铁系催化剂催化共轭二烯烃（共）聚合的研究

发布时间：2018-02-05 22:30

  本文关键词： 铁催化剂 1 3-丁二烯 异戊二烯 聚丁二烯 共聚　出处：《扬州大学》2017年硕士论文　论文类型：学位论文

【摘要】：目前,作为替代天然橡胶的选择,合成橡胶主要在主要用于制造轮胎。制造兼具安全性及高使用性能的轮胎时,要求作为原料材料的合成橡胶同时具有抗湿滑性和低滚动阻力两种性能。众所周知,轮胎的抗湿滑性和滚动阻力是两种相互矛盾的性能。丁苯橡胶抗湿滑性能好,但滚动阻力大;顺丁橡胶具有优异的耐磨性和弹性,但抗湿滑性能差,因此通过顺丁橡胶与丁苯橡胶并用已成为兼顾高抗湿滑性和低滚动阻力一种有效途径。此外,1,2-结构的聚丁二烯不但具有优良的牵引性能、拉伸强度、抗撕裂性、低滚动阻力,而且其抗湿滑性与丁苯橡胶相当,故而,控制1,2-结构的聚丁二烯在合成轮胎用橡胶时异常重要。催化剂在控制合成1,2-聚丁二烯至关重要,并且催化剂种类繁多。其中铁系催化剂因含量丰富、经济性和环境友好性,在合成橡胶催化领域得到了越来越多的关注,但铁系催化剂合成1,2-聚丁二烯,由于熔点较高,制约了其发展。为了解决这一问题,本文着力研究以铁系催化剂催化,配位聚合制备丁二烯、异戊二烯共聚物及丁二烯均聚物,并得到主要结论如下:(1)以异辛酸铁/三异丁基铝/亚磷酸二乙酯催化组分(Fe(2-EHA)3/Al(i-Bu)3/DEP)在较高温度(50℃)下、正己烷溶液中合成了丁二烯、异戊二烯共聚物。通过控制催化剂组份的配比,可制备两种不同的共聚物,即含间同1,2-结构聚丁二烯链段或无规1,2-结构聚丁二烯链段的共聚物。其中含间同1,2-结构的共聚物熔点在155℃。并且此催化体系成功制备了高1,2-结构和3,4-结构的丁二烯异戊二烯共聚物。其中异戊二烯链节中3,4结构含量为56.5%,而丁二烯链节中1,2结构含量为51.1%。(2)以异辛酸铁/(三异丁基铝、三乙基铝)/亚磷酸二乙酯催化组分(Fe(2-EHA)3/[Al(i-Bu)3、AlEt3]/DEP),在较高温度(50℃)下、正己烷溶液中,合成了丁二烯均聚物。该体系在用混铝做助催化剂下仍保持单一活性中心和高1,2选择性。通过调节两种助催化剂的比例,得到一系列具有不同微观结构的1,2丁二烯均聚物。丁二烯的熔点随助催化剂中乙基铝摩尔含量的增加而下降,从168.7℃降低到123.2℃,从而增加了聚丁二烯的可加工性。
[Abstract]:At present, as an alternative to natural rubber, synthetic rubber is mainly used in the manufacture of tyres, the manufacture of tyres with both safety and high performance. It is well known that synthetic rubber, which is used as raw material, has both wet-slip resistance and low rolling resistance. The wet skid resistance and rolling resistance of tire are two kinds of contradictory properties. Cis-butadiene rubber has excellent wear resistance and elasticity, but its wet-slip resistance is poor, so the combination of cis-butadiene rubber and styrene-butadiene rubber has become an effective way to give consideration to both high wet-slip resistance and low rolling resistance. The 2-structure polybutadiene not only has good traction properties, tensile strength, tear resistance, low rolling resistance, but also its wet-slip resistance is equivalent to that of styrene-butadiene rubber, so control 1. 2-structure polybutadiene is very important in the synthesis of rubber for tire. Catalyst is very important in controlling the synthesis of 1 / 2-polybutadiene, and there are many kinds of catalysts, among which the iron catalyst is rich in content. Economy and environmental friendliness have attracted more and more attention in the field of synthetic rubber catalysis, but the high melting point of iron catalyst for the synthesis of 1h2- polybutadiene has restricted its development. In order to solve this problem. In this paper, the preparation of butadiene, isoprene copolymer and butadiene homopolymer by coordination polymerization catalyzed by iron catalyst was studied. The main conclusions are as follows: (1) Fe _ 2O _ 2-EHAN _ 3 / Al _ 2O _ 3 / DEP _ (3 / DEP) was used to catalyze Fe _ 2O _ 2-EHA _ 2 / diethyl phosphite at higher temperatures (P < 0.05). 50 鈩，

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