Synthesis of Bulky Nitroxides, Characterization, and Their Application in Controlled Radical Polymerization

被引：21

作者：

Jing, Yuanyuan ^{[1
]}

Mardyukoy, Artur ^{[1
]}

Bergander, Klaus ^{[1
]}

Daniliuc, Constantin Gabriel ^{[1
]}

Studer, Armido ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, Dept Chem, D-48149 Munster, Germany

来源：

MACROMOLECULES | 2014年 / 47卷 / 11期

关键词：

ON BOND HOMOLYSIS; GAUSSIAN-BASIS SETS; PIPERIDINYL-N-OXYL; HINDERED AMINES; METHYL-METHACRYLATE; BUTYL ACRYLATE; MEDIATED POLYMERIZATION; MOLECULAR CALCULATIONS; DENSITY FUNCTIONALS; STYRENE;

D O I：

10.1021/ma500639y

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

This paper describes the synthesis of several highly sterical hindered alkoxyamines based on 6-membered cyclic nitroxides and their application as initiators/regulators in the controlled nitroxide-mediated radical polymerization of n-butyl acrylate and styrene. Rate constant k(d) and activation energy E-a of the C-O bond of the novel alkoxyamines are reported. Conformational studies on the new nitroxides are performed by X-ray analysis and by DFT calculations. The polymerization of n-butyl acrylate can be conducted at 60 degrees C showing that these hindered nitroxides are highly valuable to conduct nitroxide-mediated acrylate polymerization (NMP). In addition, low temperature (SO degrees C) styrene polymerizations are disclosed.

引用

页码：3595 / 3602

页数：8

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