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

利用光碱发生器的新型光交联系统的设计与应用

基本信息

批准号：
10650870
负责人：
TSUNOOKA Masahiro
金额：
$ 2.18万
依托单位：
Osaka Prefecture University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

项目摘要

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

1.通过使用苯乙酮O-丙烯酰肟和其膜中的AOI基团在紫外线照射下转化为氨基基团来制备带有酰氧基亚氨基(AOI)基团的共聚物。 1,4-苯醌、1,4-萘醌等醌类薄膜2-十二烷硫基-1,4-苯醌经辐照后，薄膜在有机溶剂中变得不溶，并且随着热处理温度高于其玻璃化转变温度，不溶部分的程度增加。发现光交联是由聚合物的反应引起的。自由基与醌的热交联是由于侧氨基与醌的反应引起的。2．薄膜中的二苯甲酮单元等敏化基团诱导了它们的不溶化，并且后烘烤对于增强不溶化程度也很有效，光交联墨迹被澄清是由氢吸收形成的聚合物自由基诱导的。激发的二苯甲酮单元和热交联是由于产生的氨基的缔合造成的，但是热交联的详细机制尚不清楚。3．发现薄膜中带有氨基甲酰氧基亚氨基的共聚物的光照射会导致其不溶化，并形成侧氨基和肼基。此外，照射后的热处理增强了不溶化程度。No1至No3的结果是非常有趣的是可以热放大的新型光交联系统。4.我们发现季铵盐的光解作用苯甲酰基和N,N-二甲基氨基甲酸酯阴离子形成叔胺，这是不同于光化学产生伯胺和仲胺的新型光产碱剂，其在阴离子聚合和环氧化物固化中的应用较少。