【作者】 李杨；

【导师】 杨锦宗； 顾明初； 洪定一；

【作者基本信息】 大连理工大学 ， 精细化工， 2000， 博士

【摘要】 近年来烷基锂引发剂的发展已从单锂转向双锂、多锂和混合锂方向发展，而其中双锂引发剂由于近年来在非极性溶剂中的溶解问题得以解决，发展非常迅速，日益引起人们普遍关注。双锂引发剂用于制备锂系聚合物具有单锂引发剂无法比拟的优势，其最大特点在于聚合物可以双端引发、增长、终止，可以制备结构对称的聚合物，加之阴离子活性聚合的特点，双锂引发丁二烯、异戊二烯、苯乙烯聚合领域已成为锂系聚合物新的技术增长点。美国DOW化学公司的双锂引发剂是目前已知综合性能最为理想的工业化产品，但仍存在诸如溶剂体系不单一、引发速度较慢、溶解性能不理想、制备时间较长等问题。 本文在确保双官能团烷基锂引发剂具有很好的溶解性能、均一的官能度、较快的引发速度、溶剂体系单一、制备工艺简单、合成时间短、成本低的前提下，研制了两种双锂引发剂，其一为双烯加成型双锂齐聚物，各项技术指标达到国际水平，并已形成专利技术；其二为双卤代烷烃取代型双锂齐聚物，对双锂的认识从传统观念上有了新的突破，从工业化实用角度出发，从产品立足于满足使用要求出发，从现实国产化条件出发，给双卤代烷烃取代型双锂注入新的生机。本文始终贯穿高分子设计思想，以双锂为引发剂、环己烷为溶剂、二乙二醇二甲醚/四甲基乙二胺为极性添加剂、立足于三种大宗单体—丁二烯、异戊二烯、苯乙烯，制备了聚丁二烯、聚异戊二烯、1，2-1，4-1，2-立构三嵌段聚丁二烯、3，4-1，4-3，4-立构三嵌段聚异戊二烯、对称型双端过渡态丁二烯/苯乙烯嵌段共聚物、对称型双端过渡态异戊二烯/苯乙烯嵌段共聚物、对称型双端过渡态丁二烯/异戊二烯/苯乙烯嵌段共聚物，并对聚合反应过程动力学行为、热效应进行了较为系统的研究，对聚合物的微观结构、序列结构、形态结构进行了较为深入的研 摘要究，同时对聚合物的物理机械性能进行了较为全面的研穴。 纵观全文，结论如下：l 双卤代烷烃取代型双理齐聚物是一种极具工业化前景的引发剂，其原料价廉易得、制备工艺简单，使用极性较低的试剂乙醚为溶剂，严格控制引发剂的浓度不低于04N，可不必按传统方式进行溶剂晋换，而确保聚合物的微观结构无较大变化，制备工艺极大简化，引发剂官能度箔以保证，采用齐聚技术可确保双钾的稳定和溶解性能，聚丁二烯的1，2－结构含量、聚异戊二烯的 3，4－结构含量均小于 15％，产品性能均可满足使用要求。对双卤代烷烃取代型双理有必要进行重新评价和认识，实事求是地对双狸引发剂是否固执追求无醚化问题进行客观分析。2以双理为引发剂，制备了聚丁二烯、聚异戊二烯、立构三嵌段聚丁二烯。立构三嵌段聚异戊二烯、对称型双端过渡态丁二烯／苯乙烯嵌段共聚物、对称型双端过渡态异戊二烯／苯乙烯嵌段共聚物、对称型双端过渡态丁二烯／异戊二烯／苯乙烯嵌段共聚物，结果表明：采用双卤代烷烃取代型双理为引发剂，可以实现对聚合物分子量的准确设计，分子量分布较窄并呈正态分布。3 在国内外首次以双钾为引发剂成功地制备了立构三嵌段聚异戊二烯、对称型双端过渡态丁二烯／异戊二烯／苯乙烯嵌段共聚物，并对两类新型聚合物的结构和物性进行了系统研究，发现具有双端过渡态的丁二烯／异戊二烯／苯乙烯嵌段共聚物均具有优良的拉伸性能，在适宜的单体配比下，断裂强度、断裂伸长率可达到较佳的平衡。4采用mC和动态粘弹谱等技术，在国内外首次对丁二烯、异戊二烯立构三嵌段聚合物和对称型双端过渡态丁二烯、异戊二烯、苯乙烯嵌段共聚物的微观相分离结构进行研究，发现在适宜的结构参数下丁二烯、异戊二烯立构三嵌段聚合物具有微观相分离结构，存在两个玻璃化转变温度，对札 2 人过理丁人学汹－DU门c生学位沦义型双端过渡态丁二烯、异戊二－烯、苯乙烯嵌段共聚物只有微观川分离纸构，在适宜的结构参数下存在三个玻璃化转变温度，即存在苯乙烯聚合物1＆段相、共轭二烯烃聚合物嵌段川1、本乙烯／共轭二烯烃过渡态人聚物1＆段州，这在国内外尚属首次发现。5在国内首次对以双理为引发剂的丁二烯、异戊二烯、苯乙烯均聚和共聚过程的聚合反应动力学行为、聚合反应过片热效应进行了系统研究，并对聚合物的微观结构、序列结构进行了系统＊究。6成功地研制出双烯加成型双挫齐聚物引发剂，彻底解决了双挫制备体系和聚合体系溶剂一致性问题，通过加入适量的极性添加剂、控制双理齐聚物的齐聚度很好地解决了双鲤制备反应速度较慢、溶解性能不理想、引发活性较低等瓶颈问题，并形成专有技术，获得专利权，但山于双烯加成型双钾制备工艺较复杂、控制步骤较多、成本较高、原材料立足囚内还有一些问题需要解决，因此，与实用型的双卤代烷烃取代型双埋相比较，双烯加成型双理的工业化时间安排可暂列其后。7 以双?更多还原

【Abstract】 During the last few years, the focus on development of alkyllithium initiator gradually shafted from monolithium to dilithium or multilithium or mixed-lithium initiators. Among them, the dilithium initiator was developed very fast and increasingly attracted extensive attentions since the dissolution problem of the dilithium initiator in non-polar solvent had been overcome. Dilithium initiator possessed the incomparable advantages over monolithium in preparing lithium-initiated polymers, among them, the most important characteristic was that the symmetrical polymer could be synthesized when the initiation, propagation and termination of the chain occurred at two ends at the same time. Combined with the features of anionic active polymerization, the dilithium initiator already created a new growth point in technology of lithium-initiated polymer through its application in the ternary copolymerization field of butadiene-isoprene-styrene. At present, the dilithium initiator manufactured by Dow Company, USA, was known as the best commercialized product in comprehensive properties, however, there still existed problems which remain to be resolved, such as non-single solvent system, slow initiation speed, inferior solubility and long preparation time, Under the precondition of ensuring the advantages such as good solubility, uniform functionality, fast initiation speed, single solvent system, simplified preparation technology, short synthesis time and low cost, the present thesis developed two kinds of dilithium initiators. One was the dilithium oligomer prepared via addition reaction of diene, named as diene addition type dilithium; the novel initiator reached the current international level in the technical indexes and formed proprietary technology. The other was dilithium oligomer prepared through substitution reaction of dihalogenated alkane, named as dihalogenated alkane substitution type dilithium. Thanks to the breakthrough in the understanding against the traditional concept of dilithium, the development of the dihalogenated alkane substitution type dilithium was injected with the fresh vigor proceeding from facilitating the practical application on industrial scale, making the initiator meet the requirements in application and realizing the localization of the initiators. Based on the philosophy of macromolecular design throughout the thesis, the author fully utilized the monomers of butadiene, isoprene and styrene produced in bulk to synthesize a series of novel copolymers with the dilithium as initiator, cyclohexane as solvent and diethylene glycol dimethyl ether / tetramethyl ethylenediamine as polar additive. Following were the typical block copolymers as prepared, including the polybutadiene, polyisoprene, 1,2-1,4-1 ,2-stereo-triblock polybutadiene, 3,4-1 ,4-3,4-stereo-triblock polyisoprene, symmetrical two-end tapered block copolymer of butadiene/styrene, symmetrical two-end tapered block copolymer of isoprene/styrene and symmetrical two-end tapered block terpolymer of butadiene/isoprene/styrene. Furthermore, this thesis also studied systematically the kinetic behaviour and heat effect in the polymerization process. The microstructure, sequential arrangement and morphology as well as the mechanical properties of the polymers mentioned above were also investigated in detail. From the summary of the full thesis, it came to the conclusions that: 1. The dihalogenated alkane substitution type dilithium was one kind of initiator that possessed pret更多还原