Liquid rubber as a reactive softener for 1-chlorobutadiene–butadiene rubber

Blending of hydroxyl-terminated liquid butadiene rubber (HT-BR) with 1-chlorobutadiene–butadiene rubber (CB–BR) was carried out in the presence of isopropylidenedicyclohexyl diisocianate (IPCI) or sulfur as a curing agent, It was found that the HT-BR/CB–BR blend displayed a good plasticity, i.e., its Mooney viscosity became lower than that of CB–BR, which brought abcut a good processability. The HT-BR fraction (E_s from the HT-BR/CB–BR blend vulcanizates, which was prepared by the IPCI-cured system, was evaluated to be ca. 20% by the equilibium swelling test in benzene. The E_s of the sulfur-cured blend was ca. 70% This result shows that HT-BR acted as a reactive softener when it was compounded with CB–BR by curing with the diisocyanate. The tensile strength of the IPCI vulcanizate was exceedingly higher than that of sulfur-cured vulcanizate at all blend raios of HT-BR to CB–BR. © 1996 John Wiley & Sons, Inc.     

1-chlorobutadiene–butadiene rubber. III. Determination of hydroxyl group content

The hydroxyl group content in 1-chlorobutadiene–butadiene rubber prepared by emulsion polymerization (CB–BR) was determined by UV spectroscopy. CB–BR was allowed to react with phenyl isocyanate at room temperature, and the resulting N-phenyl carbamate was assayed by UV measurement. The present method allowed the determination of a very small amount of hydroxyl groups contained in a high molecular weight hydrocarbon polymer. The hydroxyl group content in the hydroxyl-terminated liquid polybutadiene was also determined. The value agreed closely with that obtained by the usual titration method. Hydroxyl groups in CB–BR are presumed to be produced by the hydrolysis of the active chlorine contained in CB–BR. This hydrolysis is dependent on the work-up conditions of CB–BR, and the quantitative results were discussed with reference to the microstructure of the 1-chlorobutadiene unit in CB–BR.     

1-chlorobutadiene–butadiene rubber. IV. Increasing the hydroxyl group content in the rubber

The hydroxyl group content in 1-chlorobutadiene–butadiene rubber (CB–BR) was increased by the following two methods: (1) heating of the CB–BR latex to hydrolyze the unstable chlorine in CB–BR and (2) introduction of hydroxyl by the Menschutkin-type reaction between 2-dimethylaminoethanol (DMAE) and the chlorine in CB–BR. By heating the latex at 70°C for 12 hr, 55% chlorine was hydrolyzed to result in a marked increase in hydroxyl group content in CB–BR, i.e., at least 55% chlorine is situated in the CB units of the 1,4-configuration. Heat-treated CB–BR was found to contain a small amount of conjugated triene structure by UV spectroscopy, which indicates that elimination of some unstable chlorine as hydrogen chloride occurs during latex heating. By reaction with DMAE, 44% chlorine was converted into hydroxyl in toluene at 27°C. CB–BR compounded with DMAE does not suffer from gelation by milling on an open roll. Thus, by these methods, high molecular weight butadiene rubber having various concentrations of hydroxyl groups is obtained.     

Vulcanization kinetics of nano-silica filled styrene butadiene rubber

It was shown that the physical filler-polymer and filler–filler interactions, apart from the filler surface chemistry, has a substantial role in controlling the vulcanization kinetics of styrene butadiene rubber filled with nano-silica in a sulfur vulcanization system. Kinetic studies by the oscillating disc rheometer, differential scanning calorimeter, and swelling tests revealed that the vulcanization rate goes through a maximum as loading of silica increases, but conversion in crosslinking continuously decreases as the amount of silica increases. The effect of silica loadings on the vulcanization reactions was linked to the immobilization of rubber chains around particles as well as in a polymer-mediated filler network, which were differentiated by the nonlinear viscoelastic behavior of rubber vulcanizates. By surface modification of nano-silica, the accelerating/decelerating effects of nano-silica on the vulcanization reactions were altered corresponding to the non-linear viscoelastic behavior of the vulcanizates. Therefore, a mechanism was proposed which correlates vulcanization kinetics of rubber to the dynamics of chains influenced by the reinforcing fillers.     

Anisotropy of styrene–butadiene rubber

Anisotropy of styrene–butadiene rubber (SBR) was investigated. The anisotropy of the copolymer varies linearly with the styrene content and the ultimate value coincides with that of polystyrene at elevated temperature. From these facts, the transverse configuration of the pendant phenyl group is estimated irrespective of the styrene content of SBR.     

Structural morphology and properties of star styrene–isoprene–butadiene rubber and natural rubber/star styrene–butadiene rubber blends

Star styrene–isoprene–butadiene rubber (SIBR) was synthesized with a new kind of star anionic initiator made from naphthalene lithium and an SnCl₄ coupled agent. The relationship between the structure and properties of star SIBR was studied. Star block styrene–isoprene–butadiene rubber (SB‐SIBR), having low hysteresis, high road‐hugging, and excellent mechanical properties, was closer to meeting the overall performance requirements of ideal tire‐tread rubber according to a comparison of the morphology and various properties of SB‐SIBR with those of star random SIBR and natural rubber/star styrene–butadiene rubber blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 336–341, 2004     

Improvement of properties of silica‐filled styrene–butadiene rubber compounds using acrylonitrile–butadiene rubber

Since silica has strong filler–filler interactions and adsorbs polar materials, a silica‐filled rubber compound has a poor dispersion of the filler and poor cure characteristics. Improvement of the properties of silica‐filled styrene–butadiene rubber (SBR) compounds was studied using acrylonitrile–butadiene rubber (NBR). Viscosities and bound rubber contents of the compounds became lower by adding NBR to the compound. Cure characteristics of the compounds were improved by adding NBR. Physical properties such as modulus, tensile strength, heat buildup, abrasion, and crack resistance were also improved by adding NBR. Both wet traction and rolling resistance of the vulcanizates containing NBR were better than were those of the vulcanizate without NBR. The NBR effects in the silica‐filled SBR compounds were compared with the carbon black‐filled compounds. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1127–1133, 2001     

Short-fiber-reinforced styrene–butadiene rubber composites

Processing characteristics, anistropic swelling, and mechanical properties of short-jute-fiber-and short-glass-fiber-reinforced styrene–butadiene rubber (SBR) composites have been studied both in the presence and absence of carbon black. Tensile and tear fracture surfaces of the composites have been studied using scanning electron microscopy (SEM) in order to assess the failure criteria. The effects of bonding agent. carbon black, jute fiber, and glass fiber on the fracture mode of the composites have also been studied. It has been found that jute fiber offers good reinforcement to SBR as compared to glass fibers. The poor performance of glass fibers as reinforcing agent is found to be mainly due to fiber breakage and poor bonding between fiber and rubber. Tensile strength of the fiber–SBR composites increases with the increase in fiber loading in the absence of carbon black. However, in the presence of carbon black a minimum was observed in the variation of strength against fiber loading. SEM studies indicate that fracture mode depends not on the nature of the fiber but on the adhesion between the fiber and the matrix.     

Hydrogenation of acrylonitrile–butadiene rubber latexes

The hydrogenation of acrylonitrile–butadiene rubber (NBR) latex was carried out by a system consisting of hydrazine hydrate and hydrogen peroxide, with boric acid as catalyst. Highly saturated hydrogenated NBR (HNBR) latex was obtained through the optimization of the reaction conditions. The dried HNBR was found to be heavily gelled. The cause for the crosslink of dried hydrogenated NBR products was investigated. With the improvement of the hydrogenation system, that is, by adding gel inhibitor to the system, the crosslinking was controlled to a large extent, and dried HNBR with gel content of about 3% was prepared by the improved system. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2072–2078, 2004     

Dichlorocarbene modification of styrene–butadiene rubber

Dichlorocarbene-modified styrene–butadiene rubber (SBR) prepared by the alkaline hydrolysis of chloroform using cetyltrimethylammonium bromide as a phase-transfer agent resulted in a product that showed good mechanical properties, excellent flame resistance, solvent resistance, and good thermal stability. The activation energy for this chemical reaction calculated from the time–temperature data on the chemical reaction by the measurement of the percentage of chlorine indicated that the reaction proceeded according to first-order kinetics. The molecular weight of the polymers, determined by gel permeation chromatography, showed that chemical modification was accompanied by an increase in molecular weight. The chemical modification was characterized by proton NMR, FTIR studies, thermogravimetric analysis, and flammability measurement. Proton NMR and FTIR studies revealed the attachment of chlorine through cyclopropyl rings to the double bond of butadiene. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 153–160, 1998     

Toughening epoxy resins with solid acrylonitrile–butadiene rubber

The feasibility of using solid acrylonitrile–butadiene rubbers (NBR) with 19 and 33% w/w acrylonitrile to toughen diglycidyl ether of bisphenol A (DGEBA) epoxy resins has been investigated. Thermal analysis experiments revealed a two‐phase morphology of these rubber‐modified epoxies. However, the higher content of acrylonitrile in the rubber caused better compatibility between NBR and the epoxy resin. The rubber with 33% acrylonitrile was found to be an effective toughening agent for DGEBA epoxy resins. Fracture surface studies and also the high tensile strength of crosslinked high molecular weight NBR suggest that the toughening effect should arise from rubber bridging and tearing mechanisms. © 2000 Society of Chemical Industry     

Natural rubber and butadiene rubber blend using diblock copolymer of isoprene–butadiene as compatibilizer

Blends of natural rubber (NR) and butadiene rubber (BR) have been studied with or without diblock copolymers of isoprene–butadiene (BIR). It was found that NR/BR blends displayed the optimal properties at about 4 wt % of BIR from the tensile measurements of NR/BR blends. Increase of molecular weight of BIR resulted in the decrease of tensile properties, but had no significant effect on their hardness. Abrasion resistance of rubber blends containing BIR was about 30% higher than that without BIR. The molecular weight of BIR did not show a remarkable effect on the abrasion index. Differential scanning calorimetry and dynamic mechanical analyses of rubber blends suggested a two-phase structure even in the presence of BIR. © 1993 John Wiley & Sons, Inc.     

Thermal and scanning electron microscopy/energy‐dispersive spectroscopy analysis of styrene–butadiene rubber–butadiene rubber/silicon dioxide and styrene–butadiene rubber–butadiene rubber/carbon black–silicon dioxide composites

Silica as a reinforcement filler for automotive tires is used to reduce the friction between precured treads and roads. This results in lower fuel consumption and reduced emissions of pollutant gases. In this work, the existing physical interactions between the filler and elastomer were analyzed through the extraction of the sol phase of styrene–butadiene rubber (SBR)–butadiene rubber (BR)/SiO₂ composites. The extraction of the sol phase from samples filled with carbon black was also studied. The activation energy (E_a) was calculated from differential thermogravimetry curves obtained during pyrolysis analysis. For the SBR–BR blend, E_a was 315 kJ/mol. The values obtained for the composites containing 20 and 30 parts of silica per hundred parts of rubber were 231 and 197 kJ/mol, respectively. These results indicated an increasing filler–filler interaction, instead of filler–polymer interactions, with respect to the more charged composite. A microscopic analysis with energy‐dispersive spectroscopy showed silica agglomerates and matched the decreasing E_a values for the SBR–BR/30SiO₂ composite well. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2273–2279, 2005     

Microstructure analysis of brominated styrene–butadiene rubber

The bromine addition to the SBR double bonds in chloroform at 0°C has been investigated by FTIR, ¹H NMR and DSC techniques. In this case, bromine molecules react exclusively with the polydiene double bonds and the polystyrene units are unaffected. The bromine reacts preferentially with 1,4‐trans double bonds of the polybutadiene segment of SBR. At low bromination level (below 15%) the bromine reacts mainly with the 1,4‐trans double bonds of SBR, while at higher bromination level (up to 30%) the bromine shows the most reactivity toward the vinylic double bond. Above 30%, the addition reaction occurs on 1,4‐trans double bonds. The microstructure of modified and unmodified styrene–butadiene copolymers were fully characterized by ¹H NMR technique. Expanded regions have been utilized to resolve the complex ¹H NMR spectrum and establish the compositional and configurational sequences of styrene–butadiene copolymers. POLYM. ENG. SCI., 47:87–94, 2007. © 2007 Society of Plastics Engineers     

Oil absorbents based on styrene–butadiene rubber

Four oil absorbents based on styrene–butadiene (SBR)—pure SBR (PS), 4‐tert‐butylstyrene–SBR (PBS), EPDM–SBR network (PES), and 4‐tert‐butylstyrene‐EPDM‐SBR (PBES)—were produced from crosslinking polymerization of uncured styrene–butadiene rubber (SBR), 4‐tert‐butylstyrene (tBS), and ethylene–propylene–diene terpolymer (EPDM). The reaction took place in toluene using benzoyl peroxide (BPO) as an initiator. Uncured SBR was used as both a prepolymer and a crosslink agent in this work, and the crosslinked polymer was identified by IR spectroscopy. The oil absorbency of the crosslinked polymer was evaluated with ASTM method F726‐81. The order of maximum oil absorbency was PBES > PBS > PES > PS. The maximum values of oil absorbency of PBES and PBS were 74.0 and 69.5 g/g, respectively. Gel fractions and swelling kinetic constants, however, had opposite sequences. The swelling kinetic constant of PS evaluated by an experimental equation was 49.97 × 10^?2 h^?1. The gel strength parameter, S, the relaxation exponent, n, and the fractal dimension, d_f, of the crosslinked polymer at the pseudo‐critical gel state were determined from oscillatory shear measurements by a dynamic rheometer. The morphologies and light resistance properties of the crosslinked polymers were observed, respectively, with a scanning electron microscope (SEM) and a color difference meter.     

Dynamic mechanical analysis of ethylene–propylene–diene monomer rubber and styrene–butadiene rubber blends

The effects of blend ratio, crosslinking systems, and fillers on the viscoelastic response of ethylene–propylene–diene monomer (EPDM)/styrene–butadiene rubber (SBR) blends were studied as functions of frequency, temperature, and cure systems. The storage modulus decreased with increasing SBR content. The loss modulus and loss tangent results showed that the EPDM/SBR blend vulcanizate containing 80 wt % EPDM had the highest compatibility. Among the different cure systems studied, the dicumyl peroxide cured blends exhibited the highest storage modulus. The reinforcing fillers were found to reduce the loss tangent peak height. The blend containing 40 wt % EPDM showed partial miscibility. The dispersed EPDM phase suppressed the glass‐transition temperature of the matrix phase. The dynamic mechanical response of rubbery region was dominated by SBR in the EPDM–SBR blend. The morphology of the blend was studied by means of scanning electron microscopy. The blend containing 80 wt % EPDM had small domains of SBR particles dispersed uniformly throughout the EPDM matrix, which helped to toughen the matrix and prevent crack propagation; this led to enhanced blend compatibility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Plasma surface modification of silica and its effect on properties of styrene–butadiene rubber compound

The effects of surface modification of silicas by plasma‐polymerization coating, together with modification using a silane coupling agent for a comparison on the dispersion and physical properties of styrene–butadiene rubber (SBR) are reported. The chemical compositions of the plasma‐polymerization coating were characterized using FTIR and Auger spectrometer and it was found that the plasma coating was composed of C?C and C? H bonds. The surface modification of silica by either plasma polymerization or silane greatly improved the dispersion of silica particles in SBR vulcanizates. The plasma‐polymerization modification of silica improved the tensile modulus of SBR vulcanizates without deterioration of important basic properties such as tensile strength and elongation at break. © 2002 Society of Chemical Industry     

Filler–rubber interactions in α_cellulose‐filled styrene butadiene rubber composites

In this study, the interactions between rubber and fillers in α_cellulose‐filled styrene butadiene rubber (SBR) composites were investigated. The results obtained from the tensile and tear strength, abrasion resistance, and hardness indicate that addition of 5‐phr α_cellulose into compound not only does not affect rubber–carbon black bond but improves the mentioned physicomechanical properties. In this study, the type of carbon black was changed from N 330 to N 550. The main purpose of this investigation was to observe the possible changes in physicomechanical properties due to this change. Obtained results show that overall observation of the trends of results do not change with type of carbon black. It can be concluded that the presence of α_cellulose does not have significant influence on the performance of carbon black in the compounds used. POLYM. COMPOS., 28:748–754, 2007. © 2007 Society of Plastics Engineers     

Separation of alkane–acetone mixtures using styrene–butadiene rubber/natural rubber blend membranes

Conventionally vulcanized styrene–butadiene rubber/natural rubber blend membranes were prepared for the pervaporation separation of alkane–acetone mixtures. Swelling measurements were carried out in both acetone and n‐alkanes to investigate the swelling behavior of the membranes. The swelling behavior was found to depend on the composition of the blend. The effects of blend ratio, feed composition, and penetrant size on the pervaporation process were analyzed. The permeation properties have been explained on the basis of interaction between the membrane and solvents and blend morphology. The SBR/NR 70/30 blend membrane showed higher selectivity among all the membranes used. Flux increases with increasing alkane content in the feed composition. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3059–3068, 1999     

Impact of blend ratio on the properties of graphene oxide‐filled carboxylated acrylonitrile–butadiene rubber/styrene–butadiene rubber blends

Carboxylated acrylonitrile–butadiene rubber (XNBR) and styrene–butadiene rubber (SBR) composites with 3 phr (parts per hundred rubber) graphene oxide (GO) were prepared using a latex mixing method. Effects of XNBR/SBR blend ratios on the mechanical properties, thermal conductivity, solvent resistance and thermal stability of the XNBR/SBR/GO nanocomposites were studied. The tensile strength, tear strength, thermal conductivity and solvent resistance of the XNBR/SBR/GO (75/25/3) nanocomposite were significantly increased by 86, 96, 12 and 21%, respectively, compared to those of the XNBR/SBR (75/25) blend. The thermal stability of the nanocomposite was significantly enhanced; in other words, the temperature for 5% weight loss and the temperature of the maximal rate of degradation process were increased by 26.01 and 14.97 °C, respectively. Theoretical analysis and dynamic mechanical analysis showed that the GO tended to locate in the XNBR phase, which led to better properties of the XNBR/SBR/GO (75/25/3) nanocomposite. © 2017 Society of Chemical Industry