A new sterically highly hindered 7-membered cyclic nitroxide for the controlled living radical polymerization

被引：19

作者：

Chang, Che-Chien ^{[1
]}

Siegenthaler, Kai Oliver ^{[1
]}

Studer, Armido ^{[1
]}

机构：

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

来源：

HELVETICA CHIMICA ACTA | 2006年 / 89卷 / 10期

关键词：

D O I：

10.1002/hlca.200690206

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The synthesis of a new sterically highly hindered 7-membered alkoxyamine, 2,2,7,7-tetraethyl-1-(1-phenylethoxy)-1,4-diazepan-5-one (4), starting from known 2,2,6,6-tetraethyl-1-(1-phenylethoxy)piperidin-4-one (3) via a Beckmann-type rearrangement is presented. It is shown that ring-enlargement by insertion of an NH moiety in going from 3 to 4 leads to a more efficient regulator for nitroxide-mediated controlled living radical styrene (=ethenylbenzene) and butyl acrylate (=butyl prop-2-enoate) polymerization. In addition to the polymerization experiments, kinetic data on the reversible C-O bond homolysis of alkoxyamines 3 and 4 are presented.

引用

页码：2200 / 2210

页数：11

共 43 条

[1] Decomposition of model alkoxyamines in simple and polymerizing systems.: I.: 2,2,6,6-tetramethylpiperidinyl-N-oxyl-based compounds [J].

Ananchenko, GS ;

Fischer, H .

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2001, 39 (20) :3604-3621

[2]

[Anonymous], POLYM PREPR

[3] RAFTing down under: Tales of missing radicals, fancy architectures, and mysterious holes [J].

Barner-Kowollik, C ;

Davis, TP ;

Heuts, JPA ;

Stenzel, MH ;

Vana, P ;

Whittaker, M .

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2003, 41 (03) :365-375

[4] Development of a universal alkoxyamine for "living" free radical polymerizations [J].

Benoit, D ;

Chaplinski, V ;

Braslau, R ;

Hawker, CJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (16) :3904-3920

[5] One-step formation of functionalized block copolymers [J].

Benoit, D ;

Hawker, CJ ;

Huang, EE ;

Lin, ZQ ;

Russell, TP .

MACROMOLECULES, 2000, 33 (05) :1505-1507

[6] Kinetics and mechanism of controlled free-radical polymerization of styrene and n-butyl acrylate in the presence of an acyclic β-phosphonylated nitroxide [J].

Benoit, D ;

Grimaldi, S ;

Robin, S ;

Finet, JP ;

Tordo, P ;

Gnanou, Y .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (25) :5929-5939

[7] Polar, steric, and stabilization effects in alkoxyamines C-ON bond homolysis: A multiparameter analysis [J].

Bertin, D ;

Gigmes, D ;

Marque, SRA ;

Tordo, P .

MACROMOLECULES, 2005, 38 (07) :2638-2650

[8] The synthesis and evaluation of new α-hydrogen nitroxides for 'Living' free radical polymerization [J].

Braslau, R ;

O'Bryan, G ;

Nilsen, A ;

Henise, J ;

Thongpaisanwong, T ;

Murphy, E ;

Mueller, L ;

Ruehl, J .

SYNTHESIS-STUTTGART, 2005, (09) :1496-1506

[9] Termination kinetics of free-radical polymerization of styrene over an extended temperature and pressure range [J].

Buback, M ;

Kuchta, FD .

MACROMOLECULAR CHEMISTRY AND PHYSICS, 1997, 198 (05) :1455-1480

[10] CRITICALLY EVALUATED RATE COEFFICIENTS FOR FREE-RADICAL POLYMERIZATION .1. PROPAGATION RATE COEFFICIENT FOR STYRENE [J].

BUBACK, M ;

GILBERT, RG ;

HUTCHINSON, RA ;

KLUMPERMAN, B ;

KUCHTA, FD ;

MANDERS, BG ;

ODRISCOLL, KF ;

RUSSELL, GT ;

SCHWEER, J .

MACROMOLECULAR CHEMISTRY AND PHYSICS, 1995, 196 (10) :3267-3280

← 1 2 3 4 5 →