保护性基团引发剂负离子法制备端羟基聚丁二烯的研究
发布时间：2018-07-14 13:14
【摘要】： 本文首先合成了含保护性基团的新型引发剂3-(叔丁基二甲基硅氧烷基)-1-丙基锂,以该有机锂化合物为引发剂引发丁二烯聚合并制备了端羟基聚丁二烯。与常用的双锂引发剂相比,可以有效的避免在封端时出现的假凝胶现象。具体方法包括：用环氧乙烷封端、二溴乙烷偶联,酸化水解处理制备线型端羟基聚丁二烯；用四氯化硅、二乙烯基苯(DVB)偶联,酸化水解制备多端羟基聚丁二烯。 在丁二烯合成过程中,通过添加四氢呋喃为结构调节剂,研究了此体系对聚丁二烯的微观结构的控制。通过GPC、1H-NMR测试结果表明：丁二烯聚合在30℃下,不加入调节剂时,反应20小时左右,1,4-结构含量较高,可达92.1%,调节剂的加入可使1,4-结构含量显著下降。同时聚合物的分子量大小与设计分子量接近、分子量分布较窄。对环氧乙烷封端及二溴乙烷偶联制备线型端羟基聚丁二烯羟值分析,平均官能度接近2；四氯化硅及DVB偶联反应制备多端羟基聚丁二烯,偶联剂的加入量增加偶联效率增大。在2L反应釜聚合与250ml聚合瓶中相比,偶联剂采用分两次加入方式偶联效率较高,单臂分子量设计15000,偶联剂四氯化硅用量是计量1.2倍时,偶联效率可达95%,官能度达3.8,[DVB]/[Li]=5,偶联效率达到了88.7%,平均臂数为6.1。 对TDI作为交联剂与星型丁羟胶反应进行了初步研究,并对制得的羟丁型聚氨酯材料进行了DMTA及物理力学性能测试,结果表明星型丁羟胶([DVB]/[Li]=5)单臂分子量为15000时制得的羟丁型聚氨酯,拉伸强度可达0.8MPa,断裂伸长率为830%,0℃的Tgδ值可达0.243,60℃的Tgδ值可达0.235。
[Abstract]:In this paper, a new initiator 3- (tertiary Ding Ji dimethylsiloxane) -1-propyl lithium with protective group was synthesized. The organic lithium compound was used as initiator to initiate the polymerization of butadiene and to prepare hydroxy-terminated polybutadiene. Compared with the commonly used bislithium initiator, the pseudogel phenomenon can be avoided effectively. The specific methods include: synthesis of linear hydroxyl terminated polybutadiene by ethylene oxide sealing, coupling of dibromoethane and acidizing hydrolysis, coupling with silicon tetrachloride and divinylbenzene (DVB), and preparation of multihydroxyl polybutadiene by acidizing hydrolysis. The control of the microstructure of polybutadiene was studied by adding tetrahydrofuran as structure regulator during the synthesis of butadiene. The results of GPC-1H-NMR showed that when butadiene was polymerized at 30 鈩，
本文编号：2121766
[Abstract]:In this paper, a new initiator 3- (tertiary Ding Ji dimethylsiloxane) -1-propyl lithium with protective group was synthesized. The organic lithium compound was used as initiator to initiate the polymerization of butadiene and to prepare hydroxy-terminated polybutadiene. Compared with the commonly used bislithium initiator, the pseudogel phenomenon can be avoided effectively. The specific methods include: synthesis of linear hydroxyl terminated polybutadiene by ethylene oxide sealing, coupling of dibromoethane and acidizing hydrolysis, coupling with silicon tetrachloride and divinylbenzene (DVB), and preparation of multihydroxyl polybutadiene by acidizing hydrolysis. The control of the microstructure of polybutadiene was studied by adding tetrahydrofuran as structure regulator during the synthesis of butadiene. The results of GPC-1H-NMR showed that when butadiene was polymerized at 30 鈩，
本文编号：2121766
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