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The Effect of Functionalized Ethylene Propylene Diene Rubber (EPDM) on the Kinetics of Sulfur Vulcanization of Normal Rubber/EPDM Blends
Alex S. Sirqueira, Bluma G. Soares*

The effect of mercapto- and anhydride-functionalized ethylene propylene diene rubber (EPDM) or ethylenevinyl acetate (EVA) copolymers on the vulcanization kinetics of natural rubber/EPDM blends was investigated using the oscillatory disk rheometer. The mercapto groups in both EPDM and EVA copolymers resulted in a signicant decrease of the curing time. The Corans model was applied to set the kinetic constants within each distinct step of the vulcanization process. The highest curing velocity was perceived in a blend containing 2.5 phr of mercapto-functionalized EVA. The functionalized EVA, especially that which was functionalized with anhydride groups, also displayed a lower solvent uptake on blending, which would imply an increase of the crosslink density as well a covulcanization phenomenon.

Introduction
Blends of natural rubber (NR) and ethylene propylene diene rubber (EPDM) were extensively studied in order to achieve more suitable elastomer materials which have a better ageing resistance. However, their thermodynamic behavior associated to the cure rate incompatibility normally results in poor mechanical properties.[1,2] Several
A. S. Sirqueira, B. G. Soares culas, Universidade Federal do Rio de Instituto de Macromole Janeiro, Centro de Tecnologia, Bloco J, Ilha do Funda o, 21945-970, Rio de Janeiro, RJ, Brasil P.O.Box 68525 E-mail: bluma@ima.ufrj.br
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approaches have been reported in the literature to solve this problem, including the addition of a low molar mass third component, such as transoctylene rubber (TOR),[3] the incorporation of an accelerator molecule on the EPDM backbone,[4] and the addition of anhydride-functionalized EPDM.[57] Our group has also recently reported on the efciency of EPDM modied with mercapto group (EPDMSH) as a compatibilizing agent for this NR/EPDM blends.[811] The compatibilizer effect is based on the ability of mercapto groups to react with the double bond of the unsaturated rubber (natural rubber) which results in strong interactions between the components. The mercapto group when incorporated on ethylenevinyl acetate copoly-

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The Effect of Functionalized Ethylene Propylene Diene Rubber (EPDM) . . .

mers (EVASH) was also efcient as an interfacial agent for several blends such as: NR/ethylenevinyl acetate (EVA),[12,13] styrene butadiene rubber(SBR)/EVA,[14,15] nitrile rubber (NBR)/EVA,[1618] and NBR/EPDM blends.[11,19] Besides the compatibilization, the cure process in rubber is of large importance from the technological and economic point of view, since it can also affect the physical properties and ageing resistance of the vulcanizates. Both crosslink density and the crosslinks on elastomer blends are inuenced by the accelerator nature, the sulfur: accelerator ratio, the reaction temperature and time, and may also be inuenced by the compatibiliFigure 1. Typical curve of torque versus time obtained by oscilatory disk rheometery. zing agent. In this way the mercaptofunctionalized copolymers can also affect the vulcanization parameters.[10] region corresponds to the maturation of the network by In the case of the NR/EPDM blend, the addition of a overcure.[21,22] small amount of EPDMSH decreases both scorch and optimum cure times, and increases the maximum The period that corresponds to the curing process can be torque.[10] described by a general equation, which relates the conversion degree (degree of crosslink) (a) with the time. For isothermal Considering the different vulcanization characteristics systems, this equation may be written as follows:[21] of EPDMSH-modied NR/EPDM blends, we have decided to investigate the vulcanization kinetic of this system as well   @a other modied blends. This work reports the effect of kT f a: (1) @t T anhydride- and mercapto-functionalized copolymers on the vulcanization kinetics of accelerated sulfur NR/EPDM The function k(T ) can be expressed as an Arrhenius type blends. The functionalized copolymers used in this study relation: include EPDM and EVA copolymers containing mercapto groups (EPDMSH and EVASH, respectively) or succinic kT k0 eE=RT ; (2) anhydride groups (EPDM-g-MA and EVA-g-MA, respectively). Besides the vulcanization kinetics, the effect of these copolymers on crosslink density was also evaluated where k0 preexponential factor; E activation energy; from solvent absorption experiments. R gas constant; T temperature (K). The second term of Equation (1) is a mathematic expression for the kinetic model as a function of the converA Brief Description of Corans Kinetic Model sion degree, described as: Popular techniques used to study the kinetics of rubber vulcanization include differential scanning calorimetry (DSC), and oscillating disk rheometry (ODR).[20] The last one is based on the fact that crosslink density is proportional to the stiffness of the rubber. Figure 1 illustrates a vulcanization curve for a typical accelerated sulfur vulcanization process. The rst region corresponds to the scorch delay or induction period that provides a safe processing time. It is believed that this period involves mostly the accelerator chemistry. The second region corresponds to the curing period and the third
Macromol. Mater. Eng. 2007, 292, 6269 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

f a 1 a n ;

(3)

where n is the order of the vulcanization reaction. Several mathematical models have been proposed, based on the vulcanization parameters obtained from ODR. Good reviews on this subject can be found in the literature.[23,24] One of the most popular and simplied models for accelerated sulfur vulcanization was proposed by Coran more than four decades ago.[25,26] This model was based on a general mechanism, whose steps are summarized in Figure 2.[20,23,2729]

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Figure 2. General scheme for the accelerated sulfur vulcanization.

The rst step consists of the formation of an active accelerator complex formed by the interaction of accelerator and activator. This complex can react with molecular sulfur to form the sulfuring agent.[24,30] The sulfuring agent reacts with rubber chains to form a crosslink precursor, which was experimentally evidenced as an accelerator-terminated polysuldic pendant group attached to the rubber chains.[31,32] The precursor turns into an activated precursor, for example, a polythiyl radical, which undergoes the formation of polysuldic crosslinks. The activated precursor can also react with the active sulfuring agent, giving rise to a nonactivated precursor or can even decompose into inactive side products. In a subsequent step, there is a maturation of the polysuldic crosslinks, during which desulfuration and decomposition of these crosslinks take place. All these steps are well documented and discussed in the literature.[23,24,2728,31] The simplied kinetic scheme proposed by Coran for accelerated sulfur vulcanization takes into account the steps described above,[25,26] and was employed in the studies involved in this work. The scheme is illustrated as follows: ! B ! aVu A !B k4 ! bB AB where A is the accelerator and/or its reaction products, that is, the active sulfurating agent (see Figure 2); B is the crosslinking precursor; B is an activated form of B, for example, a polythiyl radical; Vu is the crosslink; a and b are adjustable stoichiometric parameters. To determine the constant k2, the torque variation is plotted against time, as follows:[25,26]]   DMt k2 t; ln 1 DM (4)
k1 k2 k3

time and the minimum torque. Figure 3 illustrates this plot. The velocity constant k2 corresponds to the negative slope of the straight line portion of the curve after the induction period, that is, the conversion range that follows the rst order kinetics, assuming the formation of Vu to be rst order in B.[25,26] The rst order nature of the crosslink formation is not achieved immediately upon the onset of crosslink formation. The time required for crosslinking to become an unperturbed rst order reaction is assumed to be the time tdis required for the depletion of A and corresponds to the time required for the curvature in the log plot to disappear. The time ti corresponds to the intersection of the two regions of the log plot and is considered as the induction period. Coran has also proposed the determination of the constant, k1, from a mathematical treatment, taking into consideration the rate of disappearance of species A.[25] The

where DM corresponds to the difference between maximum (MH) and minimum torques (ML) and DMt corresponds to the difference between the torque at a particular
Macromol. Mater. Eng. 2007, 292, 6269 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 3. Typical curve of ln1 DMt=DM versus time, according to the Coran model.[25,26]

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The Effect of Functionalized Ethylene Propylene Diene Rubber (EPDM) . . .

following expression was proposed in the Coran model: k1 tdis ln k1 k2 tdis ln k2 : (5)

For the solution of this equation, Coran assumed that k1/ k2 Z,[25] and k2 tdis ln Z=1 Z : (6)

sulfenamide (CBS) were of laboratory reagent grade and kindly supplied by the local rubber industries. Thioacetic acid (TAA) and thioglycolic acid (TGA), analytical grade, from Sigma Aldrich Chemistry, were used as received and 2,20 -azoisobutyronitrile (AIBN) from Merck Chemicals was recrystallized from a methanol/water solution.

Preparation of the Functionalized Copolymer

The preparation of mercapto-functionalized EPDM was carried out according to a previous report.[8] The functionalization was performed in two steps, illustrated in Figure 4. The rst step was performed in toluene solution at 70 8C for 48 h. In order to avoid crosslink formation during synthesis, the molar ratios of TAA/AIBN and diene/TAA were established as 10.0 and 1.0, respectively. The thioacetate-modied EPDM (EPDMTA) was submitted to an alkaline methanolysis using 5 wt.-% NaOH solution in order to obtain EPDMSH. At these conditions an amount of thioacetate or mercapto groups in the functionalized copolymers corresponding to 2.5 mmol 100g1 was achieved. EVASH was synthesized in our laboratory by a transesterication reaction between EVA copolymer and mercaptoacetic acid, according to the literature.[33] The mercapto content was found to be 0.13 mmol 100g1.

Coran has calculated values of k2tdis for various values of Z and plotted them against one another. From the k2tdis values obtained from rheometer traces, the Z values and consequently k1 were obtained.[25] The constants k3 and k4 cannot be determined separately. However, the k4/k3 ratio can be determined by the following equation:[26]     k1 t  k4 MA U DM k2 e k1 ek2 t ln ; CA DMt k3 k2 k1 (7)

where k4/k3 is an adimensional ratio of velocity constant; CA is the concentration of accelerator expressed as parts per 100g of rubber; MA is the molar mass of accelerator; U is the number of moles of double bonds per 100g of rubber. In NR:EPDM blends used in this work, U corresponds to 0.74 mol 100g1, which was calculated using the nuclear magnetic resonance technique. This ratio indicates the tendency of an accelerator or the product formed in the rst stages of the curing process to inhibit the crosslink.

Blend Preparation
The blends were prepared in a two roll mill operating at 80 8C and at 20 rpm. The NR was masticated for 2 min and then EPDM and the functionalized compatibilizing agents (2.5 phr) were subsequently added. After the rubber blend homogenization (about 4 min), the other ingredients were added in the following order: zinc oxide (5.0 phr), stearic acid (2.0 phr), irganox 245 (1.0 phr), sulfur (S) (2.0 phr) and CBS (1.0 phr). The processing time after each component addition was about 2 min.

Experimental Part
Materials

Natural rubber (NR, Hervea Brasiliensis, from Brazil) (SMRCV60), Mooney viscosity (ML 1 4 at 100 8C) 60, was kindly supplied by Michelin do Brasil S. A (Rio de Janeiro, Rheometric Measurements Brazil). EPDM rubber (Keltan 65) [diene content 9.11 wt.-%; ethylene content 51.7 wt.-%; Mooney viscosity (ML 1 4 at The vulcanization parameters and the mixes cure rate were 125 8C) 49.3] was kindly supplied by DSM Elastomeros Brasil determined from the torque versus time curves obtained using Ltda (Rio Grande do Sul, Brazil). EVA copolymer (containing ODR (Tecnologia Industrial, mod T100, Buenos Aires, Argentina) at 18 wt.-% of vinyl acetate (VA); mass ow index 2.3 g min1 at 120 8C) was kindly supplied by Petroqu mica Triunfo, Rio Grande do Sul, Brazil. EPDM functionalized with maleic anhydride (anhydride content 5.1 mmol 100g1 of polymer) was supplied by Uniroyal. EVA functionalized with maleic anhydride (vinyl acetate content 28 wt.-%; anhydride content 8.1 mmol 100g1) was supplied by Du Pont Inc. Zinc oxide, stearic acid, sulfur, irganox Figure 4. The reaction scheme involved in the functionalization of EPDM with mercapto 245 and N-cyclohexyl-2-benzothiazol groups.
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1 deg and 160 8C, according to the ASTM D-2084-81 method. The crosslink decomposition was evaluated from the reversion degree (R), according to the Equation (8):

R%

MH MH 30 100; MH

(8)

where MH is the maximum torque and MH30 is the torque after 30 min from the maximum torque. The solvent uptake in these blends was determined according to the literature.[34] For these experiments, the weight, w, of 20 20 2 mm cured test samples was measured accurately weighted and the samples were immersed into toluene in air-tight test bottles. At regular intervals, the test samples were removed from the solvent and dried between lter papers to remove the excess solvent on their surface. After that, the samples were weighted immediately and reimmersed in the solvent to permit the continuation of the kinetic sorption until saturation in excess liquid was established. The results of sorption experiments were expressed as the weight percent of solvent sorbed by 100g of the blend versus the square root of time.

Figure 6. Torque versus time curves of NR:EPDM (70:30 wt.-%) blends (a) without functionalized copolymer and in the presence of (b) 2.5 phr of EPDM-g-MA and (c) 2.5 phr of EVA-g-MA.

Results and Discussion

Curing Kinetics Figure 5 and 6 compare the torque versus time proles of nonmodied NR/EPDM blends, with those containing 2.5 phr of mercapto- and anhydride-functionalized copolymers, respectively. Blends containing mercaptofunctionalized copolymers presented a signicant decrease of scorch and optimum curing times, indicating an accelerating action of mercapto groups, as previously reported.[10] The EVASH-modied blend displayed the lowest curing time, in spite of the lower amount of SH in this copolymer. These results suggest a more effective interaction between SH groups of EVASH and the curatives. The anhydride-modied copolymers (Figure 6) did

not exert any signicant inuence on the curing time but did contribute to an increase in the maximum torque, which is an indication of increased crosslink density. On the basis of the different behavior of these modied blends, we decided to study the inuence of the functionalized copolymers on the kinetic involved in different steps related to the curing process, by using the Coran simplied model, previously described in the Introduction. Figure 7 and 8 illustrate the dependence of torque variation against time, for NR/EPDM blends modied with mercapto- and anhydride-functionalized copolymers, respectively. From these curves the kinetic parameters were calculated, as summarized in Table 1. The k1 values were calculated from a mathematical relationship proposed by Coran,[25] as summarized in the Introduction part of this work. As observed in Figure 7, the time tdis required for crosslinking to become an unperturbed rst order reaction was signicantly lower in the case of EPDMSH- and EVASH-modied blends. These results corresponded to an increase of k1 values, which

Figure 5. Torque versus time curves of NR:EPDM (70:30 wt.-%) blends (a) without functionalized copolymer and in the presence of (b) 2.5 phr of EPDMSH and (c) 2.5 phr of EVASH.
Macromol. Mater. Eng. 2007, 292, 6269 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 7. ln1 DMt=DM versus time for NR:EPDM (70:30 wt.-%) blends (a) without functionalized copolymer and in the presence of (b) 2.5 phr of EPDMSH and (c) 2.5 phr of EVASH.

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Figure 8. ln1 DMt=DM versus time for NR:EPDM (70:30 wt.-%) blends (a) without functionalized copolymer and in the presence of (b) 2.5 phr of EPDM-g-MA and (c) 2.5 phr of EVA-g-MA.

were summarized in Table 1. The highest k1 value was found in the EVASH-modied blend, indicating a shorter induction time; that is, those blends with higher velocity than that of the accelerator and/or their reaction products with sulfur turn into B species, the crosslink precursor. These results conrm the participation of the mercapto groups in the rst step of the curing process, which is probably due to possible interactions between the mercapto groups and the accelerator used in the vulcanizing system, which increase the consumption velocity of the accelerator. This interaction was similar to the rst step of the scheme illustrated in Figure 2 for general accelerated sulfur vulcanization. The EPDMSH also increased k1 but the effect was not as pronounced as in the case of EVASH. It is believed that EVASH is more dispersed inside the rubber system, improving the interaction between the SH groups and curatives. The presence of anhydride groups in the functionalized copolymers (EPDM-g-MA and EVA-g-MA) also increased the velocity of accelerator consumption (Figure 8), but the effect was not as high as in the case of EVASH. The anhydride group present in both EVA-g-MA and EPDM-gMA can react with the ZnO, similarly to the stearic acid

used as the activator on the formation of the sulfuring agent, in the rst step of the scheme illustrated in Figure 2. The EPDM-g-MA presented at a higher velocity probably because the higher number of anhydride groups in this copolymer. After the induction period, the conversion of B species into B (activated form of B) characterized by the constant k2 was also affected by the presence of EVASH, where a little increase of this value was observed. The functionalized EPDM (EPDMSH and EPDM-g-MA) also resulted in a little increase of this constant, whereas EVA-g-MA resulted in a decrease of k2 related to the nonmodied blend. The k4/k3 ratio was signicantly affected by the presence of the functionalized copolymer. This ratio was related to the competition between the vulcanization process (k3) and the reaction between B and the accelerators, which gives rise to the crosslinking precursor (k4). The lower the k4/k3 ratio value, the higher the tendency of the system towards crosslink formation. The presence of mercapto-functionalized copolymers resulted in lower k4/ k3 values, indicating that the crosslink formation was favored, reducing the probability of the reverse reaction. This phenomenon was particularly important in the EVASH-based blend. It is interesting to emphasize that the presence of anhydride-functionalized copolymers (EPDM-g-MA and EVA-g-MA) have resulted in an increase of this ratio, suggesting that the reverse reaction was favored, as compared with nonmodied blend. Regarding the decomposition process of the crosslinking, determined from the reversion ratio (R), a decreased tendency towards reversion in blends containing EPDM-based functionalized copolymer was observed. The lowest value was found in blend containing EPDMSH. The reversion process reects the crosslink degradation, which occurs via a free radical mechanism. The mercapto groups are able to react with the free radical species before they attack the rubber network. The NR/EPDM blends modied with EVA- based functionalized copolymers presented higher reversion degree as a consequence of the crosslink degradation during the postcure process.

Table 1. The effect of the functionalized copolymer on the kinetic parameters of NR/EPDM blends, calculated by the Coran model.

Functionalized copolymer none EPDMSH EVASH EPDM-g-MA EVA-g-MA

tdis s 3.8 2.2 1.7 3 3.4

ti s 3.7 1.6 1.2 2.8 3.1

k1

k2

Reversion degree %

1.13 1.65 2.8 1.65 1.39

0.917 0.945 1.03 0.948 0.862

3.67 1.43 3.82 2.40 5.90

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Sorption Experiments It is well established that the sorption and diffusion of penetrants through elastomer materials is controlled by the crosslink density and other parameters, such as temperature, presence of llers, nature and size of penetrants, and so on.[35,36] The effect of functionalized EPDM and functionalized EVA copolymers on the liquid sorption behavior of different NR:EPDM (70:30 wt.-%) blends is shown in Figures 9 and 10, respectively. The penetrant used was toluene. All compatibilized blends displayed lower solvent uptake than the nonmodied blend, which it is an indication of an increase of the crosslink density. The presence of 2.5 phr of EPDMSH or EPDM-g-MA resulted in a decrease of solvent uptake but the nature of the functionalized group did not exert any additional inuence on this behavior (Figure 9). Blends containing 2.5 phr of EVA-functionalized copolymers presented interesting results (Figure 10). The EVASH resulted in a signicant decrease of solvent uptake, but the lowest sorption was achieved in the blend containing 2.5 phr of EVA-g-MA. Sujith et al observed similar results in natural rubber/EVA blends and attributed this to the crystalline regions of EVA, which put up stiffer resistance to the penetrant molecules, thus leading to a lower solvent uptake.[35] Sujith et als studies were performed with blends containing 20 wt.-% or more of EVA. Our systems contained only 2.5 phr of EVA. In addition, the EVA-g-MA sample used in our system was obtained from EVA containing 28 wt.-% of vinyl acetate, whereas the EVASH sample was obtained from EVA containing 18 wt.-% of vinyl acetate. The former was considered less crystalline than EVA with 18 wt.-% of vinyl acetate. Therefore, the signicant decrease of solvent uptake behavior in EVA-g-MA could not be only attributed to

Figure 10. The effect of functionalized EVA on the toluene uptake behavior of NR:EPDM (70:30 wt.-%) blends, (a) without functionalized copolymer and in the presence of (b) 2.5 phr of EVASH and (c) 2.5 phr of EVA-g-MA.

an increase of crystallinity of the medium, but also, and more importantly, to an increase of the crosslink density of the blend, promoted by a better dispersion of this copolymer as a consequence of its lower viscosity. This lower solvent uptake was also attributed to a phenomenon known as covulcanization - when both components and the interfacial agent take part on the network. According to the literature, if interfacial bonds are formed during covulcanization, the lightly swollen phase will restrict swelling of the highly swollen phase.[36,37] This phenomenon could occur in EVASH-modied blends and especially in EVA-g-MA modied blend.

Conclusion
From the results obtained in this work, it is possible to conclude that:  EVA- and EPDM-functionalized copolymers with a low amount of mercapto or anhydride groups were able to accelerate the vulcanization process of NR:EPDM (70:30) blends in the presence of sulfur and CBS. However, they affected the distinct steps involved in the curing process in different ways.  The presence of 2.5 phr of EVASH resulted in a substantial increase in the velocity related to the rst step of the vulcanization process, which was related to the consumption of the accelerator.  Both EPDMSH and EVASH resulted in a decrease of the k4/k3 value, indicating an increase of the velocity of the crosslink formation.  Anhydride-functionalized copolymers favored the reaction between B and the accelerators, giving rise to the

Figure 9. The effect of functionalized EPDM on the toluene uptake behavior of NR:EPDM (70:30 wt.-%) blends (a) without functionalized copolymer and in the presence of (b) 2.5 phr of EPDMSH and (c) 2.5 phr of EPDM-g-MA.
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crosslink precursor (k4), as indicated by the higher k4/k3 value.  The reversion phenomenon during the overcure period was more important in blends containing functionalized EVA, whose highest value was found in the EVA-g-MA based blend.  The addition of functionalized copolymers resulted in a decrease of solvent uptake behavior indicating higher crosslink density and also a covulcanization phenomenon. This behavior was more pronounced in blends containing EVA-g-MA.

Acknowledgements: We would like to acknowledge the Conselho Nacional de Desenvolvimento Cient co e Tecnolo gico (CNPq), Coordenac a o de Aperfeic oamento de Pessoal de Nivel Superior (CAPES), Financiadora de Estudos e Projetos (FINEP), and Fundac a o de Amparo a ` Pesquisa do Estado do Rio de Janeiro (FAPERJ), for the nancial support of this project. Received: August 28, 2006; Revised: November 1, 2006; Accepted: November 2, 2006; DOI: 10.1002/mame.200600332 Keywords: curing kinetics; elastomer blends; reactive compatibilization; solvent uptake

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