Anionic Synthesis Of In-chain Multi-functionalized Copolymers With Precise Molecular Architectures

Syntheses of derivatives of1,1-diphenylbenzene (DPE) with mono-and bi-functional groups were explored. Furthermore, DPE derivates with mono-functional silyl hydride group (dimethyl (4-(1-phenylvinyl) phenyl) silane, DPESiH) and bi-functional methoxy group ((1,1-bis(4-methoxyphenyl)ethylene, BMDPE) were synthesized.1H NMR, IR, MS, GC, and LC were used for the characterization and the method for purification of functional monomers for anionic polymerization has been set up.In this thesis, well defined in-chain functionalized copolymers with styrene, butadiene and isoprene as monomers respectively were synthesized based on the anionic polymerization, while DPE derivatives used as functional monomers. The polymerization factors, initiator, stoichiometry of DPE to monomer, additive (THF), solvent and so on, were studied. A simple rule about the influences of these factors to copolymerization was obtained. The aim copolymers were prepared while benzene was used as solvents, sec-BuLi was used as initiator and THF was used as additive at50℃. The copolymers of styrene-DPESiH and styrene-BMDPE with molecular weight from10,000to50,000were prepared and low polydispersity (PDI<1.19) was obtained, while the number of silyl-hydride groups was calculated and discussed with size exclusion chromatography (SEC) and1H NMR. An appromixate alternative multi-functionalized copolymers (PS-DPESiH-5-120413) was synthesized by controlling the ratio of styrene to DPE derivatives. All the results showed that the synthesis of well defined (especially in quantity and position) functionalized copolymers could be prepared, which could also be used for the synthesis of new type polymers.In addition, hydrosilylation was also done used the copolymers obtained, while Karstedt’s catalyst was used for the synthesis in toluene at60℃. Based on hydrosilylation, some novel groups, such as ferrocene and oxhydryl group, were attached to our copolymers and a series of new type polymers were obtained, with SEC,1H NMR, IR and differential scanning calorimetry (DSC) techniques were used for the characterization. The rule of the reaction between silyl hydride groups and functionalized agents was studied and the hydrosilylation condition was optimized. Furthermore, the foundation for the applications of functionalized polymers was developed.