TY - JOUR
T1 - LED-induced polymerization (385, 405, and 455 nm) using star-shaped tris(4-(thiophen-2-yl)phenyl)amine derivatives as light-harvesting photoinitiators
AU - Zhang, Jing
AU - Sallenave, Xavier
AU - Bui, Thanh Tuan
AU - Dumur, Frédéric
AU - Xiao, Pu
AU - Graff, Bernadette
AU - Gigmes, Didier
AU - Fouassier, Jean Pierre
AU - Lalevée, Jacques
PY - 2015/1
Y1 - 2015/1
N2 - Two star-shaped tris(4-(thiophen-2-yl)phenyl)amine derivatives, namely tris(4-(5-(3 pentylthieno[3,2- b ]thiophen-5-yl)thiophen-2-yl)phenyl)amine and tris(4-(5-(3-pentyl-2 (thiophen-2-yl)thieno[3,2- b ]thiophen-5-yl)thiophen-2-yl)phenyl)amine, are developed as photoinitiators for radical and cationic polymerizations under near-UV and visible lightemitting diodes (LEDs) (e.g., 385, 405, and 455 nm). When used in combination with an iodonium salt (and optionally N -vinyl carbazole) or an amine/alkyl halide couples, they lead to excellent photoinitiating abilities for the polymerization of epoxides or (meth)acrylates under air. Compared with commercial photoinitiators, i.e., camphorquinone-based systems or bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, the novel photoinitiators exhibit noticeably higher polymerization efficiencies under air (epoxide conversions = 41-57% vs ≈0%, halogen lamp exposure; methacrylate conversions = 50-55% vs 44%, LED at 405 nm exposure; methacrylate conversions = 34-42% vs 0-8%, LED at 455 nm exposure). These systems are also interesting in overcoming oxygen inhibition. The photochemical mechanisms are studied by steady-state photolysis, electron spin resonance spin trapping, fluorescence, cyclic voltammetry, and laser flash photolysis techniques.
AB - Two star-shaped tris(4-(thiophen-2-yl)phenyl)amine derivatives, namely tris(4-(5-(3 pentylthieno[3,2- b ]thiophen-5-yl)thiophen-2-yl)phenyl)amine and tris(4-(5-(3-pentyl-2 (thiophen-2-yl)thieno[3,2- b ]thiophen-5-yl)thiophen-2-yl)phenyl)amine, are developed as photoinitiators for radical and cationic polymerizations under near-UV and visible lightemitting diodes (LEDs) (e.g., 385, 405, and 455 nm). When used in combination with an iodonium salt (and optionally N -vinyl carbazole) or an amine/alkyl halide couples, they lead to excellent photoinitiating abilities for the polymerization of epoxides or (meth)acrylates under air. Compared with commercial photoinitiators, i.e., camphorquinone-based systems or bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, the novel photoinitiators exhibit noticeably higher polymerization efficiencies under air (epoxide conversions = 41-57% vs ≈0%, halogen lamp exposure; methacrylate conversions = 50-55% vs 44%, LED at 405 nm exposure; methacrylate conversions = 34-42% vs 0-8%, LED at 455 nm exposure). These systems are also interesting in overcoming oxygen inhibition. The photochemical mechanisms are studied by steady-state photolysis, electron spin resonance spin trapping, fluorescence, cyclic voltammetry, and laser flash photolysis techniques.
KW - Cationic photopolymerization
KW - Photoinitiators
KW - Radical photopolymerization
KW - Triphenylamine dyes
KW - UV or visible LEDs
UR - http://www.scopus.com/inward/record.url?scp=84920946115&partnerID=8YFLogxK
U2 - 10.1002/macp.201400403
DO - 10.1002/macp.201400403
M3 - Article
AN - SCOPUS:84920946115
SN - 1022-1352
VL - 216
SP - 218
EP - 227
JO - Macromolecular Chemistry and Physics
JF - Macromolecular Chemistry and Physics
IS - 2
ER -