Eur. Polym. J. Vol. 24, No. 10, pp. 961-965, 1988 Printed in Great Britain.

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0014-3057/88 $3.00 +0.00 Copyright ~) 1988 Pergamon Press plc

EFFECT OF 7-MERCAPTOPROPYLTRIMETHOXYSILANE COUPLING AGENT ON tg0, TENSILE STRENGTH A N D TEAR STRENGTH OF SILICA-FILLED NR, NBR A N D SBR VULCANIZATES
M. NASIR, B. T. Port and P. S. NG School of Industrial Technology, University of Science, 11800 Minden, Penang, Malaysia
(Received 19 January 1988)
Abstract--A study has been made of the cure times (tg0), the tensile strengths and the tear strengths of

silica-filled NR, NBR and SBR, with and without the presence of 7-mercaptopropyltrimethoxysilane, (MPTS) and cured using the semi-etticient vulcanization system (semi-EV). Mixing was done using a Brabender Plasti-corder having a mixing cam attached and a two-roll mill, under approximately similar conditions. The tg0 of the Brabender mixed silica-filled NBR and NR, in the absence of MPTS display a cure retardation phenomena, while those of SBR exhibit a cure enhancement phenomenon. When MPTS is present, all Brabender mixed rubbers display a cure retardation phenomenon which can be attributed to a direct involvement of the MPTS in the sulphur vulcanization. Generally, the tensile strengths and the tear strengths of the Brabender mixed NBR and SBR are greater than those of the two-roll mill, whereas NR seems unaffected by the mixing methods. Addition of MPTS gives rise to marked improvements in the physical properties of NBR and SBR. However, the physical properties of NR are only slightly affected by the incorporation of MPTS.

INTRODUCTION

For some time, silicas and silicates of varying forms and particle sizes have been widely used as reinforcing fillers in rubbers, especially those of nonblack applications. However, their properties are usually inferior to those of carbon blacks, even when they are of comparable sizes. Furthermore, the high viscosity of a silica-filled rubber makes it more difficult to process [1, 2]. N u m e r o u s theories on filler reinforcement in rubbers habe been proposed by Smallwood [3], Guth [4], Mullins and Tobin [5] and others. Most of the mechanisms suggested to explain the reinforcement of rubber by fillers are still vague. However, the concept of rubber being occluded by a "shell" of filler, as put forward by H a r w o o d et al. [6], seems to fit most observations. Wagner [7] studied the effect of silicas having different structures in SBR vulcanizates; he concluded that silica-rubber interaction is dependent on the surface silanol content, the adsorbed water level and the surface area of silicas. The utilization of silane based coupling agents, to enhance both dynamic and mechanical properties of silica-filled rubbers, is well known and has been extensively studied by many workers such as Wagner [7,8], Dannenberg [9], Cameron et al. [10] and Fetterman [11]. Using H a r d w o o d ' s proposal of filler reinforcement, Dannenberg [9] attributed a further improvement in silica-filled rubbers, when M P T S is present, to the tightening of the shell of the occluded rubber as a consequence of coupling bonds being formed between M P T S and both the silica and the rubber phases. There is much evidence [12, 13] confirming the existence of such bonds. In all these cases, marked improvement in properties (viz. modulus, tear strength compression strength tensile strength and others) was noted [7, 11].

In order to understand further the effect of silanes on the physical properties of vulcanizates, we have studied the tg0, the tensile strength and the tear strength of N R , N B R and SBR vulcanizates, with and without an 7-mercaptopropyltrimethoxysilane coupling agent (MPTS). Brabender Plasti-corder with a mixer attached and two-roll mill mixings were utilized and the results are compared.
EXPERIMENTAL

Compounding ingredients and formulations SMR L grade natural rubber was obtained from the Rubber Research Institute of Malaysia. Nitrile-butadiene rubber (NBR) (grade Perbunun N 3307), styrene-butadience rubber (SBR), (grade 1502), precipitated silica (grade Vulcasil-S), carbon black (grade N-330) and other chemicals such as sulphur, zinc oxide, stearic acid and accelerators were all purchased from Bayer (M) Ltd. The coupling agent MPTS (grade A-169) was supplied by Union Carbide Ltd. All materials were used as supplied. Recipes used throughout the study are shown in Table 1. To allow comparison between rubbers, a semi-vulcanization system (EV) was chosen instead of the more popular conventional vulcanization system (CV). Furthermore, NR is prone to show a reversion phenomenon when the CV system is used. The amount of silane added was 2% by weight of silica. It was premixed with the silica, prior to mixing because it was reported [7, 11] that in situ addition of silane often gives rise to inferior properties of the vulcanizate. Mixing and tgo determination Mixing was separately done on the Brabender Plasticorder and the two-roll mill under approximately similar conditions. For the Brabender, the rotor speed was set at 40 RPM which is almost equivalent to the two-roll mill shear rate in which the nip size had been set at about 0.75__+0.10 me. Palmegran's method [14] was used for

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0 Silica (phr rubber) 5 10 20 40 Silane (phr silica) 0.~.0 3. O. depending on accelerator system and type of elastomer.5 (b) Silica with MPTS NR 10 5. followed by N B R and then SBR. whereas SBR shows retardation with increasing silica content. the Brabender mixed N B R is higher than the N R counterpart.2 1.0 8.0 6.6 22. resulting in coupling bond formation between the silane and both the silica and Tensile and tear strengths in the absence of M P T S Tensile strengths of silica-filled N R . N B R and SBR are shown in Figs 1 and 2.9.0.0 6.0 4. Wagner [7.0 8. The respective cure times. The cure retardation phenomenon can be attributed to a silica-rubber interaction. The tensile strengths of the Brabender-mixed silicafilled rubbers ([:]. 30 20 "~ 10 I 0 10 1 20 I 30 I 40 I 50 I 60 I 70 I 80 Silica Looding ( p h r l Fig.0 5.2 aN-Cyclohexyl-2-benzothiazole-2-sulphenamide. The t90 for both N R and N B R exhibit a cure retardation phenomenon. In fact. N R gives the highest tensile strength.0 NBR 6. all rubbers exhibit a cure enhancement phenomenon. Further increase in silica content reduces the tensile strengths. NR. However.3 20.6. as measured by tg0.5 estimating the shear rates of the mixing equipment. bTetramethylthiuram disulphide. sulphur Base recipes: .0 8.0 SBR 19 10 10 8. It was further suggested that the silane participates in the vulcanization by activating the accelerators.5 4.962 M. Dumbell and trouser test pieces were cut out o1 the sheets. to direct involvement of the silane in the vulcanization mechanism.2 0. 60 70 1. were then determined using the Monsanto Rheometer. The enhancement can be associated.0 5. concluded that the effect upon cure retardation is directly proportional to the total surface area of silica present and the functionality of sulphur is dependent on both the particle size and the total content of silica.9. Both mixing methods exhibit similar trends.9 2. for SBR t90 is further shortened. measured at 140° (a) Silica without MPTS Silica (phr) 0 5 10 20 40 60 70 80 NR 10 3.5 3. beyond 50 phr.5 9.4 Table 2. SBR and NBR )'rubber 100.5 8. thickness. studying the influence of silica on cure behaviour of rubbers.8 6. Brabender mixed N B R and SBR show higher tensile strengths than their two-roU mill counterparts.0 8. 1. TMTD b 0. CBSa 1.5 6.5 3. 15]. This can perhaps explain why SBR displays the cure enhancement phenomenon. 13]. Measurements of tensile and tear strengths The various recipes were compression moulded at 140°. NBR.5 3. NASIR et al.5.0 8. SBR). ZnO 2. it was found that the cure effect is also dependent on the accelerator system and the type of elastomer.4 17.0 8.5 8.6 80 1. instead of cure retardation like N R and N B R . Fetterman [11].6 11. stearic acid 1. Cure times (t~0) of silica-filledBrabender-mixed rubber vulcanizates with and without silane coupling agent. Tests were then carried out on the Instron Universal Testing Machine according to BS 903. CN-Isopropyl-N-phenylenediamine.0 4.8 PEG d (phr silica) 1.5 4. Only those of systems with silica are shown in Table 2.0 NBR 6. according to their respective tgo.0 4. in which the silica reacts with zinc oxide and subsequently reduces the zinc reactivity. into sheets of 1 and 2 mm. When M P T S is present. IPPD c 2.I 0. RESULTS AND DISCUSSION the rubber phases.5 3. . increasing the silica content results in a rise of tensile strengths until maximum levels are reached.0 7.4 0. Formulations of NR. A. 8] observed that mercaptosilanes generally enhance the scorch and cure time to varying extents.0 4. Similar observations were made by others [9. As expected.0 8. Cure characteristics (tgo) Only tg0 of the Brabender mixed rubber vulcanizates are given (Table 2).5 8.5 8.0 4.0 SBR 19 9. 1.5 4. Table 1.0 4. at 50 and 100mmmin -~ cross-head speeds for tensile and tear strengths respectively.8 5.0 4. so slowing down the sulphur reaction.5 8. dpolyethylene glycol. perhaps. The presence of such bonds has been confirmed by evidence previously noted [ 12. showing an improvement of cure behaviour.0 5.

The tear strengths of the Brabender-mixed silicafilled rubbers (rq. the weak bonds and interactions of silica with hydrocarbon rubber phases. 3. This is as expected since a semi-EV system was used here. 11]. SBR). SBR). This can be due perhaps to the nature of the rubbers. silica-filled NBR and SBR. O. NBR and SBR being amorphous while NR is crystalline. NBR. relative to those without silane. SBR). 2. both NBR and SBR have larger loading capacities than NR. cannot be attributed to better mixing. NBR and SBR vulcanizates 963 30F o ~: 2o ~ 10 I I I I I I I I 0 10 20 30 40 . including. respectively. When a silane is present. hence.50 60 SiLica Loading (phr) 70 80 Fig. N B R . It must be reiterated that the semi-EV system was specifically chosen for the purpose of comparing the three rubbers. especially at higher loadings. NBR. In fact. the loading capacities of the two-roll mill mixed NBR and SBR exceed 80 phr. regardless of mixing method. the difficult and poorer dispersion and also the cure retardation phenomenon. 17] that a vulcanizate cured using a CV system. Tensile and tear strengths with M P T S The tensile strengths of the rubber vulcanizates with the presence of MPTS are shown in Figs 5 and 6. NR. The tensile strengths of the two-roll mill mixed silica-filled rubbers ([~. especially for NBR and SBR and also the type of elastomer. by virtue of its polysulphidic network crosslinks. O . NR. followed by NBR and then SBR. 4. although both fillers have comparable particle sizes. the Brabender mixed NBR and SBR are greater than those of the two-roll mill but NR seems unaffected by mixing method. were observed for all rubbers. about 60 and 25 phr. The tear strengths o f the two-roll mill mixed silica-filled rubbers (F3. it is well known [16. Furthermore. as for those without silanes which were discussed previously. No distinctive differences. /k. Fig. In fact. The results show that silane efficiency is very much dependent on the mixing methods. even though lower tensile strengths were obtained here. a slight increase was seen with NR. would generally exhibit a tensile strength superior to that of a semi-EV system. /~. instead of the more popular CV system used by others. Somewhat similar trends were observed with tear strengths (Figs 3 and 4) with NR having the highest tear strength. for the others.Silica-filled NR. the enhancement in silica reinforcement can be attributed to better wetting and dispersion. The overall tensile strengths of the silica-filled rubbers are found to be inferior to those of carbon blacks. exhibit slightly higher tensile 40 40- 30-- [] 30z Z 7~ ~ 20 ~: 2o "6 I I I I I I I I I I i I I I i I 0 10 20 30 40 50 60 SiLica Looding (phr) "tO 80 0 I0 20 30 40 50 60 SiLico Loading (phr) 70 80 Fig. whereas NR seems unaffected by either mixing methods. which is predominantly monosulphidic in nature. and therefore. coupling bonds being formed between the "shell" of silica and the occluded rubber phases. Compared to carbon blacks. A. Again. Generally. However. Hewitt [1] also obtained higher loading capacities with tear strengths when compared with tensile strengths. both mixing techniques and all rubbers show higher loading capacities in tear strengths than those of tensile strengths. marked property improvements were noticed with NBR and SBR. Similar observations have been reported by others [7. Comparing the mixing methods. ©. NR is unaffected by the mixing method. NR. Dan- nenberg [9] attributed the inferior reinforcing effect of silicas to several reasons. . These anomalies are unexpected and unexplained since they were not observed with tensile strengths. the Brabender mixing is more effective than the two-roll mill.

NBR. is dependent of the network structure and the coupling bonds.964 30 r- M. It was further proposed that any particular property change can be attained by either altering the curative level or adding a silane. using the same type of silane and by varying the amount of silane and sulphur in silica-filled SBR. z~. Wagner [7]. C). 7. NR. SBR). heat build-up. lower tensile set and heat build-up and better ageing resistance. 6. SBR). The composite plot of tensile strength and tear strength of silica-filled NR ( 0 . 5. o '~ 10 I 0 10 20 I 30 I 40 I 50 I 60 I 70 I 80 SiLica Loading (phr) Fig. Edwards and Sato [18]./x. The effect of silanes on the tensile strengths of the two-roU mill mixed silica-filled rubber ([i]. also noticed a large increase in modulus. The effect of silanes on the tensile strengths of the Brabender-mixed silica-filled rubber ([1. have been reported by many workers [7. /X.=: 2o 2 . Pica Abrasion Index etc. NASlRet al. Z % a~ 20 == I. 40 20 --=. . comparing the various properties of 50phr silica-filled fun¢tionalized SBR vulcanizates with and without the same type of silane. NBR. SBR). The effect of silanes on the tear strengths of the roll-mill mixed rubbers ([i]. stress at 300%. silica/two-roll mill. Similar observations of silica improvement when silanes are present. SBR). NBR. 9. this phenomenon is not observed for NR.-- I 0 10 I 20 I 30 I 40 I 50 I 60 I 70 I 80 SiLica toading (phr) 0 I 10 I 20 Fig. Fig. NBR. silica/silane/Brabrender). However. silica/silane/two-roll mill. O. Dannenberg [9] however reported that better silane efficiency is obtainable 30 A & ~ N E z 30. NR.). silica/Brabrender. C). 8. 40- strengths than those of the carbon blacks. found that reinforcement in properties (viz. (i).~ 20 '~= 10 o o" ~ ~o I • 10 0 I 10 I 20 I I I I 30 40 50 60 SiLica Loading (phr) I 70 I 80 I 20 I 30 I 40 Tear strength (x103 Nm-2 ) Fig. 11]. The effect of silanes on the tear strengths of the two-roll mill mixed rubbers (O. 30- I I I I 30 40 50 60 SiLica Loading (phr) I 70 I 80 Fig. NR. A. A. A. NR. O.

J. N B R shows the greatest increase. M. a curve can be drawn. 16. 46. Cunnen. A. J. Again. The composite plots between tensile strengths and tear strengths of NR. Dannenberg. Techn. Kok and V. for each rubber and both mixing methods are separately combined in each figures. silica/two-roll mill. J. silica/silane/Brabrender). 46 (1971). J. 5. Sollman. For NBR and SBR. a nonlinear relationship with a correlation factor of only 0. appl. A. CONCLUSIONS The use of ~-mercaptopropyltrimethoxysilane in small quantities results in tensile strength and the tear strength enhancements in silica-filled NR. 715.Silica-filled NR. it seems to be unaffected by the mixing methods. Thomas. 758 (1941). Polym. Techn. The influences of silane on tear strengths are shown in Figs 7 and 8. Tobin. C. silica/silane/Brabrender). Phys. G. 9. M. Elastomerics 116. instead of a straight line. Macromolec. 18 (1984). 3993 (1968). e 20 _= • • A 7. G. Eur. 341 (1986). Fetterman. Eur. R. J. Harwood. Sci. Guth. 33 (1981). Hewitt [1] and Dannenberg [9] also reported similar silane influence on tear strengths. 40 (1981). For NR. Hertl. 30 (1981). Elastomerics 113. 19. 11. E. R. 15. N B R and SBR show better correlations between tensile strengths and tear strengths while N R displays a completely non-linear relationship. 2. 14. 18. Elastomerics 113. 49. 10. Rubber World 164. Wagner. N B R and SBR are shown in Figs 9. A. L. 2. 6. Ranney and K. H. Sci.87 and 0. M. J. 8. Physical Properties of Polymers. Q. N B R and SBR vuicanizates. The Chemistry and Physics of Rubberlike Substances. REFERENCES Fig. followed by SBR and then NR. with polar rubbers like N B R and CR. Phys. 11. A. D. a linear relationship can be drawn. Wagner. F. Q. appl. 20 (1945). Rubber Chem. C. Wagner. A. P J 24/10~D . Polym. Palmegran. 12. 5. 473 (1971). Fetterman. Payne and R. Techn. due to better controllable conditions. Yee. J. W. silica/Brabrender. the effect seems to be independent of the mixing method. G. Elastomerics 113. 55. Hsu. 329. E. Cameron. M. Higher silica loadings than those of tensile strengths were also 30- 1. 156. New York (1962). The Brabender mixing gives overall better tear strength than the two-roll mill in N B R and SBR. 13. M. 9. Hewitt. E . H. 15. The composite plot of tensile strength and tear strength of silica-filled NBR ( 0 . silica/silane/two-roll mill. S. Bateman. C. Brabender mixings. Interscience. silica/silane/two-roll mill. 10 and 1t respectively. P. N. Phys. 16 (1980). N. Q. 16. ~ 1o 0 I 10 I 20 I 30 I 4O Tear strength (x103 Nm -2) Fig. L Mullins and N. H. 933 (1974). J. silica/two-roll mill. J. Mullins. Eur. Hence a further increase of the silica filled N R tensile strength is not linearly linked to an expected increase in the tear strength. Polym. give rise to overall better properties in N B R and SBR. N R has the highest tear strength. with correlation factors estimated to be 0. J. Moore and A.46 was obtained. 3. M. 37 (1974). A.75 respectively. but not in nonpolar rubbers like N R and SBR. Rubber Chem. H. in the case of NR. 156. London (1963). H. Like tensile strengths. 17. Whittaker. The composite plot of tensile strength and tear strength of silica-filled SBR (O. Macromolecules 7. 22. O. 2993 (1965). for NR. a slight improvement occurs with N R but marked improvements are found with N B R and SBR. 4. L. 70 (1974). The nonlinear relation in N R is not unexpected since Mullins et aL [16] and Bueche [19] reported similar behaviour in NR. 10. although with gum vulcanizates. E. Gent and E. P. Phys. NBR and SBR vulcanizates 30 965 ° 10 S I 0 10 I 20 I 30 I 40 Tear strength ( x 103 Nm -2 ) observed. p. 704 (1976). P. The properties of silica-filled. silica/Brabrender. Polym. M. L. Bueche. J. Rubber Chem. J. 927 (1973). Sato. Smallwood. Edwards and K. M. with and without silane. p. W. appl. Chem. Maclaren. L. in fact.