Design and Construction of Synthetic Procedure of Nano-materials Exhibiting either No-shrinkage or Expansion on Polymerization

含环碳酸酯结构的降冰片烯开环合成相应的多降解物。聚合过程中的体积收缩明显低于典型的单环开环聚合，这取决于碳酸盐环的大小、聚合物的相对分子质量和主链中的顺反含量。含碳酸酯结构的降冰片烯与环辛烯的共聚也提供了体积变化可控的聚合物。所得到的具有碳酸酯环的聚合物可以通过阳离子开环聚合进行交联，以获得三维聚合物。这些结果表明，复分解聚合也构建了低体积收缩体系，这是一种重要的聚合方法。在侧链上含有螺原碳酸酯(SOC)结构的聚合物的阳离子交联中，我们发现共聚组分对交联过程中的体积变化行为有很大的影响。也就是说，即使SOC含量较低，含有给电子体单体单元的共聚物的交联也会扩大体积。相反，含吸电子单体单元的共聚物表现出适度的体积膨胀，并随着SOC单元的增加而增加。

Ring-opening methathesis polymerization of norbomenes bearing cyclic carbonate structures afforded the corresponding polynortbomenes. The volume shrinkages in the polymerization, significantly lower than typical single-ring-opening polymerizations, depended on the ring-size of the carbonate rings, the molecular weights of the polymers, and the cis-trans contents in the main chains. Copolymeriation of the norbomenes bearing carbonate structures with cyclooctene also afforded the polymers with controllable volume changes. The resulting polymers having carbonate rings can be crosslinked via cationic ring-opening polymerization to obtain three-dimensional polymers. These results have demonstrated that low volume shrinkage system has been also constructed for metathesis polymerization, which has been focused on as an industrially important polymerization method.In the cationic cross-linking of the polymers bearing spiroorthocarbonate (SOC) structures in the side chains, we have found that the copolymer component highly affects the volume change behavior during the crosslinking. That is, the crosslinking of the copolymers containing the units from electron-donating monomers expands the volume even if the SOC contents were lower. In contrast, that of the copolymers containing the units from electron-withdrawing monomers exhibits moderate volume expansion, which increased as the increase of the SOC units.