Establishment and Application of the Concept of Latent Catalyst to Control the Polymerization Reaction

为了建立“潜在引发剂”的“潜在催化剂”这一通过适当刺激引发和控制聚合反应的新概念，对各种新型潜在引发剂的合成、潜在引发剂设计原理的建立以及潜在引发剂在新型聚合体系中的应用进行了研究。澄清了各种类型的吡啶盐、磺化盐和磷盐在各种阳离子可聚合单体（如环氧化物、苯乙烯和乙烯醚）的聚合中作为优异的热和/或光潜引发剂。通过对潜在引发剂的结构、催化活性与服务于催化活性的阈值温度或阈值波长之间的关系的研究，不仅建立了在所需温度或阈值波长上服务于催化活性的潜在催化剂的分子设计原理，而且建立了用于阳离子聚合的热潜在引发剂和光潜在引发剂的概念。进一步阐明了邻苯二胺、丙二腈、磺酸酯和羧酸酯也可作为阳离子聚合的无盐热潜引发剂。新型概念材料如自催化剂固化时不收缩的新型聚合物、新型缩醛化催化剂、可光固化的普通聚合物等已被开发出来。阐明了潜在引发剂可以利用引发过程中释放的亲核试剂控制起始和延伸反应。新的概念聚合体系如可在空气中分离和稳定的新型活性聚合体系、双功能单体无交联选择性聚合等已被开发出来。应用潜在引发剂的概念，可以开发出一种新的潜在引发剂体系，该体系可以通过任何可选的刺激来控制聚合

To establish a novel concept, "latent catalyst" of "latent initiator", which initiate and control the polymerization by an appropriate stimulation, syntheses of various novel latent initiators, establishment of the principle for the design of latent initiators, and application of latent initiators for the novel polymerization system have been studied. It was clarified that various types of pyridinium salts, sulfonium salts, and phophonium salts serve as excellent thermal-and/or photo-latent initiators in the polymerization of various cationically polymerizable monomers such as epoxides, stirenes, and vinyl ethers. After the study on the relationship among the structure, catalytic activity, and threshold temperature or wave length above which the latent initator serve catalytic activity, not only the principle for the molecular design of the latent catalyst which serve catalytic activity at desired temperature or wave length, but the concept of thermal and photo-latent initiator for the cationic polymerization was established. Further, it was clarified that phthalimides, malononitriles, sulfonic acid esters, and carboxylic esters also serve as salt-free thermal-latent initiators for the cationic polymerization. Novel conceptual materials such as novel polymers which show no shrinkage on the curing by self-catalyst, novel catalysts for the acetalization, and photo-curable common polymers have been developed. It was clarified that not only initiation step but also elongation step can be controlled by the latent initiators using the nuclephiles released on the initiation step. Novel conceptual polymerization system such as novel living polymerization system which can be isolated and stable in the air and selective polymerization of bifunctional monomers without crosslinking have been developed. Novel latent initiator system by which polymerization can be control by any optional stimulation may be developed by the application of the concept of the latent initiators for