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Study of photopolymers. XXX. Syntheses of new di(meth) acrylate oligomers by addition reactions of epoxy compounds with active esters
Authors:Tadatomi Nishikubo  Eiji Takehara  Seiji Saita  Takahisa Matsumura
Abstract:Some dimethacrylate oligomers were synthesized by new addition reactions of 2,2-(4-hydroxyphenyl)propane diglycidyl ether (BPGE) or glycidyl methacrylate (GMA) with phenyl methacrylates such as phenyl methacrylate (PMA), 4-nitrophenyl methacrylate (NPMA), 2,4-dichlorophenyl methacrylate (DCPMA), 4-methoxyphenyl methacrylate (MPMA), and (4-cinnamoyloxy)phenyl methacrylate (CIPMA) using tetrabutylammonium bromide as a catalyst at 120°C. The other new dimethacrylate or diacrylate oligomers were also prepared by the addition reactions of GMA or glycidyl acrylate with active esters such as di(S-phenyl)thioisophthalate (PTIP), di(4-nitrophenyl)isophthalate (NPIP), di(4-nitrophenyl)adipate (NPAD), and di(4-nitrophenyl)sebacate (NPSB) under similar reaction conditions. Furthermore, the rates of photochemical reaction of the obtained dimethacrylate oligomers were measured with 3 mol % of various photosensitizers such as benzoin iso-propyl ether (BIPE), 2-ethylanthraquinone (EAQ), and benzophenone (BP). The rate of photochemical reaction of BPGE-DCPMA oligomer was higher than those of BPGE-PMA, BPGE-NPMA, and BPGE-MPMA oligomers using BIPE as a photosensitizer. However, the photochemical reactivity of the unsensitized BPGE-CIPMA was almost the same as that of the sensitized BPGE-DCPMA. On the other hand, when EAQ was used as a photosensitizer, GMA-PTIP oligomer showed much higher reactivity than GMA-NPAD, GMA-NPSB, and GMA-NPIP oligomers. Also it was shown that the activity of EAQ as a sensitizer was higher than BIPE and BP in the photochemical reaction of BPGE-DCPMA oligomer.
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