. . . L. 2000. Aarhus. demand and recovery for 2006 in Europe. J. The compelling facts about plastics: An analysis of plastics production. 23. E. C. Food Technol.M. Synthesis of Poly‐(ε)‐caprolactone Grafted Starch Co‐polymers using Silylated Starch Precursors Greek symbols: ∆H v : heat of vaporization [kJ/mol] : δ Hildebrand solubility parameter [cal1/2cm‐3/2] 3. A. S. of . 1997.. J. Part C: Polym.M. Polym. 2003. the Royal Veterinary and Agricultural University. 56. G. Sci. 43. Beliakova. C. 107‐113. 1251‐1253. Rev. 52.B.C. Mater. 407‐412. 1995. 311‐316. 11. Plastics Europe. K. Starch‐Starke 2000. 1996. Doane.html.
Dellacherie. D. E. A. Nouvel. Boullanger: Ring‐opening polymerisation of epsilon‐caprolactone with monosaccharides as transfer 66 . . J. W. P. L. Degee. Klemm. 10.. Gunther: Synthesis and NMR characterization of regiocontrolled starch alkyl ethers. Dellacherie. E. P. 2001. Rutot. Petzold. L. J. Heublein: Silylation of cellulose and starch ‐ selectivity. 73. 2001. 2001. 41. P. . Six: Controlled synthesis of amphiphilic biodegradable polylactide‐grafted dextran copolymers. E. . Fringant: Properties of thermoplastics blends: starch‐polycaprolactone. Stein. P. Krishnan. Macromolecules 2000. R. 4157‐4167. D. and subsequent reactions. Six. . J. E. 3091‐3100. K. 42. Dubois: Aliphatic polyester‐ based biodegradable materials: new amphiphilic graft copolymers. M. Sci. A. Macromol. regioselectivity. A. Biomacromolecules 2003. Klemm. K. Polym. I. P. C. Macromol. A. .L. . Pantiru. Part A: Polym. Fessi. structure analysis. . 2002. 1735‐ 1743. K. K. Koschella. Petzold. Dubois. Des. Polymer 2000. Dellacherie. W. D. Einfeldt: Structure design of polysaccharides: novel concepts. Hamaide. Rutot. Symp. Stein. and chemical stability of silylated dextrans. H. D. . . Dubois. Klemm: Preparative and 1H NMR investigation on regioselective silylation of starch dissolved in Dimethyl Sulfoxide. Klemm: Regioselective functionalization of starch: Synthesis and 1H NMR characterization of 6‐O‐ silyl ethers. Dubois. Dole. Petzold. Ydens. Biomacromolecules 2001. 2004.L. L. B. . Nouvel. E. Gunther. J. Dubois. 251‐269. 5. Degrad. I. 2577‐2588. 163. 43. Ydens. D. C. Polym. . W. Dubois: Controlled synthesis of poly(epsilon‐caprolactone)‐grafted dextran copolymers as potential environmentally friendly surfactants. Petzold. 1. Polymer 2002. P. 1443‐1450. Averous. I. Narayan: Aliphatic polyester‐grafted starch‐like polysaccharides by ring‐opening polymerization. Six: Partial or total silylation of dextran with hexamethyldisilazane. J. high value applications. Degee. P. L. D. Chapter 3 . 415‐426. Nouvel. Duquesne. 6713‐ 6721. Degee. Moro. 965‐969. 341‐347. 4. Dellacherie. M. Ydens. P. D. Chem.L. P. Cellulose 2003. selective syntheses. 33. Klemm. Polymer 1999.L. . T. 2. Monomers Polym. P. 40. 35‐47. Stab. Kussler. Biosci. D. C. Six: Silylation reaction of dextran: Effect of experimental conditions on silylation yield. Einfeldt. L. M. Gunther. 561‐566. Stein. Einfeldt. P.
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The fatty esters were prepared by reacting the starch with vinyl laurate or vinyl stearate in the presence of basic catalysts (Na2HPO4. 13C‐NMR and FT‐IR. and Na‐acetate) in DMSO at 110°C. The DS of the products is a function of the carbon number of the fatty acid chain. For low vinyl‐ester to starch ratios. Keywords: corn starch.96). vinyl ester to starch ratio and the type of catalyst. the DS decreases. K2CO3.24 ‐ 2. The yellowish products were characterized by 1 H‐. and Na‐acetate are superior catalysts with respect to activity compared to Na2HPO4 and products with DS values close to 3 were obtained. vinyl stearate . When performing the reactions using Na2HPO4 as the catalyst. K2CO3. the DS for the starch‐laurate compounds is higher than for the corresponding starch‐ stearates. vinyl laurate.Chapter 4 Synthesis of Higher Fatty Acid Starch Esters using Vinyl Laurate and Stearate as Reactants Abstract This chapter describes the synthesis of long fatty esters of corn starch (starch‐ laurate and starch‐stearate) with a broad range in degree of substitution (DS= 0. an increase in the vinyl‐ester concentration leads to higher product DS values. At higher ratios. esterification. presumably due to a reduction of the polarity of the reaction medium.
high brittleness. In particular starch is attractive as it is relatively cheap and abundantly available. The first paper on the acetylation of starch was already published in 1865 . Relatively low‐DS (0. To improve the mechanical properties. poor processibility (high viscosity). Esterification of starch with low molecular weight fatty acid derivatives is one of the oldest modification technologies to improve starch properties. An alternative method using methyl and glyceryl laurate esters in the absence of solvent has been recently developed .7 [1. resulting in products with DS values up to 2. most of the studies performed to date use short chain carboxylic acids (C1‐C4). the mechanical properties of high‐ DS starch derivatives of low chain carboxylic acids still need considerable improvements before large scale application as packaging materials becomes within reach.1. and particularly acetic acid derivatives (C2) [2‐4]. The hydrophobicity increases with the degree of acetate substitution (DS. However. the fatty ester substituents [1. However. even after the addition of plasticizers . For the current petrochemical based products recycling is often neither practical nor economically feasible .Chapter 4 4. the use of native starch for packaging materials is limited due to its low moisture resistance. Introduction Green biodegradable polymers derived from natural resources are potentially very interesting substitutes for non‐biodegradable petroleum‐based polymers. However.34‐0. The introduction of acetate groups on starch makes the product more hydrophobic. 5‐6] were introduced using fatty acid chloride reagents. more water‐resistant products may be obtained [3‐4]. An attractive field of application for these polymers is the use as packaging materials. and even fatty acid derivatives (C12‐C18) have been used in the modification reaction [5. and incompatibility with hydrophobic polymers. defined as the moles of substituents per mole of anhydroglucose (AHG) units) . Natural polymers such as starch. Further modification of starch is therefore required to introduce hydrophobicity and to improve mechanical and moisture barrier properties. 5]. 7]. The mechanical properties and hydrophobicity of the products were significantly improved when using these longer chain fatty acid precursors [1. cellulose or proteins are potentially very interesting starting materials for biodegradable packaging materials. and consequently.61) products were obtained using this approach. However. higher molecular weight carboxylic starch esters (C4‐C6) . Recently Mormann et al  explored the possibility of using vinyl esters and particularly vinylacetate as reagents for the preparation of starch esters. 5]. Their 70 . which are relatively expensive and rather corrosive . The major obstacle is the pronounced brittleness of the materials.
Synthesis of Higher Fatty Acid Starch Esters using Vinyl Laurate and Stearate as Reactants research focused on the synthesis of starch acetates and only two examples with a higher molecular weight fatty acid vinyl ester were reported. The reactions were either performed in water or in DMSO using a basic catalyst (Na2HPO4). The synthesis of starch stearate esters using vinyl ester reagents has. 4‐N. the Netherlands). This solvent effect is likely caused by the higher solubility of the vinyl esters in DMSO compared to water. IR spectra were recorded on a Spectrum 2000 FT‐IR Spectrometer (Perkin Elmer). The maximum attainable DS of starch acetate in water was below 1 and limited to 0. Materials Corn starch (approx.2. Germany) were used as received. leading to higher reaction rates.6 for starch acetate ester) were obtained. Germany) and acetic anhydride (Merck. The effect of the addition of a non‐polar solvent (toluene) to the reaction medium to solubilise the products and thus to enhance the reaction rates has also been studied.N‐dimethylaminopyridine (DMAP). 73% amylopectine and 27% amylose) was purchased from Sigma (Germany). The starch was dried before use for 48 h at 105 oC under vacuum (approx. We here report an investigation on the synthesis of higher fatty acid esters of starch with an emphasis on the introduction of laurate and stearate ester side chains. Materials and Methods 4. to the best of our knowledge. Analytical Equipment H‐ and 13C‐NMR spectra were recorded in CDCl3 on a 400 MHz Varian AMX NMR machine. In addition. ~1 mbar). The effects of the starch to vinylester ratio on the reaction rates and DS have been explored. the use of basic catalysts other than Na2HPO4 has been investigated. sodium acetate (Merck. vinyl laurate (Fluka. Technical grade dimethyl sulfoxide (DMSO). and tetrahydrofuran (THF) were supplied by Acros (Belgium) and were also used as received. Potassium carbonate (Boom. In DMSO. as recommended by Laignel et al .2. not been reported to date.2. leading to a moisture content of 2 %‐wt (measured gravimetrically).01 when using vinyl‐laurate. Analytical grade vinyl stearate (Aldrich.2. 4.1. The spectra were recorded at 50 oC. starch esters with a substantially higher DS value (up to 1. 4. Japan). The products were placed directly on the diamond plate and 50 scans with a resolution of 4 cm‐1 were recorded. 1 71 . Germany) and disodium hydrogenphosphate (Merck. Germany) were used without further purification.
28‐32 (C4‐9). 13 FT‐IR (cm‐1): 2920 (C‐H stretching).5 g) was first gelatinized in DMSO (5 ml) at 70 oC for 3 h. 16H. 935 (C‐O stretching).1. broad peaks. 3S. 760. 1020 (C‐O stretching).5 (m. C12). C4‐11).2.9 (t. 16H. 1110 (C‐O stretching).3 (m. broad peaks.1. 28H. 3H. C1S). After cooling. 2. 1370 (C‐H bending). 2H. 5S). 1.9 (C3). C4‐C17). broad peaks. resulting in the formation of a homogenous transparent solution.5 (m.4.3 (m. CDCl3): δ 0. 1 C‐NMR (before peracetylation.. Table 4. 1.9 (C10). O‐C3S. CDCl3): δ 14. Table 4. 3‐6 ppm (m. CDCl3): δ 0. 76‐78 ppm. the product was precipitated using methanol (100 ml) and separated from the liquid phase by decantation. C2S.. (13C‐NMR) and Figure 4.3. vinyl laurate or vinyl stearate (3 mol/mol AHG units in starch) and potassium carbonate catalyst (2 %‐wt with respect to starch) were added and the mixture was stirred at 110 oC for 24 h.1. Starch‐laurate (Sample 17. Figure 4. typical spectra are given in Figure 4.. The atom numbering scheme is given in Figure 4. broad peaks. The samples were characterized by 1H‐ and 13C‐NMR and FT‐IR. C6S).96) H‐NMR (before peracetylation. 1.5 (m. and O‐C6S).1 (C11). 2.9 (t. 1295. 3‐6 ppm (m. C3). C2). 1350 (C‐H bending). C2).0 (C12). 3H. (FT‐IR). 1410 (C‐H bending). 1 H‐NMR (after peracetylation.Chapter 4 4. 7H.1 (m. 22. 7H. 2H. Finally. C4‐11).0 (m. 1.2. C3).9 (broad. 172‐174 ppm (C=O.1. 2H. Typical example of the synthesis of laurate and stearate esters of corn starch Corn starch (0. 34.3. Starch‐stearate (Sample 19. broad peaks.8‐2. 95. 1.7 (C11). broad peaks.3. 1230 (C‐O stretching). 3H. 12). DS = 2. 720. 1740 (C=O). C1S‐6S). 2850 (C‐H stretching). 1. 2. overlap with CDCl3 (C4S). 1. broad peaks.4 (broad.52): H‐NMR (before peracetylation. CDCl3): δ 0. the product was dried in a vacuum oven (70 oC. 68‐74 (broad. 24. 2H. 2H. Methods 4. DS = 2. C18). 3‐6 ppm (m. C2). 31.6 (m. 61. C1S‐6S). 7H. broad peaks. C1S‐6S) 1 72 . 3H.9 (t. 2H.2. C3). (1H‐NMR).3 (m. Subsequently.4 (m. attached to O‐C2S. approximately 5 mbar) for 24 h until constant weight. respectively). C2’). 1150 (C‐O stretching). 1455 (CH2). The product was washed twice with methanol (50 and 25 ml.
C4‐C17). C1S‐6S) 1 C‐NMR (before peracetylation.0 (C3).6 (m. C18).0 (C16). 2850 (C‐H stretching).2. 865. 1150 (C‐O stretching). C2’). 3‐6 ppm (m. 95. 1410 (C‐H bending). 68‐74 (broad. O‐C3S. broad peaks. C3).0 (C18).2 (C2). A peracetylation reaction to substitute all of the remaining 73 .5 (broad.8‐2. 720. 75.7 (C4S). C2).7 (C17). C2S. Synthesis of Higher Fatty Acid Starch Esters using Vinyl Laurate and Stearate as Reactants H‐NMR (after peracetylation. 2H. 760. 22. 172‐174 ppm (C=O. broad peaks. 1295. 950 (C‐O stretching).4 (broad. 2. 1. Numbering scheme for carbon atoms of products 4.9 (t. 1.3 (m. C6S). 2H. 6S O R 5S O R O 4S O 1S 2S 1 3S O O 2 3 4 5 6 7 8 9 10 11 12 CH3 Starch-Laurate O 1' 6S O CH3 2' O O R O 4S 5S O 1S 2S 3S O O 1 2 3 4 5 6 7 8 9 10 11 12 CH3 Starch-Laurate peracetylated 6S 4S O O R 5S O R O O 1S 2S 3S O O 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 CH3 Starch-Stearate O Figure 4. Peracetylation procedure The presence of remaining hydroxyl groups in the products resulted in broad and overlapping starch resonances in 1H‐NMR spectra  and hampered calculation of the DS. 28H. 1740 (C=O). 1100 (C‐O stretching). 1350 (C‐H bending). 1020 (C‐O stretching).2.3.4 (m. 1. 5S).5 (m. CDCl3): δ 0. 3H. C1S). 25. 26‐32 (C4‐15). 61. 7H. 3H.1. attached to O‐C2S. and O‐ C6S) 13 FT‐IR (cm‐1): 2920 (C‐H stretching). 1370 (C‐H bending). 34. 1455 (CH2). 3S. CDCl3): δ 14. 32.
1 g) was suspended in THF (4%‐w/v) and stirred at 55 oC until the starch was fully dissolved (typically 3 h).8− 2. It was finally dried overnight in a vacuum oven at 70oC and 5 mbar until constant weight.) AC 2 = 2 × AH − fattyester The AC2 values of both the laurate and stearate side chains were calculated from the peak intensity in the range δ 0.) AH − starch = (22.214.171.124. The DS of the fatty acid esters was calculated from the DS of the products after peracetylation (eq 4. Subsequently.2.8 ppm (protons attached to the fatty acid carbons C3‐C12 for laurate and C3‐C18 for stearate) using eq. the starch ester (0.4.6. and 4.) The DS of the acetate groups of the products may be calculated by comparing the unit area of the acetate protons (AH‐acetate) to the unit area of the starch protons (calculated from the intensity of the starch peaks at δ 3.6−5.).: 74 .5‐1.). The peracetylation procedure by Einfeldt et al  was applied. The product was precipitated by the addition of methanol and washed several times with methanol.8‐2.) Determination of the unit area of the acetate H‐atoms (AH‐acetate) is hampered by peak overlap with the H‐atoms attached to C2 (AC2) of the fatty acid chains (δ 1.Chapter 4 hydroxyl groups with acetate groups was applied to obtain reliable DS data. DS fatty ester = 3 − DS acetate (4. Typically.3. 4.6 ppm).: DSacetate = AH − acetate AH − starch A3. Determination of the Degree of Substitution (DS) The DS of the product was calculated using 1H‐NMR spectra of the products after peracetylation.3.) (4.6 ppm range) and a correction has to be made (eq 4.1. The peracetylation reaction was conducted for 7 h at 50 oC. acetic anhydride and pyridine in a DMAP : acetic anhydride : pyridine : AHG molar ratio of 1: 10: 22 : 1) were added.. 4. and 4.6 7 (4.6‐126.96.36.199.3.1.6 − AC 2 3 (4.4. 4. AH − acetate = A1. the peractylating reagents (DMAP. The procedure was described earlier by Elomaa et al  and the relevant equations are shown in equation 4.
but swell in organic solvents such as toluene and THF. Subsequently. The products of these exploratory reactions are insoluble in water and DMSO. Ax‐y stands for the peak area in the range δ x‐y ppm.3. Synthesis of Higher Fatty Acid Starch Esters using Vinyl Laurate and Stearate as Reactants AH − fattyester = AH − fattyester = AC 3−C12 A0.8 = (laurate) 21 21 AC 3−C18 A0. Initially. After 24 h.8 = (stearate) 33 33 (4.1. the starch was gelatinised in DMSO at 70°C for 3 h to make the hydroxyl groups of starch more accessible for reaction.1.. while ACx‐Cy is the area of the H‐atoms attached to carbons in the range Cx‐Cy (carbon numbering scheme is given in Figure 4.5−1.7.3. The reaction was performed in two discrete steps.1. Exploratory Experiments A number of exploratory experiments were carried out with vinyl‐laurate and vinyl stearate (vinyl ester: AHG molar ratio of 1 : 3) at 110°C for 24 h in DMSO using K2CO3 as the catalyst. the brownish gel was precipitated with methanol and the product was collected after vacuum drying in the form of a transparent. 75 . 4.5−1.1).) (4.3. the esterified starch started to separate from the medium in the form of a gel.) In eq. light yellow solid. the vinylester and the catalyst were added and the reaction mixture was heated to 110°C. A schematic representation of the esterification reaction of starch with the vinyl esters is provided in Scheme 4. OH O HO OH O OH + R O CH2 O HO O R + n H3C H O n O (1) R = laurate (C12) (2) R = stearate (C18) Scheme 4. 4.7. After 2‐3 h.6. Results and Discussion 4.‐4.
3. DS = 2.1.2. Figure. Table 4. and 4. When using a vinyl‐laurate : AHG molar ratio of 3 and K2CO3 as the catalyst. For atom numbering scheme: see Figure 4.3.1. 76 . Medium DS starch laurate and starch stearate (1 < DS < 2) dissolve poorly in DMSO‐d6 and CDCl3. Higher DS products have a higher solubility in CDCl3 and good quality 1H‐ and 13C‐NMR spectra could be obtained (Figure 4.). Product Characterisation 4. Typical 1H‐NMR spectrum of: (a) native starch in DMSO d‐6 at 60oC.96. Table 4.1.52 (Sample 17.) in CDCl3 at 50oC.52 was obtained.2.3. a product DS of 188.8.131.52.Chapter 4 The DS of the products was determined by using NMR (vide infra). 4. 1H‐ and 13C‐NMR analyses The solubility of the products in common NMR solvents (DMSO‐d6 or CDCl3) is a function of the product DS.) in CDCl3 at 50oC. (c) peracetylated starch laurate. even at higher temperatures (50 oC).52 (Sample 17. A reaction with vinylstearate at similar conditions resulted in a stearate starch ester with a DS of 2. 4. DS = 2. (b) starch laurate.
The 1H‐NMR spectrum of a typical peracetylated starch laurate is shown in Figure 4.8‐2.3.c.8‐2.2. (c) starch stearate. This feature hampers the DS determination by NMR.2. The same 77 . (b) starch laurate.3 ppm. and therefore a peracetylation procedure to substitute all of the remaining OH groups with acetate groups was applied [8.5 ppm). required for DS determinations. Synthesis of Higher Fatty Acid Starch Esters using Vinyl Laurate and Stearate as Reactants A typical 1H‐NMR spectrum of starch laurate is shown in Figure 4. 10‐11]. NMR spectra of the peracetylated products are considerably improved in terms of peak resolution and allow a more reliable calculation of the DS. Clearly visible are the peaks arising from starch and the aliphatic hydrogen atoms of the fatty acid chain (δ 0.52 (Sample 17) in CDCl3 at 50oC. The proton signals of the acetate methyl group. in DMSO d‐6 at 60oC.3. Clearly visible are the carbon resonances of the fatty ester chains (δ 10‐35 ppm) and C atom of the ester group (δ 170‐175 ppm). The starch peaks (δ 3‐5. DS = 2. For atom numbering scheme: see Figure 4. Two of the carbon resonances (1S and 4S) are considerably shifted compared to native starch.96 (Sample 19) in CDCl3 at 50oC. DS = 2. are together with the CH2 groups of the acid chain adjacent to the ester moiety in the range δ 1.5 ppm) are broad and overlapping . The resonances arising from the anhydroglucose unit of starch are broadened. Figure 4. Typical 13C‐NMR spectra of the products are given in Figure 4.1. Typical 13C‐NMR spectra of: (a) native starch.
) show characteristic bands of the carbonyl group of the fatty esters in the 1750‐1700 cm‐1 region.c.b. Sample 17. In addition. a spectrum of native starch (Figure 4. The shift of the starch peaks and the presence of peaks arising from the fatty ester chains clearly indicate that the esterification reaction with vinyl laurate and vinyl stearate was successful. starch laurate C-H C=O C-O C-O a.1.3.) and native starch FT‐IR spectra of both starch laurate and starch stearate (Figure 4. Table 4. Sample 19.).4.Chapter 4 phenomenon was observed by Dicke for starch acetate . and 4.2.2. FT‐IR Spectra of starch laurate (DS= 2.) is also included. 4.4.4.a. the C‐H stretching vibrations of the alkyl groups of the fatty ester chain are clearly present at 2920 and 2850 cm‐1.4. Characteristic peaks of the polysaccharide backbone are visible in the 1250‐900 cm‐1 region (C‐O stretching) .c.96. starch stearate (DS= 2. Table 4.b.52. native starch -OH C-H 4000 3500 3000 2500 2000 1500 1000 500 Wavenumber (cm-1) Figure 4.4.4. c. For comparison.1. The near absence of remaining hydroxyl 78 .4. and 4. starch stearate C-H C=O C-O Absorbance b. FT‐IR measurements The FT‐IR spectra of starch laurate and starch stearate are shown in Figure 4.
24 2. 79 .90 1.54 2.68 0. In addition.1. 4.07 0.90 0.99 1.57 0. Synthesis of Higher Fatty Acid Starch Esters using Vinyl Laurate and Stearate as Reactants vibrations in the range 3000‐3600 cm‐1 and at 1640 cm‐1 indicates that the DS of the product is high.91 0.44 Exp. Overview of the esterification of starch using vinyl‐esters and basic catalysts a Catalyst Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 K2CO3 CH3COONa K2CO3 CH3COONa Vinyl Ester: AHG ratio [mol/ mol] 2 3 6 2 3 6 2 3 4 6 2 3 4 6 3 3 3 3 Amount of Toluene added [ml] ‐ ‐ ‐ 5 5 5 ‐ ‐ ‐ ‐ 5 5 5 5 ‐ ‐ ‐ ‐ DS 1. in line with the NMR data.05 0.08 1. type of catalyst and the effect of the addition of co‐solvents on the product DS was studied in more detail.60 1. four experiments were performed with two alternative basic catalysts (K2CO3 and Na‐acetate). The results are shown in Table 4.96 2.2.23 0. Most of the experiments (14) were performed using Na2HPO4 as the catalyst.1.52 2. Table 4. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 a Vinyl Ester laurate laurate laurate laurate laurate laurate stearate stearate stearate stearate stearate stearate stearate stearate laurate laurate stearate stearate All experiments were performed at 24 h at 110°C in DMSO with a catalyst intake of 2 wt% based on starch.3. Systematic Studies The effect of important process variables like the vinyl‐ester to AHG ratio.01 0.13 1.
5 Degree of Substitution (DS) 1 0. This behaviour is likely the result of two opposing effects. The highest DS value was 1. 2 wt% catalyst intake on starch). Effect of vinyl ester to AHG ratio on the product DS The effect of the vinyl‐ester to AHG molar ratio on the product DS was determined for both types of vinyl‐esters with Na2HPO4 as catalyst (samples 1‐ 3. At a ratio of 1:6. This reduced polarity is expected to lead to ○ : starch‐laurate □ : starch stearate (lines for illustrative purposes only) 80 .1.).5. 7‐10). A further increase in the vinyl ester intake leads to a reduction in the DS.5.Chapter 4 4. the ester intake is equal on a weight basis to the DMSO intake. The DS of the products is a clear function of the vinyl laurate and stearate ester intakes (Figure 4.5. The results are presented in Figure 4. At low to medium vinyl ester/AHG ratios (0‐3).23 for vinyl‐laurate at an intermediate vinyl‐ester‐AHG ratio of 3. this positive effect dominates the reaction rate and the DS of the products will therefore increase at higher vinyl ester intakes. 110 oC. 1. Higher concentrations of vinyl esters are expected to lead to higher esterification reaction rates.5 0 0 1 2 3 4 Vinyl Ester: AHG Starch Ratio [mol/mol] 5 6 Figure 4. This is likely due to a reduction of the polarity of the reaction medium. DS of the product as a function of the type of vinyl ester and the vinyl ester‐starch ratio (24 h reaction time. A further increase leads to a reduction in the DS.3. The DS values are increasing with higher vinyl‐ ester/AHG molar ratio until a certain maximum.3.
et al  for the silylation of starch.5. K2CO3 and Na‐ acetate were tested. These findings were rationalised by assuming that the co‐solvents increase the solubility of the silylated products. 11‐14 in Table 4. The addition of toluene for the esterification of starch with vinyl‐esters surprisingly did not lead to improved DS values. A similar procedure was proposed by Nouvel. These negative effects dominate the reaction performance at higher vinyl ester/AHG ratios and lead to a reduction in the DS values. et al  reported the synthesis of fatty esters of starch using alkanoyl chloride reactants (C8‐C18) with reactant ratio of 6 mol alkanoyl chloride/mol AHG.1.). For starch 81 . The results are given in Table 4. it also results in a dilution of the reaction mixture and a reduction in the polarity. and illustrated in Figure 4. It is clear that Na‐acetate and K2CO3 are considerably more active than Na2HPO4 and products with a significantly higher DS were obtained.3.6. Although toluene may positively effect the reaction by (partly) re‐dissolving starch ester precipitates. 4.3. Synthesis of Higher Fatty Acid Starch Esters using Vinyl Laurate and Stearate as Reactants a lowering of the reaction rates due to a reduction of the solubility and degree of ionization of the starch reactant as well as the base catalysts. 4.3. the addition of co‐solvents (toluene/ THF) led to an increase in the DS.3. Here. The difference was explained by assuming that the reaction rate is reduced for larger reagents due to steric effects and this explanation likely also holds for the reactions with the vinylesters . i.). When using Na2HPO4 as the catalyst.1. This effect is particularly evident at higher vinyl ester/ AHG ratios (>3) (Figure 4. the reactions were initiated in DMSO and toluene was added after 12 h reaction time to re‐dissolve the poorly soluble partially‐esterified starch products (entry 4‐6. with high carbon numbers leading to a reduction in the DS.2. the starch laurate esters display higher DS values than the starch stearates.e.3. Effect of the addition of toluene as a co‐solvent A number of reactions were performed using a co‐solvent.7 for lauroyl chloride to 0. Thus. A similar trend in reactivity pattern was observed in this study and the DS decreased from 1. Aburto. the DS of the product is also a function of the chain length of the fatty acid. In this case. with reductions in polarity leading to lower reaction rates. The latter factors appears to have a strong effect on reaction rates (vide supra).1. leading to enhanced reactivity.). The products have about the same DS value for vinyl‐laurate when using only DMSO and even reduced DS values for vinyl‐stearate (see Table 4. Catalysts screening A number of alternative basic catalysts for Na2HPO4.8 for stearoyl chloride.
the statement that the DS for the laurate esters is always higher than for the stearate esters is not generally valid and a.o.Chapter 4 laurate esterification.5 Degree of Substitution 2 1. function of the type of catalyst. and Na‐acetate). catalyst amount = 2%‐w. Conclusions A study on the synthesis of corn starch fatty acid esters with high DS values is reported.4. K2CO3 and Na‐acetate are superior with respect to activity when compared with Na2HPO4. 110oC. The DS of the laurate ester when using Na‐acetate is higher than for the stearate ester (Table 4. and FTIR and confirm the presence of chemically bound fatty acid chains.5 0 Laurate Vinyl-Ester Stearate Figure 4. K2CO3. and Figure 4.96) compared to Na‐acetate (DS=2. gray: Na2HPO4 black: K2CO3 white: Na‐acetate 4. 3 2. The DS of the products is a clear function of the chain length of the fatty ester and the type of catalyst. the DS of the product is also tunable by proper catalyst selection. For starch stearate. However.5 were obtained. Apparently.1. DMSO).). Thus. The yellow products were characterized by 1H‐ and 13C‐NMR. the two catalysts are equally effective and products with a DS of about 2. Comparison of DS values with different catalysts (Vinylester: AHG molar ratio = 3:1.44). in line with the findings for NaH2PO4. K2CO3 gave products with a significantly higher DS (2.6. 82 .5 1 0.6. when using K2CO3 as the catalyst. the DS for the laurate ester is lower than the stearate ester. The products were synthesised in DMSO using vinyl‐esters in the presence of basic catalysts (Na2HPO4.
and biodegradability of fatty‐acid esters of amylose and starch. 4. A maximum was observed at a vinyl ester: AHG ratio between 2 and 4. Polym. Dzenis. 1999. Koch. J. 1997. Alric. J. 1‐11. characterization. A. J. A. Y. M. Merrill: Properties of Fatty‐Acid Esters of Starch. Crops Prod. C. 1995. presumably due to a reduction of the polarity of the reaction medium. Sci. 361‐368. Borredon. . E. E. At low vinyl ester/ AHG ratio. References . Eng. Thiebaud. 2005. Prinos. 1440‐1451. average value of mole of substituted –OH per mole of anhydroglucose (AHG) units [‐] DS DS fatty ester : DS of fatty ester (laurate or stearate) group substituents [‐] DSacetate : DS of acetate group substituents after peracrtylation [‐] 4. 1647‐1656. Ind. Prinos. . Important product properties will be described in the next chapter. Gatenholm: Surface octanoylation of high‐ amylose potato starch films. Appl. S. Sci.W. the DS of the product increases at higher vinyl ester intakes. 21. Appl. Bikiaris. Thiebaud.4 could be obtained for both laurate and stearate esters. . 1208‐1217. Borredon. D. M. Ind. J. 34. E. Aburto. Alric. . Mullen and E. Synthesis of Higher Fatty Acid Starch Esters using Vinyl Laurate and Stearate as Reactants With these catalysts. Polym. Panayiotou: Properties of fatty‐acid esters of starch and their blends with LDPE. 705‐721. J. 65. Bengtsson. D. 2003. Y. Nomenclature A A x − y ppm : peak area of certain proton in 1H‐NMR spectra [‐] : peak area of certain peak at x until y ppm in 1H‐NMR spectra [‐] : Degree of Substitution. Pacsu: Starch Studies: Preparation and Properties of Starch Triesters. Sagar. K. C. Chem. Bikiaris. .6. Xu. Hanna: Water solubility. 1942. 83 . D. Polym. I. Polym. 54. Carbohydr. The DS of the products may also be tuned with the vinyl ester/AHG molar ratio. Panayiotou: Synthesis. I. 58. thermal characteristics and biodegradability of extruded starch acetate foams. W. J. J. J. 74. X. Higher ratios led to a reduction in the DS. S. and P. Appl.5. products with a DS > 2. Aburto. Sci.
Peltonen. 2001. 118‐121. M. Mater. Senocq. Sci. S. Borredon: Free‐solvent Synthesis and Properties of Higher Fatty Esters of Starch – Part 2. R. Reis: Thermal properties of thermoplastic starch/synthetic polymer blends with potential biomedical applicability. 51. H‐1 NMR and TGA/IR. Six: Partial or total silylation of dextran with hexamethyldisilazane. Polym. 1735‐1743. K. 261‐267. L. Gunther. . . 56. Mormann. R. D. G. C. . 302‐307. Bliard. . 298. E. J. 11. Ydens. 251‐260. Klemm: Preparative and H‐1 NMR investigation on regioselective silylation of starch dissolved in dimethyl sulfoxide. Soininen. H. Urtti: Determination of the degree of substitution of acetylated starch by hydrolysis. E. Kussler. C. Koniarova. J. Nouvel. Dellacherie. 2004. Polymer 2002. Carbohydr. Cellulose 2004. Elomaa. Petzold. Aburto. Alric. M. Dicke: A straight way to regioselectively functionalized polysaccharide esters. R. J. M.L. . 255‐263.Chapter 4 . B. Einfeldt. . Massiot. and E. D. 1. Dubois. Carbohydr. T. I. Al‐Higari: Acylation of starch with vinyl acetate in water. 57. Mouysset‐Baziard. F. . J. Starch‐Starke 2005. Nuzillard: Proton NMR spectroscopy assignment of D‐glucose residues in highly acetylated starch. J. Mano. 84 . Stein. Hamaili. G.F. A. Alric. I. Laatikainen. 1997. Borredon: Organic solvent‐free transesterification of various starches with lauric acid methyl ester and triacyl glycerides. J. L. 2003. A. 14(2) 127‐135. M.. W. 341‐347. I. S. . Mater. Biosci. 57. Laignel. Asplund. W. Aburto. Degee. Starch‐Starke 2004. 145‐152. 43. P. Hyvarinen. Med. Starch‐Starke 1999. Macromol. Res. P. P.
75) are still partially crystalline. elongation at break of 3‐26%. The effect of the process variables (vinyl ester to starch ratio.45‐1. The results were adequately modeled using a non‐linear multivariable regression model (R2≥0. and modulus of elasticity of 46‐113 MPa. catalyst intake.26‐2.96).39) are totally amorphous whereas the low‐DS ones (DS= 1.5 MPa. vinyl laurate. reaction temperature and type of the catalyst) on the Degree of Substitution (DS) of the starch laurate and starch stearate esters was determined by performing a total of 54 experiments. The basicity of the catalyst and the reaction temperature have the highest impact on the product DS.7‐3. The thermal stability of the esterified products is higher than that of native starch.Chapter 5 Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch Abstract This chapter describes a systematic study on the synthesis of higher fatty esters of corn starch (starch‐laurate and starch‐stearate) by using the corresponding vinyl esters. trans‐esterification. Mechanical tests show that the products have tensile strength (stress at break) between 2. The thermal and mechanical properties of some representative product samples were determined. The reactions were carried out in DMSO using basic catalysts (Na2HPO4. High‐DS products (DS= 2. vinyl stearate . K2CO3. Keywords: starch esters. and Na‐acetate).
The mechanical properties of products with longer ester chains (C4 and C6) products and plasticized acetate esters were considerably improved compared to native starch. packaging material. et al . Introduction Plastics are very useful materials and are used in large amounts (245 million ton per annum) [1‐2]. The limited use is mainly because of a number of unfavourable properties of starch such as low moisture resistance. The use of native starch as a building block for novel biodegradable polymers. 86 .1. Chemical or physical modification is required for successful applications as biodegradable polymers. Two examples using higher vinyl esters (vinyl laurate) were reported by Mormann. the research activities were mainly limited to the use of vinylacetate.65) . polyethylene  and polycaprolactone  and chemical modification by esterification with organic acids [11‐19]. The use of vinylesters has also been explored [20‐22]. The products were hydrophobic and the mechanical properties were considerably improved compared to native starch. high brittleness. the mechanical properties were still not satisfactorily. The development of novel biodegradable plastic materials capable of decomposing when given an appropriate environment and time is of utmost importance . The use of methyl and glyceryl esters to prepare starch laurate (C12) ester was investigated but only yielded products with relatively low DS values (max. Unfortunately.Chapter 5 5. The global starch production was estimated at 60 million tons in 2004 . the physicochemical properties of the products were not mentioned. however. It is cheap and abundantly available . and this causes serious environmental problems [1. Typical examples are blending with polyvinyl alcohol . 12] studied the synthesis and properties of of C1‐C6 esters of starch. 0. Most early studies mainly focused on the use of short‐chain carboxylic acid (C1‐C4). Alternative routes to avoid the use of acid‐chloride/pyridine combinations have been developed. 3‐4]. Thiebaud. and food service‐ware . et al  and Aburto. Esterification is one of the oldest methods used to improve starch properties . and particularly on the synthesis of starch acetate (C2) [11‐12]. et al [15‐19] synthesized longer chain fatty esters (C8‐C18) of potato starch and corn amylose using fatty acid chlorides and pyridine. The high DS esters showed interesting properties. The largest application area of plastics is the use as packaging material (37%) . is rather limited to date. Starch is an attractive feedstock for the synthesis of novel biodegradable plastics. however. Sagar and Merill  studied the synthesis and properties of C4‐C6 esters of high amylose starch. Mullen and Pacsu [11. and incompatibility with hydrophobic polymers . Examples are agricultural mulch . However. most of the plastic waste is not biodegradable. The products were biodegradable. However.
the thermal and mechanical properties of representative examples of the highly hydrophobic materials are described and discussed. It was dried for 48 hour at 105 oC under vacuum (~1 mbar) to reduce the moisture content below 2 % before use. and tetrahydrofuran (THF) were supplied by Acros (Belgium). Tc. All these chemicals were used as received. After a first heating run from room temperature up to 200 oC to delete the thermal history of the material. pyridine. T‐Bones samples (with thickness of 2 mm) for determination of the tensile properties were prepared using a melt press 1 87 . vinyl ester to anhydroglucose ratio. Long fatty esters of corn starch with a broad range in degree of substitution (DS= 0. This chapter describes systematic studies using Design of Experiments (DOE) to gain insights in the effect of process variables (temperature.96) were prepared by reacting the starch with vinyl laurate or vinyl stearate in the presence of basic catalysts in DMSO. 5. Materials and Methods 5. The experiments were modeled using non‐linear multivariable regression. Japan). Materials Corn starch (approx. and Tg) of each sample were determined from the spectra related to the cooling run and the second heating one.2.1. Germany). DSC analyses were performed on a TA Instruments DSC 2920. In addition. Analytical grade methanol. each sample was cooled to ‐50°C and then heated again to 200 oC (heating rate 10 oC/min). The samples were heated to 700 oC in a nitrogen atmosphere with a heating rate of 10°C/min. TGA measurements were performed using a Perkin Elmer TGA 7 Thermogravimetric Analyzer. 73% amylopectine and 27% amylose) was purchased from Sigma (Germany).2.2. The catalysts for the esterification reaction were analytical grade potassium carbonate (Boom. Technical grade dimethyl sulfoxide (DMSO). Germany). Analytical Equipment H‐ and 13C‐NMR spectra were recorded in CDCl3 on a 400 MHz Varian AMX NMR machine. catalyst type and intake) on the DS of the products. 4‐N. vinyl laurate (Fluka. the Netherlands). Analytical grade vinyl stearate (Aldrich. Germany) were used without further purification. 5. and disodium hydrogenphosphate dodecahydrate (both Merck. sodium acetate.N‐ dimethylaminopyridine (DMAP). and toluene were obtained from Labscan (Ireland). The spectra were recorded at 50 oC. as recommended by Laignel et al . The samples (about 10 mg) were placed in sealed aluminum cells. and acetic anhydride (Merck.2. The thermal properties (Tm.24 ‐ 2. Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch We have recently performed exploratory studies on the synthesis of starch esters of higher fatty acids using vinyl laurate and vinyl stearate as the reagents .
apparatus (Fontijne, Holland), operated at 150 oC and 150 bar for 3 minutes. The tensile tests were performed using an Instron Series IX Automated Materials Testing System 1.09 at 20oC and a crosshead speed of 30 mm/min. 5.2.3. Methods 184.108.40.206. Typical example of the preparation of laurate and stearate starch esters The corn starch (0.5 g) was gelatinized in DMSO (5 ml) at 70oC for 3 h. After the mixture became a homogenous, colourless solution, vinyl laurate or vinyl stearate (3‐5 mol/mol with respect to the AHG units) and the catalyst (potassium carbonate, or sodium acetate, or disodium hydrogenphosphate, 2‐5%‐w with respect to starch) were added. The reactor content was kept at 80‐110oC for 24 h. The product was precipitated using methanol (100 ml), and the liquid phase was removed by decantation. This precipitation‐decantation procedure was repeated twice using 50 and 25 ml of methanol, respectively, to purify the reaction product. Finally, the product was dried in a vacuum oven (70oC, 5 mbar) for 24 h or until constant weight. 220.127.116.11. Peracetylation procedure and Degree of Substitution (DS) determination The presence of un‐substituted hydroxyl groups in the products resulted in broad and overlapping starch resonances in 1H‐NMR spectra. A peracetylation reaction to substitute all of the remaining hydroxyl groups with acetate groups was therefore applied to obtain reliable DS values. Typically, the starch ester (0.1 g) was added to THF (4%‐w/v) and stirred at 55 oC until dissolution (typically 3 h). Subsequently, the peracetylating reagent (1 mol DMAP, 10 mol acetic anhydride, and 22 mol pyridine per mol AHG units) were added. The peracetylation reaction was conducted for 7 h at 50 oC. The product was precipitated by the addition of methanol and washed several times with methanol before finally dried overnight in a vacuum oven at 70oC and 5 mbar. The DS of the products was calculated using a procedure given in previous work . 5.2.4. Experimental Design The experiments were carried out in 6 blocks. The three variables used in each block were the vinyl ester to AHG starch mol ratio ( x1 ), catalyst intake ( x 2 ), and reaction temperature ( x3 ). All experiments in a block were conducted using a 3‐ variable, 2‐level Full‐Factorial Experimental Design with one center point, giving a total of 23+1 = 9 experiments per block. For each block, a given type of catalyst (Na2HPO4, K2CO3 or Na‐acetate) and vinyl ester (either vinyllaurate or vinylstearate) was applied. This gave a total of 54 experiments (2 types of vinyl
Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch
esters x 3 types of catalysts x 9 experiments per block). In a later stage, the type of catalyst was quantified using the pKb of the catalyst ( x 4 ). The ranges for the individual variables ( x1 ‐ x 4 ) are shown in Table 5.1. The mathematical analysis of the experimental data was performed with the software package “Matchad 13” (Mathsoft). The response (y, DS of the products) was modelled using the following expression:
y = β 0 + ∑ β i xi + ∑ β ii xi2 + ∑∑ β jk x j x k
i i j k≠ j
Here, βi, βii and βjk are the regression coefficients obtained by a multiple 2 regression procedure. One of the terms, namely x 4 , caused singularity of the matrix used for the modelling, and was therefore excluded. A t‐statistic was used to rank the individual regression coefficients (βi, βii, or βjk) according to their relative importance . An analysis of variance (ANOVA) was performed to check the adequacy of the model. The applied procedure is well described in the literature  and consists of calculating the sum of squares (SS) for the model and the error, together with the total sum of squares. In combination with the relative degrees of freedom (DF) it is possible to calculate the mean square (MS) for the model and the corresponding error. On the basis of the latter values, the F‐value for the model is calculated. With this information the P‐value for the model is determined. The latter value is related to the statistical significance of the model.
5.3. Results and Discussion
A schematic representation of the esterification reaction of starch with a vinyl ester is provided in eq. 5.2. The starch was gelatinized before the addition of the vinylester to make the starch OH groups more accessible for reaction. The reactions were carried out in DMSO for 24 h using three different basic salts (Na2HPO4, K2CO3, or Na‐acetate) as the catalysts. The products of the reaction were brownish gels which became lighter in colour after product precipitation and washing with methanol. After drying, the products were isolated as transparent, yellowish solids. The products were soluble in organic solvents such as toluene and THF.
OH O HO OH
R O CH2
O HO O R O
(1) R = laurate (C12) (2) R = stearate (C18)
The products were characterized by 1H‐NMR in CDCl3. The peaks of starch (δ 3‐ 5.5 ppm) and aliphatic hydrogen atoms of the fatty acid chain (δ 0.8‐2.5 ppm) were clearly present. The starch peaks were broad and overlapping, and only after the starch esters were peracetylated, the resolution of these peaks was considerably improved. The DS of the products was determined by using 1H‐NMR spectra of the peracetylated starch esters. The effect of three reaction parameters (molar ratio of vinyl ester to AHG units of starch x1 , catalyst intake x2 , and reaction temperature x3 ) on the DS of starch was studied using a full factorial experimental design with one center point. The ranges of the values of the independent variables ( x1 ‐ x3 ) are shown in Table 5.1. An additional variable x 4 (related to the basicity of the catalyst) was also included in order to obtain a general model for starch esterification. A total of 54 experiments were conducted. Table 5.1. Experimental Design Variables
Independent Variables Full Factorial Variables Vinyl ester to AHG‐ starch ratio [mol/mol] Catalyst intake [%‐w]a Reaction temperature [°C] Additional Variable Catalyst basicity (pKb)b
Low (‐1) Middle (0) High (+1)
2.0 3.5 5.0
80 95 110
K2CO3 (3.66) Na2HPO4 (6.8) CH3COONa (9.25)
3 4 5
in %‐wt based on starch intake, in the model (eq. 5.3.) it is transformed to 105 x catalyst mol amount. taken from ref .
The results of the experiment are given in Table 5.2.
00 5.00 2.00 2.12 2.00 5.00 5.00 5.23 2.00 5.00 5.00 5.00 5.00 5.00 5.00 3.00 5.27 1.00 5.00 5.54 2.82 2.41 1.56 1.00 2.00 3.00 5.96 0.12 0.00 5.50 0.00 3.00 3.00 2.00 4.00 2.00 3.50 2.00 3.00 Catalyst Temperature [%‐w] [˚C] 2.00 2.84 2.00 5.54 2.00 2.00 2.00 5.11 2.52 2.00 5.00 3.79 Experiment Vinyl Ester 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate laurate stearate stearate stearate stearate stearate stearate stearate stearate stearate stearate stearate stearate stearate stearate stearate stearate stearate 91 .00 5.72 2.00 5.47 1.17 2.00 2.00 3.00 5.00 2.50 2.93 0.00 3.62 0.00 3.00 5.2.00 2.53 1.70 2.42 2.00 5.00 3.00 5.00 80 80 110 110 80 80 110 110 95 80 80 110 110 80 80 110 110 95 80 80 110 110 80 80 110 110 95 80 80 110 110 80 80 110 110 95 80 80 110 110 80 80 110 110 DS 0.00 3.00 5.00 5.00 5.88 2.00 4.67 2.00 4.00 3.00 5.07 0.00 3.00 2.00 3.75 1.00 3.48 0.00 3.52 2.35 0.94 2.00 3.27 0.00 5.00 5.00 3.00 3.00 5.40 1.78 2.00 5.44 2.00 5.27 1.44 2.50 2.24 2.00 2.00 5.00 2.00 3.00 3.28 2. Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch Table 5.00 5.00 5.00 2.00 3.00 4. Overview of experimental data Catalyst Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 CH3COONa CH3COONa CH3COONa CH3COONa CH3COONa CH3COONa CH3COONa CH3COONa CH3COONa K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 Na2HPO4 CH3COONa CH3COONa CH3COONa CH3COONa CH3COONa CH3COONa CH3COONa CH3COONa Vinyl : AHGa [mol/mol] 3.00 5.00 5.32 1.09 0.59 2.87 1.46 1.50 2.00 5.00 5.
00 2.1947 β0 β1 β2 β3 β4 β5 β6 β7 β8 β9 β10 β11 β12 β13 92 .00 5. The type of catalyst was quantified using the basicity constant (pKb) in water [26‐27].0857 ‐0.0732 ‐0.).00 5.0249 ‐0. 5.2183 0.21 2.00 3.98 2.00 5.50 95 80 80 110 110 80 80 110 110 95 1.0120 0.0327 ‐2.3.00 5.0006 ‐0.3.00 2.3.96 2.3. The experimental data for both starch laurate and starch stearate esterification are best described with a quadratic model including interaction terms (eq.00 3.0066 0.) Table 5.00 2.00 5.Chapter 5 45 46 47 48 49 50 51 52 53 54 a.24 2.The modelled values for βij for the two esters are given in Table 5.0011 0.1082 ‐0.0001 0.0009 0.00 3.6939 0.00 5.5650 0.0016 0.59 2. stearate stearate stearate stearate stearate stearate stearate stearate stearate stearate CH3COONa K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 4. Mathematical Modeling Modelling of the DS data for both vinylesters was performed using non‐linear multivariable regression based on the 4 independent variables (Table 5.0023 0.3.41 mol ratio of the vinyl ester to AHG units of starch 5.0008 ‐0.1.0003 0.00 3.0017 0.0470 0.55 2.00 5. DS = β 0 + β1 x1 + β 2 x 2 + β 3 x3 + β 4 x 4 + β 5 x1 x 2 + β 6 x1 x3 + β 7 x1 x 4 + β 8 x 2 x3 + β 9 x 2 x 4 2 2 2 + β10 x3 x 4 + β11 x 2 + β12 x3 + β13 x 4 (5.90 2.0008 0.00 4. Values for the coefficients of the DS model for starch laurate and stearate Coefficient Starch Laurate 9.00 3.64 2.1748 0.00 3.0027 ‐0.1104 ‐0.00 5.1979 Starch Stearate 17.1.1568 ‐2.50 2.0010 ‐0.).64 2.
5 2.805‐0.629 P‐value 1. Analysis of variance for DS models for starch esterification Starch Laurate Model Error Total SS 16. Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch The result of the analysis of variance is given in Table 5.5 2 DS predicted DS predicted 2 1.2903 P‐value 1.805 3 3 2. starch laurate b.2569 0. respectively and it may be concluded that the models describe the experimental data well. Also in this case the reasonable R2 values (0. The R2 values for the models are 0.8167 21.5 1 1 0.5 1 1.5 1 1. which represents an “internal” validation method for the model. Parity plots of the DS models for starch laurate and stearate Moreover. The parity plots of both models are given in Figure 5.970 (starch laurate) and 0.5 DS actual 2 2.875) indicate that the model correctly predict the 93 . which indicate  that all significant variables are included in the model.5 3 a.970 0.1.5 0 0 0.967 0. Finally.96 x 10‐8 R2 values R2 R2adjusted R2press 0. the adjusted‐R2 values are very close to the R2 ones.967 (starch stearate).875 Starch Stearate Model Error Total SS 20.939 0.4.945 0.7699 DF 13 14 27 MS 1.026 x 10‐7 R2 values R2 R2adjusted R2press 0.6118 0. starch stearate Figure 5.).5 DS actual 2 2.0583 F 27.5 1.8386 DF 13 14 27 MS 1. and confirm this statement.4. The very low P‐ values indicate that the models are statistically significant.1.5 3 0 0 0.0356 F 35.9531 0. we also performed a PRESS analysis  (see corresponding R2 values in Table 5.3399 0.4986 16. Table 5.5 0.4.
A possible explanation of this peculiar behaviour of Na2HPO4 is the fact that the pKb values in water are used for quantification whereas the actual solvent for the reaction is DMSO. The highest product DS values were obtained using K2CO3.8) is intermediate between that of the other two catalysts. These results may be rationalised by considering the role of the catalyst in the modification reaction. such as carbonate or acetate salts leading to higher DS esters.18) and CH3COONa (1. A similar trend was observed by Dicke  for the acetylation of Hylon VII starch using vinylacetate. Dicke  showed that Na2HPO4 has a strong tendency to selectively deprotonate the OH group at the C2 position of starch leading to C2 substituted acetate esters. the performance of Na2HPO4 does not follow this trend. the base strengths of the catalysts in DMSO are not known.2. whereas catalyst performance is considerable lower.Chapter 5 products DS as function of the process variables within the range of experimental variables. the type of catalyst has the largest effect on the product DS for both the laurate and stearate esters (Figure 5. This is indeed the case when comparing the performance of K2CO3 with CH3COONa. The explanation for the high preference of C2 substitution for the Na2HPO4 catalyst is not yet known and needs to be established by mechanistic studies. Catalyst performance of CH3COONa was slightly less than for K2CO3 whereas the lowest DS products were produced when using Na2HPO4 as the catalyst. 94 . This was not the case for alkaline catalysts.82).). The resulting anion will react with the vinyl ester to from the product. Another explanation may be related to the regio‐chemistry of the reaction. The pKb for the latter (6.25) and this leads to higher product DS values for K2CO3. Of all the variables studied. The product DS for Na2HPO4 was considerably lower (1. for both starch laurate and starch stearate are given in Figure 5. It is assumed that the first step in the reaction sequence is activation of the starch OH groups by deprotonation by a base [21. 22]. On the basis of the sequence. K2CO3 is a stronger base (pKb 3. two plots showing the dependence of the DS on reaction temperature and catalyst amount (in %‐w).00) than for K2CO3 (2. it can be rationalised that the rate of the reaction (and thus the product DS) will be higher when using a stronger base.66) than CH3COONa (pKb 9. To evaluate the effect of each variable on the product DS. Unfortunately. However.2.
3D contour plot of the DS as a function of reaction temperature and catalyst intake (at constant vinylester to AHG mol ratio of 4) Besides the type of catalyst.2. although to a lesser extent.2. starch stearate Figure 5. As expected and in 95 . starch laurate b. Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch a. the catalyst intake and reaction temperature also affect the product DS (Figure 5.).
DSstearate = 2. .45) and high DS values (DSlaurate = 2.39) were determined. 5. . Of all variables studied.) DS ( 2. and the results for all samples are summarised in Table 5. the vinyl ester to AHG ratio has the smallest effect on the product DS. higher reaction temperatures and catalyst intakes lead to higher product DS values.75. DSstearate = 1.45 (.2. Representative DSC spectra for the starch stearate are given in Figure 5.26. Product Properties The thermal and mechanical product properties for two starch‐laurate and stearate samples with medium (DSlaurate = 18.104.22.168) 96 . DSC analysis of starch stearate esters ( ) DS 1. heating Exothermic Tm = 21 oC cooling Endothermic Tc = 12 oC -20 -10 0 10 Temperature ( C) o 20 30 40 Figure 5.5.3.Chapter 5 line with studies on starch acetates .
). 97 .d. This clearly indicates that the observed thermal transitions are not only determined by the side chains but are an interplay between that of the starch backbone and ester side chains. Thermal transitions at relatively high temperature (melting. The melting point of the potato starch stearate was close to that of model compounds for the stearate side chains (methyl stearate.a 27 n. At moderate DS values the products still display a melting temperature (at 20‐30 oC) and a crystallization temperature (at 10‐25 oC). For instance a Tm of 32 oC was reported for a potato starch stearate ester with a DS of 1.a 12 a. especially in the amylopectin part [15. Changes in the transition temperatures of native starch by esterification have been reported in the literature [13‐14.d.45 Tm [˚C] n. 17].4.5. these are the first examples of completely amorphous starch esters. 40‐42 oC.75 2. close to the value obtained in our study for the medium DS starch stearate (21 °C). or glass transition above 0 oC) were even absent for the high DS products.d. To the best of our knowledge. These values are reduced considerably compared to virgin corn starch. TGA analysis was performed to study the thermal degradation behavior of the starch laurate and stearate samples (Figure 5.8 . in the present work. Melting point (Tm) and crystallization temperature (Tc) of representative starch laurate and stearate samples Starch ester Starch laurate Starch laurate Starch stearate Starch stearate DS 2. which is known to contain crystalline areas. the Tm for the medium DS starch laurate (27 oC) is much higher than the corresponding side chain model compounds (‐10 oC for dodecane and 5 oC for methyl laurate). In particular the behaviour at relatively high temperatures (>0 oC) is further discussed. 22]. esterification of starch with vinyl laurate and stearate reduces the crystallinity of the starch considerably and leads to a lowering of the transition temperatures. In any case. 28‐30 oC) and the authors concluded that the transition temperatures are solely determined by the side chain without any significant contribution of the starch backbone.39 1. However. octadecane. crystallization.a 22 n. n.a 21 Tc [˚C] n.d.d. Unfortunately the thermal transitions for the virgin material lie above the degradation temperature and can therefore not be accurately determined . implying that these products are fully amorphous.= not detectable The thermal behavior of the products is a strong function of the DS. Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch Table 5.26 1.
The difference in thermal stability between the laurate and stearate sample is limited. TGA analysis of various starch samples. ( ): native starch ( ): starch laurate (DS 2. 98 .6. Native corn starch degrades at lower onset temperatures (250‐300 oC) than the corresponding esters (300‐350 oC).4.): starch stearate (DS 2.4. Similar trends were reported for amylose octanoate‐ stearate‐laurate esters  and potato starch octanoate‐ laurate esters .26) (. .39) The TGA (Figure 5.).) curves clearly show starch esterification with either laurate or stearate results in products with enhanced thermal stability. . The mechanical properties (stress at break.Chapter 5 100 80 %-weight 60 40 20 0 20 100 200 300 400 o 500 600 700 Temperature ( C) Figure 5. elongation at break and elasticity modulus) of the products were determined (Table 5.
e. 17]. observed for the high DS starch stearate sample. Both starch laurate samples display.2 8. A deeper understanding of the mechanical behavior can be gained by investigating the shape of the stress‐strain curves (typical examples in Figure 5. an increase in product DS results in lower tensile strengths and modulus of elasticity.1 ± 1.6. 99 . This product is more rigid compared to the product with medium DS value (higher tensile strength and elasticity modulus. elongation at break between 3‐26%.3 ± 2. however.0 ± 2.5 MPa.0 112.7 ± 1. The values of the yield strain.1 ± 15.7 ± 3. The corresponding yield strain (roughly 0.7‐3.8 Starch Ester Starch laurate Starch laurate Starch stearate Starch stearate All materials generally show tensile strengths between 2.39) does not show any plastic behavior but only an elastic one.75 2.9 46. calculated as the ratio between the stress at yield (σy.45 Stress at break [MPa] 3. but higher elongation at break. and lower elongation at break).3 21.45) displays a very similar behavior with respect to the laurate samples (i.7 ± 14. thus indicating a relatively more rigid material with respect to all other samples.05 for both laurate samples. For starch laurate. determined from the stress‐strain curves as the stress at which the material ceases to be linearly elastic) and the modulus.26 1.). These considerations strongly point out the fact that the mechanical behavior can be coarsely (plastic vs elastic behavior) but also finely (stress and strain at break but also modulus values) tuned by the chemical structure of the fatty acid chains as well as the DS values.7 ± 4.025) lies still in the typical range of engineering polymers but also close to that typical of composite materials . and modulus of elasticity between 46‐113 MPa.1 Modulus [MPa] 59. Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch Table 5.1 82.9 ± 14.7 ± 4.5 ± 1.39 1.05). a clear plastic behavior with a maximum in the stress‐strain curves. On the other hand.5.0 3. Starch stearate with a relatively low DS (1. independently of the DS values.0 3. starch stearate at relatively high DS values (2.3 3. Mechanical properties of the starch esters DS 2. plastic deformation and yield strain of about 0. This indicates that their mechanical behavior is comparable to that of typical engineering polymers . is roughly 0. This is in agreement with previous studies regarding the mechanical properties of starch esters with different chain length of the fatty acid moiety [13.2 2.1 Elongation at break [%] 26.2 ± 0. An inverse behaviour is.
Stress‐strain curves for starch esters. ‐): starch stearate (DS 2.7. Although there are many differences in the synthetics methods as well as in testing conditions and procedures. ( ): starch laurate (DS 1. . a rough comparison can be made between the mechanical properties of the esters described in this chapter and those for reported for related starch esters synthesized with alkanoyl chloride as reagent and pyridine as catalyst  (Table 5.45) (‐ .75) ( ): starch laurate (DS 2. .): starch stearate (DS 1.). 100 .Chapter 5 6 5 4 stress (MPa) 3 2 1 0 0 5 10 15 20 strain (%) 25 30 35 Figure 5.26) (.39).5.
as confirmed by DSC. n.7 MPa) coupled with a significant (1500%) elongation.a. n.7.2 MPa for corn starch esters.7) 0.2 Stress at Break [MPa] Elongation at Break [%] a.9 ±0. the high DS material is still more rigid. In this respect the difference in stress and elongation at break for the high‐DS starch laurate sample is striking. Comparison of the mechanical properties of corn starch ester (this study) with potato starch ester  Corn Starch Laurate Ester Potato Starch Laurate Ester Low DS n.3 High DS (2.4 1500 ±8. While for corn starch (DS 2.0 26.8) 3. 101 .0 ±2.7) 1.75) 3.5 ±1. confirms that the corn starch esters synthesized in our research are relatively rigid materials as compared to the potato starch esters. DS) which mainly determines the thermal and mechanical behaviour.7 ±1. we show that although no crystallization of C18 occurred (see DSC data of the high DS material in Table 5.45) 3. On the other hand at low DS values comparable stress at break (3.26) relatively high stress at break (3.7 ±0.7 ±3. They related this inverse property of starch stearate to crystallization of C18 side chains.2 8.6 9 ±2 High DS (2.7 ±4. 9% for potato starch).a.6 Corn Starch Stearate Ester Low DS (1.3 10 ±2 Property Low DS (1.5. Here. Their medium or high DS stearate esters of potato starch are more rigid compared to the starch esters from lower chain fatty acids (octanoate and laurate) .1 21. for potato starch exactly the opposite is observed: relatively low stress (0. Moreover.7 ±0.2 ±0.1 High DS (2. this comparison also confirms our conclusion derived from the analysis of thermal properties (vide supra): it is not only the individual factors (kind of starch and fatty acid.26) 3. Comparison with the literature data implies that the mechanical behaviour of starch esters of higher fatty acids is also a clear function of the type of starch used.0 3. In agreement with our own data.1 ±1.5 MPa) is coupled with a low elongation (26 %). merely because of the structural property of the C18 side chain with respect to the starch backbone.39) 2.7.3 Potato Starch Stearate Ester Low DS (1. The same considerations are valid for starch stearate at high DS values (higher stress and lower elongation when using corn starch instead of potato one). High DS (2. but the interplay between those factors.).1 ±15.a.a. 3. an unexpected behavior was also observed for the mechanical properties of the starch esters from potato starch. Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch Table 5.a.= not available Inspection of the mechanical properties of the starch esters as shown in Table 5.7 MPa for potato starch ones) are coupled with significant differences in the elongation (22% for corn starch esters.
depend on the unit of related variable x] : constant regression coefficients obtained by a multiple regression procedure [‐] : regression coefficients of variable xi obtained by a multiple regression procedure [various units] : regression coefficients of quadratic variable xi2 obtained by a multiple regression procedure [various units] : regression coefficients of interaction variable xjxk obtained by a multiple regression procedure [various units] DS β0 βi β ii β jk : Degree of Substitution. Reaction temperature and catalyst intake also affect the product DS although to a lesser extent than the type of catalyst. 0. K2CO3.5 for starch laurate.96 and P‐value of ≤10‐7) second‐order mathematical models correlating the effect of process variables (vinyl to AHG‐starch mol ratio. 5.9 for starch laurate. The use of K2CO3 and CH3COONa catalysts resulted in medium‐high DS products (2. while the use of Na2HPO4 resulted in low‐medium DS products (0. and Na‐acetate). Thus.5 for starch stearate). Statistically adequate (R2 ≥0. Comparison with literature data indicates that the properties may be (fine) tuned also by the starch source. Conclusions A systematic study.4.Chapter 5 5.3‐1. The DS of the products is a strong function of the basicity of the catalyst.4‐3 for starch stearate).1‐2. Nomenclature β : regression coefficients obtained by a multiple regression procedure [various units. and catalyst basicity) to the DS of the starch ester products were developed. catalyst intake.07‐1. including statistical modelling. on the synthesis of corn starch esters with long chain fatty acids is described. average value of mole of substituted –OH per mole of anhydroglucose (AHG) units [‐] 102 . The starch esters were synthesized by reacting gelatinized starch with vinyl laurate or vinyl acetate in DMSO in the presence of basic catalysts (Na2HPO4.5. The models may be used to determine the appropriate process conditions to obtain a product with a pre‐defined DS. reaction temperature. the chemical composition of the starting materials (either starch or the ester precursor) as well as the processing parameters affect the final product DS values and as such provide an effective toolbox to modulate the desired product properties for a given application. 1. Thermal and mechanical behaviour of the samples of different DS values clearly shows that the DS represents one of the crucial factors affecting the final product properties.
J. .html. M. Brussels. Stevens: Green Plastics. USA. 2002. Frederiksberg C. S. Prod. R. Packaging. Eng. Hanser Publishers. New Jersey. 1980. Structure – Properties ‐ Applications. in Packaging in the Environment (Ed. Marsden: The challenge of domestic waste disposal. Ehrenstein: Polymeric Materials. The Royal Veterinary and Agricultural University. References . 2000. C. Culter: Plastics Packaging.starch. Properties. C. and Regulations. Princeton University Press. . G. 1986. Germany. H. in The Food Biopack Conference: Foodstuffs. Doane: Starch‐based blown films. Belgium. S. Chem.J. D. F. E. Denmark. UK. Selke. M. Department of Dairy and Food Science. . . R. Westhoff. Denmark. demand and recovery for 2006 in Europe. 2000. A. 2000. accessed on August 01. 2008. P. 19. W.dk/isi/stat/rawmaterial. Ind. Plastics Europe. Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch DS fatty ester : DS of fatty ester (laurate or stearate) group substituents [‐] pKb T : base dissociation constant [‐] : temperature [oC] : crystallization temperature [oC] : melting temperature [oC] : experimental variables used for mathematical modelling using multiple regression procedure [various units] Tc Tm xi Greek symbols: σy : stress at yield [MPa] 5. Munich.6. . G. Processing. Weber). Glasgow. Levy). An Introduction to the New Science of Biodegradable Plastics. Blackie Academic & Professional. Website of International Starch Institute. J. M. E. Germany.W. Bastioli: Global Status of the Production of Biobased Packaging Materials. The compelling facts about plastics: An analysis of plastics production. Conference Proceedings. Applications. 592‐595. . Aarhus. Otey. Hanser Publishers. Dev. Hernandez. Copenhagen. 2008 . 27‐29 August 2000 (Ed. Association of Plastics Manufacturers. Munich. 103 . Res. Denmark: http://www. and Biopolymers.
J. Borredon: Free‐solvent synthesis and properties of higher fatty esters of starch ‐ Part 2. 118‐121. Sci. J. Department of Dairy and Food Science. . C. Pacsu: Starch studies: preparation and properties of starch triesters. E. 381‐384. Polym. C. I. Biobased packaging materials for the food industry. Rev. F. the Royal Veterinary and Agricultural University. Panayiotou: Properties of octanoated starch and its blends with polyethylene. 34. Hamaili. Al‐Higari: Acylation of starch with vinyl acetate in water. Prinos. Aburto. J. Thesis. 145‐152. Yang. E. Chem. 705‐721. A. J. Polym. 101‐112. Appl. H. A. Bikiaris. Eng. L. E. A. 1995. 1942. Macromol. 34. Chem. Starch‐Starke 2004. Polym. Broekroelofs. Borredon. A. Appl. X. K. W. Borredon. . 1997. C. Frederiksberg C. de Graaf. de Graaf: Ph. Mullen. 56. 28. Appl. I. J. 35. Sci. R. 1996 104 . . characterization. 2003. 57. Alric. D. Mormann. Sci. Prinos.D. Panayiotou: Synthesis. 1999. Merrill: Properties of fatty‐acid esters of starch. M. 1997. M. A. J. Alric. D. A. Panayiotou: Properties of fatty‐acid esters of starch and their blends with LDPE. M. J. I. 137‐144. Alric. Part C: Polym. Rijksuniversiteit Groningen. E. Alric. J. E. 51. P. 385– 409. Weber). W. C. Janssen. W. Wang: Properties of starch blends with biodegradable polymers. Y. . Starch‐ Starke 2005. 302‐307. Aburto. . C.Chapter 5 . . Ind. Mullen. Polym. Borredon. 1995. R. G. S. Ind. . 132‐135. Starch‐Starke 1999. L. Bikiaris. Aburto. B. Borredon: Preparation of long‐chain esters of starch using fatty acid chlorides in the absence of an organic solvent. J. Aburto. Aburto. C43. Polym. status and perspectives. E.. Wang. . Starch‐Starke 1999. S. 51. 2000. Bikiaris. Alric. Pacsu: Starch studies: possible industrial utilization of starch esters. E. 1440‐1451. K. Carbohydr. report of Food Biopack Project (Ed. 1943. W. Prinos. Thiebaud. 58. J. 1209‐1217. J. 74. J. Sagar. G. Z. . 65.. and biodegradability of fatty‐acid esters of amylose and starch. . Denmark. Aburto. . E. S. . J. Mouysset‐Baziard. I. D. Carbohydr. Alric. J. 1647‐1656. Senocq. J. Eng. Thiebaud. Beenackers: The kinetics of the acetylation of gelatinised potato starch. I. . Sci. J. Thiebaud. I. D. E. Borredon: Organic solvent‐free transesterification of various starches with lauric acid methyl ester and triacyl glycerides.
1997. Picchioni. 11. A. . Day. Science. J. Shercliff. M. Amsterdam. K. Dicke. J. G. A. R. D. 2008. Res. Processing and Design. A straight way to regioselectively functionalized polysaccharide esters. . the Netherlands.. New Jersey. 255‐263. Materials: Engineering. Heeres: Synthesis of higher fatty acid starch esters using vinyl laurate and stearate as reactants. Underwood: Quantitative Analysis 5th edition. Junistia. F. 1986. 2007. Massiot. 251‐260. Prentice‐Hall. Laignel. John Wiley & Sons Inc. Montgomery: Design and Analysis of Experiments 5th edition. Sugih. L. accepted for publication in Starch‐Starke. Cellulose 2004. Bliard. Janssen. 298. . B. H. Ashby. B. L. M. USA. Nuzillard: Proton NMR spectroscopy assignment of D‐glucose residues in highly acetylated starch. C. . Manurung. Cebon. A. R. New York. USA. L. Experimental and Modeling Studies on the Synthesis and Properties of Higher Fatty Esters of Corn Starch . 2001. H. . A. Carbohydr. 105 . Butterworth‐Heinemann. D. P. R. M. C.
The FD values for PCL‐g‐DEM were considerably lower (up to 7 %). At relatively low starch intakes. PCL‐g‐DEM has at least a comparable performance with respect to PCL‐g‐GMA. glycidyl methacrylate. Both act as compatibilizers for PCL/starch blends by improving the interfacial adhesion between the starch particles and the PCL matrix. In particular the elastic modulus for the compatibilized blends is significantly higher than that of uncompatibilized ones. The compounds were prepared by reacting a low molecular weight PCL (Mw 3000) with glycidyl methacrylate or diethyl maleate in the presence of benzoylperoxide at 130°C. grafting . diethyl maleate. despite the expected differences (favorable to PCL‐g‐GMA) in the in situ formation of the compatibilizers. This discrepancy could be explained on the basis of the functional groups (GMA or DEM) distribution along the PCL backbone. The effect of important process variables (intiator and monomer intakes as well as estimated solubility of the monomer in molten PCL) on the degree of grafting (FD) of the GMA and DEM units to the PCL backbone was explored in detail and quantified using multivariable linear regression. PCL‐g‐ glycidyl methacrylate (PCL‐GMA) and PCL‐g‐diethyl maleate (PCL‐g‐DEM) is decribed. compatibilizer. As a result. at relatively high GMA and BPO intakes. The reactive interfacial agents were tested for their performance in PCL‐starch blends. Keywords: starch‐PCL blend. the mechanical behavior of the compatibilized blends is in general different from that of pure PCL and of the corresponding uncompatibilized blends.Chapter 6 Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends Abstract The synthesis of two reactive interfacial agents for starch‐PCL blends. Highest values of the FD (up to 45 %) were observed for PCL‐g‐GMA.
is known to be degraded with ease by microorganisms widely distributed in nature . these synthetic polymers are poorly or non‐biodegradable. to an ideal compatibilizer having both PCL and starch blocks. To overcome this issue. 2]. of polar groups (usually epoxides or anhydrides [13‐18]) able to react with the – OH groups along the starch backbone. To reduce the tendency for phase separation. along the backbone. synthetic biodegradable polymers have been applied.e. for starch/PCL blends. an interfacial agent) may be used to improve the interfacial association between the two polymer phases. A well‐known biodegradable polyester. This phenomenon is highly undesirable and limits the application range considerably . The ester bonds are susceptible to attack by water and this leads to enhanced biodegradability. polyesters are considered very promising alternatives . As a consequence. The latter displays the presence. One of the well known modification strategies is blending the starch with polymers displaying a stronger hydrophobic character and better mechanical properties. Starch modifications to improve the product properties like enhanced hydrophobicity and mechanical properties were already reported in the early 19th century [1. PCL has gained considerable interest for possible applications in the fields of packaging materials and medical applications [10‐11]. the native material is very hydrophilic and important mechanical properties are inferior compared to most synthetic polymers and this hampers its direct use as packaging materials. Among these. Unfortunately. as in this study. However.1. blends of hydrophilic starch and hydrophobic biodegradable polyesters exhibit phase separation  due to differences in polarity of the building blocks.Chapter 6 6. upon mixing) by using a functionalized PCL. polycaprolactone (PCL). In general a compatibilizer is a block‐copolymer where each block displays a chemical structure equal or very similar to that of the polymers to be mixed. Such structure is rather difficult to achieve by simple copolymerization methods and it is usually prepared in situ (i. a compatibilizer (i. Blending of starch and synthetic biodegradable polyesters has been widely applied for the synthesis of fully‐biodegradable products. Introduction Starch is a cheap and abundantly available natural polymer with very good application perspectives in the area of biodegradable plastics. it would be actually more accurate to define the block copolymer as an “interfacial agent”. When using ungelatinized starch as a component in the blend. Unfortunately. 108 . This leads.e. Aerobic soil‐burial experiments showed that the mechanical properties of PCL films decrease rapidly in time . It must be stressed here that the word “compatibilizer” is correctly used only when the block copolymer is actually able to significantly influence the dispersion of the polymers to be mixed (most probably through a steric stabilization mechanism ). such as polyethylene (PE) or polystyrene (PS) [3‐6].
Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends which is able to mainly improve the interfacial adhesion between the polymer and starch itself. Materials Polycaprolactone (PCL) CAPA 2304. The effect of important process variables on the degree of grafting of the GMA and DEM units to the PCL backbone has been explored in detail and quantified using multivariable linear regression. 6. Corn starch (with approx. UK was used for the preparation of the interfacial agents. The intake of reagents was maximally 75‐80% of the volumetric volume to ensure proper mixing. Germany and methanol (99. Belgium.2.2.8%) from Labscan. Ireland. The various compatibilizers have been tested for their performance in PCL‐starch blends. The starch was dried for at least 24 h at 110oC under vacuum (approx. Compatibilizer synthesis The compatibilizers were prepared in a Brabender Plasticorder PL2000 batch‐ kneader (chamber volume 35 cm3). a solution of BPO in GMA or DEM was added drop by drop over a period of 5 minutes. 16]. 73% amylopectin and 27% amylase) was obtained from Sigma and high molecular weight PCL (CAPA 6503.2. Materials and Methods 6.2. Tetrahydrofuran (THF. The materials were mixed for another 5 minutes. however. >99%) was obtained from Acros. PCL‐g‐glycidyl methacrylate (PCL‐g‐ GMA) and PCL‐g‐diethyl maleate (PCL‐g‐DEM). after which the equipment was stopped and the chamber was opened to collect the samples. 6. Methods 6. xylene (99. systematic studies and subsequent quantification of the functionalization reaction has not been reported to date.1. This chapter describes a systematic study on the synthesis of two reactive interfacial agents for starch‐PCL systems. Germany) were used as received.2. diethyl maleate ≥97% purity (Fluka). UK. an absolute novelty of the present research. After the PCL was melted (1‐2 minutes). and benzoyl peroxide 75% (Merck. Mw=3000 from Solvay Caprolactones. Exploratory studies on the synthesis of PCL‐g‐GMA and its applications for starch/PCL blends have been published [13.8%) from Merck.1. ~1 mbar) prior to use. The synthesis and application of PCL‐g‐DEM is. to the best of our knowledge. This low molecular weight PCL grade was used without further purification. 109 . Glycidyl methacrylate 97% purity (Aldrich). Intakes for each experiment are given in Table 1 and 2. The kneader was heated to 130 oC and PCL (CAPA 2304) was added while maintaining a rotational speed of 80 rpm. Mw=50000) from Solvay Caprolactone.2.
PCL‐g‐DEM (5 g) was dissolved in xylene and refluxed at 150 oC for 2 h. The error on the transition temperature is assumed to be ± 1 oC and 5 % of the calculated values for the corresponding enthalpies. The content was blended for 15 minutes. Preparation of PCL‐starch blends with the reactive compatibilisers The PCL‐starch blends were prepared in a Brabender Plasticorder PL2000 batchkneader (chamber volume 35 cm3). 6. Digital Scanning Calorimetry (DSC) measurements were performed using a Q1000 TA Instruments equipped with a TA Instruments DSC cooling system. and then filtered. the chamber was opened and the resulting material was collected. Before analysis.3. Subsequently. Work‐up of PCL‐g‐GMA products  To remove unreacted GMA monomer and GMA homopolymer.Chapter 6 6. created using a Cressington 208 sputter coater. The transition temperatures of each sample were further determined by first cooling down the samples from 100 oC to 0 oC and subsequently heating up back to 100 oC (cooling and heating rate were 10 oC/min). Each sample was first heated from 0 oC to 100 oC (heating rate 10 oC/min) to remove the thermal history of the material. stirred for 1. The solvent was decanted and the solid product was dried in a vacuum oven (40 oC.2. 5 mbar). Aldrich) as the solvent.2. Analytical Methods H‐NMR measurements were performed using a 400 MHz Varian AMX Oxford NMR apparatus with CDCl3 (99. PCL was added to the chamber followed by the addition of the starch and the reactive compatibilizer. and the product was precipitated at 6‐8 oC. PCL‐g‐GMA (5 g) was dissolved in 50 ml THF. 5 mbar). the samples were covered with a paladium/platinum conductive layer of 3 µm thickness.5 h.2.2. Methanol (450 mL) was added to the filtrate.4. 6.2. 6.8%. The solvent was decanted and the solid product was dried in a vacuum oven (40 oC. Infrared spectra were collected with a FT‐IR apparatus in the ATR mode using a Spectrum 2000 instrument from Perkin Elmer. Scanning Electron Microscopy (SEM) was performed using a Jeol 6320 F Scanning Electron Microscope.3. Tensile tests were performed using an Instron 4301 1 110 .2. An operation temperature of 170°C and a rotation speed of 80 rpm were applied .2. Work‐up of PCL‐g‐DEM products Purification of the PCL‐g‐DEM product was performed according to a modified procedure for PCL‐g‐maleic anhydride .2. The resulting suspension was filtered and precipitated using methanol (450 mL) at 6‐8°C.
Statistical Modeling The influence of different processing parameters on the FD values has been determined by performing a multivariable regression procedure on the available data.3. it is possible to calculate the mean square (MS) for the model and the error. For a given sample/blend. the F‐ value for the model is determined followed by the P‐value. strain at break (ε). The T‐bone samples were prepared using a Fontijne Holland TH 400 hot‐ press.2 ppm) or DEM (‐CH2‐ protons at δ 4. This procedure is described in detail in the literature  and consists of calculating the sum of squares (SS) for the model and the error. 8 different T‐bones were used. leading to a 10% relative error in the FD values.) The FD was calculated using 1H‐NMR by comparing the area of protons belonging to the GMA (‐CH< proton at δ 3. The corresponding value for every blend was calculated as an average of the 8 measurements while the standard deviation was taken as absolute error on the average values. The FD is defined as: FD = number of moles of GMA/DEM attached to PCL (mol) × 100% number of repeating units of the PCL backbone (mol) (6. stress at break (σ) and modulus (E) were measured.4.2.2 ppm) side chains with that of a characteristic proton resonance of the PCL backbone (‐CH2‐ protons at δ 4.0 ppm [13. The latter is a measure of the statistical significance of the model. Calculation of the Degree of Functionalization (FD) of the reactive compatibilizers The number of moles of GMA or DEM present on the PCL backbone was quantified using the degree of functionalisation (FD).1. 15‐16. As a result we were able to obtain a model for the FD of the reaction. On the basis of the latter values. 6. The validity of the model was determined by performing an analysis of variance (ANOVA. When the relative degrees of freedom (DF) are known. 111 .1. 6. 19]. Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends machine. For every T‐bone.2. A 5% relative error in the peak area of the NMR spectra was assumed. Table 3).
3.1. Results and Discussions 6. 112 .1.1. COOEt COOEt * O O n DEM BPO n * PCL-g-DEM * O O * GMA BPO * O O O O O n * PCL-g-GMA Scheme 6. Preparation of the Reactive Compatibilizers Twelve compatibilizers were prepared by either reacting glycidyl methacrylate (GMA) or diethyl maleate (DEM) with low molecular PCL as the starting polymer and benzoyl peroxide (BPO) as the radical initiator (Scheme 6.3.1. Functionalization reactions (only showing reactivity for the >CH2 in α position on PCL backbone) Typical 1H‐NMR spectra for the products are shown in Figure 6.Chapter 6 6.).
Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends
Figure 6.1. Typical 1H‐NMR spectra of PCL‐g‐GMA (top) and PCL‐g‐DEM (bottom) Peak assignments were based on available data reported for related products [13, 15‐16, 20]. The FD values and the thermal properties of the products are shown in Table 6.1. (PCL‐g‐GMA) and Table 6.2. (PCL‐g‐DEM).
Overview of experiments for the PCL‐g‐GMA compatibilisers a
Intake FD (%) ‐ 5.7 15.2 27.9 3.2 45.2 c 6.3 T cryst. ( C)
(%‐mol) b GMA BPO ‐ 0.6 0.6 0.6 0.3 1.1 0.3
ΔH cryst. (J/ g‐PCL) 75 72 68 67 73 66 71
T melt. ( C)
ΔH melt. (J/ g‐PCL) 79 72 69 68 73 68 67
PCL PCL‐g‐GMA 1 PCL‐g‐GMA 2 PCL‐g‐GMA 3 PCL‐g‐GMA 4 PCL‐g‐GMA 5 PCL‐g‐GMA 6
‐ 12 24 36 6 24 12
27 22 19 29 25 20 28
51 47 47 48 47 46 47
Experiments were carried out at 130 °C. %‐mol with respect to the CL repeating units in the PCL c based on the soluble fraction of the compatibilizer
Table 6.2. Overview of experiments for the PCL‐g‐DEM compatibilisers a
Intake Sample (%‐mol) b DEM PCL PCL‐g‐DEM 1 PCL‐g‐DEM 2 PCL‐g‐DEM 3 PCL‐g‐DEM 4 PCL‐g‐DEM 5 PCL‐g‐DEM 6
FD (%) ‐ 3.5 2.1 7.2 3.6 6.5 0.9
T cryst. ( C)
ΔH cryst. (J/ g‐PCL) 75 70 68 64 61 63 70
T melt. ( C)
ΔH melt. (J/ g‐PCL) 79 72 62 66 60 66 69
BPO ‐ 0.6 0.6 0.6 1.1 1.1 0.3 27 27 30 21 26 25 30 51 44 47 45 42 41 47
‐ 15 30 45 30 60 7.5
Experiments were carried out at 130 °C %‐mol with respect to the CL repeating units in the PCL
One of the PCL‐g‐GMA compatibilizers (PCL‐g‐GMA 5, see Table 6.1.), was only partly soluble in CDCl3, and therefore the FD is based on the soluble fraction of the compatibilizer only. The presence of an insoluble fraction, combined with a relatively broad molecular weight distribution (as shown by GPC, but not shown here for brevity), suggests that cross‐linking occurred during this experiment. In general, the FD of the PCL‐g‐GMA (3.2‐45.2%) products is much higher than those of PCL‐g‐DEM (0.9‐7.2%). This difference may be either due to the difference in mutual solubility of the GMA and DEM in PCL or differences in the molecular
Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends
mechanism of the grafting reaction. The mutual solubility may be expressed in terms of the differences of solubility parameters of PCL and the reagents . The difference between the solubility parameters of GMA and PCL is 0.29 cal1/2cm‐3/2, while it is much higher (6.3 cal1/2cm‐3/2) for DEM and PCL . Thus, GMA is likely better soluble in PCL, leading to higher values for FD of the products, as confirmed by our experiments. However, the higher experimental grafting efficiencies for PCL‐GMA may also be rationalised by considering the reaction mechanism for the preparation of the compatibilisers. GMA molecules may either react directly with a radical at the PCL backbone or with a radical present on an already coupled GMA molecule. The latter leads to longer GMA grafts on a PCL backbone . A simplified representation of the reactivity of GMA is shown in Figure 6.2.
O (CH2)4 CH2 C O + RO
O (CH2)4 CH
+ GMA O (CH2)4 CH H2C H3C C
C O CH2 HC O O
Termination + H or + R or + RO (CH2)4
+ k GMA O CH C O
H2C H3C C
C O CH2 HC O O
Figure 6.2. Simplified scheme of the GMA Grafting Reaction Mechanism  The reactivity of DEM in radical reactions is expected to be different from that of GMA. Previous studies on maleic anhydride (MA), a compound resembling the
116 . Effect of GMA and DEM to CL‐units ratio (mol/mol) on the FD of the products (constant PCL intake.3. This trend is independent of the BPO amount and matches with data reported by other groups [13. BPO=0.).Chapter 6 chemical structure of DEM.e. the length of a MA graft is always unity whereas longer grafts are possible for GMA. subsequent reactions of MA to an already grafted MA molecule hardly occur. showed that MA reacts easily with a radical on the PCL backbone. i. It is most probably related to the fact that GMA is able to propagate to longer grafted chains when reacted with PCL (Figure 6.1.2. Our experimental findings. 22]. 30 25 20 FD (%) GMA. However.3.6% mol/mol-CL units DEM. 130°C) Higher GMA intakes lead to higher FD values. Effect of substrate (GMA/DEM) to PCL ratio on the FD The effect of the substrate (GMA or DEM) to PCL ratio on the FD was studied by changing the GMA/DEM intake at different BPO amounts.3% mol/mol-CL units DEM. 6. Hence.1. higher FD values for GMA than for DEM are in line with this explanation and support the proposed molecular reaction mechanisms.6% mol/mol-CL units 15 GMA. BPO=1. BPO=0.1% mol/mol-CL units 10 5 0 10 20 30 40 50 60 Substrate Intake (mol% on CL units) Figure 6. Thus an increase in the GMA intake will provide more monomer available for the growing of the grafted chains leading to higher FD values. The results are graphically provided in Figure 6.3. BPO=0.
no detectable influence of the BPO amount on the FD is observed (Figure 6. for which a levelling off and eventually a decrease of the FD values for relatively higher MA amounts has been observed. Effect of the BPO intake on the product FD The effect of the BPO intake on the FD was studied by using different intakes of BPO (Figure 6. at relatively lower GMA intakes. Apparently. However. This will lead to a higher proportion of PCL radicals by hydrogen abstraction from the polymer backbone and thus to higher FD values.4 0. there 117 . GMA=24% mol/mol-CL units GMA.4. GMA=12% mol/mol-CL units DEM. Effect of the BPO intake on the product FD (130°C.8 0.3.1.4. DEM=30% mol/mol-CL units 0. Such discrepancy is probably related to the relatively low intake of DEM as well as to the different reactivity of DEM compared to MA .4.2. 15. 17].).2 GMA.7 0. 17].6 0. The FD values are within a rather narrow range.3 0.). constant substrate to PCL ratio) For high GMA to CL ratio (24%‐mol/ mol CL units).1 1. Such behavior is slightly in contrast to what observed for maleic anhydride [13. 6.9 1 1. although a slight increase in the FD values might be appreciated. The use of higher initiator concentrations will result in an increase in the number of formed radicals. 50 45 40 35 30 FD (%) 25 20 15 10 5 0 0.2 BPO Intake (mol% on CL units) Figure 6.5 0. doubling the amount of initiator results in considerable higher product FD. Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends The experimental trend for DEM is different. These results are in line with earlier work [15.
gives the best description of the experimental data: FD = −1. a statistical model has been developed by performing a multivariable linear regression on the data reported in Table 6.2729nm niδ (6. Here. i. In addition.1. ni the molar amount of initiator in the feed and δ the difference in solubility parameters calculated using group contributions .2.5431niδ + 1.1. If many macroradicals are created in the system (relatively high BPO intakes) at low GMA intake. 6. the possibility of side reactions will become significant. This phenomenon is likely related to the different nature of the radical grafting mechanism of GMA and DEM on PCL as mentioned before. the mutual solubility of DEM in PCL and DMA in PCL was included in the model by using a parameter δ. the BPO and monomer intakes are considered as independent parameters. A doubling of the initiator intake for PCL‐g‐DEM only results in a 70% increase in the FD (compared to 300% for PCL‐g‐GMA).) where nm is the molar amount of monomer in the feed. δ ) (6. as well as several transfer reactions might be responsible for the observed trend . In particular the occurrence of “cage effects”. ni .) 118 . This leads to the following equation: FD = f (nm .3. However. 6. these investigations focused on a better understanding of the individual variables by studying the effect of higher peroxide and monomer intakes while keeping for example their ratio constant.6022nm ni − 0. The effect is however much less pronounced than for GMA. recombination of (macro) radicals. Modeling of the combined effects of the GMA/ DEM and BPO intakes on the FD Previous studies showed the importance of the initiator to monomer ratio on the FD values [15. and 6.3.3. defined as the difference in solubility parameters between PCl and the substrates.e.Chapter 6 is an optimum ratio between the BPO concentration and available monomer (GMA in this case) on the FD. To quantify synergic effects of monomer and initiator molar intakes on the FD of GMA and DEM on the PCL backbone. namely an increase in the BPO intake results in higher product FD.0325nmδ + 0. The model provided in eq.8875 + 0. 17]. The data for PCL‐g‐DEM shows a similar trend as for the experiments with a high GMA to CL ratio (24%‐mol/ mol CL units).3. The results described in the previous paragraph imply that the mutual interaction between these variables and not the absolute value itself determines the final FD values to a great extent.2.
respectively. SS 1828 81.5. a.358 DF 4 8 12 MS 456.3.358 1909. Graphical representation of the FD models for PCL‐g‐GMA and PCL‐g‐DEM are given in Figure 6.6.4 BPO Intake (mol% on CL units) 0.3. b.3 10 10 20 30 20 0. Contour plot..8 0. b.941) also suggests that all important variables have been included in the model.908 10. The R2 value for the model (0. Figure 6.9 60 70 40 50 80 BPO Intake (mol% on CL units) 0. Graphical representation of the FD model for PCL‐g‐GMA. 3D plot. Model Error Total Analysis of variance for the FD model provided in eq 6.2 10 15 20 25 30 35 40 GMA Intakes (mol% on CL units) 45 50 a.3.17 F 44.6 0.8 0. and Figure 6.4 0.5 0. 1 0.2 10 20 GMA Intake (mol% on CL units) 40 30 50 0.957) and its closeness to the adjusted R2 (0.928 P‐value <10‐9 The value of the coefficients in the model imply that the FD is positively influenced by the interaction between monomer and initiator intake ( nm ni ). Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends The analysis of variance data are given in Table 6. Table 6. the interaction between (PCL‐monomer) intake and solubility parameter difference ( nmδ ) and the interaction between the latter factor and the initiator intake ( ni δ ).7 0. 119 .6 20 10 20 40 50 30 60 FD (%) 40 FD (%) 30 40 20 0 1 0.5. The very low P‐value implies that the model is statistically significant. This was also confirmed by inspection of the residue distribution by a normal probability plot (not reported here for brevity) .
) of the compatibilizers were determined by DSC. a higher BPO intake leads to a reduction of the FD values while an opposite trend is observed at lower DEM intakes. This induces irregularities and is expected to result in a lowering of the Tc and the Tm. the melting temperature and the relative enthalpy decrease with respect to pure PCL. While for GMA an increase in BPO or monomer intakes invariably leds to higher FD values. Contour plot. 3D plot. a. Similar observations have also been made by Kim. Furthermore.3 5 6 0.4 BPO Intake (mol% on CL units) 0. Graphical representation of the FD model for PCL‐g‐DEM.8 0. 7 6 3 3 4 Figure 6. the statistical model provides besides a reliable description of the experimental data also a good mathematical description to modulate the FD values of the two substrates by changing the chemical composition (monomer.6 2 FD (%) 5 2 0 1 0.5 0.2. Remarkable is once more the different trends for the two substrates.1. 6. for DEM a clear transition is observed. and a favored nucleation 1 2 50 120 .3. For all samples.2 10 15 20 25 30 35 40 DEM Intake (mol% on CL units) 45 7 a.2 10 20 DEM Intake (mol% on CL units) 40 30 50 6 0. b.6.6 0.4 0. and 6.7 3 4 6 FD (%) 4 0. Thermal properties of the compatibilizers The thermal properties (Table 6.4. For relatively high DEM intakes (> 30 % mol/mol). the crystallization temperature and enthalpy are not a clear function of the FD values. Such changes in the thermal properties compared to pure PCL may be caused by the introduction of grafts on the PCL chains. b. These differences in dependency of the FD values on the DEM and GMA intakes may be explained on the basis of the different grafting mechanisms as previously discussed. radical initiator and PCL intakes).9 4 5 8 BPO Intake (mol% on CL units) 0.Chapter 6 1 0. From a more practical point of view. The random behavior of the Tc as function of the FD values is probably the result of two concurring effects: the presence of irregularities.8 0.1. et al  working with PCL‐g‐GMA. which is expected to lead to a Tc reduction. although both properties are significantly lower than those of pure PCL.
8 371.7 %. 121 . PCL‐g‐GMA has an FD of 9.3 380.0 401.3 Tc (oC) 35 36 36 36 30 30 30 29 31 30 29 28 29 ∆Hc (J/gPCL) 55 69 51 40 52 54 55 53 58 57 63 54 55 T m (oC) 57 57 57 57 57 57 57 57 58 57 57 58 56 ∆Hm (J/gPCL) 62 68 53 43 46 50 52 51 54 50 60 51 48 PCL‐g‐DEM has an FD of 1.2 321.9 11.6%.5 ε (%) 640.7 10. The lower crystallization and melting enthalpy of the compatibilizers compared to virgin PCL is possibly caused by the presence of side chains on the PCL backbone which are expected to have a negative effect on the crystallinity of the products.3 15.9 379.6 168. 22.214.171.124 368.8 329.0 332.5 357.2.8 372.0 341.6 11.6 305.2 342.9 424.9 E (MPa) 270.1 10.1 11. a series with PCL‐g‐DEM (different intakes of the latter at fixed starch/PCL ratio) and two series with PCL‐g‐GMA (one with different intakes of PCL‐g‐GMA at a fixed starch/PCL ratio and one with a fixed compatibilizer intake at three different starch/PCL ratios). Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends of the PCL chains in the compatibilizers compared to virgin PCL (higher Tc) induced by the presence of polar groups.3 10. Table 6.0 9.0 430.8 384. Our experimental design allows comparisons of thermal and mechanical properties as function of the starch content for binary blends (no compatibilizer) and intake of PCL‐g‐DEM and of PCL‐g‐GMA.2 343.2 337. An overview of all prepared blends together with their thermal and mechanical (tensile tests) properties is given in Table 6.2 9.4 230. A total of 12 blends were prepared: a series of binary ones (not containing any compatibilizers) constituting our reference points. Synthesis and Properties of Starch‐ PCL Blends The two compatibilizers (PCL‐g‐GMA and PCL‐g‐DEM) were further used as interfacial agents in blends of PCL with starch. Thermal and mechanical properties of starch/PCL blends a Sample PCL S/PCL 10/90 S/PCL 20/80 S/PCL 30/70 S/PCL/PCL‐g‐DEM 20/80/1 S/PCL/PCL‐g‐DEM 20/80/2 S/PCL/PCL‐g‐DEM 20/80/5 S/PCL/PCL‐g‐GMA 20/80/1 S/PCL/PCL‐g‐GMA 20/80/2 S/PCL/PCL‐g‐GMA 20/80/5 S/PCL/PCL‐g‐GMA 20/80/10 S/PCL/PCL‐g‐GMA 10/90/2 S/PCL/PCL‐g‐GMA 30/70/2 a σ (MPa) 16.5 425.6 386.4 431.4.5 489.1 13.6 5.5 7.
75 70 65 60 55 50 45 40 35 ∆ H (J/ g-PCL) 0 5 10 15 20 Starch content (%) 25 30 Figure 6.7. respectively from 16. This is most probably due to a nucleation effect of the starch on PCL as observed also for other kinds of polymer blends .8 % at 30 % starch content.43 MPa and 640.Chapter 6 6.8 MPa) clearly indicates that the rigidity of the blends increases at higher starch contents. This is in agreement with the data previously reported on PCL/starch blends and related to the lack of interfacial adhesion between the starch particles and the PCL matrix .2.2 MPa up to 341. The simultaneous increase in the modulus (from 270. The thermal and mechanical properties indicate no or very little interaction of the starch particles with the PCL ○ : ∆Hc □ : ∆Hm 122 .1. The thermal behavior is characterized by no significant changes in the Tm and Tc values but unreported trends of the corresponding enthalpies as function of the starch content (Figure 6.5 % for pure PCL to 7.1 MPa and 341.3. The two trends are remarkably mirroring each other and are both characterized by an increase of ∆Hm and ∆Hc with respect to pure PCL at 10 % starch content followed by a monotonous decrease of both quantities as function of the starch intake.). Binary blends of starch and PCL For binary blends (no compatibilizer is added) a monotonous decrease of the stress and strain at break is observed as function of the starch intake.7. Melting and crystallization enthalpy as function of the starch content for binary blends with PCL.
8. either by heating or in combination with mechanical stress . 6. This is visually confirmed by the morphology of the prepared blends (Figure 6. 123 . 26] and explained by assuming that the voids are formed by water in the starch. In this respect the thermal properties remain substantially unchanged with the exception of the Tc. and the lack of interface adhesion cause void formation.2. The presence of these voids was also observed for sago starch/PCL blends [25. Morphology of starch/PCL binary blends. Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends matrix.). The thermal behavior is characterized (Table 6. As consequence one might expect a slight different structure of these ternary blends as compared to the corresponding binary one.) by constant values of the Tm (with respect to pure PCL) while the Tc is slightly lower (30 vs 35 oC) than that of pure PCL and it is independent of the compatibilizer content. in order to fully understand the role of PCL‐g‐DEM. Ternary blends compatibilized with PCL‐g‐DEM PCL‐g‐DEM.e. The latter trend is also valid for the corresponding enthalpies: i. (a) S/PCL 10/90 (b) S/PCL 20/80 (c) S/PCL 30/70 Indeed starch particles are clearly dispersed in the PCL matrix but no interaction (adhesion) between the two phases is actually detected. b. Figure 6. This is confirmed by examination of the blend morphology by SEM (Figure 6.8. c. Such behavior is consistent with the hypothesis that the starch particles hinder the melting and crystallization processes of the PCL chains.4.9. However. Evaporation of the water during blend preparation. was used as compatibilizer for the preparation of ternary blends with starch and PCL. whose synthesis is described for the first time in this work.). a. the starch particles are simply inserted into voids of the PCL matrix. Thus. for which a 6 oC drop is observed when using PCL‐g‐DEM. a decrease with respect to pure PCL is observed and then a substantial invariance as function of the PCL‐g‐DEM content.2. the corresponding binary blend (S/PCL 20/80) contitutes a better reference point compared to pure PCL.3.
Indeed starch particles in the ternary blends display a smoother interface with the PCL matrix compared to the corresponding binary blends (Figure 6.). Morphology of ternary blends compatibilized with PCL‐g‐DEM.10.Chapter 6 a.). (a) S/PCL/PCL‐g‐DEM 20/80/1 (b) S/PCL/PCL‐g‐DEM 20/80/2 (c) S/PCL/PCL‐g‐DEM 20/80/5 124 . resulting in more rigid material with higher modulus. At higher PCL‐g‐DEM intakes the lower average molecular weight of the compatibilizer as compared to the one of the unmodified PCL used in the blends (3000 vs 50000) is probably responsible for the observed decrease in the E values. A closer inspection of the SEM pictures reveals that the starch particles are clearly embedded in the PCL matrix with almost no void spaces at the interface. At 1 %‐wt of PCL‐g‐DEM in the blends the modulus increases with respect to the binary blend (0 %‐wt compatibilizer in Figure 6. As a result of the different morphology also the mechanical behavior display differences with the virgin PCL and the binary blend. b. Figure 6. This can be explained by the improved interfacial adhesion  between PCL and starch. which will hinder the flowability and fibre forming ability of PCL matrix under cold drawing. c.9.9. The stress and strain at break remain constant as function of the compatibilizer intake while the modulus display an optimum as function of the compatibilizer intake (Figure 6.10.).
in all cases (i. Ternary blends compatibilized with PCL‐g‐GMA When using PCL‐g‐GMA as compatibilizer two possible comparisons can actually be made: one at fixed starch/PCL ratio and changing the amount of PCL‐ g‐GMA and one at different starch/PCL ratios but with fixed amount of PCL‐g‐ GMA (2 %‐wt). Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends 390 380 370 360 E (MPa) 350 340 330 320 0 1 2 3 PCL-g-DEM amount (wt%) 4 5 Figure 6.2. The first comparison as function of the PCL‐g‐GMA intake (ternary blends with starch/PCL ratio of 20/80) results in quite similar considerations as the ones made for PCL‐g‐DEM. In particular also in the case of PCL‐g‐GMA.3. the modulus is higher and hardly a function of the compatibilizer amount. it can be observed that: 1) the melting temperature as well as the crystallization and melting enthalpies do not change significantly (discrepancies in the values are within the boundary defined by the experimental error). Modulus of ternary blends S/PCL/PCL‐g‐DEM as function of PCL‐g‐ DEM amount. by taking as reference the corresponding binary blend (S/PCL 20/80).e. the stress and strain at break are lowered and hardly a function of the PCL‐g‐GMA amount.10. 2) 3) 4) Remarkable is that in the case of PCL‐g‐GMA no optimum is found in the modulus as function of the compatibilizer intake.3. at all PCL‐g‐GMA contents) there is a clear increase of the modulus with respect to the 125 . the crystallization temperature experiences a drop of about 5‐6 oC. However. 6.
Thus. c. 126 . (a) S/PCL/PCL‐g‐GMA 20/80/1 (b) S/PCL/PCL‐g‐GMA 20/80/2 (c) S/PCL/PCL‐g‐GMA 20/80/3 In this case we observe structural features (partially smooth interface between the components. b. partial interfacial adhesion) which render these ternary blends a kind of “intermediate” case between the binary ones and those compatibilized with PCL‐g‐DEM.4.). despite a much more favourable FD value for PCL‐g‐GMA with respect to PCL‐g‐ DEM and even despite a relative low reactivity of ester groups towards the –OH groups on starch and nucleophilic groups in general [27.Chapter 6 binary blend. and morphologies in Figures 6.11. a.) than PCL‐g‐GMA for blends containing 20 %‐wt of starch. These differences in compatibilizing effect are not yet fully understood. Figure 6. one might speculate that the longer length of the GMA grafts compared to DEM (vide supra) plays a negative role in the in situ formation of the compatibilizer. 29].9. (left) the structure of PCL‐g‐GMA is inhomogeneous at the molecular level with long poly(GMA) branches pending from the PCL backbone. As a result. This is surprising if one takes into account the different FD values: 9. upon reaction of PCL‐g‐GMA with one of the –OH groups on the surface of the starch particles the remaining GMA groups are actually scarcely available for further reaction with other –OH groups spatially distant from the reacted one.12. and 6. As given schematically in Figure 6.11. presence of voids. 28. clearly indicating that also PCL‐g‐GMA (like PCL‐g‐DEM) acts as compatibilizer in the blends Such hypothesis is partially and qualitatively confirmed by the blends morphology (Figure 6. Morphology of ternary blends S/PCL/PCL‐g‐GMA.7 % for PCL‐g‐DEM.8 % for PCL‐g‐GMA against 1. However. PCL‐g‐DEM is at least as active as compatibilizer (compare modulus values in Table 6. This confines all reactive GMA groups in relatively “isolated” spots along the PCL backbone.11.
thus probably ensuring a better coverage of the surface.3 MPa for S/PCL/PCL‐g‐GMA 30/70/2) clearly indicates that the efficiency of PCL‐g‐GMA as compatibilizer becomes more relevant at relatively higher starch contents (>30 %) . In order to check this we compared blends with the same amount of PCL‐g‐GMA (2 %‐wt) but with different starch intakes (10.12.) for further reaction.12.).).) and relating the “coverage” of the starch particle surface upon reaction with PCL‐g‐GMA with the compatibilization efficiency. Schematic representation of the in situ reaction between functionalized PCL and starch. the stress and strain at break decrease while the modulus is unchanged at low starch contents and increases significantly for S/PCL blends with 30 %‐wt starch. for all starch amounts (Table 6. 20 and 30 %‐wt respectively). the Tc decreases (with respect to the corresponding binary blends) while all other factors (Tm and enthalpies) remain virtually unchanged with respect to the binary blends and also as function of the starch intake. Synthesis and Properties of Reactive Interfacial Agents for Polycaprolactone‐Starch Blends PCL-g-DEM PCL-g-GMA OH O OH O OH Starch particle OH Starch particle Figure 6.8 MPa for S/PCL 30/70 up to 430. On the other hand (right of Figure 6. We can therefore conclude that the efficiency of PCL‐g‐GMA in the 127 . Concerning the thermal behavior (Table 6. but since DEM is preferentially grafted as monomer. once PCL‐g‐DEM has reacted with one –OH groups on the starch particle. other groups will presumably remain available (arrows in Figure 6.) PCL‐g‐DEM has much less reactive groups (lower FD) than PCL‐g‐GMA. thus attenuating the effect discussed above. As consequence. at higher starch contents more –OH groups would be available for reaction with the GMA groups. This is in agreement with the hypothesis made above (Figure 6.12. when comparing ternary blends (compatibilized with PCL‐g‐ GMA) with the binary ones.4.4. Moreover.12. the distribution of the reactive group along the PCL backbone is more “homogenous”. Indeed. The proposed explanation implies however that at relatively higher starch contents (> 20 %‐wt) the segregation of the poly(GMA) chains in “isolated” spot along the PCL backbone would become less important. The latter result (from a modulus of 341.
5. The latter hypothesis is indirectly confirmed by the observation that PCL‐g‐GMA becomes more efficient at relatively higher starch contents in the blends. 6. has been performed on the synthesis of two reactive compatibilisers. This is in contrast with chemical reactivity and amount of chemical groups along the PCL backbone (both factors favorable to GMA as compared to DEM) but it is explainable on the basis of the group distribution along the PCL backbone. moles of GMA or DEM present per mole of CL repeating units : : ni nm amount of initiator intake [mol% on CL units] amount of monomer GMA or DEM intake [mol% on CL units] 128 . Conclusions A systematic study. mutual solubility of the monomer into the molten polymer) on the FD adequately described the experimental results (R2=0. The reactive compatibilizers were used in blends of starch with PCL. firstly reported in this work. Nomenclature E FD : initial modulus [MPa] : functionalization degree. The most important variable for the final product FD is the interaction between the amount of monomer and initiator used. The PCL‐g‐GMA and PCL‐g‐DEM compatibilizers display lower melting temperatures and melting enthalpies compared to virgin PCL. From a more practical point of view it can be concluded that the newly synthesized PCL‐g‐DEM. PCL‐g‐glycidyl methacrylate (PCL‐g‐ GMA) and PCL‐g‐diethyl maleate (PCL‐g‐DEM). At a fixed starch content (20 %‐wt) PCL‐g‐DEM seems to have sligthly more efficient compatibilizing effect than PCL‐g‐GMA as shown by blends morphology and elastic modulus values.4. P‐value ≤10‐9).957. The proposed model to quantify the effects of process variables (monomer and initiator intake. This represents an unreported mathematical confirmation of the fact that these kinds of functionalization reactions are mainly governed by the synergy between the different process variables and only slightly by their individual values. can replace PCL‐g‐GMA as compatibilizer at relatively low starch contents offering at the same time the advantage of a less pronounced modification of the polymer backbone and a reduced consumtpion of polar groups to be grafted on PCL. including statistical modeling.Chapter 6 compatibilization of starch/PCL blends can be significantly improved by changing the blend composition. 6.
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while amylopectin is branched polymer. containing periodic branches linked with the backbones through α‐D‐(1. Starch is relatively cheap and available from a broad range of plants.6)‐glucosidic bonds. Its production has increased significantly since 1950. tensile and flexural strength).o oil and gas) are very attractive materials for a broad range of applications. For instance. The application of an alternative method involving hydrophobisation of starch by the introduction of large hydrophobic SiMe3 groups followed by a ROP with a polyester precursor and subsequent removal of the SiMe3 groups is expected to result in higher grafting efficiencies. There are two types of polymers present in starch: amylose and amylopectin. Starch is also too sensitive to water. The content of amylose and amylopectine in starch varies and largely depends on the starch source. After use. In combination with the current high prices for petrochemical products. The main reasons are the water sensitivity of common catalysts and the fact that starch is poorly or even insoluble in the common organic solvents used for ROP. chemical modification or combinations thereof. To gain insight in the potential of this approach. Examples are the use as packaging and construction materials. we have . The use of virgin starch for packaging materials is restricted because it cannot be shaped to films with adequate mechanical properties (high percentage elongation. plastics may end up in the environment and cause serious environmental problems. blending with other materials. Starch is a polymer consisting of anhydroglucose (AHG) units. such as thermoplasticization. There are several starch modification methods available. it has a high volume to weight ratio and is generally resistant to degradation. The synthesis of such grafted products by the in situ ring opening polymerization (ROP) of the monomers on the hydroxyl groups of starch is unfortunately not very straightforward. there is a strong need for renewable alternatives for plastics from fossil resources. with a rate of almost 10% every year. The application of a number of prospective methods for developing starch‐based biomaterials will be described in this thesis.4)‐glucosidic bonds. Chemical grafting of biodegradable polyesters on the starch backbone is expected to result in less hydrophilic and thus less water sensitive materials with improved mechanical properties. Starch must therefore be modified before it can be applied as a biodegradable plastic.Summary Plastics made from fossil resources (a. Starch‐based biodegradable materials are considered interesting candidates to replace certain types of conventional plastics. Amylose is essentially a linear polymer in which AHG units are predominantly connected through α‐D‐(1.
The silylation reaction was performed using hexamethyl disilazane (HMDS) in DMSO/ toluene mixtures at 70°C. The results are described in detail in Chapter 3. Characterization of the products using 1H‐ and 13C‐NMR as well as MALDI‐TOF mass spectrometry showed the presence of significant amounts of p‐dioxanone polymers with an isopropoxide end group (20‐30%) The knowledge obtained from the model system was applied for the synthesis of starch‐g‐poly‐ε‐caprolactone using hydrophobised silylated starch.46‐0.3.3.72. A statistical model has been developed to quantify the effects of process variables (time. Most of the previous starch esterification studies involved the use of short chain carboxylic acids (C1‐C4). with higher temperatures (100°C) leading to lower yields. The grafting of ε‐caprolactone to the silylated starch by a ring‐opening polymerisation catalysed by Al(OiPr)3 was performed in THF at 50oC. The use of higher carboxylic (fatty) acid to esterify starch resulted in products with significantly improved 134 . Average molecular weights of the products were between 970 and 6200 (7 – 58 monomer units) and were a clear function of the p‐ dioxanone/ 1. The yield of the polymers was a function of the reaction temperature and the reaction time. The results for the model system involving the ROP of p‐dioxanone initiated by hydroxyl groups of a protected monosaccharide (1. temperature and monomer: monosaccharide ratio) on the average degree of polymerization. are described in Chapter 2.2. The silyl groups of the poly‐(ε)‐caprolactone grafted starch co‐polymers were finally successfully removed using a mild dilute hydrochloric acid treatment in THF at room temperature.21‐0.2.4‐di‐O‐isopropylidene‐α‐D‐galactopyranose ratio (at constant Al(OiPr)3 intake). and particularly acetic acid derivatives (C2) have received considerable attention. depending on the ε‐CL to starch ratio. The DS of the PCL chains was between 0. even in the presence of plasticizers. and subsequent removal of the silyl groups. Esterification of starch with carboxylic acid derivatives is one of the oldest strategies to improve starch properties. The hydrophobicity of starch acetates is higher than virgin starch.Summary initially performed research on the ROP with a simpler model system involving a simple protected mono‐saccharide instead of starch. Considerable amounts of ε‐CL homopolymers with isopropyl end‐groups were also formed. with higher ratios leading to higher molecular weights.4‐di‐O‐isopropylidene‐α‐D‐ galactopyranose) using Al(OiPr)3 as the catalyst. but the products are still very brittle. Poly‐(ε)‐ caprolactone grafted silylated starch co‐polymers with average chain length of 40‐ 55 monomer units (molecular weight of 4500‐6300) were obtained. The grafting efficiency for the desired reaction was 28‐58%. The synthetic procedure may be divided into three steps: hydrophobisation of starch by the introduction of SiMe3 groups followed by in situ ROP. The polymerizations were performed at 60‐100°C. and off‐white solid products with isolated yields of 30‐96% were obtained.68) was obtained. Silylated starch with a low to medium DS (0.
K2CO3. In Chapter 5. Summary mechanical properties and hydrophobicities. however. the DS decreased. The thermal stability of the esterified products is higher than that of native starch. the synthesis of two polycaprolactone (PCL)‐based reactive interfacial agents.4‐3 for starch stearate). a systematic study. while the use of K2CO3 and CH3COONa catalysts resulted in medium‐high DS products (2. PCL‐g‐ 135 . elongation at break of 3‐26%. The last part of this thesis deals with reactive blending of starch and biodegradable polymers using reactive interfacial agents.9 for starch laurate. and modulus of elasticity of 46‐113 MPa. an alternative method for higher fatty starch esters by using fatty vinyl esters is reported.1‐2.96 and P‐value of ≤10‐7) second‐order mathematical models correlating the effect of process variables (vinyl to AHG‐ starch mol ratio. In Chapter 6.39) are totally amorphous whereas the low‐DS ones (DS= 1. usually performed using fatty acid chlorides which are relatively expensive and rather corrosive.3‐1. High‐DS products (DS= 2. The starch esters were synthesized by reacting gelatinized starch with vinyl laurate or vinyl acetate in DMSO in the presence of basic catalysts (Na2HPO4. vinyl ester to starch ratio. catalyst intake.4 could be obtained for both laurate and stearate esters. 0. The DS of the products is a strong function of the basicity of the catalyst. 1. Chapter 4 describes the results of a preliminary study on the synthesis of long fatty esters of corn starch (starch‐laurate and starch‐stearate) using vinyl fatty esters. and Na‐ acetate). The synthesis of these fatty starch esters is. and Na‐acetate) in DMSO at 110°C. 13C‐NMR and FT‐IR.5 for starch stearate). presumably due to a reduction of the polarity of the reaction medium. reaction temperature.5 for starch laurate. The use of methyl and glyceryl esters results in products with only relatively low DS.75) are still partially crystalline.07‐1.26‐2.7‐3. K2CO3. The DS of the products was a clear function of the chain length of the fatty ester. K2CO3 and Na‐acetate are superior with respect to activity when compared with Na2HPO4. products with a DS > 2. Reaction temperature and catalyst intake also affect the product DS but only to a lesser extent. and the type of catalyst.5 MPa. The thermal and mechanical properties of some representative product samples are also described. In Chapter 4‐5. The starch esters were prepared by reacting starch with vinyl laurate or vinyl stearate in the presence of basic catalysts (Na2HPO4. including statistical modelling on the synthesis of long fatty esters of corn starch (starch‐laurate and starch‐stearate) using corresponding vinyl fatty esters is reported. Mechanical tests show that the products have tensile strength (stress at break) between 2. At higher ratios. The products have a broad range of degree of substitution (DS = 0. The yellowish products were characterized by 1H‐. With these catalysts.96). Statistically adequate (R2≥0. an increase in the vinyl‐ester concentration led to higher product DS values. and catalyst basicity) to the DS of the starch ester products were developed. For low vinyl‐ester to starch ratios.24 ‐ 2. The use of Na2HPO4 resulted in low‐medium DS products (0.45‐1.
the mechanical behavior of the compatibilised blends is in general different from that of pure PCL and of the corresponding uncompatibilised blends. The FD values for PCL‐g‐DEM were considerably lower (up to 7 %). A statistically adequate model (R2=0. Both of the PCL‐based compatibilisers improve the interfacial adhesion between the starch particles and the PCL matrix in starch/ PCL blends. This is in contrast with chemical reactivity and amount of chemical groups along the PCL backbone (both factors favorable to GMA as compared to DEM) but it is explainable on the basis of the group distribution along the PCL backbone. In particular the elastic modulus for the compatibilised blends is significantly higher (reaching up to 430 MPa) than that of uncompatibilised ones (320‐340 MPa). and their use in compatibilising starch‐PCL blends is described. Highest values of the FD (up to 45 %) were observed for PCL‐g‐GMA. The latter hypothesis is indirectly confirmed by the observation that PCL‐g‐GMA becomes more efficient at relatively higher starch contents in the blends. As the result. 136 .Summary glycidyl methacrylate (PCL‐GMA) and PCL‐g‐diethyl maleate (PCL‐g‐DEM). PCL‐g‐DEM seems to have slightly more efficient compatibilising effect than PCL‐g‐GMA as shown by blends morphology and elastic modulus values.957. at relatively high GMA and BPO intakes. P‐value ≤10‐9) has been developed to quantify the effects of process variables (monomer and initiator intake. mutual solubility of the monomer into the molten polymer) on the functionalisation degree (FD) of the GMA and DEM units to the PCL backbone. At a fixed starch content (20 %‐wt). The PCL‐based compatibilisers were prepared by reacting a low molecular weight PCL (Mw 3000) with glycidyl methacrylate or diethyl maleate in the presence of benzyolperoxide initiator at 130°C.
chemische modificaties en combinaties van deze methoden.4)‐glucoside bindingen verbonden zijn. De belangrijkste redenen zijn de watergevoeligheid van de katalysatoren en het feit dat zetmeel slecht of zelfs onoplosbaar is in de typische organische oplosmiddelen die voor de ROP gebruikt worden. Er zijn verschillende methodes beschikbaar om zetmeel te modificeren. De toepassing van een alternatieve methode waarbij zetmeel eerst minder hydrofiel gemaakt wordt door de introductie van grote hydrofobe SiMe3 groepen. Biologisch afbreekbare polymeren op basis van zetmeel kunnen mogelijk bepaalde conventionele kunststoffen vervangen. Dit. Het chemisch grafting van biologisch afbreekbare polyesters op de zetmeel ketens zou kunnen leiden tot minder hydrofiele en dus minder water gevoelige materialen met betere mechanische eigenschappen.Samenvatting Kunststoffen gemaakt van fossiele grondstoffen als olie en gas zijn zeer aantrekkelijke materialen voor een breed scala aan toepassingen. De synthese van dergelijke producten met een in situ katalytische ringopening polymerisatie (ROP) van geschikte monomeren als b. ε‐caprolactone op de hydroxy‐groepen van zetmeel is helaas niet eenvoudig. Modificatie van zetmeel kan het aantal toepassingen sterk vergroten. Dit proefschrift beschrijft een aantal methodes om nieuwe polymere materialen op basis van zetmeel te maken. Voorbeelden zijn thermo‐ plastificatie. Het zetmeel is daarnaast ook erg gevoelig voor water. Na gebruik kunnen de materialen in het milieu eindigen en grote problemen veroorzaken. mede omdat het niet mogelijk is om films met goede mechanische eigenschappen te maken.6)‐glucoside bindingen met de hoofdketen zijn verbonden. De productie van kunststoffen is sinds 1950 met bijna 10% per jaar gestegen. Zetmeel is een polymeer bestaande uit anhydroglucose (AHG) eenheden. in combinatie met de huidige hoge prijzen voor de grondstoffen. Zetmeel is relatief goedkoop en te winnen uit een breed scala aan planten. De AHG eenheden kunnen op een aantal manieren aan elkaar gekoppeld worden. Amylose is een lineair polymeer waarin de AHG eenheden hoofdzakelijk via α‐D‐(1. menging met andere materialen. De verhouding amylose en amylopectine in zetmeel varieert en hangt grotendeels af van de plant waaruit het zetmeel gewonnen wordt. Twee type polymeren zijn dominant aanwezig in zetmeel: amylose en amylopectine. heeft geleid tot een grote interesse voor biologisch afbreekbare alternatieven gemaakt uit hernieuwbare grondstoffen. Het amylopectine is een vertakt polymeer waarbij de vertakkingen via α‐D‐(1. gevolgd door de ROP met een polyester precursor en verwijdering van de SiMe3 groepen . Het gebruik van zetmeel voor verpakking materialen is momenteel beperkt.v.
De gemiddelde molecuul massa van de producten lag tussen de 970 en 6200 (7 ‐ 58 monomeereenheden) en was een functie van de verhouding p‐ dioxanone/1.3. waarin hogere temperaturen (100°C) tot lagere opbrengsten leiden. temperatuur en monomeer: monosaccharide verhouding) op de gemiddelde polymerisatie graad zijn gekwantificeerd met een statistisch model. De silylerings reactie werd bij 70°C uitgevoerd met hexamethyl disilazane (HMDS) in DMSO/tolueen mengsels. Een hogere verhouding leidde tot hogere molecuul massa’s. De resultaten worden in Hoofdstuk 3 in detail beschreven.68). De effecten van procesvariabelen (tijd. Karakterisering van de producten met 1 H‐ en 13C‐NMR en MALDI‐TOF massaspectrometrie toonden de aanwezigheid aan van de gewenste producten en daarnaast significante hoeveelheden van p‐ dioxanone polymeren met een isopropoxide eindgroep (20‐30%).46‐0.Samenvatting zou in theorie moeten leiden tot een hogere grafting efficiency. De grafting efficiency van de gewenste reactie was 28‐58%. De grafting van ε‐ caprolactone aan het gesilyleerde zetmeel werd in THF bij 50°C uitgevoerd met Al(OiPr)3 als katalysator.21‐0. Er werden ook aanzienlijke hoeveelheden homopolymeer van ε‐ caprolacton met isopropyl eindgroepen gevormd. De substitutiegraad van de SiMe3 groepen varieerde van laag tot middelhoog (degree of substitution. De kennis verkregen met het modelsysteem is toegepast om ε‐caprolactone te graften op zetmeel.3.4‐di‐O‐isopropylidene‐α‐D‐galactopyranose) met Al(OiPr)3 als katalysator worden in Hoofdstuk 2 beschreven. De opbrengst van de polymeren was een functie van de reactietemperatuur en de reactietijd. DS = 0. gevolgd door in situ ROP met ε‐ caprolacton en daarna de verwijdering van de silyl groepen.2. De polycaprolacton eenheden (PCL) van het verkregen poly‐ε‐caprolactone gesilyleerde zetmeel hadden een gemiddelde ketenlengte van 40‐55 monomeereenheden (molecuul massa 4500‐6300).72 en was afhankelijk van de ε‐caprolacton/zetmeel verhouding. De polymerisaties werden tussen 60‐100°C uitgevoerd en leverde vaste producten in geïsoleerde opbrengsten tussen de 30 en 96%. Om inzicht in het potentieel van deze benadering te krijgen is onderzoek verricht naar de ROP met een eenvoudig modelsysteem bestaande uit een beschermde mono‐saccharide in plaats van zetmeel. De DS van de PCL ketens lag tussen de 0. 138 .4‐di‐O‐isopropylidene‐α‐D‐galactopyranose (bij constante i Al(O Pr)3 concentratie). De gevolgde procedure bestaat uit drie stappen: hydrofobisering van het zetmeel door de introductie van SiMe3 groepen. De silyl groepen van het poly‐ε‐caprolactone gesilyleerde zetmeel werden uiteindelijk succesvol verwijderd door middel van een milde behandeling met verdund zoutzuur in THF bij kamertemperatuur.2. De resultaten voor het modelsysteem waar de ROP van p‐dioxanone wordt geïnitieerd door de hydroxy‐groepen van een beschermde mono‐saccharide (1.
3‐1.96 en P‐ waarde van ≤ 10‐7). Samenvatting De esterificatie van zetmeel met carbonzuur derivaten is één van de oudste strategieën voor het verbeteren van zetmeeleigenschappen. In de meeste zetmeel esterificatie studies wordt gebruikt gemaakt van kleine carbonzuren (C1‐C4). Hoofdstuk 4 beschrijft de resultaten van een voorstudie naar de synthese van lange vetzuur esters uit maïszetmeel (zetmeel laureaat en zetmeel stearaat) met de vinyl esters van de vetzuren al reagens. bij verdere verhoging van de verhouding verminderde de DS. en Na‐acetaat) te laten reageren. 13C‐NMR en FT‐IR gekarakteriseerd. katalysator concentratie en katalysator basiciteit) op de DS zijn gekwantificeerd met een statistisch model (R2 ≥ 0. Echter de producten zijn nog steeds zeer bros. Echter. inclusief statistische modellering.96. Het gebruik van Na2HPO4 resulteerde in producten met een laag tot middelhoge DS (0. De synthese van deze esters wordt in het algemeen uitgevoerd met vetzuurchloriden die vrij duur en sterk corrosief zijn. De temperatuur en de katalysator concentratie beïnvloeden de DS ook maar in mindere mate. Bij lage vinyl‐ester/zetmeel verhoudingen leidde een verhoging van de vinyl‐ester concentratie in eerste instantie tot hogere DS waarden. In Hoofdstuk 4‐5.07‐1. wordt een systematische studie. vermoedelijk als gevolg van een verlaging van de polariteit van het reactiemengsel. naar de synthese van lange vetzuur esters uit maïszetmeel (zetmeel laureaat en zetmeel stearaat. De substitutiegraad varieert van 0. zelfs in aanwezigheid van plastificeermiddelen. De zetmeel esters werden bereid door zetmeel met vinyl laureaat of vinyl stearate in DMSO in de aanwezigheid van basische katalysatoren (Na2HPO4. de vinyl‐ ester/zetmeel verhouding en het type katalysator. reactietemperatuur. en in het bijzonder azijnzuur derivaten (C2). In Hoofdstuk 5.4 verkregen.5 voor zetmeel stearaat). K2CO3 en Na‐acetaat vertonen superieure activiteiten vergeleken met Na2HPO4. 0. De zetmeel esters werden bereid door het zetmeel met vinyl laureaat of vinyl stearaat in aanwezigheid van basische katalysatoren (Na2HPO4. Het gebruik van methyl en glyceryl esters resulteert in producten met een lage substitutiegraad.24 tot 2. De DS van de producten was een duidelijke functie van de keten lengte van de vetzure vinylester. K2CO3 en Na‐acetaat) in DMSO bij 110°C te laten reageren. De acetaat esters zijn in het algemeen minder hydrofiel dan zetmeel. Met deze katalysatoren worden voor zowel de laureaat als stearaat esters producten met een DS van boven de 2. De DS van de producten is een sterke functie van de basiciteit van de katalysator.5 voor zetmeel laureaat. De producten werden met 1H‐. terwijl het gebruik van de K2CO3 en Na‐acetaat katalysatoren 139 . De thermische en mechanische eigenschappen van sommige representatieve producten zijn uitgebreid bepaald. Het gebruik van hogere (vet‐) zuren resulteerde in producten met beduidend betere mechanische eigenschappen en hydrofobiciteit. wordt een alternatieve methode voor de synthese van zetmeel esters met lange vetzuren beschreven. De effecten van belangrijke procesvariabelen (vinyl ester/zetmeel molverhouding. K2CO3.
Beide reactieve compatibilisers verbeteren de interactie tussen de zetmeeldeeltjes en de PCL matrix.45‐1.7‐3. De hoogste FD waarden (tot 45%) werden gevonden voor PCL‐g‐GMA bij relatief hoge GMA en BPO concentraties.39) zijn volledig amorf terwijl de producten met een DS van 1. De FD waarden voor PCL‐g‐DEM waren aanzienlijk lager (tot 7%).9 voor zetmeel laureaat.Samenvatting resulteerde in producten met een middelhoog tot hoge DS waarden (2. PCL‐g‐glycidyl methacrylaat (PCL‐GMA) en PCL‐g‐diethyl maleaat (PCL‐g‐DEM). De thermische stabiliteit van de geësterificeerde producten is hoger dan die van zetmeel. De PCL gebaseerde compatibilisers werden bereid door reactie van laag moleculair PCL (Mw 3000) met glycidyl methacrylaat of diethyl maleaat in de aanwezigheid van een benzyolperoxide initiator bij 130°C. Dit leidt tot verschillen in mechanische eigenschappen tussen gecompatibiliseerde mengsels en van de niet‐ gecompatibiliseerde mengsels van zetmeel en PCL.0 voor zetmeel stearaat). en een elasticiteit modulus van 46‐113 MPa. 140 . een uitrekking tot breuk van 3‐26%. Als reactieve compatibilisers zijn twee polycaprolactone derivaten. Er is een statistisch model (R2 =0.1‐2. gebruikt. De synthese van deze verbindingen wordt uitgebreid beschreven.26‐2. Mechanische tests tonen aan dat de producten een treksterkte hebben variërend van 2. Zo is bijvoorbeeld de elastische modulus van de gecompatibiliseerde mengsels beduidend hoger (tot 430 MPa) dan die van niet‐gecompatibiliseerde mengsels (320‐340 MPa).957 en P‐ waarde van ≤ 10‐9) ontwikkeld waarmee de effecten van procesvariabelen (monomeer en initiator concentratie. wederzijdse oplosbaarheid van het monomeer in het gesmolten polymeer) op de functionalisatie graad (FD) van de GMA en DEM eenheden aan de PCL keten adequaat gekwantificeerd kunnen worden. Het laatste hoofdstuk van dit proefschrift (Hoofdstuk 6) behandelt de menging van zetmeel en biologisch afbreekbare polymeren met reactieve compatibilisers.75 nog gedeeltelijk kristallijn zijn.4‐3. De producten met een hoge DS (2.5 MPa. 1.
not in the last place because of the problems related with conventional plastics. Minnaard. Anno Wagenaar and Wim Kruizinga taught me how to operate the NMR machines and to interpret the spectra. since the mechanical properties as well as hydrophobicity of this starting material is relatively poor. Prof. especially on his opinions about the statistical modelling and mechanical properties. and Laurens Bosgra for being always helpful with technical issues and Jan Henk Marsman for the help with analytical equipment. People from other groups have also been very kind and supportive to my research. who was my first daily supervisor for about two months. I also want to give my deep appreciation to my reading committee. Gert Alberda van Ekenstein and Harry Nijland helped me a lot with mechanical and thermal property measurements. Prof. Prof. Anno was also always there when . and Prof. for his efforts to make every foreign students feel at home in Groningen. Mosiscki. and for helping me arranging many things when I was not able to do it from Indonesia. A. Francesco Picchioni. for her hospitality and solving administrative matters. Leon Janssen. Erik Heeres.J. together with difficulties in managing plastic waste. which improved the quality of this thesis. as well as taking the SEM pictures. He has also been a good friend and always supported me during the hard times. I want to thank Erik Heeres for being more than a good supervisor. Marcel de Vries. the raw material for fossil derived plastics. I found out that developing a better fully‐biodegradable‐material from starch is not an easy job. Anne Appeldoorn. for upgrading my writing quality. I want to thank the persons of Building 18 in Nijenborgh 4 for making me feel at home in Groningen and for their help during my research. Thank you Erik. I want to thank Marya van der Duin‐de Jonge. L. and for always encouraging me to finish this thesis. I also want to thank Ineke Ganzeveld. and Prof. Prof.A. This thesis is a summary of my research on developing novel biodegradable polymers from starch. Thank you very much for spending your valuable time reading my thesis and for the constructive comments and corrections you have made. Although it is indeed a very interesting topic. I want to thank my three promoters. for your consistent support.Acknowledgements The synthesis of biodegradable materials is currently receiving a lot of attention. These include the current high oil prices. for valuable discussions during my early PhD period and for handing me over to the right hands. I want to thank Francesco Picchioni for being always there when I needed him to discuss anything. Broekhuis. First of all. I want to thank Leon Janssen for his hospitality. A. for the inspiring ideas during the discussions. Erwin Wilbers.
Jasper Huijsman. for never leaving me alone. Vincent Nieborg and Fesia Lestari. Ais Jenie. and passion. Hofman. and Henk van de Bovenkamp for cheering my days and being my friends during summer and winter. Anneke Toxopeus. and for my wife and family. Dado. kak Atha. Henky Muljana (my paranymph) and Anindhita Widyadhana. 142 . Agnes R. Tante Smith. Wangsa. Thank you my parents and sister. Thyara. and assistant professors have shared the days with me in Groningen.Acknowledgements I had questions or needed specific equipments. Abdul Osman. Mita. Louis Daniel. Togi. Tenny. Mahfud. for your love. and many others for the good old times! Thank you Tante Ietje. Bima and Wisnu (also my paranymph). support. Yongki. Yao Jie. Wahyudin. Boelo Schuur. C. Taufik. Iwan Harsono. for your never‐ending blessings. I want to thank Edwin A. in the lab. and Tante Alma for being like my parents and family in Groningen. Sari Fabianti. Francesca Gambardella. Asal Hamarneh. for everything. Thank you Tresna. Anna Nizniowska. Hans Heeres. Albert Kieviet helped me with the MALDI‐TOF measurements. Tiara. Chalid. R. kak Roga. Tante Oppie. Jaap Bosma. Endy. Judy Retti Witono. mbak Mia. Gerard Kraai. Francesca Fallani. The chemical and glassware magazijn as well as the FWN library personnel were always patient. My special thanks are for Laura Junistia and Jan‐Pieter Drijfhout. Our collaboration has also become part of this thesis. Thank you AW. pak Harry. Tante Caroline. Groningen is also a place where I found true friendship. I have met a lot of Indonesian students in Groningen. and helpful. Buana Girisuta and Rina Karina. our memories will never fade away. Ardiyanti. Teddy. Wuri Raspati. August Kurniawan. Kuslan. Wita Sondari. mas Pandu. master students who worked with me. mbak Ika. Nadia Gozali. M. and although we seldom met afterwards. and the ISD staff helped me a lot with visum and residence permit arrangements as well as tax papers.B. Arjan Kloekhorst. Erna Subroto. Teguh. Thank you God. Niels van Vegten. Nidal Hammoud Hassan. Oscar Rojas. Annette Korringa. and on many occassions. Thanks also for Marcel and Connie. Rasrendra. patience. You all have always been my inspiration and motivation. Patrick and Oppie. A lot of thanks for Henk Stegeman and Poppy Sutanto. Many master and PhD students. Egi. friendly. Ronny Sutarto. Diana Santangelo. bu Ida Susanti. Puspita Kencana. Ignacio Melian Cabrera. spring and autumn in Groningen. Farchad H. visiting researchers. Marcel Wiegman. and Iwan Kustiawan for becoming my family. Ita. Jelle Wildschut. Diana Jirjis. in the office. and Mahesa for being my brothers and sisters in Groningen. Samuel. Zhang Youchun. Taufik.
P. A. Heeres: Green. Picchioni.J. A. Sugih. L. Drijfhout. Janssen. Drijfhout. J.K.A. L.J. Picchioni: Functionalization and blending of polycaprolactone. 25‐28 September 2007 (oral presentation). Heeres. Junistia. presented in “Polymers for Advanced Technologies”. A. A. Sugih. South China University of Technology. L. Sugih.K. Junistia. A. L.P.B. Broekhuis.K. Heeres: Synthesis of higher fatty acid starch esters using vinyl laurate and stearate as reactants.J.J. 9th National Conference organized by the Society for Polymer Science. L. presented in the 1st International Symposium on Sustainable Chemical Product and Process Engineering. Polym. Heeres. Manurung.Drijfhout. A. India.Picchioni. Heeres. Picchioni. Synthesis and properties of reactive interfacial agents for polycaprolactone‐starch blends. 8. Bratislava (Slovak Republic). Sugih.P. and H. H. Junistia. 17‐20 December 2006 (oral presentation).J.J.K. 2008 (accepted for publication in Starch‐ Starke).M. 4.P. Polym. L. J.K. presented in International Workshop: “From Polymer Modification to Multicomponent Polymer Systems”. Heeres: Synthesis and properties of novel green biopolymers derived from starch and fatty acids. DOI: 10.B.P. 2008.010). J. A. Picchioni: Biodegradable polymer materials based on polyesters and starch/proteins. Experimental Studies on the ring opening polymerization of p‐dioxanone using an Al(OiPr)3‐monosaccharide initiator system. 3.K.J. Heeres. Kuala Lumpur (Malaysia). F. Heeres.M.J. 26‐28 November 2006 (oral presentation). F. F. Synthesis of poly‐ (ε)‐caprolactone grafted starch co‐polymers by ring‐opening polymerisation using silylated starch precursors. A. 2. A. Sci.B.B. L. (in press. H. Sugih.Heeres.M.List of Publications 1. 2008 (submitted to Carbohydr.) 6. Picchioni.Janssen.1016/j.10.). Picchioni. 5. L. . Manurung. A. 9. R.K.P. starch‐based innovative product: The synthesis of grafted polycaprolactone‐starch by ring opening polymerisation. and F.2008. Sugih.eurpolymj. Sugih. H. Pune Chapter. 2008 (accepted for publication in Starch‐Starke). F. Picchioni. Eur. and H.K.M Janssen and H.P. Janssen. Experimental and modeling studies on the synthesis and properties of higher fatty esters of corn starch. H. and F. Guangzhou (China). Polym. presented in 11th Asia Pacific Confederation of Chemical Engineering (APCChE) Congress. H. Sugih. Broekhuis. Appl. 2008 (submitted to J.J. R. F. Junistia. Picchioni. A. J. F. Mumbai (India). Sugih. 27‐30 August 2006 (oral presentation) 7.K. H. F.A.
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