Development of New Anionic Polymerization Initiators Based on Metal Ate Complexes

基于金属盐配合物的新型阴离子聚合引发剂的研制

• 批准号: 15350071
• 负责人: IHARA Eiji
• 金额: $ 4.54万
• 依托单位: Ehime University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15350071/
• 关键词: Ate complex; Transition metal; Main group metal; Anionic polymerization; Cationic polymerization; Methyl methacrylate; t-Butyl acrylate; Isobutyl vinyl ether; 金属アート錯体; リビング重合

We have succeeded in demonstrating that ate complexes of various metals are effective as polymerization initiators.1.Transition metal ate complexes as initiators for anionic polymerization of methyl methacrylate (MMA).We have found that transition metal ate complexes generated by the reaction of transition metal halide with organolithium can initiate the anionic polymerization of MMA. Living polymerization of MMA was achieved by using ate complex of Fe in conjunction with an organoaluminum as an additive or by the polymerization at -78℃ using ate complexes of V and Cr. Ate complexes of Nb, Mo, and W bearing secondary amide ligands afforded highly isotactic PMMA at -78℃. Y-ate complexes with secondary amide ligands initiated the living polymerization of MMA, giving PMMAs with narrow molecular weight distributions and amino groups at chain ends.2.Living polymerization of t-butyl acrylate (tBA) initiated with an ate complex of Al.The Al-ate complex generated by the reaction of iBu_3Al with tBuOK initiated living polymerization of tBA. Block copolymerization of tBA with MMA was also successful using the initiating system.3.Cationic polymerization of isobutyl vinyl ether (IBVE) initiated with ate complexes of NbThe ate complex of Nb with trityl cation was found to be effective for the cationic polymerization of IBVE. The ate complex bearing a secondary amide ligand afforded poly(IBVE)s with narrow molecular weight distributions.

我们成功地证明了不同金属的配合物作为聚合引发剂的有效性。1.过渡金属配合物作为甲基丙烯酸甲酯（MMA）阴离子聚合的引发剂我们发现过渡金属卤化物与有机锂反应生成的过渡金属配合物可以引发MMA的阴离子聚合。用Fe的络合物与有机铝配合作添加剂或用V、Cr的络合物在-78℃下进行MMA的活性聚合。含仲酰胺配体的Nb、Mo和W的配合物在-78℃下得到高度全同立构的PMMA。2.铝的配合物引发丙烯酸叔丁酯（tBA）的活性聚合，iBu_3Al与tBuOK反应生成的铝配合物引发tBA的活性聚合。3.铌与三苯甲基阳离子的络合物引发异丁基乙烯基醚（IBVE）的阳离子聚合研究发现，铌与三苯甲基阳离子的络合物对IBVE的阳离子聚合是有效的。含仲酰胺配体的酯配合物得到了分子量分布窄的聚（IBVE）。

项目成果

遷移金属アート錯体を開始剤とするアクリレート類の重合

使用过渡金属酸酯络合物作为引发剂聚合丙烯酸酯

• 发表时间: 2003
• 期刊: 接着 47
• 作者: Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;井原栄治
• 通讯作者: 井原栄治

Anionic Polymerization of Methyl Methacrylate Initiated with Chromium and Vanadium Ate Complexes Incorporating Diisopropylamide Ligand

含有二异丙酰胺配体的铬钒配合物引发甲基丙烯酸甲酯的阴离子聚合

• 发表时间: 2003
• 期刊: Polym. J. 35
• 作者: Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;Eiji Ihara;井原栄治;Eiji Ihara
• 通讯作者: Eiji Ihara

Cationic Polymerization of Isobutyl Vinyl Ether Initiated with Transition-Metal Ate Complexes

过渡金属配合物引发异丁基乙烯基醚的阳离子聚合

• 发表时间: 2006
• 期刊: J. Polym. Sci., Part A., Polym.Chem 44
• 作者: Eiji Ihara

Eiji IHARA: "Anionic Polymerization of Methyl Methacrylate Initiated with Lithium Diphenylamide (Ph_2NLi) in the Presence of Divalent Transition Metal Halide"J Polym.Sci., Part A., Polym.Chem.. 42・1. 31-37 (2004)

Eiji IHARA：“在二价过渡金属卤化物存在下用二苯酰胺锂（Ph_2NLi）引发的甲基丙烯酸甲酯的阴离子聚合”J Polym.Sci.，Part A.，Polym.Chem.. 42・1（2004）。

井原 栄治: "遷移金属アート錯体を開始剤とするアクリレート類の重合"接着. 47・5. 225-229 (2003)

Eiji Ihara：“使用过渡金属酸盐配合物作为引发剂的丙烯酸酯的聚合”Adhesion 47・5（2003）。