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Phosphonium ylide/organoaluminum-based Lewis pairs for the highly efficient living/controlled polymerization of alkyl (meth)acrylates
Polymer Chemistry ( IF 4.1 ) Pub Date : 2023-04-17 , DOI: 10.1039/d3py00301a
Zhikang Chen 1 , Wuchao Zhao 2 , Conglei Liu 1 , Liuying Jiang 1 , Gang Fu 1 , Yuetao Zhang 2 , Hongping Zhu 1
Affiliation  

The development of living/controlled polymerization technologies is of great importance in both fundamental studies and in industrial applications. Herein, we report for the first time the use of easily synthesized phosphonium ylides Ph3P = CR1R2 (R1,R2 = H,H (P-ylide-1), H,Me (P-ylide-2), H,Et (P-ylide-3), H,Ph (P-ylide-4), Me,Me (P-ylide-5)) as the Lewis base (LB) in the Lewis pair polymerization (LPP) of (meth)acrylates. The P-ylide-2–P-ylide-5/Al(C6F5)3, P-ylide-1–P-ylide-5/AlR(BHT)2 (R = Me, Et, iBu; BHT = 2,6-tBu2-4-MeC6H2O), and P-ylide-1–P-ylide-5/AliBu2(BHT) systems are all highly effective initiators of methyl methacrylate (MMA) polymerization, of which the P-ylide-2/AlMe(BHT)2 system is the best for living/controlled polymerizations, resulting in high initiation efficiencies (I* > 90%). The relative Lewis acidities of the Lewis acids (LAs), Al(C6F5)3, AlR(BHT)2, and AliBu2(BHT), are evaluated using the Gutmann–Beckett method whilst the basicity of the P-ylides is evaluated through natural bond orbital computations. Model reactions using the P-ylides, LAs, and MMA were accomplished, and revealed that the active species in the MMA polymerization, the enolate Ph3PCH(Me)CH2C(Me)C[OAlMe(BHT)2](OMe) (>99%), is efficiently generated. Furthermore, homopolymerizations and block copolymerizations of MMA, ethyl methacrylate, benzyl methacrylate, n-butyl methacrylate, n-butyl acrylate, and ethylhexyl acrylate were successfully realized using the P-ylide-2/AlMe(BHT)2 system.

中文翻译:

叶立德/有机铝基路易斯对用于(甲基)丙烯酸烷基酯的高效活性/可控聚合

活性/可控聚合技术的发展在基础研究和工业应用中都非常重要。在此,我们首次报道了使用易于合成的鏻叶立德 Ph 3 P = CR 1 R 2 (R 1 ,R 2 = H,H (P-ylide- 1 ), H,Me (P-ylide- 2 ), H,Et (P-ylide- 3 ), H,Ph (P-ylide- 4 ), Me,Me (P-ylide- 5 )) 作为路易斯对聚合 (LPP) 中的路易斯碱 (LB) (甲基)丙烯酸酯。P-ylide- 2 –P-ylide- 5 /Al(C 6 F 5 ) 3, P-ylide- 1 –P-ylide- 5 /AlR(BHT) 2 (R = Me, Et, i Bu; BHT = 2,6- t Bu 2 -4-MeC 6 H 2 O), 和 P- ylide- 1 –P-ylide- 5 /Al i Bu 2 (BHT)体系都是甲基丙烯酸甲酯(MMA)聚合的高效引发剂,其中P-ylide- 2 /AlMe(BHT) 2体系最适合活性/受控聚合,引发效率高 ( I * > 90%)。路易斯酸 (LAs)、Al(C 6 F 5) 3、AlR(BHT) 2和 Al i Bu 2 (BHT) 是使用 Gutmann–Beckett 方法评估的,而 P-叶立德的碱性是通过自然键轨道计算评估的。完成了使用 P-叶立德、LAs 和 MMA 的模型反应,并揭示了 MMA 聚合中的活性物质,烯醇 Ph 3 PCH (Me)CH 2 C(Me)C[OAlMe(BHT) 2 ](OMe ) (>99%), 是有效生成的。此外,使用 P-叶立德成功实现了MMA、甲基丙烯酸乙酯、甲基丙烯酸苄酯、甲基丙烯酸正丁酯、丙烯酸正丁酯和丙烯酸乙基己酯的均聚和嵌段共聚。2 /AlMe(BHT) 2体系。
更新日期:2023-04-17
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