Synthesis and Application of polymers Containing Pendant Vinyl Ether Moiety Using Phase Transfer Catalysis

相转移催化法合成乙烯基醚聚合物及其应用

• 批准号: 59550636
• 负责人: NISHIKUBO Tadatomi
• 金额: $ 1.28万
• 依托单位: Kanagawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1984
• 资助国家: 日本
• 起止时间: 1984 至 1985
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-59550636/
• 关键词: Phase Transfer Catalysis; Vinyl Ether Moiety; Photo-Decomposization; Positive Photo-Resist; Negative Photo-Resist; 光カチオン分解反応; 光マイケル付加反応; 光学活性高分子; NーアセチルーLーシスティーン残基; ポジ型フォトレジスト; ネガ型フォトレジスト

Syntheses of polymers containing pendant vinyl ether moiety using phase transfer catalysis and applications of the resulting polymers were investigated. Polymer containing pendant vinyl ether moiety (P-1) was synthesized by the elimination reaction of poly(epichlorohydrin) (PECH) with potassium hydroxide or potassium tert-buthoxide using phase transfer catalysis under mild reaction conditions, and the resulting polymer decomposed by the irradiation of UV light using photo-generated cataionic catalyst (PGCC). However, the Tg of P-1 was low. Accordingly, synthesis of high Tg polymer (P-3) containing vinyl ether moiety and bulky substituent group was carried out by the elimination and substitution reactions of PECH using phase transfer catalysis. Although P-3 with PGCC decomposed by the irradiation of UV light, P-3 with aromatic bis-azide or di-thiol compounds gave the crosslinked gel compounds by the irradiation. This result indicates that P-3 can be applied to positive and negative types photoresists by the selection of the catalyst or photosensitizer. P-1 produced new optically active polymer containing pendant amino acid moiety by photochemical addition reaction with N-acetyl-L-cysteine using benzophenone as a photosensitizer in THF. A new polymer (P-4) containing pendant vinyl ether moiety was also prepared with about 80 mol-% conversion by the substitution reaction of poly(vinyl phenol) with 2-chloroethyl vinyl ether using phase transfer catalysis, and the photosensitivity of the resulting polymer with bis-azide or di-thiol compounds was examined. This result indicates that P-4 has high photosensitivity, and can be applied to negative type photo-resist.

研究了相转移催化法制备乙烯醚悬垂聚合物及其应用。在温和反应条件下，以聚环氧氯丙烷（PECH）与氢氧化钾或叔丁二氧化钾进行相转移催化，合成了含悬垂乙烯醚（P-1）的聚合物，并利用光生阳离子催化剂（PGCC）在紫外光照射下分解所得聚合物。P-1的Tg较低。在此基础上，利用相转移催化的聚乙二醇（PECH）的消除和取代反应，合成了含乙烯醚基团和大取代基的高Tg聚合物（P-3）。虽然P-3与PGCC在紫外光照射下可以分解，但P-3与芳香双叠氮化物或二硫醇化合物在紫外光照射下得到交联凝胶化合物。这一结果表明，通过催化剂或光敏剂的选择，P-3可以应用于正负型光阻剂。P-1以二苯甲酮为光敏剂，在四氢呋喃中与n -乙酰- l-半胱氨酸进行光化学加成反应，制备了含有悬垂氨基酸片段的新型光学活性聚合物。以2-氯乙基乙烯醚取代聚乙烯酚，采用相转移催化法制备了含悬垂乙烯醚基团的新型聚合物P-4，转化率约为80摩尔%，并考察了该聚合物与双叠氮化物或二硫醇类化合物的光敏性。结果表明，P-4具有较高的光敏性，可用于负极型光致抗蚀剂。

项目成果

Tadatomi Nishikubo,;Takashi Iizawa,;Yoshihiko Sugawara,;Tsutomu Shimokawa: "Degradation of Dehydrochlorinated Poly(epichlorohydrin) using Photo-Generated Cationic Catalysts" Journal of Polymer Science: Polymer Chemistry Edition. 24. 1079-1108 (1986)

Tadatomi Nishikubo,;Takashi Iizawa,;Yoshihiko Sugara,;Tsutomu Shimokawa：“使用光生阳离子催化剂降解脱氯化氢聚（环氧氯丙烷）”高分子科学杂志：高分子化学版。

Tadatomi Nishikubo,;Tsutomu Shimokawa,;Hiroki Arita: "Photochemical Reaction of a Polymer Containing Vinyl Ether Moieties with Thiol Compounds" Makromol. Chem.188. 2105-2110 (1987)

Tadatomi Nishikubo,;Tsutomu Shimokawa,;Hiroki Arita：“含有乙烯基醚部分的聚合物与硫醇化合物的光化学反应”Makromol。

T.Nishikubo;T.Shimokawa;T.Fijii;T.Iizawa;Y.Harita;M.Koshiba: J.Polym.Sci.,Polym.Chem.Ed.26. 2881-2896 (1988)

T.Nishikubo;T.Shimokawa;T.Fijii;T.Iizawa;Y.Harita;M.Koshiba：J.Polym.Sci.，Polym.Chem.Ed.26。

Tadatomi Nishikubo,;Tsutomu Shimokawa,;Takeshi Fujii,;Takashi Iizawa,;Yoshiyuki Harita,;Mitsunobu Koshiba: "Study of Photopolymers. XXXIII. Chemical Modification of Poly(epichlorohydrin) and Its Application as Photosensitive Polymers" Journal of Polymer S

Tadatomi Nishikubo,;Tsutomu Shimokawa,;Takeshi Fujii,;Takashi Iizawa,;Yoshiyuki Harita,;Mitsunobu Koshiba：“光聚合物的研究。XXXIII.聚环氧氯丙烷的化学改性及其作为光敏聚合物的应用”聚合物 S 杂志