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Fluorinated Poly(substituted methylene)s Prepared by Pd-Initiated Polymerization of Fluorine-Containing Alkyl and Phenyl Diazoacetates: Their Unique Solubility and Postpolymerization Modification
Macromolecules ( IF 5.1 ) Pub Date : 2017-12-29 00:00:00 , DOI: 10.1021/acs.macromol.7b01964
Hiroaki Shimomoto 1 , Tomohiko Kudo 1 , Shogo Tsunematsu 1 , Tomomichi Itoh 1 , Eiji Ihara 1
Affiliation  

Pd-initiated polymerization of fluorine (F)-containing alkyl and phenyl diazoacetates is described. Polymerization of 2,2,2-trifluoroethyl diazoacetate [Et(CF3)DA] with π-allylPdCl afforded a C–C main chain polymer bearing a 2,2,2-trifluoroethoxycarbonyl group on each main chain carbon atom. The polymer showed upper critical solution temperature (UCST)-type phase separation in multiple common organic solvents with differing polarities. Although homopolymerization of 3,3,4,4,5,5,6,6,6-nonafluorohexyl diazoacetate [Hex(C4F9)DA] with a higher fluorine content yielded an insoluble product, copolymerization of Hex(C4F9)DA with non-fluorinated ethyl diazoacetate (EDA) proceeded homogeneously to give a soluble F-containing copolymer. Polymerization of a series of F-containing phenyl diazoacetates was also conducted with the same initiator, giving poly[(F-containing aryloxycarbonyl)methylene]s, which showed significant solubility differences depending on the substitution pattern of F atoms on the phenyl ring. Efficient postpolymerization modification of poly[(F-containing aryloxycarbonyl)methylene]s was achieved with a primary amine, affording a polymer with both a five-membered cyclic imide structure and an N-alkylcarbamoyl group in its side chains.

中文翻译:

Pd引发的含氟烷基和苯基重氮乙酸酯的Pd聚合制备的氟化聚(取代亚甲基):其独特的溶解性和后聚合改性

描述了含氟(F)的烷基和重氮苯基乙酸酯的Pd引发的聚合。2,2,2-三氟乙基重氮乙酸乙酯[Et(CF 3)DA]与π-烯丙基PdCl的聚合得到了一个在每个主链碳原子上带有2,2,2-三氟乙氧基羰基的CC主链聚合物。该聚合物在极性不同的多种常见有机溶剂中显示出较高的临界溶液温度(UCST)型相分离。3,3,4,4,5,5,6,6,6,6-九氟己基重氮乙酸酯[Hex(C 4 F 9)DA]的均聚具有较高的氟含量,产生不溶性产物,但Hex(C 4 F 9用非氟化的重氮乙酸乙酯(EDA)进行的DA均相处理,得到可溶的含F共聚物。还使用相同的引发剂进行一系列含F的苯基重氮乙酸酯的聚合,得到聚[(含F的芳氧基羰基)亚甲基] s,根据苯环上F原子的取代方式,其显示出显着的溶解度差异。用伯胺实现了聚[(含F的芳氧基羰基)亚甲基] s的有效后聚合改性,提供了在其侧链上具有五元环状酰亚胺结构和N-烷基氨基甲酰基的聚合物。
更新日期:2017-12-29
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