Syntheses of High Sensitive Photocrosslinking Reagents and Their Application to Visible Light (Laser) Sensitive Polymer Systems.

高灵敏度光交联试剂的合成及其在可见光（激光）敏感聚合物体系中的应用。

基本信息

批准号：
60550647
负责人：
TSUNOOKA Masahiro
金额：
$ 1.28万
依托单位：
University of Osaka Prefecture
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1986
项目状态：
已结题

项目摘要

We have found that benzoquinones are very effective photocrosslinking reagents for polymers and that some of them are very sensitive to visible light. In this study we have investigated the photocrosslinking mechanism of polymers with benzoquinones and, at the same time, on the basis of the mechanism we have investigated preparation methods of visible light (especially, laser) sensitive polymers by the use of benzoquinones. The photocrosslinking of poly(methyl methacrylate) (PMMA) by p-benzoquinone proceeded via a free radical mechanism and the introduction of alkyl groups as substituents to p-benzoquinone depressed the activity in the photocrosslinking. On the other hand, in the photocrosslinking of polymers which have pendent epoxy or epithio groups, alkyl(e.g., ethyl or t-butyl) group subsitituted benzoquinones were more effective than p-benzoquinone. This photocrosslinking was explained by ring opening polymerization of pendent groups. Moreover, alkylthiobenzoquinones have an absorption maximum between 400 and 500nm,and were very effective in the visible light ( <lambda> >370nm) induced crosslinking of the polymers which had episulfide groups. Quinonoid units bound to polymer chains were found to play an important role in the photocrosslinking of PMMA by p-benzoquinone. On the basis of this finding, preparations of the polymers bearing pendent quinonoid groups were examined. The copolymer of methyl methacrylate bearing benzoquinonylthioacetoxy groups were prepared and found to be very sensitive to visible light in spite of its low content. Polyurethanes bearing quinonylthio groups were also prepared. Although the content of functional groups could be increased, the rates of their photocrosslinking were pretty low. The addition of another alkanediol to the polyurethanes and the use of aliphatic diisocyanate instead of aromatic one improved their photocrosslinking rates.

我们发现苯醌是非常有效的聚合物光交联试剂，其中一些对可见光非常敏感。本研究研究了苯醌类聚合物的光交联机理，同时在此基础上研究了苯醌类可见光（特别是激光）敏感聚合物的制备方法。对苯醌对聚甲基丙烯酸甲酯(PMMA)的光交联是通过自由基机理进行的，并且向对苯醌引入烷基作为取代基会降低光交联的活性。另一方面，在具有侧环氧基或环硫基的聚合物的光交联中，烷基（例如乙基或叔丁基）取代的苯醌比对苯醌更有效。这种光交联可以通过侧基的开环聚合来解释。此外，烷硫基苯醌在400至500nm之间具有最大吸收，并且在可见光(λ>370nm)诱导的具有环硫基团的聚合物的交联中非常有效。研究发现，与聚合物链结合的醌类单元在对苯醌引起的 PMMA 光交联中发挥着重要作用。在此发现的基础上，对带有醌型侧基的聚合物的制备进行了检查。制备了带有苯醌基硫代乙酰氧基的甲基丙烯酸甲酯共聚物，发现尽管其含量较低，但对可见光非常敏感。还制备了带有醌硫基的聚氨酯。虽然官能团的含量可以增加，但其光交联率很低。在聚氨酯中添加另一种链烷二醇并使用脂肪族二异氰酸酯代替芳香族二异氰酸酯提高了它们的光交联速率。