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

• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05650897/
• 关键词: Substituted Acetylene; Stereoregular Polymer; Living Polymer; Catalyst Design; tert-Butylacetylene; (o-Methylphenyl) acetylene; Stereospecific Living Polymerization; Molybdenum Catalyst; (ロ-メチルフェニル)アセチレン; 炭素13核磁気共鳴

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.

为了使聚合物具有优异的性能和功能，聚合物的分子量分布和空间结构必须得到很好的限定。本论文主要研究了由取代乙炔合成有规立构活性聚合物的方法以及用于此类聚合物的新型催化剂的开发。叔丁基乙炔（tBA）在MoOCl_4-n-Bu_4Sn-EtOH（1：1：1）催化剂上的立体定向聚合反应，得到了分子量分布窄（Mw/Mn=1.12，顺式97%）的立体定向活性聚合物。在甲苯中，0 ℃和-30 ℃时，聚合物的Mn随单体用量的增加而增加，而分子量分布（MWD）保持较窄。聚合物的顺式含量通过13 <13>C NMR光谱评估。用MoCl_5-n-Bu_4Sn-EtOH（1：1：1）体系（Mw/Mn=1.24 ;顺式90%）得到类似但稍差的结果。富顺式活性聚邻甲苯基乙炔（oMePA）的合成--在0 ℃甲苯中，MoOCl_4-n-Bu_4Sn-EtOH催化剂催化下聚合oMePA，得到顺式含量为77%，Mw/Mn= 1.21的活性聚合物。在-30 ° C下聚合得到的结果与0 ° C下的结果相似，而在30 ° C下获得的聚合物表现出更宽的MWD和更低的顺式含量。MoOCl_4基活性聚合新催化体系的开发--以Et_3Al为助催化剂，尝试开发新的活性易位聚合催化体系。[o-以[（三氟甲基）苯基]乙炔为单体，在苯甲醚中于30 ℃进行聚合，最终得到了分子量分布很窄（Mw/Mn=1.02）的聚合物。

项目成果

T.Mizumoto: "Effects of ortho-Substituents on the Living Polymerization of Phenylacetylenes by MoOCl_4-Based Catalysts" Macromol.Chem.Phys.(印刷中).

T. Mizumoto：“邻位取代基对 MoOCl_4 基催化剂对苯乙炔活性聚合的影响”Macromol.Chem.Phys.（出版中）。

M.Nakano: "Stereospecific Living Polymerization of tert-Butylacetylene by Molybdenum-Based Ternary Catalyst Systems" Macromolecules. 27. 1344-1348 (1994)

M.Nakano：“基于钼的三元催化剂体系的叔丁乙炔立体定向活性聚合”大分子。

M.Nakano: "Stereospecific Living Polymerization of tert-Butylacetylene by Molybdenum-Based Ternary Catalyst Systems" Macromolecules. (印刷中).

M. Nakano：“基于钼的三元催化剂系统的叔丁乙炔立体定向活性聚合”大分子（正在出版）。

M.Nakano et al.: "Stereospecific Living Polymerization of tert-Butylacetylene by Molybdenum-Based Ternary Catalyst Systems" Macromolecules. 27. 1344-1348 (1994)

M.Nakano 等人：“通过钼基三元催化剂系统进行叔丁基乙炔的立体定向活性聚合”大分子。

T.Masuda: "Design,Synthesis and Properties of Substituted Polyacetylenes" J.Macromol.Sci.,Pure Appl.Chem.(印刷中).

T.Masuda：“取代聚乙炔的设计、合成和性能”J.Macromol.Sci.，Pure Appl.Chem.（印刷中）。