高性能集成橡胶SIBR的合成与应用

The synthetic methodology of integral rubbers (SIBR) with high-performances is presented systematically in this research, through extending traditional lithium SIBR to ESIBR or rare-earth SIBR. The goal is to establish the efficient synthetic methods for SIBR based on lithium initiator, emulsion polymerization and rare earth catalyst. Through the methodological research of lithium SIBR, an optimization design is finished to improve integral rubber performances in wide brand and wide temperature range. Further, SIBR rubber shows more trans-forms by emulsion polymerization or reflects its high cis-structures with rare earth catalyst. An integrated research is to develop which it can benefit from the advantage of three kinds of integral rubbers, such as lithium SIBR, ESIBR or rare-earth SIBR. Based on methodological research, a synthesis method is established to lithium SIBR and their application in ABS resin is also given. More, novel ESIBR is to study by emulsion polymerization and an applied study is followed in ABS resin. To further study, rare-earth SIBR is also to study for developing a new situ polymerization on ABS resin. This research aims at creating a new generation ABS resin with high performance on toughening and reinforcing, which systematically studies are followed on their new morphological structures and toughening mechanisms, a novel situ synthesis method for ABS resin is developed finally.

围绕高性能集成橡胶SIBR合成方法开展全面系统地研究，将传统锂系集成橡胶的概念拓展到乳聚集成橡胶以及稀土集成橡胶领域，建立高性能锂系集成橡胶、乳聚集成橡胶、稀土集成橡胶三种集成橡胶的合成方法。通过锂系集成橡胶合成方法的研究，优化设计合成宽频带宽温域集成橡胶；与锂系集成橡胶相比，乳聚集成橡胶具有较高的反式结构，稀土集成橡胶具有较高的顺式结构，三种集成橡胶结构特征各异，性能优势互补。立足于合成方法研究，建立基于锂系集成橡胶、连续本体法ABS树脂，基于乳聚集成橡胶胶乳、乳液本体法ABS树脂，基于稀土集成橡胶、原位本体法ABS树脂三种高性能ABS树脂的合成方法。创制新一代高性能超高抗冲击强度ABS树脂，系统地研究ABS树脂新的形态结构和新的增韧机理，开发原位本体法ABS树脂全新的合成方法。

成功合成了硅氧功能化DPE衍生物、炔基功能化DPE衍生物、胺基功能化DPE衍生物、羟基功能化DPE衍生物，并深入探究了各自的活性阴离子共聚合特性，为制备功能化聚合物提供了理论基础。设计合成非官能化聚苯乙烯、单端硅氧官能化聚苯乙烯、链中硅氧聚苯乙烯三种硅氧官能化聚苯乙烯，发现硅氧功能基团能明显改善白炭黑分散性。通过多种聚合加料方法，将上述DPE衍生物成功引入到了聚合物主链中，合成了多种链中、链端功能化的SIS、SBC、SIBR共聚物，实现了对材料性能的大幅度调节。设计合成了一系列胺基苯乙烯单体，采用单茂钪催化得到一系列不同立构规整的胺基苯乙烯均聚物，并以高间规胺基苯乙烯为载体得到sPDMAS-Pd纳米复合物。并且采用单茂钪催化得到一系列胺基功能化丁苯共聚物，以二乙烯基类单体为偶联剂，成功制得立构规整的星形丁苯共聚物以及胺基功能化丁苯共聚物。采用三元钕系催化体系制得胺基功能化苯乙烯-异戊二烯共聚物。采用单茂钪催化得到一系列不同组成的窄分布胺基功能化苯乙烯-丁二烯-异戊二烯三元共聚物。采用单茂钪配合物考察了丙烯与乙烯、苯乙烯、异戊二烯的二元和三元共聚合规律，获得了一系列组成可控、结构新颖的共聚物。进行具有可逆交联功能的乙丙橡胶的催化合成研究，获得了具有吸水性能的乙丙橡胶水凝胶。通过新型多功能自由基聚合引发剂的设计合成，实现了对丁二烯/异戊二烯/苯乙烯三元乳聚集成橡胶分子结构、序列组成的有效调控。深入探究了乳聚集成橡胶胶乳粒径大小与分布的调控方法及其对ABS树脂结构与性能的影响规律。