【摘要】 通过大分子设计合成了一种荧光温敏性聚丁二烯功能橡胶弹性体.首先以辛酸亚锡为催化剂,用ε-己内酯扩链改性端羟基聚丁二烯液体橡胶,获得聚丁二烯己内酯大分子单体,在保留端部羟基(—OH)官能团的基础上改善了原聚丁二烯橡胶的分子量和耐热性;然后采用自由基聚合法,以N-异丙基丙烯酰胺为单体、巯基乙酸为链转移剂,合成端羧基聚N-异丙基丙烯酰胺大分子单体;最后通过缩合反应,在N,N-二环己基碳二亚胺作用下将端羧基聚N-异丙基丙烯酰胺与聚丁二烯己内酯大分子连接,获得一种分子量为8000~15000的聚丁二烯橡胶共聚物.采用傅里叶红外光谱(FTIR)、核磁共振波谱(NMR)、凝胶渗透色谱(GPC)、X射线光电子能谱(XPS)、紫外-可见分光谱计(UV-Vis)、荧光光谱等对相应产物进行结构与性能的表征.结果表明,聚丁二烯橡胶共聚物在274 nm处存在紫外吸收,能被304 nm的波长激发,具有荧光特性;聚丁二烯橡胶共聚物存在临界相转变温度LCST=30℃,即当温度低于30℃时,聚丁二烯橡胶共聚物为亲水-疏水嵌段共聚体;当温度高于30℃时,则转变成完全疏水共聚体,具有温敏特性.聚丁二烯橡胶共聚物同时具有荧光性与温敏性,将在发光、分离材料等领域作出贡献.更多还原

【Abstract】 Polybutadiene rubber with the fluorescence and thermo-responsive properties was synthesized by macromolecular design. Firstly,the block copolymer polybutadiene-b-poly( ε-caprolactone)( HTBCP) was synthesized via the ring-opening polymerization of ε-caprolactone in presence of a hydroxyl-terminated polybutadiene( HTBP),which was catalyzed by stannous octanoate [Sn( Oct)2]. With the help of ε-caprolactone,polybutadiene rubber was improved in molecular weight and heat resistance,which was also terminated by hydroxyl( —OH). Then the macro-monomer of carboxyl- terminated poly( N-isopropyl acrylamide)( PNIPAm-COOH) was synthesized via the free radical polymerization in presence of mercaptoacetic acid( MAA). Finally the copolymer of polybutadiene rubber( HTBCP-b-PNIPAm) with moderate molecular weights( Mn= 8000 ~ 15000) was synthesized from polybutadiene-b-poly( ε-caprolactone)and the macro-monomer of carboxyl- terminated poly( N-isopropyl acrylamide) by the condensation reaction,which was catalyzed by dichloroacety chloride( DCC). The polymer of polybutadiene-b-poly( ε-caprolactone)( HTBCP),poly( N-isopropyl acrylamide)( PNIPAm-COOH) and polybutadiene rubber( HTBCP-b-PNIPAm)were characterized by Fourier transform infrared spectroscopy( FTIR),nuclear magnetic resonance( NMR),gel permeation chromatography( GPC),X-ray photoelectron spectroscopy( XPS),UV-Visible spectroscopy( UV-Vis),fluorescence spectroscopy etc. The results suggested that the copolymer of polybutadiene rubber was fluorescent having UV absorption at 274 nm and fluorescence excitation at 304 nm; besides the copolymer of polybutadiene rubber showed a critical phase transition temperature( LCST) at 30 ℃,at temperatures higher than 30 ℃,the copolymer HTBCP-b-PNIPAm has hydrophobic / hydrophobic chain segments,on the other hand it has hydrophobic / hydrophilic chain segments. The polybutadiene rubber with the fluorescence and thermoresponsive properties will make contribution in the field of luminescent or separating material.更多还原