Reinforcement of Styrene-Butadiene Rubber with Silica Modified by Silane Coupling Agents: Experimental and Theoretical Chemistry Study

The properties of styrene-butadiene rubber (SBR) reinforced by modified silica was investigated according to national standards. Silica was modified by silane coupling agents KH-570, KH-590, and KH-792. The optimized geome-tries of molecular modified silica reinforced SBR were obtained by using B3LYP calculation of density functional theory with the 6-31+G basis sets. The natural bond orbital analyses were carried out. The Si—O bond length of silica modified by KH-792 was the shortest and the electronegative of O was the highest. It indicated that the connection between silica and KH-792 was the tightest. Higher tensile strength and elongation of reinforced SBR was obtained by silica modified with the KH-792. It was caused by large delocalization of lone pair electrons of the two N atoms in KH-792. The S—C bond length in silica modified by KH-590 was longer than the ordinary S—C bond length. Then the sulfur free radical (·S·) was produced more easily in vulcanization. The degree of crosslink was increased by the cross-linkage of the rubber molecule and the sulfur free radical. That was why the highest stress and tear strength of reinforced SBR was produced when silane coupling agent KH-590 was used. The calculation results was in accord with experimental data.

Pyrolysis of vulcanized styrene-butadiene rubber via ReaxFF molecular dynamics simulation

Styrene-butadiene rubber(SBR)is widely used in tires in the automotive segment and vulcanization using sulfur is a common process to enhance its mechanical properties.However,the addition of sulfur as the cross-linking agent usually results in impurities in pyrolysis products during rubber recycling,and thus the desulfurization during tire pyrolysis attracts much attention.In this work,the pyrolysis of vulcanized SBR is studied in detail with the help of Reax FF molecular dynamics simulation.A series of crosslinked SBR models were built with different sulfur contents and densities.The following Reax FF MD simulations were performed to show products distributions at different pyrolysis conditions.The simulation results show that sulfur products distribution is mainly controlled by sulfur contents and temperatures.The reaction mechanism is proposed based on the analysis of sulfur products conversion pathway,where most sulfur atoms are bonded with hydrocarbon radicals and the rest transfer to H_(2)S.High sulfur contents tend to the formation of elemental sulfur intermediate,and temperature increase facilitates the release of H_(2)S.

MORPHOLOGY,INTERFACIAL INTERACTION AND PROPERTIES OF STYRENE-BUTADIENE RUBBER/MODIFIED HALLOYSITE NANOTUBE NANOCOMPOSITES

A natural nanotubular material,halloysite nanotubes(HNTs),was introduced to prepare styrene-butadiene rubber/modified halloysite nanotube(SBR/m-HNT) nanocomposites.Complex of resorcinol and hexamethylenetetramine (RH) was used as the interfacial modifier.The structure,morphology and mechanical properties of SBR/m-HNT nanocomposites,especially the interfacial interactions,were investigated.SEM and TEM observations showed that RH can not only facilitate the dispersion and orientation of HNTs in SBR matrix at ...

Strengthening and toughening styrene-butadiene rubber by mechanically interlocked cross-links

Styrene-butadiene rubber(SBR)is an indispensable material in modern society,and the necessity for enhanced mechanical properties in SBR persists,particularly to withstand the rigors of challenging environmental conditions.To surmount the limitations of conventional cross-linking modes,mechanical bonds stabilized by host-guest recognition are incorporated as the cross-linking points of SBR to form mechanically interlocked networks(MINs).Compared with covalently cross-linked network,the representative MIN exhibits superior mechanical performance in terms of elongation(1392%)and breaking strength(4.6 MPa),whose toughness has surged by 17 times.Dissociation of host-guest recognition and subsequent sliding motion provide an effective energy dissipation mechanism,and the release of hidden length is also beneficial to enhance toughness.Furthermore,the introduction of the rotaxane cross-links made the network more pliable and possess damping and elastic properties,which can return to initial state with one minute rest interval.We aspire that this direct introduction method can serve as a blueprint,offering valuable insights for the enhancement of mechanical properties in conventional commercial polymer materials.

Improving Thermal-oxidative Aging Resistance of Styrene-butadiene Rubber by Antioxidant Loaded Silica Aerogel

The antioxidant N-isopropyl-N'-phenyl-p-phenylenediamine(4010NA)was dissolved in ethanol and impregnated into silica aerogel(SAG)via vacuum-pressure cycles,yielding composite particles(A-N)with enhanced sustained-release and reinforcing capabilities.The effect of A-N on the mechanical properties and thermal-oxidative aging resistance of styrene-butadiene rubber(SBR)vulcanizates was investigated.TGA and BET assessments indicated that the loading efficiency of 4010NA in SAG reached 14.26%within ethanol's solu bility limit.Incorporating A-N into SBR vulcanizates significantly elevated tensile strength by 17.5%and elongation at break by 41.9%over those with fumed silica and free4010NA.Furthermore,A-N notably enhanced the thermal-oxidative aging resistance of SBR.After aging for 96 h at 100℃,the tensile strength and elongation at break of SBR with A-N sustained 70.09%and 58.61%of their initial values,respectively,with the retention rate of elongation at break being 62.8%higher than that of SBR with fumed silica and free antioxidant.The study revealed that A-N composite particles significantly inhibited the crosslinking in SBR's molecular chains,reducing hardening and embrittlement during later thermal-oxidative aging stages.

Insights into the Payne Effect of Carbon Black Filled Styrene-butadiene Rubber Compounds

As a widely used reinforcing filler of rubber, carbon black(CB) often enhances the nonlinear Payne effect and its mechanism still remains controversial. We adopt simultaneous measurement of rheological and electrical behaviors for styrene-butadiene rubber(SBR)/CB compounds and CB gel(CBG) during large deformation/recovery to investigate the contribution of conductive CB network evolution to the Payne effect of the compounds. In the highly filled compounds, the frequency dependence of their strain softening behavior is much more remarkable than that of their CB network breakdown during loading, while during unloading the unrecoverable filler network hardly affects the complete recovery of modulus, both revealing that their Payne effect should be dominated by the disentanglement of SBR matrix. Furthermore,the bound rubber adjacent to CB particles can accelerate the reconstruction of continuous CB network and improve the reversibility of Payne effect. This may provide new insights into the effect of filler network, bound rubber, and free rubber on the Payne effect of CB filled SBR compounds.

New Fabrication and Mechanical Properties of Styrene-Butadiene Rubber/Carbon Nanotubes Nanocomposite

A novel technology to prepare styrene-butadiene rubber （SBR）/carbon nanotubes （CNTs） composites was developed by combining a spray drying method and a subsequent mechanical mixing process. The cross-linking degrees of the vulcanized composites increased gradually with the additive CNTs contents. By comparing with those of the pure SBR composites, the mechanical properties such as tensile strength, tear strength and hardness of the composites filled with CNTs at certain contents were dramatically improved almost by 600%, 250% and 70%, respectively. The fabrication of the CNTs filled with SBR composites by combination of the spray drying method and subsequent mechanical mixing process was effective for enhancing the reinforcement effects of CNTs in rubbers. The novel technology can also open a new route for the modification and reinforcement on the nanocomposites with large amount of CNTs.

Synthesis and performance of miktoarm star copolymers of styrene and butadiene

A novel multifunctional macromolecular organolithium initiator （PD-Sn-（RLi）3） was prepared via living anionic polymerization and used for the synthesis of miktoarm star copolymers in cyclohexane. The average molecular weight, polydispersity index, microstructure and unit composition of the miktoarm star copolymers were characterized with GPC and 1H-NMR. Performances of the miktoarm star styrene-butadiene rubbers were investigated in comparison with those of the blend rubbers such as the tin-coupled star-shaped random copolymers of styrene-butadiene rubber（S-SBR）/natural rubber （NR） blend rubber and S-SBR/Cis-1, 4-polybutadiene rubber （Cis-BR） blend rubber.

A rheological method for selecting nano-kaolin powder as filler in SBR rubber

This paper shows that the stiffness ofstyrene-butadiene solid rubber with added kaolin powder is related to the yield stress of kaolin dispersion in liquid polybutadiene rubber up to the percolation threshold. For five kinds of kaolin powder, the value of τ° spans the range of 100-430 Pa, while the corresponding compressive elastic constant of SBR varies from 12 to 21 MPa. A relationship between τ° and △E^i^＊/ER^＊ is proposed. Critical examination of these data infers that kaolin powder dispersed in solid rubber matrix acts as an additive which decreases the random movement of the polybutadiene chains. Consequently, dispersions of nano-particles in liquid and in solid SBR are considered to be related, thus leading to a theological method for selecting nano-particles as fillers in solid SBR.