Synthesis,Cyclization,Thermal Decomposition And Dehydrogenation Of Diphenyl-containing Ethylene Polymers

The precise design and synthesis of polymers has always been one of the most concerned research directions in the field of polymer chemistry.By designing the polymer structure,a variety of fine-structure polymers and functional polymers can be obtained.In this paper,a variety of diphenyl-containing rigid hydrocarbon polymers were designed and synthesized,and a variety of functional polymers were synthesized by post-modification methods such as cyclization,dehydrogenation,and pyrolysis.The main research contents and results are as follows:1.Design and synthesis copolymer of TS and 1,3-CHD.A novel hydrocarbon copolymer PCTS was synthesized by anion polymerization.PCTS with alternating structure can be obtained by using THF/25℃/n-BuLi system.With the increase of nTs/n 1,3-CHD in the copolymer,the Tg of the copolymer increases,and the alternating copolymer can reach a maximum of 155℃.2.Cationic cyclization produces high Tg hydrocarbon polymers.Using PCTS and P12DPB as cyclization precursors to cation cyclization to prepare high Tg hydrocarbon polymers.The cyclization degree of PCTS with alternating structure is close to 100%,and the cyclization increases the Tg by about 60℃,up to 213℃;the Tg of the P12DPB cyclization product increases with the increase of its 1,4-structure content,reaching a maximum of 233℃.3.Synthesis of polymers with carbon-carbon weak bonds structure in the main chain and preparation of new block copolymers.Using TS as the building block,copolymerizing it with 1,3-CHD,St,MANH to prepare three alternating copolymers PCTS、PSTS、P(TS-MANH)with weak bonds structure in the main chain.They can pyrolysis to initiate polymerization of MMA.Finally,three new block copolymers PCTS-b-PMMA,PSTS-b-PMMA,P(TS-MANH)-b-PMMA were synthesized..4、Preparation of AIE conjugated polymers and high carbon forming polymers.Conjugated polymers of various structures were synthesized by dehydrogenation of PCTS.The dehydrogenation product of PCTS with alternating structure has AIE characteristics and can effectively detect TNT;When n1,3-CHD/nTS in the copolymer is greater than 2,the dehydrogenation product of PCTS exhibits ACQ behavior.The dehydrogenation products of P12DPB have a higher carbon formation rate than P12DPB.The carbon formation rate increased with the decrease of 1,4-structure content in P12DPB,reaching a maximum of 54.0%.