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Porphyrin derivatives act as vinylene monomers in TEMPO-mediated radical copolymerization with styrene
被引：8
|作者：
Obata, Makoto
[1
]
Ohtake, Eiko
[2
]
Hirohara, Shiho
[3
]
Tanihara, Masao
[3
]
Yano, Shigenobu
[3
,4
]
机构：
[1] Univ Yamanashi, Interdisciplinary Grad Sch Med & Engn, Kofu, Yamanashi 4008510, Japan
[2] Nara Womens Univ, Fac Sci, Kitauoyanishimachi, Nara 6308506, Japan
[3] Nara Inst Sci & Technol, Grad Sch Mat Sci, Nara 6300101, Japan
[4] Kyoto Univ Katsura, Kyoto Univ, Off Soc Acad Collaborat Innovat, Nishikyo Ku, Kyoto 6158520, Japan
基金：
日本学术振兴会;
关键词：
copolymerization;
dyes;
pigments;
living radical polymerization (LRP);
porphyrin;
TEMPO-mediated radical polymerization;
POLY(ISOBUTYL-CO-2,2,2-TRIFLUOROETHYL METHACRYLATE);
PHOTODYNAMIC THERAPY;
ALUMINUM PORPHYRIN;
STAR POLYMERS;
POLYMERIZATION;
PLATINUM(II);
COMPLEXES;
MOIETY;
CORE;
ATRP;
D O I：
10.1002/pola.26147
中图分类号：
O63 [高分子化学（高聚物）];
学科分类号：
070305 ;
080501 ;
081704 ;
摘要：
In this article, we offer clear evidence for the radical copolymerizability of porphyrin rings in 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-mediated radical copolymerizations with styrene. The radical copolymerizations of styrene with 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (H2TFPP) was conducted using 1-phenyl-1-(2,2,6,6-tetramethyl-1-piperidinyloxy)ethane as an initiator. The refractive index (RI) traces for the size-exclusion chromatography of the resulting copolymers were unimodal with narrow molecular weight distributions. The RI traces shifted toward higher molecular weight regions as the polymerization progressed, and the number-average molecular weights were close to those calculated on the basis of the feed compositions and monomer conversions. These features were in good agreement with a TEMPO-mediated mechanism. The traces recorded by the ultraviolet-visible (UV-vis) detector (430 nm) were identical to those obtained by the RI detector, indicating a statistical copolymerization of styrene with H2TFPP. This also indicated that H2TFPP acted as a monomer and not as a terminator or a chain-transfer agent under the conditions used. A benzyl radical addition to H2TFPP was conducted as a model reaction for the copolymerization using tributyltin hydride as a chain-transfer agent, affording a reduced porphyrin, 2-benzyl-5,10,15,20-tetrakis(pentafluorophenyl)chlorin 1, via radical addition to the beta-pyrrole position. The UV-vis spectrum of 1 was fairly similar to that of poly(styrene-co-H2TFPP), indicating that H2TFPP polymerized at its beta-pyrrole position in the TEMPO-mediated radical polymerization. TEMPO-mediated radical copolymerizations of styrene with several porphyrin derivatives were also demonstrated. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012
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页码：3592 / 3597
页数：6
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