화학공학소재연구정보센터
Journal of Polymer Science Part A: Polymer Chemistry, Vol.37, No.7, 917-926, 1999
Synthesis and photochemical properties of poly(ester-amide)s containing norbornadiene (NBD) residues
N,N'-Bis[(3-carboxynorbornadien-2-yl)carbonyl]-N,N'-diphenylethylenediamine (BNPE) was synthesized in 70% yield by the reaction of 2,5-norbornadiene-2,3-dicarboxylic acid anhydride with N,N'-diphenylethylenediamine. Other dicarboxylic acid derivatives containing norbornadiene (NBD) residues having N,N'-disubstituted amide groups were also prepared by the reaction of 2,5-NBD-2,3-dicarboxylic acid anhydride with certain secondary diamines. When the polyaddition of BNPE with bisphenol A diglycidyl ether (BPGE) was carried out using tetrabutylammonium bromide as a catalyst in N-methyl-2-pyrrolidone at 100 degrees C for 12 h, a polymer with number average molecular weight of 69,800 was obtained in 98% yield. Polyadditions of other NBD dicarboxylic acid derivatives containing N,N'-disubstituted amide groups with BPGE were also performed under the same conditions. The reaction proceeded very smoothly to give the corresponding NBD poly(ester-amide)s in good yields. Photochemical reactions of the obtained polymers with N,N'-disubstituted amide groups on the NBD residue were examined, and it was found that these polymers were effectively sensitized by adding appropriate photosensitizers such as 4-(N,N-dimethylamino)benzophenone and 4,4'-bis(N,N-diethylamino)benzophenone in the film state. The stored energies in the quadricyclane groups of the polymers were also evaluated to be about 94 kJ/mol by DSC measurement of the irradiated polymer films.