Properties of vinyl ester resins containing methacrylated fatty acid comonomer: the effect of fatty acid chain length Tania Dey* Depatment ef ChamcalEngneeang, Creel nrersty, Prisco, PA 19108, USA Abstract: This paper reports the formulation ofa low-cost vinyl estor-baced composite resin suitable for liquid ‘molding, which has signficanty lower volalleorganlc compound emission asoclated with ft. Methacrylated fatty acid comozomers were used to replace the conventional et environmentally hazardous reoctive diluent, styrene. “The chata lent of Uhewe futty ackde played = hey role In obualning better Vincenty, a He was proved to affect ‘two intrplayiag factors intermolecular friction and hydrogen bonding. The thermomechanical performance wae sreatly affected by the chaln length of the fatty acids as well asthe crossllak density ofthe polymer networks. A carbon aumber of 6 to 8 was good enough In optimizing the viscostry parameter suitable for handling; the dynamic ‘mechanical analysis values, namely giss transition temperature and storage modulus, were in the range 6~121°C (snd 0.9"-28 GPa, reepectively, a the carbon number was varied from te 16, making the material suitable for ‘various applications. Microstructures obtained from scanning electron microscopy results were correlated with polymer properties t obtain a better insight Into these polymer networks. (© 2007 Society of Chemical Industry Keywords: blends; resins; mechanical properties; viscosity; structure—property relation INTRODUCTION Polymer composies nave immense applicaion poten tial, dus 1 their low cost, low weight and good performance. The increasing demand for low-cost ‘composites is accompanied by the need to use low ost processing methods, such as liguid molding, that require low-viscosity resin systems (<500mP1 s). A typical vinyl ester composite contains styrene fa @ monomer a well as a reacuve clluent, Walch fs a significant source of volaile organic compound (VOC) emission. Hur styrene has been targeted a5 2 ‘major Hazardous Ais Pollutant (HAP) by arecent US Environmental Protection Agency (EPA) act and it is given off during all tages of composite manufac- ture and even during the shelf life of a composite. ‘VOC emission occurs durig the maxing oF diluents, catalysts and initiators into the system. Some 20% of the inital styrene content is lost to the atmosphere ring the molding stage. The cure step causes risk ‘orpollution, as elevated cure temperature significantly increases the vapor presure of low-molecular-weight diluent. Moreover the level of trapped and unreacted monomers! that relsase slowly 0 ihe environment daring service life i of significant importance, e=pe- Cally for structures with lane surfice-to-volume ratio, ‘which are usually cured at room temperature and not een post-cured. Therefore, VOC emission must be mitigated not only during composite processing, but aso dunng curing and felcing of the composite Fart Ths problem can be approached trom three ‘Gumerent ways: (1) reducing the styrene content by Using a bimodal Blend (blend containing toth high and low molecular weights) of vinyl ester monomer; (2) eplacing stsene with otter reactive diluents; and G) developing styrene suppressant systems that may act as vapor barriers. The discussion in this paper is ‘confined to the former, ie, replacing styrene parly or fully by some other monomer. Refined plantoils, suchas soybean ol, are composed of over 90% trigiyceride molecules? Triglycerides are composed of three fatty acids connected by a lycerol center. The triglycerides in plant oils typically ‘contain 10 of more different fatty acids, which range {in length, level of unsaturation and functionality (eg. epouide and hydroxy! funcuoualty as found in vernonia and castor cils, respectively)” Although the use of fatty acids and triglycerides as plasticizers ‘and toushening agents,” pressure-senstive aihesives* ‘and crosslinkers>-" has been well accounted, reports of fay acids beng used as reactive diluents in ‘thermosetting resins are rare ‘The idea of using fatty ach-based monomers omer ‘advantages that are manifold: (1) they can act at reactive ciluents instead of styrene; (2) they are of low ‘cost and volatility; (3) they are renewable as derived {rom plant oils; and (4) they are able toffee radically polymerize ike styrene. Previous stucies have shown {that shorter chan length together witha lower number‘of unsaturation sites in 2 fatty acid and a small amount of styrene (10-20 wt%) is optimum for achieving good processability and cure kinetics as well as ocd. ermomechanical and nactuse properties? ‘The sim of the study reported here was to gain an in-depth Imowledge of how the viscosity and thermomechanical behavier of these binary blends are affeced by the chain length of faty acids alone. Fence for this work, the carbon numbers of the long-chain ‘unsaturated fatty acids were varied to a considerable extent, 25 wellas ine proportion of the fatty acid-based. ‘comencmcr in the binary blends, EXPERIMENTAL Vinyl ester monomer ‘Sontiesis of vinyl ester manomer ‘Vinyi ester (VE) monomers were prepared via methacrylation of digiycidyl ether of bisphenol-A (DGEBA) (Scheme 1) catalyzed by AMC-2 (Aerojet ‘Chemicals, Rancho Cordora, CA), which s amisture resins was aot tested, Dut Wille used in te future 10 ‘optimize the resin system, Oaractriaton of Epon resin by epoxy tration “To determine the epoxy equivalent weight ofthe Epon resins, epogy titration was performed a per ASTM 1652-00, Procedure B. The epoxy resin (0.4) ‘was dissolved in 10-15mL methylene chloride and 10m. tetraethylzmmonium bromide solution (100g dissolved in 400m glactalaceticacid) wasthen aded to the mixture. The sample was titrated with 0.1 mol 1 perchloric acd reagent solution (131 of 60% perchloric acid aided to 250mL glacial acetic acid, followed by an addition of 50mL acetic anhydride and making up the volume to 1 L with glacial acetic acid) until the indicator changed color from blue 10 green, Epon 828 (Mlle-Stephenson, Danbury, CT) ‘yas sed asthe scurce of DGEBA. The epoxy titration £2y, i Ar decn pi Opoocgnos o> , on fs bs Diglycidy! ether of bisphenol-A (DGEBA) results agreed well with literature values forthe epoxy ‘equivalent weight (EEQ)."* Characterisation of VE monomer Ad number tiraton, Ada HUMDeE tration Was Used uring the course of the reaction to measure we ‘amount of free (unseacted) acid in the VE system, ‘The acid number tests were performed in accordance with ASTM D1930-87. Approximately 1g of the VE reaction mixture was dssolved in 5g acetone. Three drops of0.5 w1% phenolphthabsinin 50% ethanol were ‘added to the mixture to determine the neutralization point. The solution wasthen trated with 0.5 molL~ Sedium hydroside until the solution remained slighty Dink in color for 30s. The acid number of the VE ‘mixture was then calculated: mgofNaOH Vx NxMWsou ‘cd number = PETS w ‘where V isthe volume in mL of NaOH solution used, ‘Nis thenommality ofthe NaOH solution and m isthe ‘weight of VE in g. I the acid number was too nigh, the methacryltion reaction was allowed to continue ‘unt the acid numbers were below 10. Friar transform infrared (FTIR) specroscopy. FTIR spectroscopy was used to measure the concentration of ‘unreacted epotides in the near-IR region. A Thermo ‘Nicolet Nexus 670 FTIR instrument was used in absorbance mode, taking 32 scans per spectrum with aa resolution of an, The FTIR spectra of the resins indicated that all ofthe epoxide groups (4530em~!) nad reacted, Sise exclsion chromatography. A Waters 515 GPC instrument was used with two 5m styrene-divingl benzene columns in series. The columns were ‘equilibrated and run at 30°C: using teranyaroruran (THE) as the elution solvent at a flow rate of UmL min-!. The columa lflcent was monitored by two detectors operating at 30°C: a Waters 2410 refractive index detector and a Waters 2487 dual absorbance detector operating at 270 and 254nm (absorbance by phenyl rings). Samples were prepared by dissolving 4mg sample in mL THF. Because hgh-melecular-weight species cannet difuse into the - A a Dporcrardnty 4 ce e—omoH by Methaciylic Ac AMo2 1%, 80-100°0 one oscil QpociepennQhQpocwiiotrcdcea by by be - bay Vil Ester (VE) Scheme 1. Prpaatin vin ater nonerat. bepacking, they elute fist from the columa, while wer molecular weight species elute later." Previous ‘work has shown that if a significant amount of epoxy nomopotymertation occurs, @ broad peak appearing at an clutin time of 10min or les ‘sould appear!!! Hacause mo such peak appeared in the scans for these samples, we conclude that ro epoxy bomopolymerizaiion occurred. In addition, these resuls also show that samples were of higher molecular Weight. ‘Synthesis and characterization of fatty acid-based monomer ‘A number of synthetic procedures have been estab- lished for preparing fatty acid-based monomers 10 ‘be used as reactive diluents in VE resins. Scheme 2 depicts one such synthetic route used to form the (MFAs, showing only one representative fatty acid out of the rest in this study. The carboxylic acid group of ‘uty acids undergoes a simple addition reaction with the epoxide group of glycicy] methacrylste to form the monomer at fry low temperatures (100°C) with short reaction times if properly catalyzed. AMC-2 was, used to catalyze this reaction. FTIR (near-IR regior) 2 aA + Caprylic Acid ‘Cumene Hydroperoxide Sthome 8 Chumial stucures ofconpounds used nthe ou proess. ‘was used to determine the extent of reaction. The epoxide peak 2t 4530cm~' was tracked during the reaction, Resin cure ‘VE monomer was cured with MFA monomer at com temperature using Trigoncx 239A (which contains 45% cumene hydroperoxide) 25 an initiator snd cobalt nnaphthenate (CoNap) 2s an accelerator. Scheme 3 shows the structures of initiator and accelerater. The proportion of mokes of cumene hydroperoxide wed ‘was one-hundredth the number of moles of Vinyl functionality. A 10:1 weight ratio of Trigonox to (CoNap was used. The resins were then poured into a ‘mold and allowed to cure. This was again post-cured ‘at 150°C fo 1, These cure conditions are ypical for ‘VE resins and yield highly cured polymers with good polymer propertes.* Methoas Viscosity ‘The viscosity of the fany acid monomers and \VEMFA binary blends was measured at 25°C using 42 Brookfield digital viscometer in Couette geometry. Aa Glycidyl Methacrylate wt AMC-2 Cobalt Nepthenate“Approximetely Sm. of the sample were placed into the sample holder. The apprepriate spindle and shear nite were selected to maximize the allowable torque Dynamic mechanical analysis (DMA) ‘The thermomectanical properties of VE/MFA biends ‘were measured using DMA. Rectangular samples with approximate dimensions of 17.85 x 125 x 3mm? ‘vere sted using a TA Instruments DMA 2980 analyzer ina single cantilever geometry. The samples ‘yore tested at 11z with « deflection of 15ym while ramping the temperature from 30 t9 200°C at arate of 5°C min“. Two temperature ramp experiments ‘vere run for each sample. The first ramp usually completely post-cured the polymer, but another ramp ‘was performed to ensure this, The temperature at whieh the peak inthe loss modulus occurred inthe uly post-cured polymer was considered the glass wansitien temperature (T,) of the material! Storage modulus ata temperature above T, can be used to estimate the molecular weight between crosslinks, M, according, to the theory of rubber elasticity: B RT P/M 2 ‘where is the rubbery modulus, R is the Heal gas constant, Tis the absclute temperature and ps the sample density 1617 Gold_palladiam coatings were made on the speci ‘mens prior tothe experiment, usinga Denton Desk cold sputter/etch unit, employing 40mA current ard 100 matoor (~13 Pa) pressure for 455. RESULTS AND DISCUSSION “The success of using new reactive diluents hinges on cotanmg 2 fundamental understanaingor the polymer petvorls that are formed during cure. The network seructures formed in these systems were found 10 be ‘Significantly influenced by the chain lergth of reactive cdluent. Rheological properties “The viscosity values of VE/MFA binary blends were considerably higher than that of VEstyrene resin (05 and 35mPas for 35 and 45 w0% styrene, respectively), ‘which is quite nkely fora MFA comonomer tat itself thas ahigh viscosiy. In this espect 45 w1% comonomer should be a beter cheice, the viscosity being much Inver than that of the 35 92% ons. ‘The viscosity resulis indicated an interplving interaction that may be operative inside the network ssructure. With increasing chain length of fatty acid, the viscosity was found to decrease inital, followed. e180. “= VEIMA=S5/25 wi + VEIMFAS85/5 8 A 5150 4150. 2180 viscosiy (mPa) 2150 4 6 8! lw ‘c-number Figure 4. Yaron of VENA ray bend aca natin cheatin be eat ac, by an increase (Fig. 1), showing a minimum at C-6 ‘aid C-Sfor 33 and 49 we MEA, respecuvels ‘The shorter the chain length, the higher the mumber ‘of potential sites for hydrogen bending (between the [hydroxy] group of MFA and the end of VE monomers) for a given wt‘ of MFA. The greater the number of Inydrogen bones formed, the more viscous the system. ‘This offers an explanation for the decreasing part of the viscosity curves. The increase may be attibuted 10 a greater intermolecular inceracton in the higher chain Tengts region, as larger molecules experience higher fiction in solution. ‘Thermomechanical properties ‘The T, values of VE/MEA blends were obtained fom ‘DMA resulls rom the peak oftheloss modulus curve) and the values ranged between 66 and 121°C, which |ssignificandy lower Wian Wat ofthe VEsstyrene resins. ‘Table 1 gives the values of T; and storage modulus at 35°C (B) of VE blends having different MEA: as well 3s styrene as a comonomer and for different ‘comonomer weight percentages. The storage modulus for 35 wi% comonomer blends wes always higher than that ofthe corresponding 45 w1% blend, and 2 ‘decreasing rend with increasing fatty acid chain length ‘was cbserved. The theory ofrubber elasticity [Ea. 2), although based on 2 Gaussian distribution and not holding goed for highly crossinked systems, can stil provide an approximate value for molar crosslink density, N/Nq (Where N is chain segments per unit volume and N, is Avogadro's number). N/N is azain equal to p/M,=B/3R1, where T 1s 2 temperature above 7, 0n this case T=, +30K), also sted in Table 1. The molar crosslink density increased with decreasing faty acid chain length, indicating greater reactivity. The flexible pendent groups, lke the unreacted faty acid chains in the comonomer, ‘were found to be the determining factor. Less reactive ‘comenomer may have more of these pendent chains,“Toble1.Themorachurical popatiesof VENFA and VEtyene Hands oredat om teers 26 me concnenner THEO) ESSEC GPR WN (movi) 107 Ta) Eat B5°C (GPa) NNA (red) x 107 121 23 to ae 100206 ams a 1m 188 153 26 m3 (2m 23 26 Moe 22 26 ars 2a 22 ae) ww 20 16 ww 19 m1 13 uw 0 © og 10 chains. As a result, crosslinking is directly related 10 the stiffies of the polymer. In fact an almost Linear relationship was observed between elastic modulus and crosslink density ‘As far as a general trend is concemed, both Ty and the corresponding loss modulus increased a6 the faty acid chain length decreased Figs 2 and 3). “This was expected because longer fatty acid chains Increase the flee volume of the polymer and increase the effective molecular weight between crosslinks. The rate of increase was und to be almost nea for 63/33 1w0% blend, whereas a clear diffrence in slopes was ‘observed from C-10 onivands for 55.45 wH% (Fig). "The difference in the rate of increase of thermo ‘mechanical parameters for 45 wi% comonomer may ‘be attributed to the greater number of double bonds that aries fom MFA with shorter chai lengih (fora Corrie) — Comte) — tanec Loe Med 0) eo 20 coon) comico) Loss Modus (MP) Tomgeraure(“O) Figure, OMA behav oh VENA — 55/500. ‘ven higher wetgnt ratio). Tis prompted tne need for 4a contrel experiment with blends of equimolar rates ‘of comenomers, where the number of double bonds fom each of VE and MFA are the some, implying the distance between VE backbones to be the same [see Eq. (2)]. Therefore the two interplaying factors, namely the chain length of faty acid and ccostlink density of the polymer network, Were found to govern ‘the mermomechanical behavier. Microstructural features ‘The microstructure of these systems revealed some interesting features that were helpful in obtaining 2 better understanding of the structure-property relationship of the networks, The faty acid structures resemble quite markedly that of surfactants, as they have 2 long hydrocarbon chain, which may show 2 “hydrophobic effect” and cause aggrezation. The SEM.; 100 Hom me oun be fay ai experiments showed ihe presence of densely packed. ‘microstructures for higher C-aumbers like 1 oF 16, ‘none for C-number 4 and in between for numbers $ ‘0r12 only one wi% shown in Fig. 5), The broadening ‘of peaks in loss modulus with increasing chain lengt as shown in Figs 2 and 3 may be dueto the increasing phase disorder, hence supporting the microstructural esulls, Note that the loss modulus § the measure of ‘out-of phase component of the complex modulus of a material ina dynamic experiment. Iti the amcunt ‘ofmolecular motion that dissipates energy inthe form, ‘of heat. A peak in loss modulus is 2 good indicator ‘of T, and homogeneity ofthe material, as mentioned beso. In two extreme cases, Pig. (A) suggests that the ‘comonomer dees act form inclusions vie phase spa ration but acts as a binding agent fer morphological cetities, whereas the nodular morphology in Fig. 5D) indicates ‘crack bifurcation’ to be the dominant frac ‘ture mechanism," further dscussion of which is beyond the scope ofthis tex. ‘The nodular structure in sampbs wun C-numbers (of 14 or 16 ranged from 360 to 730mm, which is ‘comparable with the wavelength of visible light. This ‘explains the hary appearance of samples made ftom ‘mytisic and palmitic acid, remarkably distinct ftom the othersamples, although all ofthe fttyacid diluents ‘were miscible with VE resins at all concentrations ‘efore cure. ‘Tis kind of pase separation can occur ‘because of two scenarics: (1) no polar character in the resin and (2) high molecular weight of monomer. In fact the tendency for phase separation increases ‘with molecular weight as evidenced from Fis. 5. It ‘was found that phase separation does not occur if ‘monomers are similar in character, e. Ebecryl with ‘ay acie-besee monomer. pure. SeM mages ct VEMEA bends fer vaio MFAs 8 wt (A buticsc (ate aod) myc cid panticac.CONCLUSIONS MMPAS can be used as styrene replacement in. VE. rsins to lower VOC emission, The chain length of the fany acid can be judiciously chosen to obtain VEUMFA binary blends of low viscosity yet pood themnomechanical properties. While a C-number of 6 to 8 was found to be optimum as far as viscosity is concerned, a C-number ashigh as 16 for palmiticacid (an ofr Superior DMA behavior. The occurrence of 2 minimum in the viscosity ecm chain length Plot ca be attributed to the interplaying action of intermolecular friction and hydrogen bonding. T, and ‘modulus were affected not only by the chain length but ‘so by the crosslink densty of the polymer network. ‘Microstructural analysis revealed the existence of ‘odular structures for fattyacids orhigher chain engin lke myrisuc or palmiticacid, whieh corretates wid the cptical appearance and DMA behavior of the blends Hence she chain length ofthe fatty acid can play vital rolein obtaining VEMFA blends of desired polymeric Properties. ACKNOWLEDGEMENTS “This project was funded by contract grant sponsor SERDP PP-1271 and ARE cooperatve agreement DAAD 19-02-2-0010. The author acknowledges Dr GRPalmese 2 Drexel University forsharing ideas and facilities. The author also thanks Dr Weille Zhou at the Advanced Materials Research Insttute (AMRU}, University of New Orleans, for offering its SEM REFERENCES 1 Zine S and Pelee GR, 7 Ryn Sui Be Puy Phe 97.723 1999) 2 LUK, Soseam: Chom, Teng and Usizaion. Chap "and Hat, New Yak, poz? 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