Toward Nitroxide-Medlated Photopolymerization

被引:162
作者
Guillaneuf, Yohann [1 ]
Bertin, Denis [1 ]
Gigmes, Didier [1 ]
Versace, Davy-Louis [2 ]
Lalevee, Jacques [2 ]
Fouassier, Jean-Pierre [2 ]
机构
[1] Univ Aix Marseille 1, UMR 6264, Lab Chim Provence, F-13397 Marseille 20, France
[2] Univ Haute Alsace, Dept Photochim Gen, CNRS, Ecole Natl Super Chim Mulhouse, F-68093 Mulhouse, France
关键词
LIVING RADICAL POLYMERIZATION; N-BUTYL ACRYLATE; N; N-DIETHYLDITHIOCARBAMATE DERIVATIVES; MEDIATED POLYMERIZATION; METHYL-METHACRYLATE; 2,2,6,6-TETRAMETHYLPIPERIDINE-1-OXYL; PHOTOINITIATORS; ALKOXYAMINES; PHOTOLYSIS; MECHANISM;
D O I
10.1021/ma902774s
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A new alkoxyamine(methyl-2-((4-benzoylphenyl)((1-methoxy-2-methyl-1-oxopropan-2-yl)oxy)-amino)-2-methylpropanote 4) hearing a chromophore group directly linked to the aminoxyl function is proposed as a photoinifierter. This original compound decomposes under UV irradiation to generate the corresponding alkyl and nitroxide radicals. Drastic changes of the photophysical or photochemical properties of the starting chromophore are noted. Laser flash photolysis experiments showed both a singlet state cleavage and an efficient shortening of the triplet state lifetime of 4. MO calculations suggest a C-O bond homolytic dissociation under UV irradiation through both S, and T, pathways. However, an ESR study evidences that both N-O and C-O homolysis occur under UV irradiation. The efficiency of 4 as a conventioal photoinitiator is close to that of 2,2'-dimethoxyphenyl acetophenone. When 4 was used as a photoiniferter in nitroxide-mediated photopolymerization (NMP2), a linear growth of the poly(n-butyl acrylate) chain, reaching 80% of conversion in < 500 s, is observed combined with a reinitiation of the photopolymerization after the end of the irradiation: this is the first report showing a at least partial NMP2 process.
引用
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页码:2204 / 2212
页数:9
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