Syntheses of New Functionalized Materials by Radical Ring-Opening Polymerization and Their Evaluation of Physical Properties

我们研究了市售乙烯基单体与自由基开环聚合性单体的共聚反应，以开发新的官能化材料，包括聚合物主链中的酯基、醚基和酮基等官能团。新型自由基开环聚合单体的合成：（1）以2，2-二苯基-4-亚甲基-1，3-二氧戊环（DPMD）为单体，进行自由基聚合，得到了二苯甲酮定量消除的聚酮。(2)亚甲基环丁烷进行乙烯基不开环聚合，而乙烯基环丁烷进行自由基开环聚合，得到聚（1，6-己-2-烯）。(3)乙烯基硫杂环丙烷的自由基聚合反应是在碳硫键上开环的，而乙烯基环氧乙烷的聚合反应中环氧环上的碳碳键断裂。(4)制备了带有苯基、酯基和氰基等官能团的乙烯基环丙烷，发现它们都发生了自由基开环聚合.共聚：（1）乙烯基环氧乙烷与乙烯进行共聚，以获得在聚合物主链中带有乙烯基醚基团的聚乙烯。(2)DPMD与乙烯共聚得到主链上含有酮和醚基团的聚乙烯。(3)进行DPMD与苯乙烯的共聚以获得在聚合物主链中包含酮基团的聚苯乙烯。此外，通过改变DMPD的投料比，可以任意控制聚合物中酮基的含量。(4)DPMD还可以与其他乙烯基单体如N-乙烯基-2吡咯烷酮、乙酸乙烯酯和甲基丙烯酸甲酯共聚，以产生在聚合物主链中包含酮基的相应共聚物。目前对这些共聚物的物理性质的研究正在进行中。

We have investigated the copolymerization of commercially available vinyl monomers with radical ring-opening polymerizable monomers in order to develop new functionalized materials including the functional groups such as the ester group, ether group, and ketone group in the polymer backbone.1. Syntheses of New Radical Ring-Opening Polymerizabel Monomers: (1) Radical polymerization of 2,2-Diphenyl-4-methylene-1,3-dioxolane (DPMD) was carried out to obtain poly(ketone) with a quantitative elimination of benzophenone. (2) Methylenecyclobutane underwent vinyl polymerization without ring-opening, whereas vinylcyclobutane did radical ring-opening polymerization to afford poly(1,6-hex-2-ene). (3) Vinylthiirane underwent radical polymerization with the ring-opening at the bond between carbon and sulfur atom, although carbon-carbon bond of the oxirane ring was cleaved in the polymerization of vinyloxirane. (4) Vinylcyclopropanes bearing functional groups such as the phenyl group, ester group, and cyano group were prepared, and all of them were found to undergo radical ring-opening polymerization.2. Copolymerization: (1) Copolymerization of vinyloxirane with enhylene was carried out to obtain polyethylene bearing the vinyl ether groups in the polymer backbone. (2) Copolymerization of DPMD with enhylene afforded polyethylene containing the ketone and ether groups in the polymer backbone. (3) Copolymerization of DPMD with styrene was carried out to obtain polystyrene including the ketone groups in the polymer backbone. furthermore, the content of the ketone group in the polymer can be arbitrarily controlled by the change of DMPD's feed ratio. (4) DPMD can copolymerize also with other vinyl monomers such as N-vinyl-2 pyrrolidone, vinyl acetate, and methyl methacrylate to yield the corresponding copolymers including the ketone groups in the polymer backbone. Further investigation on physical propaties of these copolymers is in progress now.