Synthesis and Photochemical Behaviour of Poly [p-(p-azidocinnamoyloxy)styrene] and 1, 4-bis(p-azidocinnamoyloxy) benzene

Abstract

Poly [p-(p-azidocinnamoyloxy)styrene] (PACS) and 1, 4-bis (p-azidocinnamoyloxy) benzene (BACB) were newly synthesized in order to obtain high photosensitive polymer, which had two photoreactive sites, azido and active ethylenic double bond. P-azidocinnamoyloxy chloride necessary for this synthesis was prepared by the method approximately similar to that reported by Yabe et al., Using this acid chloride poly (p-hydroxy styrene) and dihydroxy benzene were independently esterified in pyridine. Synthesized esters were identified to be PACS and BACB from their IR and NMR spectra. Photochemical behaviour of them was investigated and the following results were obtained: 1) The photosensitivity of PACS containing no sensitizer was about 10 times that of poly (vinyl cinnamate) (cinnamolized; 75%) containing 10 wt% michlersketone in gray-scale method. 2) The photosensitivity of acrylonitrile-butadiene-styrene resin containing 25 wt% BACB was about 0.5 times that of the above poly (vinyl cinnamate) system. 3) Disappearance rate of azido group in PACS was faster about 1.6 times tham that of active ethylenic double bond of it when it was irradiated by UV lamp at the initial stage, although in BACB it was faster about 1.1 times. 4) The photosensitive groups of PACS and BACB were preserved without any reaction at the oven temperature less than 100°C when they were heated in the oven for 10 minutes. 5) PACS solubilized (-5wt%) in monochlorobenzene showed a good stability of the preservation without gelation for about 6 months in the refrigerator, whereas BACB in the same state did it for 2 months.