权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

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.

我们已经发现，苯醌是非常有效的聚合物的光交联剂，其中一些是非常敏感的可见光。本文研究了含苯醌类聚合物的光交联机理，并在此基础上研究了利用苯醌类聚合物制备可见光（特别是激光）敏感聚合物的方法。对苯醌对聚甲基丙烯酸甲酯（PMMA）的光交联反应是通过自由基机理进行的，对苯醌上引入烷基取代基降低了光交联反应的活性。另一方面，在具有环氧或环硫侧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。这种光交联解释为开环聚合的侧基。此外，烷基硫基苯醌在400至500 nm之间具有最大吸收，并且在可见光（<lambda>> 370 nm）诱导的具有环硫基团的聚合物的交联中非常有效。结合到聚合物链上的醌单元被发现在对苯醌光交联PMMA中起重要作用。基于这一发现，制备的聚合物轴承侧quinidine基团进行了检查。合成了含苯醌基硫代乙酰氧基的甲基丙烯酸甲酯共聚物，发现其含量虽低，但对可见光非常敏感。还制备了带有醌基硫基的聚芳醚。虽然可以增加官能团的含量，但其光交联速率很低。在聚氨酯中加入另一种链烷醇，并用脂肪族二异氰酸酯代替芳香族二异氰酸酯，可提高聚氨酯的光交联速率。