Materials Applications of Olefin Metathesis Polymerization

提出了利用烯烃歧化和烯烃歧化聚合催化合成新型聚合物材料。这项工作旨在证明这些反应是否是通向一系列分子拓扑的通用路线，并且在聚合物界面应用中是有用的。嵌段共聚物将通过端乙烯基聚合物的歧化反应、使用聚合链转移剂以及在歧化聚合中顺序添加两种特定单体来制备。接枝共聚物将由环烯烃和环烯烃封端的聚合物(大单体)合成。大环聚合物将通过使用多相催化剂对二乙烯基端基聚合物进行歧化反应来制备。通过端二环-烯烃聚合物的歧化反应和环烯烃与交联剂的共合反应，可以制备单一聚合物和共聚聚合物网络。开发一种多功能交联剂也是这项工作的目标。星形聚合物将通过环状烯烃端基聚合物的环状齐聚反应来制备。梯度模数材料将通过改变宏观聚烯烃对象的一维交联度来制备。聚合物的催化粘合工艺将使用聚烯烃和环烯烃表面改性的乙烯基聚合物、金属和金属氧化物来开发。改性金属、金属氧化物和乙烯基聚合物表面将通过表面接枝复分解来构建聚烯烃的薄膜涂层。这项研究使用创新的方法来生产各种新材料，包括一些在聚合物表面具有新型结构的材料。这些新材料的性质应该引起人们相当大的兴趣。

The synthesis of new polymeric materials is proposed, using olefin matathesis and olefin metathesis polymerization catalysis. This work is intended to demonstrate whether these reactions are versatile routes to a range of molecular topologies and are useful in polymer interface applications. Block copolymers will be prepared by the metathesis of vinyl-terminated polymers, the use of polymeric chain-transfer agents and the sequential addition of two specific monomers to a metathesis polymerization. Graft copolymers will be synthesized by the cometathesis of cyclic olefins and cyclic olefin-terminated polymers (macromonomers). Macrocyclic polymers will be prepared by metathesis of divinyl-terminated polymers using a heterogeneous catalyst. Single polymer and copolymer networks will be prepared by metathesis of dicyclic-olefin-terminated polymers and cometathesis of cyclic olefins and a crosslinking agent. The development of a versatile crosslinking agent is an objective of this work as well. Star polymers will be prepared by cyclic oligomerization of cyclic olefin-terminated polymers. Gradient modulus materials will be prepared by varying the crosslink density across one dimension of macroscopic poly(alkenamer) objects. Catalytic adhesion processes for polymers will be developed using both poly(alkenamers) and cyclic olefin- surface-modified vinyl polymers, metals and metal oxides. Thin film coatings of poly(alkenamers) will be constructed by surface graft metathesis from modified metal, metal oxide, and vinyl polymer surfaces. This research uses innovative methods to produce a variety of new materials, including some that have new types of structure on the surfaces of polymers. The properties of these new materials should be of considerable interest.