Study of photopolymers, 18. Synthesis and photochemical reaction of novel polymers with pendant photosensitive and photosensitizing groups

Abstract

Self-sensitized photosensitive polymers with pendant photosensitive and photosensitizing groups were prepared by reaction of polystyrene containing pendant chloromethyl and photosensitizing groups, with the potassium salts of photosensitive compounds such as cinnamic acid, crotonic acid, or 2-cyano-3-(a-styryl)acrylic acid in DMF using tetrabutylammonium bromide as phase transfer catalyst. The photochemical reactivity and the practical photosensitivity of the resulting polymers were measured by IR spectrometry and by the gray-scale method, respectively. Pendant 4-nitro-1 -naphthyloxy and 4-nitrophenoxy groups in the polymers show the highest photosensitizing activity for pendant cinnamoyl groups. The photochemical reactivity and the sensitivity of these polymers are affected by the content of photosensitizing units in the polymer skeleton, the glass transition temperature of the polymers, however, is not influenced. Pendant 2-benzoylbenzoyl groups act as excellent photosensitizers for pendant crotonoyl groups, however, the photochemical reactivity of this polymer was found to be lower than that of the polymer with pendant cinnamoyl and suitable photosensitizing groups. Pendant 2-cyano-3-(a-styryl)acryloyl groups in the polymer, which exhibit high photochemical activity, are also sensitized by pendant methyleosin moieties.

Study of polymeric photosensitizer. 2. Syntheses of multifunctional polymeric photosensitizers containing a pendant nitroaryl group and a quaternary phosphonium salt and their application to the photochemical reaction of potassium cinnamate

“…Substitution Reaction of PCMS with the Potassium Salt of Photosensitizing Compounds. Typical examples of the reaction of PCMS with the potassium salt of the photosensitizing compound are as follows: 19,20 Typical Procedure for the Substitution Reaction of PCMS with PNP. PCMS (1.53 g, 10.0 mmol) was dissolved in 20 mL of DMF, and PNP (0.36 g, 2.0 mmol) and TBAB (0.32 g, 1.0 mmol) as a PTC were added to the solution.…”

Novel Synthesis of Self-Sensitized Photosensitive Polymers by Addition Reaction of Pendant Epoxide Groups in the Polymer with Some Cinnamic Esters

“…This communication describe a successful synthesis for highly photoreactive polymers having pendant cinnamate and 4-nitrophenyl or 4-nitro-1-naphthyl ether as photosensitizing groups for the cinnamate group, 4 by the addition reaction of PGMA with 4-nitrophenyl cinnamate 5 (NPC) or 4-nitro-1-naphthyl cinnamate (NNC) using quaternary salts as catalysts.…”