一端接异氰酸酯基的聚丙烯酸酯低聚物的合成及表征  

Synthesis and Characterization of the Monoisocyanate-terminated Low Molecular Polyacrylic Ester

作　　者：张峰[1] 徐国永[2] 章于川[1] 

机构地区：[1]安徽大学化学化工学院,安徽合肥230039 [2]安徽大学现代实验技术中心,安徽合肥230039

出　　处：《精细化工》2009年第12期1235-1239,共5页Fine Chemicals

基　　金：国家支撑计划项目资助(2007BAE22B02)~~

摘　　要：用两步法合成出一端接异氰酸酯基(—NCO)的聚丙烯酸酯低聚物。首先以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为单体,巯基乙醇(2-ME)为链转移剂,低浓度的偶氮二异丁腈(AIBN)为引发剂,在110℃将按n(MMA):n(BA):n(2-ME):n(AIBN)=500:500:25:1配制的溶液,在2.5h内滴加到甲苯中,反应4h,得到多分散系数Mw/Mn=1.8、一端带羟基的聚丙烯酸酯低聚物〔(MMA—BAOH〕;再加入甲苯-2,4-二异氰酸酯(TDI)与其端羟基反应,合成出一端接异氰酸酯基的聚丙烯酸酯低聚物〔(MMA—BANCO〕。该低聚物结构与热性能用FTIR、1HNMR、13CNMR、GPC、DSC、TGA进行了表征。结果表明,产物的分子结构符合分子设计,即一端接有异氰酸酯基(—NCO),数均相对分子质量Mn在4500左右,DSC显示合成的低聚物的Tg在40℃左右,TGA测出其主要热失重在300～450℃。该低聚物可作为大分子表面改性剂,用于氮化硅、氮化铝等纳米粉体的表面修饰改性。A two-stage process was developed to synthesize the low molecular weight copolymer of monoisocyanate-terminated polyacrylic ester. Firstly, monohydroxyl-terminated copolymers[ （MMA-BA OH] were synthesized from methyl methacrylate （MMA） and butyl acrylate （BA） by the radical adjusting copolymerization using a functional chain-transfer agent, 2-mercaptoethanol （2-ME） , and a very low initiator lever, azobisisobutyronitrile （AIBN）. Solutions of 2-ME and AIBN in the monomers having a monomer/2-ME/AIBN mole ratio of 1 000/25/1 were added continuously during 2. 5 h to refluxing toluene at 110 ℃. Stirring and refluxing were continued throughout the adddition for 4 h. Then, the monoisocyanate-terminated copolymers[ （MMA-BA NCO ] was obtained by the reaction of toluene-2,4-diisocynate （ TDI ） and （ MMA-BA OH. The is structure characterized by ^1HNMR,^13 CNMR, FFIR, GPC and TGA. The results and thermal properties were showed that the molecular structure of the product in line with the advance of molecular design,which monoisocyanate-terminated polyacrylic ester was synthesised and the number-average relative molecular mass（Mn） of the product is about 4 500. DSC and TGA show that there is only one Tg about 40 ℃ and the main weight loss is between 300 and 450 ℃. The oligomers can be used as the surface modifier, which was used for the surface modification of native nano-sized silicon nitride（Si3N4） and aluminum nitride（AIN） powder.

关 键 词：链转移剂 调节聚合 聚丙烯酸酯低聚物 端羟基 端异氰酸酯基 大分子表面改性剂 丙烯酸系列化学品 

分 类 号：O632.52[理学—高分子化学]