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Feature Article

Cellulose-Based Sustainable Polymers: State of the Art and Future Trends
Marcus Rose, Regina Palkovits*

Nowadays, nearly all polymeric materials are produced from crude oil-derived monomers. With the steadily increasing demand for oil-based products and their decreasing availability in the near future, one of the main challenges of mankind is the replacement of crude oil as raw material by renewable resources such as biomass. So far, only a few polymers are available derived directly from cellulose as a main component of biomass by regeneration. On the other hand, a significant potential lies in the production of polymers from cellulose-derived monomers. A huge variety of different monomers is already available by convenient catalytic processes. This feature article focuses on the current status of mono- and resulting polymers derived either directly from cellulose processing and regeneration or by catalytic conversion to a number of monomers for the production of novel polymers and co-polymers.

The crude oil-based society, as we know it, is drawn to a close since peak oil will be reached in the near future and the worldwide consumption of oil-based products is steadily increasing. Besides the recycling of materials from crude oil, new and in the ideal case renewable resources have to be opened up to solve the problem. A conceivable option is the processing of biomass to obtain novel fuels comparable to gasoline and diesel for chemical energy storage. Also the biomass conversion into fine and bulk chemicals for the replacement of mineral oil-based products such as the most polymers is aspired. In 2009, the global plastics production

Prof. R. Palkovits, M. Rose Institute for Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 1, D-52074 Aachen, Germany E-mail: Prof. R. Palkovits Max-Planck-Institut fu ¨r Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mu ¨lheim/Ruhr, Germany
Macromol. Rapid Commun. 2011, 32, 1299–1311 ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

was about 230 million tonnes including mainly oil-based polymers.[1] And with an average growth rate of approximately 9% per year the demand is further increasing. Soon, the production of oil-based products may be hindered due to limited sources and rising raw material prices paving the way for alternative raw materials based on renewable feedstocks. In the past, especially vegetable fats or oils and sugars found application as renewable resources not least in the production of biodiesel and bioethanol. These resources, however, are in competition with the food chain and only available in limited amounts. In contrast, lignocellulosic biomass refers to plant biomass which is not in competition with food supply and worldwide produced in amounts of 170 Â 109 tonnes plant material per year.[2] One of the main components of lignocellulosic biomass besides lignin and hemicellulose is cellulose with a fraction of 35–50%.[3] As a renewable resource produced by plants, algae, and fungi it seems to be an ideal feedstock. Cellulose itself is a fascinating and versatile biopolymer that consists of linear, covalently linked chains of D-glucose units. These chains form highly stable networks with a high degree of

DOI: 10.1002/marc.201100230


D. A detailed view on this pool of chemicals is given with regard to (potential) applications as monomers for the production of established but also novel polymers. S. Her current research focuses on the development of solid catalysts and processes for the efficient utilization of renewable and conventional resources. An extensive and informative review on cellulose as biopolymer and sustainable raw material was published in 2005 by Klemm et al. R. thesis in the group of Prof.[4] Therefore. cellulose can be catalytically depolymerized to glucose. USA) was about the characterization of electrochemical energy storage in carbon-based supercapacitors. This C6 monosaccharide is the starting material for a huge variety of compounds that can be obtained by catalytic or biotechnological conversion.D. a few methods such as the Cuoxam and the Lyocell process are known for physically dissolving and processing of the cellulose to polymeric products. She studied chemical engineering at the Technical University Dortmund and carried out her Ph. in many products celluloid has been replaced by other polymers due to improved properties and performance (Figure 1).de hydrogen bonds in between. Kaskel on the development and characterization of novel polymeric high performance adsorbents and their processing by electrospinning. which can be dissolved and Figure 1. Rose. a composite of cellulose nitrate and camphor as plasticizer. Regenerated Cellulose Processing by Cellulose Derivatization Utilization of cellulose in the form of wood as building material and energy source. This metastable intermediate can be dissolved in an aqueous sodium hydroxide solution to form the so-called viscose. but still in use. A research stay funded by the DAAD in the group of Prof. in the group of . Processing to fibers or films is carried out in a wet process from which the shaped product is precipitated and high purity cellulose is regenerated by removing the substituent. he is a scientific co-worker in the group of Prof. 32. Ferdi Schu ¨th at the Max-Planck-Institut fu ¨r Kohlenforschung. Conventional methods for utilization of cellulose in polymer processing.M.[4] Celluloid. These compounds pose a constant ecological threat despite complex technologies and environmental standards. R. After a research stay in the group of Prof. Weinheim www. Regina Palkovits is Associate Professor for Nanostructured Catalysts at RWTH Aachen. G.[4] describing the structure. an aqueous or organic urea solution is used to convert the native cellulose into cellulose carbamate. Also over 100 years old. Currently. Palkovits at the RWTH Aachen University developing novel heterogeneous catalysts for biomass conversion. This feature article focuses on established and potential processes for the conversion of cellulose to sustainable monomers for production of biopolymers highlighting recent advances in the field as well as future challenges. or cotton as raw material for clothing is as old as civilized mankind itself. Palkovits www. is the viscose process for the production of cellophane (films/membranes) and rayon (fibers). The first chemical utilization of cellulose as a polymeric material can be dated back to the middle of the nineteenth century short after its discovery.[5] Marcus Rose studied chemistry at the Dresden University of Technology and prepared his Ph.MaterialsViews. is supposed to be the first thermoplastic material which has been produced on the industrial scale for decades. Nowadays. Instead of derivatization. KGaA. Bert Weckhuysen at Utrecht University. properties and chemistry of cellulose derivatives. 1299–1311 ß 2011 WILEY-VCH Verlag GmbH & Co. The viscose process suffers from the disadvantage of the required chemicals such as the CS2 and heavy metal compounds for the precipitation process. Yushin (Georgia Institute of Technology in Atlanta/Georgia. the cellulose is alkalized and by addition of CS2 derivatized to cellulose xanthogenate. Rapid Commun. Concerning application of cellulose in polymer production. she returned as a group leader to the Max-Planck-Institut fu ¨r Kohlenforschung before she became Professor at RWTH Aachen.mrc-journal. 1300 Macromol.[6] Instead of the highly hazardous CS2 as in the viscose process. while complete value chains for future biorefinery concepts may be found elsewhere. Alternatively. An alternative method retaining the viscose spinning technology is the CarbaCell process avoiding hazardous sulfur-containing compounds for derivatization which is based on a finish patent from 1979. cellulose can be converted to regenerated cellulose without depolymerization but derivatization as in the viscose process for the production of cellophane and rayon known for decades. 2011.

Schweizer published his discovery of the cellulose solubility in an aqueous ammoniacal solution of copper(II) hydroxide.. so called Schweizer’s reagent. a pool of other. also the ILs are promising candidates in future cellulose processing methods. long reaction times.mrc-journal. ethanol. 1299–1311 ß 2011 WILEY-VCH Verlag GmbH & Co. To our knowledge. BASF in cooperation with ITCF Denkendorf und TITK Rudolstadt started the development of an ionic liquid based process for production of viscose. and high temperatures.[4. Another method developed 30 years ago is the Lyocell process for the production of regenerated cellulose fibers using N-methylmorpholine-N-oxide monohydrate (NMMO) as solvent. the CarbaCell process has not yet been industrially established due to certain requirements such as a catalyst.[4.14] The clear advantage is the good solubility of cellulose in NMMO which can be nearly quantitatively recovered in the process. especially since side products and harmful waste is avoided and no raw material is lost. This renders the Lyocell process a highly economic and ecological friendly method.[15] ILs are non-flammable and possess a negligible low vapor pressure which renders them much better suited for large-scale processes than volatile organic solvents.[8] For largescale application. In comparison to the cotton production. . In a recent study from Righi et al.[7] Due to a well controllable heating process. In comparison to alternative methods. this method is usually counted to the non-derivative processes for cellulose regeneration since it is a method for direct dissolution without the need for producing a cellulose derivative precursor for subsequent dissolution. However.[10] Despite this complex being a cellulose derivative. pulp could be directly www. . ammonium rhodanide in liquid ammonia. organic solvents. By highly efficient solvent recycling in the cellulose regeneration process. KGaA. In recent years. more exotic solvent systems have been identified.11] The CELSOL process requires steam-exploded pulp as cellulose source. such as hydrazine. the major environmental impact is a result of the solvents syntheses.[4. In the last decades much effort has been made for the development of new methods to dissolve cellulose for further processing to fibers. the microwaveassisted process is highly ecological.12] Several other.[16] It was shown.g. 2011. the use of ionic liquids (ILs) for cellulose processing has gained an enormous interest. or comparable environmentally benign solvents. etc. other methods are available for direct processing of physically dissolved cellulose (Figure 1). www.or 1-allyl-3-methylimidazolium chloride ( Macromol. only small amounts of sodium hydroxide solution and sulfuric acid are necessary. especially since some ILs such as 1-butyl. DMSO/methylamine. In 1857. the Lyocell process requires not more chemicals whereas the chemicals in the cotton production pose a higher environmental hazard.MaterialsViews.[4.8] Even concentrated phosphoric acid can be used. that can be dissolved in aqueous sodium hydroxide solution for further processing. An important advantage of the cellulose carbamate is the relatively high stability at room temperature allowing storage for over a year. (CH3)3SiCl/DMF. the cellulose dissolution by BMIMCl in comparison to the dissolution in NMMO in the Lyocell process has been analyzed by a life cycle assessment (LCA).[4] Recent studies focused on the use of microwave irradiation as promising method for the production of cellulose carbamate. these methods are more or less out of the question due to the required hazardous chemicals showing no significant ecological improvement to the state-of-theart processes.[13] Due to high concentrations of cellulose in most of the above mentioned solvent systems liquid crystalline phases are formed which can be processed to high-strength cellulose filaments by spinning. AMIMCl) are able to completely dissolve cellulose under relatively mild conditions without additional chemicals. In line. Cupro silk. Weinheim 1301 . NOSO4H/DMF. In addition to the above mentioned processes. Additionally. SO2/aliphatic amine. films.[9] Tetraaminecopper(II) hydroxide [Cu(NH3)4](OH)2 is formed and the cellulose is directly dissolved by formation of chelate complexes of deprotonated cellulosic hydroxyl groups and copper ions. Even the recovery of regenerated cellulose from solution in an IL can be accomplished with water. this procedure is only rarely used in a few countries anymore since the use of large amounts of copper compounds and ammonia pose environmental hazards. The annual production of Lyocell fibers especially for manufacturing of textiles worldwide is over 100 kt and still increasing. ILs can be used over a wide range of processes and parameters. This method is known as the Cuoxam process and has been employed since the beginning of the 20th century for the production of fibers and films (e. Rapid Commun. Therein. that the IL can dissolve higher amounts of cellulose with a lower time and energy consumption and that there is a small reduction of the hazardous compound emission. conversion of the cellulose is successful within a few minutes under catalyst-free and solvent-free conditions. 32. Processing of Dissolved Cellulose Without Derivatization Besides the production of regenerated cellulose by derivatization. solutions of lithium chloride. processed identically to viscose. mainly non-aqueous solvent systems for the dissolution of cellulose by derivatization has been described. Cuprophane). membranes. trifluoracetic acid/chlorinated alkanes. Despite the advantages over the viscose process.Cellulose-Based Sustainable Polymers . or zinc chloride in dimethylacetamide (DMA). Due to their high chemical and thermal stability. such as N2O4/dimethylformamide (DMF). (CH2O)x/dimethyl-sulfoxide (DMSO).8. none of these processes is used on the industrial scale so far. and CCl3COH/dipolar aprotic liquid.

[25] itaconic. acid catalyzed dehydration of glucose gives access to 5-hydroxymethylfurfural via dehydration. if applicable we will highlight recent developments in this direction. 1302 Macromol.(white) or chemocatalytic (light gray) transformations). For comprehensive overviews with regard to possible transformations and utilization schemes of lignocellulose. cellulose can be depolymerized by hydrolysis of the b-1. we will mainly focus on intermediates which found increasingly attention by academia and chemical industry with regard to their potential to serve as substitutes of monomers currently derived from fossil resources and future feedstocks for the production of novel polymers. Instead. a huge variety of products is available and can by far not be covered in the current review.4glycosidic bond to glucose.g.23] Herein.[18] or simple combustion to synthesis gas and consequent build-up via established procedures. Palkovits www. Rose.[26] glutamic. ethanol from renewable resources is mainly produced by fermentation of sugars derived from sugar cane or sugar beet with yeast.[29] Further promising chemocatalytic transformations of glucose include the hydrogenation to sorbitol. we will focus on compounds which are exclusively available based on cellulose and may give rise to the development of novel polymer materials or substitution of petrochemical building blocks. the reader is referred to several recent reviews.[30] or direct hydrogenolysis of cellulose to sugar alcohols.[3. Rapid Commun.. Comprehensive reviews covering available synthesis procedures of these compounds can be found elsewhere. microorganisms are under investigation to convert even xylose and other pentose contained in hemicellulose into ethanol. R. 1299–1311 ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA. various further transformations are possible and can by far not be covered in the present review. e.21] Figure 2 illustrates selected transformations of cellulose to novel intermediates which have also been identified by the Department of Energy (DoE) as potential future bulk chemicals and provide a high potential to serve as future feedstocks for the production of polymers. General Motors together with Coskata. the goal will be the production of cellulosic ethanol which will be mainly dependent on the further development of more efficient and economic processes for hydrolysis of cellulose. sorbitol may be dehydrated to sorbitan and isosorbide or reacted via further hydrogenolysis or hydrodeoxygenation reactions to yield glycerol and propylene or ethylene glycol as well as various C1ÀC6 mono-and polyols and even alkanes.[32] .[28] whereat the latter might also be produced by chemocatalytic means.M. The depolymerization can be carried out enzymatically[19] or catalyst free in supercritical water. 32. On a long run.[34] Additionally. biomass offers the possibility to derive most of the conventional petrochemical monomers.[33] Besides. via gasification to syngas and subsequent reassembly to methanol and hydrocarbons or via dehydration of ethanol to ethylene. Glucose Conversion to Ethanol by Fermentation Currently.[17] Cellulose-derived Monomers Depolymerization of Cellulose Beside the thermal degradation of lignocellulosic biomass to pyrolysis products for further conversion similar to petrochemical processes. Transformation scheme of cellulose to potential bulk chemical for future polymer production (mainly available via bio. Figure 2. however. Starting from these compounds.[23] while herein only recent developments will be pinpointed.mrc-journal.[24] Further products available via biocatalytic transformations of glucose include succinic. also homogeneous or heterogeneous acid catalyzed processes have attracted considerable attention.MaterialsViews.[31] Consequently.[35] In 2008.[27] and lactic acid. which may be rehydrated to levulinic acid. This reaction opens up a huge variety of new possibilities to obtain basis chemicals and potential monomers. 2011. glucaric. Although such transformations and products are not in the closer scope.[22] Certainly. Weinheim processed out of the ionic liquid avoiding any derivatization.[5. Possible reactions include the enzymatic or acid catalyzed hydrolysis of cellulose to yield glucose which may be subsequently converted into ethanol via fermentation.[20] Recently.

While the projects of Baskem and Solvay with 180 000 and 55 000 t Á aÀ1. transforming ethanol to 1. polyvinylchloride and polystyrene. acetic acid is produced via carbonylation of methanol and to a smaller extent via bacterial fermentation yielding in total around 5 Mt Á aÀ1 of which 65% go into polymer production in the form of vinylacetate (43%) or celluloseacetate (25%). while microbial fermentation usually results in formation of racemates with 50–90% L-lactic acid. KGaA. In 2005. In such vapor phase dehydration reactions at around 400 8C. 1299–1311 ß 2011 WILEY-VCH Verlag GmbH & Co.3-butadiene from ethanol compared to steam cracking. 2CH3 CH2 OH ! CH2 ¼ CHÀCH ¼ CH2 þ 2H2 O þ H2 Alternatively. 32. Weinheim 1303 . and 1. ethylene production exceeded 107 million tonnes and further market growth is expected.[37] Instead. lactobacilli allow the production of both pure enantiomers. China. Dow. enzymatic production of ethanol usually yields low concentrated aqueous solution of ethanol. Lactic Acid Lactic acid is a naturally occurring acid which plays an important role in the metabolism of most organisms. At the end of the 18th century it has been isolated from sour milk. .[39] Nevertheless. are on the way.30 LÀ1.[45] www. The full-scale plant capable of producing 50–100 million gallons of ethanol a year (200–400 ML Á aÀ1) is planned to start operation in 2011. while today it is only used in China and India. Figure 3. close to full conversion of ethanol with around 99.3-butadiene at 400– 450 8C catalyzed by metal oxide catalysts.[40] Technical implementation was realized in fluidized bed reactors over solid acid catalysts such as activated alumina. CH3 CH2 OH þ CH3 CHO ! CH2 ¼ CH-CH ¼ CH2 þ 2H2 O The presented process concepts proceed via dehydration of ethanol in the gas-phase after separation from water. which has to be purified to obtain pure lactic acid. lactic acid is commercially produced by fermentation of glucose yielding around 90% calcium lactate. Rapid Commun. Low cost of sugar cane and an increasing oil price have renewed the interest in ethanol dehydration. .[38] Via dehydration biomass derived ethanol can be converted into ethylene which is currently exclusively produced in petrochemical industry via steam cracking and mainly used in the production of polyethylene. This process has been developed by the Russian chemist Ivan Ostromoslensky and used in the United States to produce government rubber during World War II. its use remained limited to Russia and Eastern Europe. Thus.Cellulose-Based Sustainable Polymers . and Solvay announced separate projects to build ethanol-to-ethylene plants based on sugar cane.[44] However. respectively. Two possible routes have been reported and are even used on industrial scale in several parts of the world including Eastern Europe.[41] This technology might become economic not only dependent on the market price of oil and bio-ethanol. various conventional monomers for polymer production can be obtained (Figure 3). Dow and Braskem will manufacture ‘‘green’’ polyethylene while Solvay plans to use ethylene to supply its polyvinylchloride capacity.3-butadiene which finds not only application in the production of polybutadiene but also for the production of various copolymers including acrylonitrile-butadiene-styrene.MaterialsViews.9% selectivity to ethylene could be reached. announced the production of price competitive cellulosic ethanol with a goal of $0. a direct dehydration of ethanol avoiding prior separation from water would be highly attractive and presents a major challenge to improve applicability and economics of the described utilization schemes. Transformation of ethanol into acetic acid. In commercial processes. ethanol can be oxidized to acetic acid via acetaldehyde. ethylene. and India due to lower capital costs for small scale production of 1. in the early 20th century. www.[36] Based on ethanol. Inc. One process option has been developed by Sergei Lebedev. 2011. and there have been industrial fermentation processes for more than a hundred years now.3-butadiene as potential platform chemicals and application in polymer processing. Braskem which is Brazil’s largest plastics producer. Dow (320 000 t) announced a delay in construction of their 320 000 t Á aÀ1 plant.[43] Although carried out on an industrial scale to serve the synthetic rubber industry of the Soviet Union’s during and after World War II. Although currently not of industrial relevance. ethanol and acetaldehyde may be converted at 325–350 Macromol.[42] Another interesting possibility concerns the transformation of ethanol into 1. ethylene was mainly produced by dehydration of ethanol.mrc-journal. polyethylene oxide. but also the growing public interest in polymeric products derived from renewable feedstocks promotes the development. acrylonitrile-butadiene or styrenebutadiene.

Concerning application of lactic acid. lactic acid is produced with around 250 000 t Á aÀ1. are under debate. With respect to commercial applications. Rose. dishes. more sophisticated polymerization technologies could facilitate direct utilization of racemic mixtures. the primary producer of PDLLA is PURAC. food containers.g.MaterialsViews. cups.and disaccharides into methyl lactite over lewis acidic zeotypes. but has a significantly lower maximum service temperature. Also Galactic and Total Petrochemicals operate a joint-venture.g. or propylene oxide and subsequent application in polymer production or direct polymerization to polylactide. but estimations foresee a growth up to 15 Mt Á aÀ1 in 2020. R. it is utilized in food and cosmetics industry. 1299–1311 ß 2011 WILEY-VCH Verlag GmbH & Co. Figure 4. lactic acid is already intensively used in polymerization to form polylactide. Palkovits www.[51] The biodegradable polylactide is utilized in the production of packaging materials. e.mrc-journal. -carbonates. and carrier bags as well as disposable products including bottles. PLA is produced by ring opening polymerization of the dilactide and exhibits similar mechanical properties to polyethylene terephthalate (PET). either suitable catalyst systems allowing for asymmetric synthesis of lactic acid or efficient technologies for post-synthesis separation of racemic mixtures have to be developed. poly(L-lactide) (PLLA) can be produced which exhibits high crystallinity (37%). Preparation of polylactide via dimerization to dilactide and subsequent ring-opening polymerization to yield polylactide. Nebraska (US) from its joint venture partner Cargill. 32. NatureWorks was the first to launch a commercial production in 2002 with a capacity of 150 000 t Á aÀ1 and remained to be the primary producer of polylactide (PLA) in the United States till middle of 2010. With regard to polymerization of racemates. Weinheim www.50] Currently. propylene glycol. Via physical blending with PDLA [poly(D-lactide)]. the dominant application area with the largest expected market growth regards the area of polymer production. production of hygiene articles for private and medical use and paper coatings. At the moment. e. Nevertheless. however. Holm et al. Besides. Utilization of lactic acid via transformation into acrylic acid. Therein. via heterogeneously catalyzed transformation of glucose have found reasonable attention. Polymerizing L-lactide. Rapid Commun.. Further areas of application cover fibers and non-wovens for application as textile fibers. a Dutch company and several Chinese manufacturers. Uhde Inventa-Fischer now licensed this technology based on the pilot plant for facilities of up to 60 000 tons PLA per year. Scheme 1.and L-enantiomers and determines most physical properties. 60 to up to 190 8C.. Consequently.[45.[46] Alternative process options. PDLLA does not exhibit the required properties for most applications. or trays. One German company who deals with the production of PLA is Uhde Inventa-Fischer. flexible films. Nevertheless. Inventa Fischer built a pilot plant with an annual PLA production of 500 tons in 2010. is related to the need for pure enantiomeric lactic acid for production of PLA with sufficient properties.[49] Currently. 2011. called Futerro including a PLA pilot plant with 1 500 t Á aÀ1 in Belgium. such as . already 3–10% PDLA result in a substantial improvement induced by PDLA acting as nucleating agent and thereby increasing the overall crystallinity of the The production of pure lactic acid results in around 1 ton of CaSO4 per ton of lactic acid which presents the major drawback of the current commercial process. reaching up to 68% yield with sucrose as substrate. 1304 Macromol. the melting temperature can be increased by 40–50 8C and its heat deflection temperature can be increased from ca. alternative process options with main focus on improved purification and separation techniques. part of CSM which recently acquired the remaining 50% of the shares of the lactic acid production facility in Blair.g.[48] The main challenge.[47] Therein. e.M.. lactic acid could serve as potential renewable feedstock for the production of acrylic acid (polyacrylic acid) and propylene glycol with applications in polyesters. utilizing desalting and water splitting electrodialysis. Due to the fact. The monomer is available from lactic acid by polycondensation up to a limited molecular weight followed by depolymerization (Scheme 1). and urethanes or even for further transformation to propylene oxide as feedstock for classical polypropylene oxide production (Figure 4). that crystallinity depends mostly on a defined ratio of D. Meanwhile several other companies entered the business including PURAC Biomaterials. a glass transition temperature between 60 and 65 8C and a melting temperature around 175 8C. PDLA and PLLA form a stereocomplex with increased crystallinity and maximum temperature stability for a 50:50 blend. an amorphous poly-DL-lactide (PDLLA) is obtained. presented the conversion of mono. Consequently. KGaA. a biodegradable polymer.

[56] Due to its two carboxy functionalities it is highly interesting as monomer for manufacturing new polyesters or for polyamide production via transformation into itaconic diamide or 2-methyl-1.[53] Bechthold et al.[52] Nevertheless. especially since additional CO2 is utilized in this process.g. e. Department of Energy (DOE) in 2004 and revisited by Bozell and Petersen recently. 1299–1311 ß 2011 WILEY-VCH Verlag GmbH & Co. the methylidene group renders itaconic acid highly promising as a substituent for crude oil-derived monomers such as acrylic or methacrylic acid (Figure 6). www.4butanediol together with succinic acid or adipic acid.[52] Additionally. as comonomer for styrene-butadiene-acrylonitrile and acrylate latexes.and L-lactic acid will be decisive to further market growth and application areas. e. E. (2) acyclic O.g.4-butanediamine has been described in literature. and N-vinylpyrrolidone as potential monomers for production of polyester.4-butanediamine.mrc-journal.. Figure 5.g.Ncontaining.55] Itaconic Acid Itaconic acid is a C5 unsaturated dicarboxylic acid.4butanediamine. 32. g-butyrolactone.[56] Chemical synthesis is also known. also the commercially available polymer PA 46 known as Stanyl1 from DSM uses 1. amides. Although attractive for substitution of PET.4-butanediol is accessible starting from itaconic acid and offers various possibilities for application in polyesters and -amides.[52] Nowadays. KGaA. Transformations of succinic acid into 1. especially succinic acid is of great interest as platform chemical for polymer production.[52] Especially the bifunctional acyclic compounds such as 1. the polyamide PA 44 which is based on succinic acid and 1. It is produced by fermentation of carbohydrates such as glucose by fungi with a current worldwide production of about 15 kt Á aÀ1. but so far it is economically and ecologically not interesting for large scale production.4-butandiol and 1. 2011.g. the succinic acid used for these polymers is produced from biomass by fermentation as mentioned above. Therein. 6–9 Euro Á kgÀ1.4-butanediol.[52] Both polymers have been recently introduced to the market.[22b] By fermentation of glucose C4 dicarboxylic acids such as succinic. a polyester based on ethylene glycol and 1. succinic acid is a potential platform chemical for the production of g-butyrolactone that can be further converted to 2-pyrrolidone by reaction with ammonia. 2-Pyrrolidone itself is a precursor in the synthesis of N-vinylpyrrolidone. Itaconic acid is already utilized as a co-monomer in resins and in the production of synthetic fibers.. Figure 6. Therein. and (4) cyclic O. Weinheim 1305 . and malic acid can be obtained. a significant market growth for both lactic acid demand and production is expected in the upcoming years. Companies such as Mitsubishi Chemical Corporation and Showa Denko have developed the polymers GS Pla1. Macromol.S. Besides. Besides. which is obtained by reaction of 2-pyrrolidone with acetylene in the presence of elemental potassium at 100 8C. fumaric. and polyvinylpyrrolidone. Additionally. . 2-methylene-1. Itaconic acid as potential cellulose-derived C5 carbon building block for synthesis of novel polymer materials. e. a poly(butylene succinate) and Overall. (3) cyclic O-containing..[54] The current market demand of succinic acid is around 15 kt with a price of ca. further improvements in polymerization technology as well as possible catalysts for the efficient enantioselective transformation of glucose into D. Rapid Commun. 1. 2-pyrrolidone. the monomer of polyvinylpyrrolidone (PVP). as substitute of conventional diols. succinic acid is produced from the C4 fraction of crude oil via maleic anhydride.4-butanediamine as monomer. starting from citric acid.Cellulose-Based Sustainable Polymers . But also the biotechnological production by fermentation of cellulose-derived sugars is a well-established process. the broad field of applications results in an estimated market potential of several hundred thousand tonnes.[52.Ncontaining. . Succinic Acid Succinic acid presents another potential future building block highlighted by the U.4-butandiamine in combination with succinic acid or other dicarboxylic acids are of interest for the production of polyesters and polyamides (Figure 5).MaterialsViews. classified succinic acid-derived monomers in the four following groups: (1) acyclic O-containing..

5-pentanedicarboxylic acid. 1. in which CO2 is dissolved in an aqueous solution under the in situ formation of H2CO3. 1. Alternatively. Glutamic acid as monomer for production of polyamides. or mannose.[64] Nevertheless. It is derived by dehydration of hexoses such as glucose. biodegradable and edible. Liquid Bro ¨nsted acids can be used in homogeneous processes.[57] Nevertheless.5-pentanediol.[21a. materials for water treatments and super absorbent polymers.S.8 million grant through the Joint Biomass Research and Development Initiative of the U. -esters.[22] By reduction and/or hydrogenation it can be converted to several bifunctional compounds such as 1. Different reaction pathways have been proposed for this reaction since the mechanism of the hexose dehydration is not fully clear so far and may proceed via cyclic or acyclic intermediates. These monomers are under consideration for the production of novel polyamides and polyesters. or polyglutamic acid and starting material for transformation into 1. R.S. fructose. Abbadi and van Bekkum have investigated the performance of a commercial Pt/C catalyst in the selective oxidation of glucose with oxygen showing promising results.62] Very recently. Department of Energy and U. 1299–1311 ß 2011 WILEY-VCH Verlag GmbH & Co. 5-hydroxymethylfurfural (HMF) is a key intermediate in the catalytic conversion of cellulose to potential monomers based on furan derivatives.5-pentanediol.[63] published an extensive review on the synthesis and properties of HMF. heterogeneously catalyzed reactions have been described using solid acids such as ion exchange resins and others.MaterialsViews. 32. On the other Figure With regard to the properties of potential polymer products containing such building blocks.5-pentanedicarboxylic acid (glutaric acid). foods.[60] For industrial scale production of glucaric acid the development of more efficient and heterogeneous catalyzed processes is necessary. Ester derivatives of PGA have been shown to be well suited for the production of thermoplastics and can be processed into fibers or Figure 8. Glutamic Acid Another platform chemical.[63] Beside these methods also heterogeneous gas–liquid systems have been discussed. transparency and elasticity. little investigations exist and future studies need certainly to focus on the impact of these substitutes on mechanical and chemical properties. Concerning commercial . and 2-amino-1. Therein. polyitaconic acid exhibits biodegradability and a superior calcium binding capacity compared to polyacrylic and polyaspartic acid which suggests its application in detergent and antiscaling applications. Rose. 2011. Weinheim www. the American start-up Itaconix has received a $1.5-pentanediol and 2amino-1.5-pentandiol (Figure 7). Rapid Commun. which is also a fermentation product of glucose. especially the reactive methylidene group in itaconic acid could allow a simple chemical modification to deliver tailor-made monomers for certain applications or even post-polymerization functionalization.[59] This polymer is soluble in water. These properties render PGA an interesting polymer for applications in medicine. the most efficient and selective conversion to HMF starts from fructose due to its high reactivity and is generally catalyzed by acids. Glucaric acid as monomer for use in hyperbranched polyesters and hydroxylated nylons. membranes with excellent strength.[59] Glucaric Acid By selective oxidation of the terminal carbon atoms to carboxy groups by nitric acid. is the amino acid glutamic acid.mrc-journal. a C5 building block. levulinic acid and even sorbitol-based chemicals. and pharmaceuticals.[58] Therein.[22] It is not only a valuable C6 building block for further conversion but it is also under discussion for the production of hyperbranched polyesters and hydroxylated nylons (polyhydroxypolyamides) (Figure 8).[61] Nevertheless. KGaA. Glutamic acid can undergo a polymerization with itself to poly(glutamic acid) (PGA) which is naturally produced by bacteria. Rosatella et al. little investigations concerning this interesting building block and its derivatives exist and further investigations are certainly necessary to elucidate its full potential.M. 5-Hydroxymethylfurfural and Levulinic Acid Another interesting class of potential platform chemical for polymer production includes bifunctional derivatives of furan such as furandicarboxylic acid (FDC). 1306 Macromol. Department of Agriculture and offers product lines based on polyitaconic acid including detergents. Palkovits www. glucose can be converted to glucaric acid.

5-bis(hydroxymethyl)tetrahydrofuran.5-furandicarboxylic acid (FDC) catalyzed e.5-bis(aminomethyl)furan can be synthesized from DFF as reported by El Hajj et al. Lewis acids are also able to catalyze the formation of HMF. and other metals are under consideration. the reaction can be also carried out thermally without a catalyst using hand.[71] The above mentioned side reaction occurring during the acid catalyzed synthesis of HMF from cellulose and cellulose-derived sugars by re-hydration of HMF yields levulinic acid (LA) and one equivalent of formic acid.MaterialsViews.[21a. KGaA. The direct utilization of ketals of LA as monomers for polyurethanes and thermoplastics is commercially investigated by the company Segetis.[62. ionic liquids have proven useful as solvents in combination with Bro ¨nsted or Lewis acids resulting in nearly quantitative conversion of fructose to HMF.5-furandicarboxylate) (PPF) in analogy to polyethylene terephthalate (PET).5-furandicarboxylate) (PEF) or poly(propylene 2. Rapid Commun. Other bifunctional HMF derivatives such as amino or isocyanate compounds may prove useful as monomers for novel polyurethanes.g. www. but also zirconium.66] Since HMF cannot be efficiently removed from an aqueous or ionic liquid phase by distillation is not favorable due to its high reactivity. 2011.[15b] Also the acid catalyzed polymerization of LA with glycerol yields a polymeric material of commercial interest. especially (FDC) is under discussion as a substituent for the crude oil-derived terephthalic acid in the production of polymers like poly(ethylene 2.63] Other catalytic active species like Pd/C or Raney nickel result in additional hydrogenation of the furan ring to yield 2.. HMF is a versatile platform chemical that can be catalytically converted to an enormous number of bifunctional furan derivatives as recently shown in a comprehensive review by Tong et al. Due to very similar properties of the monomers.[21a. ..Cellulose-Based Sustainable Polymers . Its production in a one-step reaction directly from cellulosic biomass is under intense research. The selective oxidation of HMF to 2. respectively (Figure 9). E. a direct further conversion is intended in recent production strategies. Several attempts have been made to develop nonaqueous catalytic systems for a more selective conversion of fructose to HMF. Weinheim 1307 .63] Ribeiro and Schuchardt[68] reported the successful one-pot dehydration and oxidation of fructose to FDC using a cobalt acetylacetonate encapsulated in sol–gel silica with a fructose conversion of 72% and a selectivity for FDC of 99%.[65] In recent efforts. The research in this area focuses mainly on chromium compounds.[62] HMF itself is not sufficiently stable for long term storage.[62. E. .[67] Thus. Alternatively. several lanthanides.g. other methods for the product separation have to be developed. hydroxyl. 32. LA poses another platform chemical of high importance (Figure 9).22b] The importance of LA as a platform chemical for applications as monomer can be shown by the following examples: The conversion of LA into diphenolic acid has been investigated using supported heteropoly acids as heterogeneous catalysts. Especially ionic liquids are in the focus of research as reaction media since they provide outstanding properties for this type of reaction. BHF as a bifunctional monomer is an important precursor for manufacturing of new polyesters or polyurethane foams by replacing the respective diol compounds.[62. polyamides and other polymers based on monomers with the respective functionalities. the conversion of LA to a-angelica www. by carbon or alumina-supported platinum with nearly quantitative yields under mild conditions (60 8C) is under intense study revealing a high feasibility of these processes.[14b. 5-Hydroxymethylfurfural and levulinic acid as potential building blocks for synthesis of various cellulose-derived monomers.5-diformylfuran (DFF) using classical oxidants such as molecular oxygen or hydrogen Figure 9. titanium. 2.[65.63] In aqueous solutions several by-products are observed such as difructodianhydrides and humins significantly reducing the final yields of HMF.g. amino or isocyanate functionalities.. biphasic systems are under discussion to continuously extract HMF into an organic phase from which it can be removed easily. formyl.mrc-journal. 1299–1311 ß 2011 WILEY-VCH Verlag GmbH & Co.[67] Even polyamides with comparable properties like a high strength in aramid fibers (Kevlar) are conceivable using FDC instead of terephthalic acid as monomer.63] However.[14b] Macromol.15a] This diphenolic acid is considered as sustainable replacement for Bisphenol A as an additive in the production of polycarbonates.5-diisocyanatofuran is derived from FDC by reaction with sodium azide. peroxide or direct oxidation to 2. rehydration products of HMF such as levulinic and formic acid can be found. Target molecules that are considered as potential monomers show carboxy.[69] Besides the oxidation of HMF to FDC. it can be converted to 2.or supercritical solvents or solvents such as dimethylsulfoxide (DMSO) as reaction promoters.5-bis(hydroxymethyl)furan (BHF) by hydrogenation with NaBH4 or catalytically by hydrogen over Cu or Pt.[70] while 2. Additionally.

[77] described the reductive splitting of cellulose dissolved in BMimCl. xylitol. and ethylene glycol as well as methanol. While other combinations mainly provided glucose rather than sorbitol together with dimers and even 5-hydroxymethylfurfural indicating that the hydrogenation reaction preceded rather slowly under these reaction conditions when compared to hydrolysis. It is considered a valuable polymer made from renewables that is degradable by light or under acidic/basic conditions. Combining HRuCl(CO)(PPh3)3 as molecular catalyst with Pt/C or Ru/C allowed full conversion of cellulose. 32. and erythritol as well as glycerol for polymer production or further CÀC cleavage to yield propylene and ethylene glycol as well as glycerol.[78] Interestingly. Rapid Commun. PEIT–polyethylene isosorbide terephthalate in which some ethylene glycol is substituted by isosorbide.g. Moreover. adding CuCl2 or NiCl2 as co-catalysts or working at elevated reaction temperature allowed not only hydrolyzing cellulose to glucose which is further hydrogenated to sorbitol. Additionally. lactone has been reported using H3PO4 as catalyst.[80] Further investigations indicated even simple bimetal catalysts to be suitable for the application although superior yields with up to 72% ethylene glycol were reached over tungsten carbide supported on three dimensional mesoporous carbon.72] By ring opening polymerization this intermediate can be transformed into an aliphatic polyester. Therein. Isosorbide itself is interesting as product for polymer production. pilot plant studies have already been carried out. yielding up to 30% of sorbitol. propylene. isosorbide exhibits reduced polarity when compared to sorbitol and thus facilitates extraction from the molten salt solution.[76] report the conversion of cellulose to hexitols catalyzed by ionic liquid stabilized ruthenium nanoparticles and a reversible binding agent. respectively. but catalyses the further dehydration yielding isosorbide as main reaction product. Sorbitol. could optimize the reaction system towards sorbitol formation reaching up to 85% yield of hexitols (15% sorbitan) at 463 K. 1299–1311 ß 2011 WILEY-VCH Verlag GmbH & Co. presented the hydrogenolysis of cellulose over supported Pt. Recently. Palkovits www.[74] Fukuoka and Luo et al. e.M. Sorbitan and Isosorbide and Further Polyols Besides the presented transformations. MaineBioproducts developed the so called Biofine Process and announced the commercial production of LA via acid catalyzed dehydration of lignocellulosic feedstocks in a two-stage process. cellulose can be hydrolyzed to release glucose which is consequently hydrogenated to sorbitol.[75] Therein. we could demonstrate the carbon efficient utilization of cellulose at 433 K only combining hydrolysis and hydrogenation with above 90% yield of sugar alcohols including sorbitol and its dehydration products. recent studies indicate the possibility to convert cellulose directly into sugar alcohols such as sorbitol via CÀC and CÀO bond cleavage in so called hydrogenolysis reactions over supported metal catalysts (Figure 10).[16.[79] While Geboers et al. Moulijn and co-workers addressed this issue and dissolved cellulose in ZnCl2 in the presence of Ru/C and hydrogen pressure. catalyst system and product selectivity to allow tailored synthesis of individual products as this reaction type allows not only access to sorbitol but further hydrogenolysis can deliver various sugar alcohols. erythritol. Interestingly. via formation of isosorbide ethers could be an interesting approach to allow efficient recovery of the reaction product.MaterialsViews. respectively. Future investigations need certainly to focus on insights concerning the relation between reaction conditions. recent publications even describe the direct hydrogenolysis of cellulose over nickel-modified tungsten supported on activated carbon as catalysts with remarkable selectivity to the formation of ethylene glycol. Alternatively. the main challenge for reactions in ionic liquids refers to the separation of the very polar products from the ionic liquid. has already been demonstrated. 2011. Weinheim www. or Ru catalysts in aqueous phase at 463 and 518 K. C4–C6 sugar alcohols account for the main fraction of products summing up to around 80% yield. Zhu et al. formation of acidic surface sites via spill-over of hydrogen from the metal onto the support was suggested together with an increased amount of H3Oþ and OH– groups induced by the temperature dependent shift of the autoprotolysis equilibrium of water. glycerol. reactive extraction.g.[81] 1308 Macromol. Alternatively. Up to 85% yield of sorbitol and mannitol could be obtained.. xylitol. but only in combination with Ru/C up to 74% yield of sorbitol could be reached.. R. Nevertheless. Interestingly. Conversion of cellulose and glucose. Additionally. opening the way for commercialization of this . the combined hydrolysis and hydrogenation of cellulose combining molecular acids and suitable hydrogenation catalysts in aqueous phase has been described. Rose.[73] Figure 10. into sorbitol. e. Therein. Pd.mrc-journal. Ignatyev et al. several attempts for controlled hydrogenation in ionic liquids have been presented. KGaA.

an initiative of the state of North Rhine-Westphalia and the EU. Acknowledgements: We acknowledge financial support by the NanoEnergieTechnikZentrum at University Duisburg-Essen. and textiles. Biorefineries – Industrial Processes and Products... dehydration of cellulosic bioethanol to yield ethylene. 1299–1311 ß 2011 WILEY-VCH Verlag GmbH & Co. further chemical transformations. S. erythritol. Additionally. also sorbitan could potentially be utilized in polyester production.[85] Consequently. Vol. monomers. isomannide. Int. published a comprehensive review on polymers based on isosorbide. Additionally. 2005. M. [2] B. via further dehydration to obtain sorbitan and isosorbide or via further hydrogenolysis yielding various sugar alcohols including xylitol. [3] R.MaterialsViews. Fenouillot et al. A. Kamm. cellulose. . only to mention the substitution of terephthalic acid with furandicarboxylic acid in the production of PET equivalent products. current commercial interest focuses on substitution of building blocks conventionally derived via petrochemical processes by biomass based compounds. propylene and ethylene glycol could be dehydrated to deliver propylene and ethylene for production of biomass derived polyethylene and poly(propylene). The C4 and C5 sugar alcohols. presents glycerol. especially isosorbide is discussed.Cellulose-Based Sustainable Polymers . Chem. renewable resources [1] www. biopolymers. xylitol and erythritol together with their dehydration products. 610.. Chem. R. 1. Recently. p. as already mentioned for partial substitute of ethylene glycol in PET production. Nevertheless.g. [4] D.-P. KGaA. DOI: 10. Wiley-VCH. Therein. This work was performed as part of the Cluster of Excellence ‘‘TailorMade Fuels from Biomass’’ funded by the Excellence Initiative by the German federal and state governments to promote science and research at German universities. Velty. Part of the work has been funded by the Robert Bosch Foundation in the frame of the Robert Bosch Fellowship for sustainable utilization of renewable natural resources. Iborra. Ed. Heublein. Published online: June 10. B. 15. S. [5] [5a] G. Chem. F. via biochemical means to yield bioethanol. attract increasing attention and future investigations will certainly pinpoint various polymers based on novel building blocks which allow production of biopolymers which cannot only substitute existing products but exhibit alternative properties and open the possibility for new product lines. Rev. isosorbide is discussed as substitute for Bisphenol A for application in epoxy resins and polycarbonates. the potential of novel polymers to substitute classical products is explored. have till now only been minor products in hydrogenolysis of cellulose but could additionally be obtained via hydrogenoylsis of hemicellulose and as well be transformed to yield shorter sugar alcohols or be oxidized to further potential monomers for polymer production. 4044. Weinheim 1309 . Instead. Corma. Additionally. Gruber. but further transformations allow access to acrolein an important intermediate in acrylic acid production and even the catalytic reaction of glycerol to lactic acid appears feasible. are possible. Corma.201100230 Keywords: biomass. Angew. www. . 2011. Weinheim. 2011. Energy Environ. Rinaldi. With regard to the mentioned reaction products.[83] For glycerol itself hardly any direct application as monomer in polymer production has been discussed. Concerning applications of these products in the field of and isoidide. Huber. e.[84] Therefore. Conclusion With regard to the need of sustainable carbon sources and an increasing public interest in products based on renewable feedstocks. together with propylene and ethylene Macromol. which found increasingly attention not last due to its increasing availability in the frame of biodiesel production. e. the overview intends to highlight recent trends in the fields and pinpoint promising research directions. 3358. 2011. Received: April 7. Rev. glycerol.mrc-journal. Iborra. 106. 2. Another monomer accessible via hydrogenolysis of sorbitol. Schu ¨ th. cosmetics. Kamm. Besides. 107. e.[82] In line. A. sorbitol is already used in today’s chemical industry serving as dispensing agents and humectants in pharmaceuticals. H. [5b] A. and for further chemical synthesis of surfactants and ascorbic acid. Klemm.. W. also novel biomass derived polymer types.g. even the presented transformations can by far not cover the whole range of monomers available based on cellulose.1002/marc. Additionally. polyitaconic and polylactic acid. A. 2009. The obtained polyethylene isosorbide terephthalate was reported to exhibit improved mechanical and thermal properties. www.g. especially propylene and ethylene oxide together with glycerol present potential compounds to bridge today’s value chains and future biorefinery schemes. Bohn. especially propylene and ethylene glycol exhibit high commercial value as they are already part of the value chain today and the petrochemically derived version could simply be exchanged by cellulose based compounds. 2006.plasticseurope. Sci. P. 32. Concerning further monomers. 2007. Rapid Commun. Germany 2006. cellulose could serve as a valuable resource for the direct integration into polymer materials and provide a variety of ‘‘classical’’ and also novel monomers for integration into polymer production. 44. 2411. Li and Huber[32] even demonstrated complete hydrodeoxygenation of sorbitol to alkanes.

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