Synthesis of Stereoregular Living Polymers from Substituted Acetylenes and Design of Polymerization Catalysts

取代乙炔合成立构活性聚合物及聚合催化剂的设计

基本信息

批准号：
05650897
负责人：
MASUDA Toshio
金额：
$ 1.41万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

项目摘要

The molecular weight distribution (MWD) and steric structure of a polymer should be well defined so that the polymer would exhibit excellent properties and functions. The present study deals with the synthesis of stereoregular living polymers from substituted acetylenes and development of novel catalysts useful for such purposes.1. Stereospecific living polymerization of tert-butylacetylene (tBA) by Mo-based catalysts-The polymerization of tBA by the MoOCl_4-n-Bu_4Sn-EtOH (1 : 1 : 1) catalyst led to living and stereoregular polymers with narrow MWDs (Mw/Mn=1.12 ; cis 97%) . The living nature of this polymerization was confirmed by the fact that, in toluene at 0 and -30ﾟC,the Mn of the polymer increases in direct proportion to monomer consumption, while the MWD remains narrow. The cis content of polymer was evaluated by ^<13>C NMR spectroscopy. Similar but somewhat inferior results were obtained with the MoCl_5-n-Bu_4Sn-EtOH (1 : 1 : 1) system (Mw/Mn=1.24 ; cis 90%) .2. Synthesis of a cis-rich, living poly [ (o-methylphenyl) acetylene] (oMePA) -Polymerization of oMePA by MoOCl_4-n-Bu_4Sn-EtOH catalyst in toluene at 0ﾟC provided a cis-rich living polymer ; cis 77%, Mw/Mn=1,21. The polymerization at-30ﾟC gave results similar to those for 0ﾟC,whereas the polymer obtained at 30ﾟC exhibited a broader MWD and a lower cis content.3. Development of MoOCl_4-based new catalyst systems for living polymerization-In this study, we tried to develop new catalyst systems for the living metathesis polymerization using Et_3Al as cocatalyst. [o- (Trifluoromethyl) phenyl] acetylene was used as monomer, and polymerizations were carried out in anisole at 30ﾟC.Eventually, a polymer with very narrow MWD (Mw/Mn=1.02) could be obtained by use of MoOCl_4-Et_3Al-EtOH at 1 : 1 : 4 ratio.

聚合物的分子量分布（MWD）和空间结构应得到很好的定义，以便聚合物表现出出色的特性和功能。本研究涉及从取代的乙酰烯烯和新型催化剂的发育中的立体牙性活聚合物的合成。1。 MOOCL_4-N-N-N-BU_4SN-ETOH（1：1：1）通过MO基于MO的催化剂对TERT叔丁基乙烯（TBA）的立体生存聚合 - TBA的聚合导致了催化剂的催化剂，导致了生命和立体的聚合物（MW/MN = 1.12; CIS 977％）。这种聚合的生命性是通过以下事实证实的：在0和-30℃的甲苯中，聚合物的MN与单体消耗成正比，而MWD保持狭窄。通过 ^<13> C NMR光谱评估聚合物的顺式含量。使用MOCL_5-N-N-BU_4SN-ETOH（1：1：1）系统（MW/MN = 1.24; CIS 90％）.2获得了类似但有些劣等的结果。2。通过MOOCL_4-N-N-N-BU_4-N-N-BU_4-N-BU_4SN-ETOH催化剂在0 c时，合成了富含顺式的富含顺式的聚聚（O-甲基苯基）乙炔]（Omepa） - Omepa的聚合物。顺式77％，MW/MN = 1,21。聚合AT-30 c的聚合得出的结果类似于0℃的结果，而在30°C下获得的聚合物暴露了更宽的MWD和较低的顺式含量。3。基于MOOCL_4的基于MOOCL_4的新型催化剂系统用于生存聚合化，我们试图使用ET_3AL作为Cocatalyst开发新的催化剂系统，以用于生存分解聚合。 [o- (Trifluoromethyl) phenyl] acetylene was used as monomer, and polymerizations were carried out in anisole at 30ﾟC.Eventually, a polymer with very narrow MWD (Mw/Mn=1.02) could be obtained by use of MoOCl_4-Et_3Al-EtOH at 1:1:4 ratio.