Design and Applications of Novel Photo-crosslinking Systems by the Use of Photobase Generators

1.以邻苯乙酮o -丙烯酰肟和共聚物（如苯乙烯）为原料，制备了含AOI基团的共聚物。在紫外线照射下，薄膜中的AOI基团转化为氨基。辐照膜可溶于有机溶剂。对1,4-苯醌、1,4-萘醌和2-十二烷基硫-1,4-苯醌等醌类薄膜进行辐照后，薄膜在有机溶剂中不溶，在玻璃化转变温度以上，随着热处理的增加，不溶部分的程度增加。光交联是由聚合物自由基与醌的反应引起的，热交联是由悬垂氨基与醌的反应引起的。同时含有AOI基团和敏化基团（如二苯甲酮）的共聚物在紫外照射下可引起其不溶化，后焙也可有效提高不溶化程度。光交联现象的发生是由于受激发的二苯甲酮单元吸氢形成的聚合物自由基和氨基缔合产生的热交联引起的。然而，热交联的具体机理尚不清楚。光照射膜中含有氨基氧基的共聚物可诱导其不溶化，形成悬垂的氨基和肼基。此外，辐照后的热处理增强了不溶化程度。No1到No3的结果是非常有趣的，因为它们是新型的光交联体系，可以被热放大。我们发现，含苯基和N，N-二甲基氨基甲酸酯阴离子的季铵盐光解会生成叔胺。这是一种不同于光化学合成伯胺和仲胺的新型光碱发生器。展望了它们在阴离子聚合和环氧化物固化中的应用。少

1.Copolymers bearing acyloxyimino (AOI) groups were prepared by the use of aceophenone O-acryloyloxime and comonomers (e.g.styrene). AOI groups in their films are transformed into amino groups upon UV irradiation. The irradiated films are soluble in organic solvents. When the films with quinones such as 1,4-benzoquinone, 1,4-naphthoquinone and 2-dodecylthio-1,4-benzoquinone were irradiated, the films became insolale in organic solvents and the degree of the insoluble fraction increased with thermal treatment above their glass transition temperature. The photo-crosslinking was found to be induced by the reaction of polymer radicals with quinones and the thermal crosslinking to be due to the reaction of pendant amino groups with quinones.2. UV irradiation of copolymers bearing both AOI groups and sensitizing groups such as benzophenone units in films induced their insolublization and the post-baking also was effective for the enhancement of the degree of insolublization. The photo-crossl … More inking was clarified to be induced by the polymer radicals formed by the hydrogen-abstraction of the excited benzophenone units and the thermal crosslinking to be due to the association of resulting amino groups. However, the details of mechanism of the thermal crosslinking is not clear.3. Photo-irradiation of copolymers bearing carbamoyloxyimino groups in films was found to induce their insolublization with the formation of pendant amino and hydrazino groups. Furthermore, the degree of the insolubilization was enhanced by the thermal treatment after the irradiation.The results from No1 to No3 are very interesting as the novel photo-crosslinking systems which can be amplified thermally.4.We have found that the photolysis of quaternary ammonium salts bearing phenacyl groups and N,N-dimethylcarbamate anion results in the formation of tert-amines. This is the novel photobase generators different from photobase generator which generate photochemically primary and secondary amines. Their use in anionic polymerization and curing of epoxides are expected. Less