【作者】 史云龙；

【导师】 刘炼；

【作者基本信息】 大连理工大学 ， 材料学， 2005， 硕士

【摘要】 高顺式聚丁二烯橡胶具有高弹性、优异的耐磨性、良好的耐热、耐低温、抗龟裂、滞后损失小以及优良的动态性能等特点。采用镍系催化剂制备高顺式聚丁二烯首先由松本毅等人在1958年发现。从此，揭开了镍系引发丁二烯定向聚合的序幕。尽管用镍系引发丁二烯聚合已经有40多年的历史，但是国内外的学者对开发新的催化体系、新的催化剂配制技术的研究却一直没有间断过。本文研究了采用ZnR₂和MgR₂分别与Al（i-Bu）₃组成复合的烷基化试剂以及他们分别取代Al（i-Bu）₃作为烷基化试剂制备了顺丁橡胶；还对采用向Ni-Al-B三元体系添加ROH来制备高门尼的顺丁橡胶，及对其充油进行了研究；本文还研究了催化剂的预混工艺技术。通过膨胀计法和小瓶聚合实验来研究聚合反应的动力学和链转移反应，并求取了假一级表观增长速率常数和表观活化能；对有工业化前景的采用5L间歇的聚合釜实验对小瓶实验进行放大，得出中试实验所需的数据；用40L连续聚合装置进行中试实验，以获得工业试生产所需的工艺参数。通过红外光谱、DSC、GPC对聚合物进行了表征，得到了各种催化体系制备的产物的微观结构、热性能、分子量及其分布。同时还对聚合物的力学性能进行了测试。实验结果表明，ZnR₂和MgR₂分别与Al（i-Bu）₃组成复合的烷基化试剂以及他们分别取代Al（i-Bu）₃作为烷基化试剂制备顺丁橡胶，体现了与Ni-Al-B体系某些不同的特点，各有优缺点。加ZnR₂体系制备的顺丁橡胶凝胶含量低，分子量分布低而且可控，但聚合反应速率变慢；加MgR₂体系聚合反应速率加快，但是顺式含量略有降低。以ROH作为第四组分添加到Ni-Al-B体系中，可制备用于充油的高门尼粘度顺丁橡胶；实验表明，填充油的份数、充油的时间、温度对充油顺丁橡胶的力学性能都有较大的影响。催化剂预混工艺实验结果表明，预混釜的结构、催化剂的预混方式、进入预混釜的丁二烯的比例，物料在预混釜内的停留时间都对聚合反应活性和聚合物性能有很大的影响。综合上述因素，得出了最佳的预混工艺参数，确定了工业试生产的工艺包，并制备了力学性能优异且凝胶含量低的顺丁橡胶产品。更多还原

【Abstract】 High cis 1, 4- polybutadiene rubber has the character such as outstanding resilience, excellent abrasion resistance, good heat resistance, low temperature properties,good resistance to light crazing, low hysteresis and excellent dynamic properties. High cis 1,4- polybutadiene is synthesized with nickel catalyst, which was first discovered by Macitomoki et al. in 1958. And thence the prelude of orientated polymerization of butadiene with nickel catalyst system was drawn back. Although more than 40 years have passed, a lot of scholars of all of the world are still studying new catalyst systems and techniques of confecting catalyst.In this paper, ZnEt₂ and MgBu₂ as the new agent introduced into the nickel catalyst system was studied. They can compose multiple alkylating agent with Al（i-Bu）₃ or be using as an alkylating agent along substitutiting Al（i-Bu）₃. Furthermore high Mooney viscosity high cis1,4-polybutadiene BR is synthesized with Ni-Al-B-ROH and then is charged oil, which is studied. And catalyst premix crafts are also studied.Polymerization kinetics and the chain transfer reaction were investigated by the use of dilatometers and polymerizing bottles, respectively. So the superficial velocity constant of pseudo-one order reaction and the apparent activation energy are gotten. The amplification polymerization is investigated by the use of a 5L batch reactor and one continuous polymerization equipment composed by three 40L reactors, so that the parameters which commercial pre-production need are obtained. Produced polymers were mainly characterized by infrared spectrometry , DSC and GPC. The microstructure, heat capability, molecular weight and distribution of the products synthesized by vary kinds of catalyst system are determined, tooAnd the mechanical abilities of cis1, 4- polybutadiene BR are examined.The experimental results indicate that ZnEt₂ and MgBu₂ in nickel catalyst system exhibits some different characteristics from Al（i-Bu）₃. When ZnEt₂ is added into the catalyst system, content of gel in the BR becomes lower; and the molecular weight distribution decreases and is controllable; but the velocity of polymerization is slow. When MgBu₂ is added into the catalyst system, velocity of polymerization increases remarkably, however content of cis1,4- structure decreases slightly. Adding ROH into the Ni-Al-B catalyst system, it can be used to preparing high cis1, 4-polybutadiene rubber with high Mooney viscosity. The experimental results indicate that the content of oil, time and temperature of oil charging will greatly influence abilities of resulting oil-extended rubber.Experiments of catalyst premix crafts indicate that design of reactor, order of adding catalysts, the proportion of the butadiene into premixing reactor and the residence time of material all greatly influence the activity of polymerization and abilities of BR. In the end, parameters of catalyst premix crafts and the process condition of commercial pre-production are obtained. Furthermore cisl, 4- polybutadiene robber with good menchanical capabilities and low gel is prepared.更多还原