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.携带acyloxyimino（AOI）组的聚合物是通过使用芳酮O-丙酰氧基和群落（例如styrene）来制备的。紫外线照射后，他们的电影中的AOI组被转变为氨基。辐照膜在有机溶液中是固体的。当用1,4-苯甲喹酮，1,4-萘醌和2-二甲基硫酸酮和2-二甲基硫酮1,4-苯喹酮被照射时，膜变成有机溶液中的不溶液，并且在其玻璃过渡温度上方的热处理中，不溶性分数的程度增加了。发现光合物自由基与奎因酮的反应和热交联的反应发现，这是由于吊坠氨基与喹酮的反应引起的。2。具有AOI组和敏化群体（例如甲oi单元）的共聚物的紫外线辐照诱导了他们的不确定，并且烘烤后也有效地增强了不可分解的程度。照片交叉…更多的墨水被阐明是由激发的苯甲酮单元的氢 - 氢 - 因产生的氨基组缔合而引起的聚合物自由基和热交联。但是，热交联的机制的细节尚不清楚3。发现膜中带有卡巴米氧氨基群的共聚物的照片 - 呈现，可引起他们因吊坠氨基和氢锌组的形成而导致他们的不公开。 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.这是与光化学生成原胺和次级胺不同的新型光酶发生器不同的光酶发生器。它们在阴离子聚合和环氧化物的固化中的使用。较少的