聚氨酯-聚甲基丙烯酸丁酯共聚体水分散体的制备及性能研究  

Synthesis and Characterization of Polyurethane-Poly( butyl methacrylate)Copolymer Aqueous Dispersions

作　　者：孙仪琳 陈柏祥[1] 马立翔 冯皓[1] 李坚[1] 任强[1] 汪称意[1] 

机构地区：[1]常州大学材料科学与工程学院材料化学系,常州213164

出　　处：《高分子学报》2015年第6期624-632,共9页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号51203014);江苏省普通高校研究生科研创新计划(项目号CXLX13_723);江苏省大学生实践创新计划(项目号2014102920282);常州大学科技创新基金暨"挑战杯卓越"计划(项目号201410292028Z)资助

摘　　要：研究了聚氨酯-聚甲基丙烯酸丁酯共聚体水分散体(PUBMA)的制备及其性能.首先采用电子转移再生催化剂原子转移自由基聚合(ARGET ATRP),以α-溴代异丁酸羟丁酯为引发剂,溴化铜(Cu Br2)为催化剂,五甲基二乙烯三胺(PMDETA)为配体,辛酸亚锡(Sn(EH)2)为还原剂,制备了端羟基聚甲基丙烯酸丁酯(PBMA-OH).其次以聚醚二元醇(N220)、聚醚三元醇(N330)、PBMA-OH、甲苯-2,4-二异氰酸酯(TDI)、二羟甲基丙酸(DMPA)为原料,制备聚氨酯-聚甲基丙烯酸丁酯共聚体水分散体(PUBMA).研究了PBMA-OH含量对PUBMA水分散体及其薄膜性能的影响.结果表明成功制备了聚氨酯-聚甲基丙烯酸丁酯共聚体水分散体.随着PBMA-OH含量的增加,乳液粒径增大,分布变宽;力学性能和耐水性测试表明其薄膜的拉伸强度增大,从6 MPa增强至8 MPa,断裂伸长率降低,由1500%降至800%,耐水性变好.通过原子力显微镜(AFM)和动态热机械分析(DMA)测试说明PUBMA呈现两相分离形态,并且随着PBMA-OH的含量增加,PUBMA的玻璃化转变温度升高.Polyurethane-poly（ butyl methacrylate） copolymer aqueous dispersions（ PUBMA） were synthesized via hydroxyl-terminated poly（ butyl methacrylate）. The hydroxyl-terminated poly（ butyl methacrylate）（ PBMAOH） was synthesized via atom transfer radical polymerization with activators regenerated by electron transfer（ ARGET ATRP） using hydroxylbutyl α-bromoisobutyrate as an initiator,copper（ II） bromide（ Cu Br2）（ 0. 05% molar fraction of monomer） as a catalyst,pentamethyldiethylene triamine（ PMDETA） as a ligand,and stannous octoate（ Sn（ EH）2） as a reducing agent. Polyurethane-poly（ butyl methacrylate） copolymer aqueous dispersions（ PUBMA） were then synthesized using polyether diols（ N220）,polyether triols（ N330）,PBMA-OH,toluene diisocyanate（ TDI） and dimethylol propionic acid（ DMPA） as the main raw materials.The effects of the amount of PBMA-OH on the properties of PUBMA aqueous dispersions and films were investigated. The results showed that polyurethane-poly（ butyl methacrylate） copolymer aqueous dispersions were successfully synthesized. With the increment of the amount of PBMA-OH,the particle sizes of the PUBMA aqueous dispersions increased and the particle size distribution of the PUBMA became broader than that of the pure PU. The results of mechanical properties and water resistance test indicated that the tensile strength of the PUBMA films increased from 6 MPa to 8 MPa,but the elongation at break decreased from 1500% to 800%,and water resistance of the films improved significantly after the PBMA segment was introduced into PU.Atomic force microscope（ AFM） and dynamic mechanical analysis（ DMA） confirmed that there were obvious two phases in PUBMA,and the PUBMA films had two glass transition temperatures,both the glass transition temperatures increased with the increment of the amount of PBMA.

关 键 词：ARGET ATRP 端羟基聚甲基丙烯酸丁酯 聚氨酯水分散体 共聚体 薄膜性能 

分 类 号：TQ317[化学工程—高聚物工业]