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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650870/
• 关键词: acyloxyimino groups; photobase generator; photo-crosslinking; crosslinking; quinone; benzophenone; carbamoyloxyimino group; sensitization; 増感基; ベンゾキノン; ナフトキイン

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-丙烯酰肟和共聚单体（例如苯乙烯）制备带有酰氧基亚氨基（AOI）基团的共聚物。在紫外线照射下，其膜中的AOI基团转化为氨基。辐照膜可溶于有机溶剂。当含有醌类如1，4-苯醌、1，4-萘醌和2-十二烷硫基-1，4-苯醌的膜被辐照时，膜在有机溶剂中变得不溶，并且在其玻璃化转变温度以上的热处理使不溶部分的程度增加。光交联是由聚合物自由基与醌类反应引起的，热交联是由侧链氨基与醌类反应引起的.同时含有AOI基团和敏化基团（如二苯甲酮单元）的共聚物在紫外光照射下会导致其不溶，后烘也能有效地提高其不溶度。照片交叉 ...更多信息 明确了上墨是由激发的二苯甲酮单元的夺氢形成的聚合物自由基引起的，而热交联是由于所得氨基的缔合。但热交联机理的细节尚不清楚.光辐射的共聚物轴承氨基甲酰氧基亚胺基团的薄膜中被发现，诱导其不溶与形成侧氨基和肼基。此外，光照后的热处理也提高了不溶度，其中1号到3号的结果是非常有趣的，因为它们是可以热放大的新型光交联体系。4.我们发现带有苯甲酰甲基和N，N-二甲基氨基甲酸根阴离子的季铵盐的光解导致叔胺的生成。这是一种不同于光化学产生伯胺和仲胺的光生碱剂的新型光生碱剂。它们在阴离子聚合和环氧化物固化中的应用是有希望的。少

项目成果

M.Tsunooka, H.Tachi, K.Asakino, K.Suyama: "Oxime Derivatives as Photobase Generators : Their Use for Novel Photo-Crosslinking Systems"Proc.RadTech Europe. (Berlin). 405-410 (1999)

M.Tsunooka、H.Tachi、K.Asakino、K.Suyama：“肟衍生物作为光碱生成器：它们在新型光交联系统中的用途”Proc.RadTech Europe。

M. Tsunooka, H. Tachi, K. Asakino, K. Suyama: "Oxime Derivatives as Photobase Generators: Their Use for Novel Photo-Crosslinking Systems"Proc. RadTech Europe '99 (Berlin). 405-410 (1999)

M. Tsunooka、H. Tachi、K. Asakino、K. Suyama：“肟衍生物作为光碱生成器：它们在新型光交联系统中的用途”Proc。

M. Tsunooka, H. Tachi, K. Asakino, K. Suyama: "Synthesis of Photobase Generators and Their Use for Design of Polymeric Photosensitive Systems"J. Photoscience. 6・3. 145-151 (1999)

M. Tsunooka、H. Tachi、K. Asakino、K. Suyama：“光碱发生器的合成及其在聚合物光敏系统设计中的应用”J. Photoscience 6・3（1999）。

M.Tsunooka et al.: "Photo-and Thermo-Chemical Behavior of Polymeric Photobase Generators Bearing Pendant Sensitizing Groups" J. Photopolym. Sci. Technol. ,. 11・1. 123-124 (1998)

M. Tsunooka 等：“带有悬垂敏化基团的聚合物光碱发生器的光化学行为”J. Photopolym，11・1。

M. Tsunooka, H. Tachi: "Polymeric Photobase Generators : Their Use in Developmets of Novel Photo-Crosslinking Systems"Proc. RadTech 98 North America (Chicago). 228-234 (1998)

M. Tsunooka，H. Tachi：“聚合物光碱发生器：它们在新型光交联系统开发中的用途”Proc。