绿色轮胎用高性能丁二烯基橡胶合成技术进展

Progress in the synthesis of high performance butadiene-based elastomer for green tires

绿色轮胎在节能、环保、安全方面的优势使其成为当今世界轮胎的发展趋势.稀土(钕系)顺丁橡胶(Nd-BR)和溶聚丁苯橡胶(SSBR)是制造绿色轮胎胎面重要的合成橡胶原材料.本文主要介绍绿色轮胎发展现状、Nd-BR合成技术进展、工业化产品及新型丁二烯基共聚橡胶合成技术进展,着重介绍微观结构、拓扑结构及共聚组成对其加工性能、物理机械性能及动态力学性能的重要贡献,为制造绿色轮胎用高性能合成橡胶原材料提供参考.顺式结构含量在98%以上的Nd-BR具有更加优异的物理机械性能及动态力学性能,可有效降低轮胎生热、滚动功率损耗、压缩永久变形及终动压缩率,降低轮胎磨耗并延长轮胎寿命,更适用于制造绿色轮胎.长链支化结构Nd-BR可以改善生胶的抗冷流性能、加工性能及与填料的混合性能,进一步提高硫化胶的物理机械性能和动态力学性能.高顺式含量丁苯无规共聚弹性体及立构规整丁二烯/苯乙烯共聚物集高顺式聚丁二烯橡胶、丁苯橡胶的优异性能于一体,综合性能提高,冰雪路面抓着力提高,滚动阻力下降,符合高性能绿色轮胎对合成橡胶原材料的要求.

The advantages of green tires in energy saving,environmental protection and safety make it become the trend of the tire. Neodymium-based high cis-polybutadiene rubber（Nd-BR） and solution styrene-butadiene rubber（SSBR） are two important raw materials for manufacturing green tire. Situation of green tire,progress in the synthesis of Nd-BR and butadiene-based copolymer,current status of some industrialized Nd-BR and development of rare earth catalysts have been reviewed,which is helpful for the production of high-performance synthetic rubber for green tire. The main Nd-BR producers are Lanxess,Versalis,ChiM ei,Kumho,Japan Synthetic Rubber,Nizhnekamskneftekhim,Goodyear,Firestone,Sibur,Synthos and Karbochem. The commercial Nd-BR products are normally divided into three grades according to the various Mooney viscosity（ML1＋4^100°C） of around 45,55 and 63. Furthermore,the effect of microstructure,composition and topology on processing property,mechanical properties and dynamic mechanical properties of Nd-BR and butadiene-based copolymer were introduced. Stereo-specificity is a key factor for the performance of Nd-BR product. The results of the characteristic relaxation time（？）,yield stress（Ty）,300% modulus（T300）,and T300/Ty for various Nd-BR indicated that the increase of cis-1,4 content was benefit for the improvement of processing properties. The decrease of（35）G？ with an increase in cis-1,4 content indicated that Nd-BR with high cis-1,4 content of around 98.5% behaved low Payne effect,which was mainly attributed to the strong interaction between polymer and filler. Excellent processing performance means that the addition of fillers to rubber compounds are easy to scatter. These can short the mixing time and produce the highest quality product with the lowest possible cost. Nd-BR products with higher cis-1,4 content possess the superior mechanical properties and dynamic mechanical properties of BR vulcanizates,such as modulus at 300%,tensile strength,abrasion resistance,heat build-up,compression properties and rolling resistance and wet-skid resistance. Nd-BR which possesses cis-1,4 content of more than 98% has more excellent mechanical properties,dynamic mechanical properties,and is suitable for green tire as raw materials for the excellent properties such as low heat build-up,rolling power loss,compression deformation,compression ratio and abrasion loss. Long chain branched Nd-BR possesses an improved cold flow resistance,processing performance and mixing performance with the filler. High cis-1,4 butadiene/styrene elastomer and stereospecfic butadiene/styrene copolymer combine excellent performance of Nd-BR and SBR. Both mechanical performance and skid resistance ability on ice road were increased,while rolling resistance was decreased for the vulcanizates. These excellent properties of the synthetic rubbers are beneficial for manufacture of high-performance green tires.