Photocrosslinkable vinylamine copolymers. I. Synthesis and photosensitivity of cinnamoylated polyvinylamine

Abstract

Vinylamine copolymers prepared by the Hofmann reaction were functionalized by amidification with cinnamoyl chloride. The resulting photosensitive polymers, which are the nitrogen analogues of poly(vinylcinnamate), can be prepared with various contents of cinnamamide side groups. The polymers exhibit a marked hydrophilicity and undergo efficient crosslinking upon exposure to 250–300 nm UV light. The sensitivity S expressed in cm2·J−1 was shown to be higher for a given content, τ, in cinnamamide groups expressed in mol·g−1 when the residual vinyl amine units are in the ammonium form. The dependence of S upon τ was of the second order for the free base form of the photopolymers, but a higher order with S approximately proportional to τ3 for the hydrochloride form of the photosensitive polymers. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2513–2520, 1997

The synthesis of poly(vinyl cinnamates) and its self‐assembled structure

“…For another thing, PVA is one typical hydrophilic and chemically active polymer because of the abundant hydroxyl groups. So it is easy to modify PVA with other compounds containing functional groups [17]. However, the hydrophilic nature of PVA sometimes limits its use [14].…”

Studies on photosensitive homopolymer and copolymers having a pendant photocrosslinkable functional group

“…15,16 High photosensitivity, the ability to form films, good thermal stability, good solubility, and resistance toward solvents after crosslinking are essential requirements for practical use of the pho-topolymers as negative photoresist materials. Polymers with a pendant photofunctional group such as cinnamoyl esters of poly(2-hydroxyethyl methacrylate), 17 poly(vinylamine) 18 and polyvinyl alcohol, 19 poly(vinyloxy carbonyl chalcone), 20 poly(vinyloxyethyl cinnamate), 21 and many other groups [22][23][24] have been synthesized and tested for their photosensitivity. The technological applications of many photoresists and their photochemistry have been reviewed.…”

“…30 The synthesis and photosensitivity of copolymers having pendant photosensitive groups have been reported. 18,22,31,32 The accurate estimation of copolymer composition and determination of reactivity ratios are significant for tailor-making copolymers with required physicochemical properties and in evaluating the end application of copolymers. In the past few decades, 1 H-NMR has been established as a powerful tool for the determination of tacticity and sequence distribution as well as for the estimation of copolymer composition because of its simplicity, rapidity, and sensitivity.…”