Mechanism of Photoinitiated Free Radical Polymerization by Thioxanthone-Anthracene in the Presence of Air

被引：72

作者：

Balta, Demet Karaca ^{[1
]}

Arsu, Nergis ^{[1
]}

Yagci, Yusuf ^{[2
]}

Sundaresan, Arun K. ^{[3
]}

Jockusch, Steffen ^{[3
]}

Turro, Nicholas J. ^{[3
]}

机构：

[1] Yildiz Tech Univ, Dept Chem, TR-34210 Istanbul, Turkey

[2] Istanbul Tech Univ, Dept Chem, TR-34469 Istanbul, Turkey

[3] Columbia Univ, Dept Chem, New York, NY 10027 USA

来源：

MACROMOLECULES | 2011年 / 44卷 / 08期

基金：

美国国家科学基金会;

关键词：

CHAIN THIOXANTHONE; SINGLET OXYGEN;

D O I：

10.1021/ma200147f

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The mechanism of formation of initiating radicals for free radical polymerization by the thioxanthone anthracene (TX-A) photoinitiator was investigated by laser flash photolysis, fluorescence and phosphorescence spectroscopy, and polymerization studies. The proposed mechanism of photoinitiation involves photoexcitation of TX-A and quenching of triplet excited states of TX-A by molecular oxygen to generate singlet oxygen. Singlet oxygen reacts with the anthracene moiety of TX-A to form an endoperoxide. The endoperoxide intermediate was isolated and characterized by MS and H-1 NMR The endoperoxide undergoes photochemical or thermal decomposition to generate radicals which are able to initiate free radical polymerization. A significant deuterium effect on the polymerization rates using CDCl3 and CHCl3 as solvents confirmed the involvement of singlet oxygen in the initiation process.

引用

页码：2531 / 2535

页数：5

共 25 条

[1]

Arsu N, 2009, PLAST ENG-CRC, V73, P141

[2] Reversible binding of oxygen to aromatic compounds [J].

Aubry, JM ;

Pierlot, C ;

Rigaudy, J ;

Schmidt, R .

ACCOUNTS OF CHEMICAL RESEARCH, 2003, 36 (09) :668-675

[3] Mechanistic study of photoinitiated free radical polymerization using thioxanthone thioacetic acid as one-component type II photoinitiator [J].

Aydin, M ;

Arsu, N ;

Yagci, Y ;

Jockusch, S ;

Turro, NJ .

MACROMOLECULES, 2005, 38 (10) :4133-4138

[4] Thioxanthone-anthracene: A new photoinitiator for free radical polymerization in the presence of oxygen [J].

Balta, Demet Karaca ;

Arsu, Nergis ;

Yagci, Yusuf ;

Jockusch, Steffen ;

Turro, Nicholas J. .

MACROMOLECULES, 2007, 40 (12) :4138-4141

[5] 2-mereaptothioxanthone as a novel photoinitiator for free radical polymerization [J].

Cokbaglan, L ;

Arsu, N ;

Yagci, Y ;

Jockusch, S ;

Turro, NJ .

MACROMOLECULES, 2003, 36 (08) :2649-2653

[6] Novel water soluble copolymers based on thioxanthone: photochemistry and photoinitiation activity [J].

Corrales, T ;

Catalina, F ;

Allen, NS ;

Peinado, C .

JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 2005, 169 (01) :95-100

[7] Photochemical study and photoinitiation activity of macroinitiators based on thioxanthone [J].

Corrales, T ;

Catalina, F ;

Peinado, C ;

Allen, NS ;

Rufs, AM ;

Bueno, C ;

Encinas, MV .

POLYMER, 2002, 43 (17) :4591-4597

[8]

DAVIS R, 1983, Australia Commonwealth Scientific and Industrial Research Organization Division of Tropical Crops and Pastures Tropical Agronomy Technical Memorandum, P1

[9] FLUORESCENCE YIELDS OF AROMATIC COMPOUNDS [J].

DAWSON, WR ;

WINDSOR, MW .

JOURNAL OF PHYSICAL CHEMISTRY, 1968, 72 (09) :3251-&

[10] The influence of the photophysics of 2-substituted thioxanthones on their activity as photoinitiators [J].

Encinas, MV ;

Rufs, AM ;

Corrales, T ;

Catalina, F ;

Peinado, C ;

Schmith, K ;

Neumann, MG ;

Allen, NS .

POLYMER, 2002, 43 (14) :3909-3913

← 1 2 3 →