硅烷偶联剂对SSBR/SiO_2混炼胶体系动态流变行为的影响

研究了高填充白炭黑(SiO2)补强溶液聚合丁苯橡胶(SSBR)混炼胶体系的动态流变特性,分别考察了在2个混炼温度(120℃、160℃)下添加3种不同偶联剂(TESPT、TESPD、NXT)对其体系中SiO2粒子表面改性的效果.结果表明,在较低混炼温度下添加偶联剂,不利于SiO2粒子表面改性.在较高混炼温度下,偶联剂TESPT、PESPD、NXT均对SiO2粒子表面有改性效果,但同时引起混炼胶不同程度的焦烧,其中以TESPT最明显.随SiO2粒子表面改性程度的提高,出现“Payne效应”的临界应变(γc)值以及低频率(ω)区域lgG′-lgω曲线的斜率值均增大,反映出偶联剂对SiO2与SSBR相互作用的促进以及SiO2粒子分散的改善.     

Structure and properties of star‐shaped solution‐polymerized styrene‐butadiene rubber and its co‐coagulated rubber filled with silica/carbon black‐I: morphological structure and mechanical properties

The morphological structure and mechanical properties of the star‐shaped solution‐polymerized styrene‐butadiene rubber (SSBR) and organically modified nanosilica powder/star‐shaped SSBR co‐coagulated rubber (N‐SSBR) both filled with silica/carbon black (CB) were studied. The results showed that, compared with SSBR, silica powder could be mixed into N‐SSBR much more rapidly, and N‐SSBR/SiO₂ nanocomposite had better filler‐dispersion and processability. N‐SSBR/SiO₂/CB vulcanizates displayed higher glass‐transition temperature and lower peak value of internal friction loss than SSBR/SiO₂/CB vulcanizates. In the N‐SSBR/SiO₂/CB vulcanizates, filler was dispersed in nano‐scale resulting in good mechanical properties. Composites filled with silica/CB doped filler exhibited more excellent mechanical properties than those filled with a single filler because of the better filler‐dispersion and stronger interfacial interaction with macromolecular chains. N‐SSBR/SiO₂/CB vulcanizates exhibited preferable performance in abrasion resistance and higher bound rubber content as the blending ratio of silica to CB was 20:30. Copyright © 2008 John Wiley & Sons, Ltd.     

橡胶-填料相互作用对丁苯橡胶/白炭黑复合材料性能的影响

本文研究了硅烷偶联剂原位改性白炭黑对溶聚丁苯橡胶(SSBR)性能的影响,结果表明,通过哈克转矩流变仪对含有偶联剂的SSBR/白炭黑混炼胶进行原位热处理后可明显减弱混炼胶的Payne效应,改善白炭黑在橡胶基体中的分散.原位热处理方法能够明显提高硫化胶的300%定伸应力,降低动态压缩温升,同时可使硫化胶在0℃附近具有较高的损耗因子(tanδ),60℃附近具有较低的tanδ.对不同聚合方式得到的丁苯橡胶,即溶聚丁苯橡胶与乳聚丁苯橡胶(ESBR)/白炭黑复合材料的力学性能及动态力学性能进行了研究,结果表明,白炭黑在SSBR2305中分散效果优于在ESBR1502中;采用偶联剂原位改性白炭黑可以使SSBR2305硫化胶获得与ESBR1502硫化胶相当的物理机械性能,更理想的动态力学性能,从而得到力学性能、抗湿滑性、滚动阻力及耐磨性更加均衡的理想轮胎材料.通过对具有不同偶联效率的SSBR/白炭黑体系的微观结构与性能研究发现,随偶联效率的增加,其结合橡胶含量增加,Payne效应减弱;高偶联效率的S-SBR具有较低的动态压缩温升及较好的耐磨性.     

The effect of accelerator contents on the vulcanizate structures of SSBR/silica vulcanizates

Physical properties of rubber compounds are affected by the filler–rubber interaction, filler dispersion in the rubber matrix, and cross-link structure formed during vulcanization. In particular, the cross-link structure is closely related to the physical properties of vulcanizates and has been analyzed using the swelling test and Flory-Rehner equation. However, the relationship between the structure and physical properties of vulcanizates cannot be explained by the cross-link density obtained using these methods. The cross-link density obtained from the swelling test is a complex result of the filler–rubber interaction occurring during the compounding as well as the chemical cross-link structure formed by sulfur during the vulcanization. Moreover, the rubber vulcanizates that use silica need to be separately analyzed for each factor as its physical properties are affected more by the filler–rubber interaction than by carbon black. Therefore, this study determines the factors that contribute to the total cross-link density of vulcanizates into chemical cross-link density and filler–rubber interaction via quantitative analysis using the swelling test results and Flory-Rehner and Kraus equations. The vulcanizates used for the analysis were carbon black-filled and silica-filled non-functionalized SSBR compounds with varying cure accelerator for each filler loading. Their chemical cross-link density was measured and the effect of the filler–rubber interactions on their mechanical and dynamic viscoelastic properties was investigated. Furthermore, the relationship between the structure and physical properties of rubber vulcanizates was elucidated.     

Influence of the silanes on the crosslink density and crosslink structure of silica-filled solution styrene butadiene rubber compounds

The effects of three silane coupling agents, triethoxy(octyl)silane (TEOS), bis[3-(triethoxysilyl)propyl]disulfide (TESPD), and bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT) on the filler-rubber interaction, crosslink density and crosslink structure of the silica-?lled solution styrene butadiene rubber (SSBR) vulcanizates were studied. High dispersion silica, 7000GR, was used as the ?ller, and the loading range was varied from 0 to 60 phr. Crosslink density was measured by the swelling method. Experimental results showed that Kraus plot can be applicable to the silica-filled SSBR vulcanizates to separate filler-rubber interaction from the measured swelling data. Filler-rubber interaction increased by increasing sulfur rank in the silane as TEOS < Silica without silanes < TESPD < TESPT. Sulfurless silane, i.e. TEOS, only worked as a covering agent for hydrophobating silica surface. Silica without silane show high filler-rubber interaction than TEOS system because chain-end functionalized SSBR was used in this study. Unfilled system showed similar amounts of poly, di, and mono-sulfidic crosslinks. On the contrary to this, all of the silica-filled vulcanizates showed high mono-sulfide contents due to longer cure time.