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

研究了相转移催化法合成含乙烯基醚侧链的聚合物及其应用。采用相转移催化法，在温和的反应条件下，通过氢氧化钾或叔丁醇钾与聚环氧氯丙烷（PECH）的消除反应合成了含乙烯基醚侧链的聚合物（P-1），并用光生阳离子催化剂（PGCC）对所得聚合物进行了紫外光降解。然而，P-1的Tg较低。因此，通过使用相转移催化剂的PECH的消除和取代反应，进行含有乙烯基醚部分和大体积取代基的高Tg聚合物（P-3）的合成。虽然P-3与PGCC在紫外光照射下分解，但P-3与芳香族双叠氮化物或二硫醇化合物在照射下得到交联凝胶化合物。该结果表明，通过选择催化剂或光敏剂，P-3可以应用于正型和负型光致抗蚀剂。P-1在四氢呋喃中以二苯甲酮为光敏剂，与N-乙酰基-L-半胱氨酸发生光化学加成反应，合成了一种新型的含侧基氨基酸的光学活性聚合物。用2-氯乙基乙烯基醚与聚乙烯基苯酚在相转移催化下发生取代反应，合成了一种含乙烯基醚侧链的新型聚合物（P-4），转化率约为80 mol-%，并考察了该聚合物与双叠氮化合物或双硫醇化合物的光敏性。该结果表明P-4具有高的光敏性，并且可以应用于负型光致抗蚀剂。

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.