Highly Controlled Random and Alternating Copolymerization of (Meth)acrylates, Acrylonitrile, and (Meth)acrylamides with Vinyl Ethers by Organotellurium, Organostibine, and Organobismuthine Mediated Living Radical Polymerization Reactions
Highly Controlled Random and Alternating Copolymerization of (Meth)acrylates, Acrylonitrile, and (Meth)acrylamides with Vinyl Ethers by Organotellurium, Organostibine, and Organobismuthine Mediated Living Radical Polymerization Reactions
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(甲基)丙烯酸酯、丙烯腈和(甲基)丙烯酰胺与乙烯基醚通过有机碲、有机锑和有机铋介导的活性自由基聚合反应进行高度受控的无规和交替共聚
DOI：
10.1002/pola.26004
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发表时间：
2012
期刊：
影响因子：
--
通讯作者：
S
中科院分区：
文献类型：
--
作者：
Mishima;E.; Yamago;S
研究了丙烯酸酯、甲基丙烯酸酯、丙烯腈和丙烯酰胺与乙烯基醚在有机碲-、有机锑-和有机铋-介导的活性自由基聚合（分别为TERP、SBRP和BIRP）下的无规和交替共聚。合成了具有可控分子量和多分散性的结构良好控制的无规和交替共聚物。在丙烯酸酯和乙烯基醚以及丙烯腈和乙烯基醚的组合中，通过使用相对于丙烯酸酯和丙烯腈过量的乙烯基醚，发生高度交替的共聚。相反，即使使用过量的乙烯基醚，丙烯酰胺和乙烯基醚的组合也不会发生交替共聚。通过理论计算估算了聚合物端基与乙烯基醚的反应活性，并认为聚合物端基的单占据分子轨道（SOMO）能级决定了聚合物端基的反应活性.通过将活性无规和交替共聚与活性自由基或活性阳离子聚合相结合，成功地合成了具有可控大分子结构的新型嵌段共聚物，如（PBA-alt-PIBVE）-block-（PtBA-co-PIBVE）、PBA-block-（PBA-alt-PIBVE）和（PTFEA-alt-PIBVE）-block-PIBVE。© 2012 Wiley Periodicals，Inc. J Polym Sci Part A：Polym Chem，2012
Random and alternating copolymerizations of acrylates, methacrylates, acrylonitorile, and acrylamides with vinyl ethers under organotellurium‐, organostibine‐, and organobismuthine‐mediated living radical polymerization (TERP, SBRP, and BIRP, respectively) have been studied. Structurally well‐controlled random and alternating copolymers with controlled molecular weights and polydispersities were synthesized. The highly alternating copolymerization occurred in a combination of acrylates and vinyl ethers and acrylonitorile and vinyl ethers by using excess amount of vinyl ethers over acrylates and acrylonitorile. On the contrary, alternating copolymerization did not occur in a combination of acrylamides and vinyl ethers even excess amount of vinyl ethers were used. The reactivity of polymer‐end radicals to a vinyl ether was estimated by the theoretical calculations, and it was suggested that the energy level of singly occupied molecular orbital (SOMO) of polymer‐end radical species determined the reactivity. By combining living random and alternating copolymerization with living radical or living cationic polymerization, new block copolymers, such as (PBA‐alt‐PIBVE)‐block‐(PtBA‐co‐PIBVE), PBA‐block‐(PBA‐alt‐PIBVE), and (PTFEA‐alt‐PIBVE)‐block‐PIBVE, with controlled macromolecular structures were successfully synthesized. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012