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.     

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     

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     

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.     

Quantitative characterization of kaolinite dispersibility in styrene–butadiene rubber composites by fractal dimension

A fractal method was introduced to quantitatively characterize the dispersibility of modified kaolinite (MK) and precipitated silica (PS) in styrene–butadiene rubber (SBR) matrix based on the lower magnification transmission electron microscopic images. The fractal dimension (FD) is greater, and the dispersion is worse. The fractal results showed that the dispersibility of MK in the latex blending sample is better than that in the mill blending samples. With the increase of kaolinite content, the FD increases from 1.713 to 1.800, and the dispersibility of kaolinite gradually decreases. There is a negative correlation between the dispersibility and loading content. With the decrease of MK and increase of PS, the FD significantly decreases from 1.735 to 1.496 and the dipersibility of kaolinite remarkably increases. The hybridization can improve the dispersibility of fillers in polymer matrix. The FD can be used to quantitatively characterize the aggregation and dispersion of kaolinite sheets in rubber matrix. POLYM. COMPOS., 36:1486–1493, 2015. © 2014 Society of Plastics Engineers     

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     

Mechanical reinforcement in magadiite/styrene‐butadiene rubber composites

This work investigates mechanical properties of styrene‐butadiene rubber (SBR) composites incorporating magadiite (MGD), a synthetic layered silicate (Na₂Si₁₄O₂₉·9H₂O) with surface chemistry similar to precipitated silica used in tire tread formulations. Treatment with cetyltrimethylammonium (CTA⁺) expands the MGD layers and makes the interlayer face surfaces accessible to sulfur‐functional silane TESPT (Si69) and SBR, primarily during batch mixing. DMA and tensile testing of cured CMGD/SBR composites show that CTA‐treated MGD (CMGD) provides substantially higher levels of mechanical reinforcement than equivalent amounts of silica. However, CMGD/SBR composites exhibit larger loss tangent values above T_g, probably due to lower SBR‐SBR crosslink density resulting from interlayer trapping of sulfur released by Si69 during vulcanization. DMA and tensile testing also demonstrate Si69′s critical role in forming MGD‐SBR graft sites essential to mechanical reinforcement. Replacing silica with CMGD reduces composite weight without sacrificing tensile modulus, suggesting that use of CMGD in tire rubber formulations could improve vehicle energy efficiency. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44763.     

Physicomechanical properties of α‐cellulose–filled styrene–butadiene rubber composites

In this research, the influence of adding α‐cellulose powder to styrene–butadiene rubber (SBR) compounds was investigated. Physicomechanical properties of SBR–α‐cellulose composites, including tensile strength, elongation, Young's modulus, tear strength, hardness, abrasion, resilience, and compression set, before and after ageing, were determined and analyzed. Young's modulus, hardness, and compression set increased and elongation and resilience decreased with increasing α‐cellulose loading in the composites, whereas tensile strength, tear strength, and abrasion resistance initially increased at low α‐cellulose concentration (5 phr), after which these properties decreased with increasing α‐cellulose content. Lower loadings of α‐cellulose (5 phr) showed better results than higher loadings, given that tensile strength, tear strength, and abrasion resistance increased at low α‐cellulose concentration. Theoretical prediction of elastic modulus was carried out using rule of mixtures, Hashin, Kerner, and Halpin–Tsai equations. Calculated results show that these equations are not suitable for accurate prediction for the work carried out. However, these models can be used with confidence for the prediction of elastic modulus because experimental results are higher than the calculated values. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2203–2211, 2005     

Ultraviolet-initiated photografting of glycidyl methacrylate onto styrene–butadiene rubber

Photografting reaction onto styrene–butadiene rubber (SBR) as a function of monomer concentration, grafting method, irradiation time, and the carbon black content has been studied using ultraviolet (UV). Glycidyl methacrylate and benzophenone are used as monomer and initiator, respectively. The occurrence of graft reaction onto SBR surface is identified by infrared attenuated total reflection (IR-ATR) analysis. The degree of monomer graft increases with monomer concentration and tends to level off at high monomer concentration (>8.3M/L). Graft ratio also increases with UV irradiation time. Carbon black content is found as one of important factors that determine the monomer graft efficiency. The amount of monomer graft onto SBR decreases with increasing carbon black content and it is attributed to the reduction of irradiation absorbance due to the presence of carbon black. The occurrence of reaction between glycidyl methacrylate grafted SBR and nylon-6 via melt phase reaction is also identified using IR-ATR analysis. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1733–1739, 1999     

Thiol‐containing ionic liquid for the modification of styrene–butadiene rubber/silica composites

To introduce thiol–ene chemistry in the modification of composites by ionic liquid (IL), a novel functional IL, 1‐methylimidazolium mercaptopropionate (MimMP), was synthesized and investigated as a modifier for styrene–butadiene rubber/silica composites. MimMP could be hydrogen‐bonded with silica and react with the double bonds of rubber chains via thiol–ene chemistry. The filler networking, curing behavior, filler dispersion, crosslink density, and mechanical performance were fully studied. The filler networking in the uncured rubber compounds was effectively restrained. The vulcanization was largely accelerated by MimMP. The interfacial interaction was quantitatively evaluated and found to consistently increase with increasing MimMP. The mechanical performance and abrasion resistance of the modified vulcanizates improved considerably. The remarkable improvements were mainly ascribed to the improved interfacial structure comprised of MimMP–silica hydrogen bonding and MimMP–rubber covalent bonds via thiol–ene chemistry. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheological behavior of blends of natural rubber and styrene–butadiene rubber latices

The rheological behavior of blends of natural rubber (NR) and styrene–butadiene rubber (SBR) latices has been studied with reference to the effects of blend ratio, shear rate, surface-active agents (casein and sodium carboxymethyl cellulose), and temperature. When the SBR content was less than 50%, the viscosities of the blends appeared to be a nonadditive function of the viscosities of the constituent homopolymers; i.e., a positive deviation was observed. This was due to the structural buildup of the SBR domains. The SBR domains underwent agglomeration and consequently so-called microflocculation took place. The viscosities of all the blends were found to decrease with increase of temperature and shear rate. The increase in temperature and shear rate marginally weakened the structural buildup as evidenced by the lowering of viscosity. As the SBR content in the system increased, the pseudoplasticity of the blend increased. Even in the presence of surface-active agents the blends showed composition-dependent positive deviation. However, surface-active agents marginally reduced the extent of structural buildup by reducing the microflocculation behavior of SBR domains. © 1995 John Wiley & Sons, Inc.     

Accelerator adsorption onto carbon nanotubes surface affects the vulcanization process of styrene–butadiene rubber composites

The multiwalled carbon nanotubes (MWCNT) filled styrene–butadiene rubber (SBR) composites were prepared by incorporating MWCNT in a SBR/toluene solution and subsequently evaporating the solvent. These composites have shown a significant improvement in Young's modulus and tensile strength with respect to SBR gum without sacrificing high elongation at break. However, this improvement is less than expected at the higher filler content. Then, the influence of low concentrations of MWCNT on the vulcanization process of the SBR composites was studied by means of rheometer torque curves, swelling measurements, differential scanning calorimeter (DSC) analysis, and Fourier transform infrared (FTIR) spectroscopy. Also, their thermal degradation was studied by thermogravimetric analysis (TGA). It has been noticed that MWCNT affects the cure kinetics of SBR gum matrix reducing all parameters, i.e., the total heat rate and order of the reaction, scorch delay, maximum torque, and crosslink density. This effect increases as MWCNT content does, and it was attributed to the adsorption of the accelerator employed in the vulcanization (N‐tert‐butyl‐benzothiazole‐2‐sulfenamide) onto the MWCNT surface. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Overall properties of fibrillar silicate/styrene–butadiene rubber nanocomposites

The mechanical properties, heat aging resistance, dynamic properties, and abrasion resistance of fibrillar silicate (FS)/styrene butadiene rubber (SBR) nanocomposites are discussed in detail. Compared with white carbon black (WCB)/SBR composites, FS/SBR composites exhibit higher tensile stress at definite strain, higher tear strength, and lower elongation at break but poor abrasion resistance and tensile strength. Surprisingly, FS/SBR compounds have better flow properties. This is because by rubber melt blending modified FS can be separated into numerous nanosized fibrils under mechanical shear. Moreover, the composites show visible anisotropy due to the orientation of nanofibrils. There is potential for FS to be used to some extent as a reinforcing agent for rubber instead of short microfibers or white carbon black. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2725–2731, 2006     

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     

Influence of starch on the properties of carbon‐black‐filled styrene–butadiene rubber composites

The influence of starch on the properties of carbon‐black‐filled styrene–butadiene rubber (SBR) composites was investigated. When the starch particles were directly melt‐mixed into rubber, the stress at 300% elongation and abrasion resistance decreased evidently with increasing starch amount from 5 to 20 phr. Scanning electron microscopy observations of the abrasion surface showed that some apparent craters of starch particles were left on the surface of the composite, which strongly suggested that the starch particles were large and that interfacial adhesion between the starch and rubber was relatively weak. To improve the dispersion of the starch in the rubber matrix, starch/SBR master batches were prepared by a latex compounding method. Compared with the direct mixing of the starch particles into rubber, the incorporation of starch/SBR master batches improved the abrasion resistance of the starch/carbon black/SBR composites. With starch/SBR master batches, no holes of starch particles were left on the surface; this suggested that the interfacial strength was improved because of the fine dispersion of starch. Dynamic mechanical thermal analysis showed that the loss factor at both 0 and 60°C increased with increasing amount of starch at a small tensile deformation of 0.1%, whereas at a large tensile strain of 5%, the loss factor at 60°C decreased when the starch amount was varied from 5 to 20 phr. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Surface modification of lignosulfonates for reinforcement of styrene–butadiene rubber compounds

In this study, surface modification of lignosulfonates (LSs) was investigated for potential reinforcement of styrene–butadiene rubber compounds. Lignins are naturally occurring amorphous, highly branched polymers consisting of aromatic and aliphatic segments with polar functional groups such as hydroxyl, methoxy, carbonyl, and carboxyl. The polarity and hydrophilic nature render lignin incompatible with nonpolar rubber materials. In this study, cyclohexylamine (CA) modification of LS was evaluated for enhancement of compatibility with rubber via proton transfer and hydrogen bonding interactions. X‐ray photoelectron spectroscopy data confirm attachment of CA onto the surface of LS. The cure and scorch times of rubber compounds were shortened, and the crosslink density enhanced with an increase of the amount of CA in modified LS. The tensile strength at break increased by almost 45%; the 100% modulus and elongation at break also showed significant improvements. The values of storage modulus and loss tangent increased by 13% and 18%, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40123.     

Sulfur‐free lignin as reinforcing component of styrene–butadiene rubber

The potential application of lignin biopolymer as a component of styrene–butadiene rubber was examined with regard to its ability to reinforce the vulcanizates. It was shown that the sulfur‐free lignin preparation improved physicomechanical properties of rubber. The determination of the coefficient of lignin activity confirmed that lignin acts as an active filler. FTIR characteristics of lignin isolated from the vulcanizate containing 20 phr lignin indicated its interaction with the sulfur system, resulting in formation of noncyclic sulfide structures. In the case of higher lignin amount in the vulcanizate, some interfacial interaction between lignin and SBR may occur. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 924–929, 2005