Applied Catalysis A: General 349 (2008) 198203

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Applied Catalysis A: General

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Transesterication of vegetable oils promoted by poly(styrene-divinylbenzene) and poly(divinylbenzene)

Simone M. de Rezende a, Michele de Castro Reis b, Marcelli Garcia Reid b, Paulo Lucio Silva Jr.b, Fernanda M.B. Coutinho a, Rosane Aguiar da Silva San Gil b, Elizabeth R. Lachter b,*
o Departamento de Processos Qumicos, Instituto de Qumica/UERJ, Rua Sa Francisco Xavier 524, 20550-900 Rio de Janeiro, RJ, Brazil nica do Instituto de Qumica, Universidade Federal do Rio de Janeiro, Ilha do Funda Centro de Tecnologia, Bloco A 617, o, Departamento de Qumica Orga 21949-900 Rio de Janeiro, Brazil
b a

A R T I C L E I N F O

A B S T R A C T

Article history: Received 7 March 2008 Received in revised form 21 July 2008 Accepted 25 July 2008 Available online 3 August 2008 Keywords: Transesterication Biodiesel Vegetable oil Ion-exchange resins Morphology structure

Ion-exchange resins based on styrene (S) and divinylbenzene (DVB) were prepared by aqueous suspension polymerization using toluene and n-heptane as diluents for the monomers. The different morphological structures were characterized by surface area, pore volume, optical appearance and surface morphology. Sulfonic catalysts were prepared from these resins in the presence of solvents with solvating and non-solvating characteristics. These catalysts were characterized and their activities were evaluated in vegetable oil transesterication with methanol and compared with the performance of a commercial sulfonic resin. The synthesized resin presented better results than the commercial one representing a convenient route for biodiesel production. 2008 Elsevier B.V. All rights reserved.

1. Introduction Transesterication reactions are important synthetic organic transformations in industrial and academic point of view. Transesterication is an equilibrium process. The transformation occurs essentially by simply mixing two components (ester and alcohol), and adding catalyst (acid or base) in order to accelerate the reaction [15]. In the transesterication of vegetable oils, a triglyceride (TG) reacts with an alcohol in the presence of a strong acid or base, producing a mixture of fatty acids alkyl esters and glycerol (Scheme 1). The stoichiometric reaction requires 1 mol of triglyceride and 3 mol of alcohol. However, the excess of alcohol is used to increase the yields of the alkyl esters so as to allow its phase separation from the glycerol formed in the reaction medium. Several aspects, including the type of catalyst (base or acid), alcohol/vegetable oil molar ratio, temperature, purity of the reactants (mainly water content) and free fatty acid content have an inuence on the course of the transesterication [1,2]. There are many catalysts available for transesterication. Homogeneous catalysts, though effective, lead to serious con-

* Corresponding author. E-mail address: lachter@iq.ufrj.br (E.R. Lachter). 0926-860X/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2008.07.030

tamination problems, since they are toxic, corrosive and produce by-products which are difcult to separate from the reaction medium, which results in higher production costs. The removal, handling and disposal of corrosive waste have motivated a large number of studies concerning the development and application of heterogeneous catalyst systems [4,5]. The application of ion-exchange resins as heterogeneous acid catalysts in different reaction systems has been investigated in the last years. Besides being easy to separate the use of these catalysts results in the improvement of product purity and yield [69]. Among the most employed resins there are those synthesized by aqueous suspension copolymerization of styrene (S) and divinylbenzene (DVB). These resins have excellent physical strength, they are not easily degraded by oxidation, hydrolysis, or high temperatures. The production of different morphological structures is controlled by the polymerization conditions, mainly by the molar ratio between styrene and divinylbenzene, the presence or absence of a porogen agent, and by the dilution degree of the monomeric mixture. The aromatic rings of those copolymers can react with several reagents, specially the electrophilic ones and at least one active group can be introduced in each aromatic ring, giving rise to resins with high exchange capacities [10,11]. Resins based on styrene/divinylbenzene are of great interest, specially cation-exchange resins functionalized with sulfonic acid groups which also play an important role as heterogeneous acid

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Scheme 1. Transesterication of vegetable oils.

catalysts [1215]. The sulfonation of the resins causes no problems if one takes the proper precautions. Depending on the reaction conditions, the functional groups (sulfonic groups) may be uniformly distributed throughout the resin or, when the modication reaction is diffusion controlled, functionalization can start at the surface of the polymer particle and then move inwards, initially into the pores and nally into the matrix [16,17]. Amberlyst-15 was applied in the transesterication of sunower oil at 60 8C and a 6:1 methanol-to-oil initial molar ratio. The conversion was reported to be less than 1% [4]. A cation-exchange resin was studied in transesterication reactions of triolein with ethanol and the desired product (ethyl oleate) was not signicantly formed [18]. The transesterication of Brazilian vegetable oils with methanol was carried out at 60 8C in presence of commercial ionexchange resins (Amberlyst). The conversion in methyl ester for babac oil was >70%; however, the methanol:oil molar ratio u employed was 300:1 [19,20]. In the present paper, we propose to investigate the inuence of the morphological structure of two resins in the transesterication of Brazilian vegetable oils such as babac and soybean with u methanol. 2. Experimental 2.1. Materials For the synthesized resins commercial styrene and divinylben zene donated by Nitriex Industria e Comercio (Brazil) were used. Styrene was washed with sodium hydroxide aqueous solution (5%, w/w) in order to remove the inhibitor, followed by several washings with water. DVB was used as received. The initiator, benzoyl peroxide (BPO, VETEC Qumica Fina Ltda, Brazil), and the

diluents, toluene (Tol., VETEC Qumica Fina Ltda, Brazil) and n heptane (Hep., VETEC S.A. Industria e Comercio, Brazil) all P.A. grade, were used as received. The components of the aqueous phase, 2-hydroxy-ethyl-cellulose (HEC donated by Union Carbide do Brazil S.A. Industria e Comercio) and sodium chloride (NaCl, Reagen-Quimibras Industrias Qumicas S.A., Brazil) all P.A. grades, were used as received. Aqueous solutions were prepared in distilled deionized water. Sulfuric acid (H2SO4, 9597%), p-toluene-sulfonic acid (Aldrich), nitromethane (CH3NO2), methanol, tetrahydrofuran (THF), hexane (all commercial grade products purchased from VETEC S.A. Industria e Comercio, Brazil), 1,2-dichloroethane (DCE, TEDIA S.A. Industria e Comercio, Brazil) and other P.A. reagents were used as received. The beads of sulfonated styrene-divinylbenzene (S-DVB) commercial copolymers were obtained in the H-form from Rohm and Haas (Amberlyst-15, Amberlyst-35). Prior to using them in a transesterication reaction, the commercial resins and the synthesized resins were dried at 105 8C under vacuum for 12 h. Soybean oil (commercial oil, Liza, Brazil) and babac coconut oil u (VETEC S.A. Industria e Comercio, Brazil) were used without further purication. 2.2. Synthesis of support beads Beads of poly(styrene-divinylbenzene) [poly(S-DVB)] or poly(divinylbenzene) [poly(DVB)] were synthesized by aqueous suspension polymerization technique in the presence of mixtures of toluene and n-heptane as diluents and benzoyl peroxide (1 mol% in relation to the monomers) as polymerization initiator. The polymerization details were described in an earlier work [21]. The polymerization product was ltered, washed with deionized hot water in order to remove the stabilizers, and ethanol for the removal of all traces of monomers and diluents. Before drying, the support beads were sieved to be separated in different size ranges, and nally washed with methanol and dried at 50 8C for 48 h [2224]. 2.3. Sulfonation of S-DVB and DVB supports beads For the sulfonation it was used an air-dried sample of poly(SDVB) or poly(DVB) beads that was swollen in DCE or CH3NO2 for

Scheme 2. Schematic representation of poly(S-DVB) and poly(DVB) sulfonation.

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24 h at room temperature. Afterwards, sulfuric acid (9597%) was added and the reaction was carried out for 1 h at 90 8C. The methodology used for dilution of the sulfonated beads was also described in the earlier work [21]. After the third dilution the catalyst beads were ltered and washed with methanol and nally dried at 50 8C for 48 h. The sulfonation of poly(S-DVB) and poly(DVB) is represented in Scheme 2. 2.4. Characterization of poly(S-DVB) and poly(DVB)sulfonic catalyst Textural properties, e.g., surface area (S) and pore volume (ypBJH) of the catalysts were determined by nitrogen adsorption at the normal boiling temperature of liquid nitrogen, 77 K, in a volumetric apparatus, ASAP 2010 (Micromeritics) [2529]. Surface morphology of the beads was observed in a scanning electron microscope (SEM) (Digital Scanning Microscope DSM 960 ZEISS and Digital Scanning Microscope JSM 5610 LV JEOL). The beads were fractured and xed, by means of colloidal carbon, on metallic supports. Then, the samples were coated with a thin layer of gold and the morphological aspects were observed in a SEM microscope [23,24]. The local concentration and distribution of the sulfonic groups (SO3H) was investigated through energy dispersive X-ray analysis (EDS). The beads were fractured and xed, by means of colloidal carbon, on metallic supports and coated with a thin layer of carbon. EDS provides a distribution prole of sulfonic groups in the polymer material [21,2830,32] (SEM Digital Scanning Microscope JSM 6460 LV JEOL and EDS Noran System SIX Model 200 Thermo). The exchange capacity was determined as described in the literature [31]. 2.5. Analysis of the vegetable oils The free fatty acids present in the vegetable oils were analyzed as described in the literature [20]. Soybean oil has the highest concentration of free fatty acids (1.74 mg KOH/g oil) compared with babac oil (0.74 mg KOH/g oil). u The chemical composition of the oils used in this work was determined through chromatographic analysis of the methyl esters obtained by transesterication with methanol. A methanol/oil molar ratio = 10:1 with potassium carbonate as catalyst and a reaction time of 1 h at methanol boiling temperature was the method employed [20]. The products were analyzed by using gas chromatography performed in a HP-5890 GC series II coupled with a HP-5972 mass spectrometer and a 30-m DB-5 capillary column, using helium as carrier gas. The GC injector temperature was

260 8C and the oven temperature was programmed from 60 up to 250 8C at 8 8C/min. 2.6. Reaction procedure All experiments were performed in a 100-ml two-necked ask equipped with a reux condenser and magnetic stirrer. Reactions were carried out using varied molar ratios alcohol:triglyceride (TG) functions (3 TG), between 50 and 16.7. The resin amount was introduced between 50 and 25%, w/w (0.56 and 0.28 mmol H+) based on the quantity of oil. The mixture was reuxed at 63 65 8C (methanol boiling temperature) and 0.2 ml samples were removed from the reactions mixture, in pre-dened time intervals, during 8 h. 2.7. Analysis and product separation The samples were washed with water, and the organic phase (esters) were extracted with hexane, dried with magnesium sulfate and submitted to 1H NMR (Bruker Avance DPX-200 spectrometer) analysis in CDCl3 using tetramethylsilane (TMS) as internal standard. The conversion of the oils (TG) into a mixture of fatty acid methyl esters (FAME) was followed by measuring methyl ester/triglyceride ratio through the areas of CH3O/CH2O protons at 4.14.3 and 3.7 ppm in 1H NMR spectra [20]. 3. Results and discussion 3.1. Physical characteristics of cation-exchange resins In this work two types of catalysts, one based on poly(styrenedivinylbenzene) and another one based on poly(divinylbenzene), were evaluated. The physical properties of catalysts obtained by sulfonation of poly(S-DVB) and poly(DVB) beads are listed in Table 1. Table 1 shows the physical characteristics of the catalysts obtained by sulfonation of poly(S-DVB) in the presence of 1,2dichloroethane (CAT-10 to CAT-26a, CAT-30a), which is a solvent capable of swelling the polymer matrix, so that the sulfonation reaction occurred in the whole structure of the support (in the surface of the pores and in its interior) (Table 1) [21,32]. The catalysts obtained from copolymers with 20 and 40% of DVB content presented a very low porosity. That result is conrmed by the low values of surface area (7 and 3 m2/g). Only the catalysts obtained from copolymers with 60% of DVB presented a measurable value of surface area, which indicates that these catalysts are more porous than those with smaller amounts of DVB (Table 1).

Table 1 Physical characteristics of poly(S-DVB) and poly(DVB) sulfonics catalysts obtained at different dilution degree and compositions of the diluents mixture prepared in presence of DCE or CH3NO2 Sample CAT-10 CAT-22 CAT-11 CAT-23 CAT-19 CAT-12 CAT-24 CAT-26a CAT-26b CAT-30a CAT-30b DVB molar (%) 20 20 40 40 40 60 60 100 100 100 100 Dilution degree, v/v (%) 100 150 100 150 150 100 150 150 150 200 200 Tol/Hep ratio, v/v (%) 50/50 50/50 50/50 50/50 30/70 50/50 50/50 50/50 50/50 50/50 50/50 S (m2/g) Nm Nm 7 3 Nm 83 19 463 518 442 574

ypBJH (cm3/g)
Nm Nm Nm Nm Nm 0.03 0.04 0.91 0.91 0.90 1.10

CEC meqSO3 H =gcat 4.8 4.9 4.3 4.4 4.4 3.7 3.7 2.7 2.5 3.4 2.0

Ref. [19] [19] [19] [19] [19] [19] [19] This This This This

work work work work

CAT, catalyst; Tol, toluene; Hep, n-heptane; a-DCE, 1,2-dichloroethane; b-CH3NO2, nitromethane; S, surface area; ypBJH, xed pore volume determined by nitrogen adsorption/desorption; CEC, cation-exchange capacity; Nm, not measurable.

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Fig. 1. SEM micrographs of internal surface of catalyst obtained with 150% the dilution degree and sulfonated in presence of DCE: (a) CAT-24; (b) CAT-26 or obtained with 200% the dilution degree in presence of DCE; (c)CAT-30.

Table 1 shows that the values of cation-exchange capacity decreased with DVB content independent of the dilution degree used. These values decreased due to the difcult access to the sulfonic groups located within the polymer structure. The increase of the DVB content has favored the formation of more crosslinked and consequently more rigid structures. The catalysts were produced from poly(DVB) prepared in presence of 1,2-dichloroethane a solvent capable of swelling the polymers support and in nitromethane, a bad solvent incapable of swelling the copolymer matrix of poly(DVB) [21,32]. As result, in the presence of nitromethane the sulfonation occurs more extensively in the external surface of the bead than in its internal surface [32]. The catalysts produced from poly(DVB) presented the highest values of surface area and pore volume independent of the dilution degree employed in the synthesis. When 100% DVB was used macroporous structures were obtained. Fig. 1 presents scanning electron micrographs of the internal surface of catalysts CAT-24, CAT-26 and CAT-30 using as diluent mixture 50/50 Tol/Hep. Those micrographs show that the increase of DVB proportion provokes the formation of larger agglomerates with large voids between them. The porosity consists of wide and narrow spaces between the particles, microspheres or agglomerates (CAT-30). The low values of the cation-exchange capacity for the catalysts CAT-26 and CAT-30 can be attributed to the more crosslinked structures (more rigid) that hinder the access of the water solution to the sulfonic groups, and consequently, to the occurrence of ionexchange reaction, producing, as a consequence, the lowest values of exchange capacity (Table 1). The distribution of sulfonic acid groups was determined using EDX [21,32]. Poly(S-DVB) catalyst presented homogenous distribution of the sulfonic groups across the bead. However the catalyst obtained with poly(DVB) presented heterogeneous sulfonic distributions [21,32]. 3.2. Composition of vegetable oils The results of chemical analysis of the fatty acids present in the vegetable oils are shown in Table 2. The main constituent of babac u coconut oil is lauric acid (C12:0), whereas, the soybean oil employed in this work has high content of di-unsaturated linoleic acid (C18:2). The composition of both TG were similar to others

indicated in the literature [20]. Due to this fact we decided to perform the experiments using the TG with lower chain length. 3.3. Effect of different macroporous resins The macroporous resins synthesized were employed in order to compare the catalytic activity of different macroporous cationexchange resins on the transesterication reaction of babac u coconut oil with methanol (using 100:1 alcohol:ester function molar ratio and 1 g of resin). The results obtained are shown in Table 3. The catalysts obtained from poly(DVB) prepared in presence of 1,2-dichloroethane (entry 10) show the best results, being the conversion in methyl ester superior to 90%. The catalysts synthesized with 100% of DVB (CAT-26a and CAT-30a) presented the lowest values of cation-exchange capacity but the highest values of the catalytic activity. The structure of those catalysts is macroporous and therefore they do not need to swell for the active sites (SO3H groups) accessing by the reaction mixture. 3.4. Effect of reactant molar ratio In this work the effect of alcohol:oil molar ratio on the transesterication reaction of the babac oil with the CAT-30a u (prepared in dichloroethane) was studied (Fig. 2). Similar results were obtained when 50:1 or 33.3:1 alcohol:ester function ratio (=alcohol:3 TG ratio) was employed. The results obtained with ratio 16.7:1, in other hand show lower FAME production. The results are in accordance with the results of the literature, the necessity of higher ratio alcohol in acid catalysis [4,20]. 3.5. Effect of catalyst loading The catalyst loading varied from 50 to 25% (%w/w in relation to the oil; 0.56 and 0.28 mmol H+, CAT-30a). The overall reaction rate was found to increase with the increase of the catalyst loading in
Table 3 Methanolysis reaction of babac oil catalyzed by different resins u Entry 1 2 3 4 5 6 7 8 9 10 11 Resin CAT-10 CAT-22 CAT-11 CAT-23 CAT-19 CAT-12 CAT-24 CAT-26a CAT-26b CAT-30a CAT-30b %FAME 54 57 72 65 62 66 66 77 65 97 75 Ref. [19] [19] [19] [19] [19] [19] [19] This This This This

Table 2 Chemical composition of vegetable oils Vegetable oil Fatty acid composition (%) C8:0 Babac u Soybean 1.4 C10:0 3.7 C12:0 51.5 C14:0 18.4 C16:0 8.9 12.7 C18:0 2.5 4.6 C18:1 12.2 32.7 C18:2 1.6 50

work work work work

FAME, fatty acid methyl ester = FAME/FAME + TG.100 by 1H NMR; conditions:ratio methanol/oil 100/1, 1 g cat.

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Fig. 2. Effect of the alcohol/oil molar ratio in biodiesel production from the transesterication reaction of babac oilmetanol:oil, 50/1 or 150/1; 0.5 g CAT-30. u

acid and H2SO4 in the transesterication reaction of the babac u coconut and soybean oil with methanol (Table 4). Table 4 shows the reaction yield obtained for all catalytic systems studied, after the same period of time (8 h). It can be observed that, for the soybean oil and coconut oil, the sulfonated resins presented higher conversions than H2SO4 (homogeneous catalysis) and commercial resins (Table 4, entries 1, 3, 4 and 5 or 6, 8, 9 and 10) and the same conversion of the p-toluene-sulfonic acid in homogeneous catalysis conditions (Table 4, entries 2 and 5 or 7 and 10). Therefore, ion-exchange resins can be used with success in the transesterication of babac oil and soybean oil. It also became u clear, from Table 4, that the reaction yields are strongly inuenced by the nature of the resins. Poly(DVB) resins show better results and the conversion of the vegetable oil in fatty acid methyl ester (FAME) was superior to 90%. 4. Conclusions Sulfonated poly(S-DVB) and poly(DVB) shown active in the transesterication of soybean oil and coconut oil. TG conversion increased with increasing catalyst amount. Superiority of physical properties of resins may be a dominant factor for higher catalytic activity. The performance of synthesized resins was higher than the commercial resins Amberlyst-15 and Amberlyst-35. The highest values of FAME (>90%) was obtained with a sulfonated poly(DVB) that presented a higher surface area (442 m2/g). That is the rst example of using DVB ion-exchange resins as catalysts in Brazilian vegetable oils methanolysis. Acknowledgements The authors are grateful to Rohm & Haas for supplying ionexchange resins, to FAPERJ and CNPq for nancial support, and to CG/MS laboratory of IQ/UFRJ. References
[1] B. Freedman, E.H. Pryde, T.L. Mounts, J. Am. Oil Chem. Soc. 61 (1984) 16381643. [2] U. Schuchardt, R. Sercheli, R.M. Vargas, J. Braz. Chem. Soc. 9 (1998) 199210. [3] J.M. Encimar, J.F. Gonzalez, J.J. Rodriguez, A. Tejedor, Energy Fuels 16 (2002) 443 456. [4] E. Lotero, Y. Liu, D.E. Lopez, K. Suwannakarn, D.A. Bruce, J.C. Goodwin Jr., Ind. Eng. Chem. Res. 44 (2005) 53535363. [5] A.C. Pinto, L.L.N. Guariero, M.J.C. Rezende, et al. J. Braz. Chem. Soc. 16 (2005) 13131330. [6] E.R. Lachter, R.A.S. San Gil, D. Tabak, V.G. Costa, C. Parpinelli, J.A. Santos, React. Funct. Polym. 44 (2000) 17. [7] M.A. Hamer, Q. Sun, Appl. Catal. A 221 (2001) 4562. [8] J. Lilja, D. Yu Murzin, T. Salmi, J. Aumo, P. Maki-Arvela, M. Sundell, J. Mol. Catal. A: Chem. 182/183 (2002) 555563. [9] G. Gelbard, Ind. Eng. Chem. Res. 44 (2005) 84688498. [10] I.M. Abrams, L. Benezra, in: M.H. Frank, N.M. Bikales, C.G. Overberg, G. Menges (Eds.), Encyclopedia of Polymer Science & Technology, vol. 7, John Wiley, New York, 1965. [11] O. Okay, Prog. Polym. Sci. 25 (2000) 711779. [12] M. Struck, H. Widdecke, Die Angew. Makromol. Chem. 235 (1996) 131. [13] K. Dofner, Ion Exchangers and Properties and Applications, Ann Arbor Science Publishers, Michigan, 1972, Chapter 3. [14] C.N. Rhodes, D.R. Brown, S. Plant, J.A. Dale, React. Funct. Polym. 40 (1999) 187 193. [15] E.S. Sujatha, A.K. Kolah, V.C. Malshe, M.M. Sharma, React. Funct. Polym. 31 (1996) 3946. [16] D.C. Sherrington, New J. Chem. 6 (12) (1982) 661. [17] G.M. Guyot, P. Hodge, D.C. Sherrington, H. Widdecke, React. Polym. 16 (1991/ 1992) 233259. [18] N. Shibasaki-Kitakawa, H. Honda, H. Kuribayashi, T. Toda, T. Fukumura, T. Yonemoto, Bioresour. Technol. 98 (2007) 416421. [19] S.M. de Rezende, F.M.B. Coutinho, B.G. Soares, S.C.M. dos Reis, M.G. Reid, E.R. Lachter, R.S.V. Nascimento, Polmeros Ciencia e Tecnologia 15 (3) (2005) 186 192. [20] S.C.M. dos Reis, E.R. Lachter, R.S.V. Nascimento, J.A. Rodrigues, M.G. Reid, J. Am. Oil Chem. Soc. 82 (9) (2005) 661665. [21] F.M.B. Coutinho, S.M. Rezende, B.G. Soares, J. Appl. Polym. Sci. 102 (2006) 3527 3616.

Fig. 3. Effect of the alcohol/oil molar ratio and concentration of resin in biodiesel production from the transesterication reaction of babac oilmetanol/oil, 150/1; u 0.5 g CAT-30 and 100/1; 0.25 g CAT-30.

the range employed in this work (Fig. 3). An increase in the catalyst loading results in increasing the number of SO3H groups, which leads to the formation of protonated triglyceride per unit of time, and increases the reaction rate [6]. It was also compared the catalytic activity of the different macroporous resins with the performance of p-toluene-sulfonic
Table 4 Methanolysis reaction of babac and soybean oil catalyzed by different resins, pu toluene-sulfonic acid and H2SO4 after 8 h Entry 1 2 3 4 5 6 7 8 9 10
a b c d e f g h i

Vegetable oil Babac u

Catalyst H2SO4 PTASb A15c A35d CAT-30ae H2SO4f PTASg A15h A35i CAT-30ai
a

Yield (%) 44 98 74 87 99 18 97 56 30 97

Ref. [19] This work [19] This work This work [19] This This This This

Soybean

work work work work

Methanol/oil 300/1, 3% of H2SO4, Ref. [19]. Methanol/oil 30/1, 7% PTSA. Ref. [19]. Metahnol/oil 150/1, 0.5 g resin. Methanol/oil 150/1, 0.5 g CAT-30. Ref. [19]. Methanol/oil 20/1, 7% PTSA. Metahnol/oil 150/1, 0.5 g resin. Methanol/oil 300/1, 1 g CAT-30; yield = FAME/FAME + TG.100.

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