纳米TiO_2/P(MMA-BA-MAA)复合粒子的制备及聚合动力学  

Synthesis and kinetics study of TiO_2/P(MMA-BA-MAA) composite particles by emulsion polymerization

作　　者：张建民[1,2] 孙秀果[1] 王彩辉[1] 高俊刚[2] 

机构地区：[1]石家庄铁道学院材料科学与工程分院,河北石家庄050043 [2]河北大学化学与环境科学学院,河北保定071002

出　　处：《化工学报》2009年第10期2640-2649,共10页CIESC Journal

基　　金：河北省自然科学基金项目(E200800440)~~

摘　　要：用乳液聚合法制备了纳米Ti O2/甲基丙烯酸甲酯-丙烯酸丁酯-甲基丙烯酸共聚物[Ti O2/P(MMA-BA-MAA)]复合粒子。考察了乳化剂的浓度、单体的用量比对复合粒子形貌的影响。系统研究了乳化剂浓度、引发剂用量、单体用量比、共乳化剂浓度、反应温度对Ti O2/P(MMA-BA-MAA)复合粒子包覆反应动力学影响。用TEM、FTIR及TG分析等证实P(MMA-BA-MAA)包覆在Ti O2表面形成表面光滑、分散性好的球形核-壳复合粒子。根据动力学实验结果,求出整个乳液聚合包覆反应的反应速率方程,反应的表观活化能为163.0kJ.mol-1。推测可能的包覆反应机理应为无机纳米Ti O2表面吸附乳化剂分子形成所谓的Ti O2/surfactant胶束成核或均相凝聚成核。TG结果显示,复合粒子的热稳定性高于相同条件下得到的共聚物的稳定性。ζ电位、接触角实验表明,与纳米Ti O2相比,复合粒子亲水性能下降、亲油性能提高。The TiO2/methyl methacrylate-butyl acrylate-methacrylic acid copolymer [TiO2/P（MMA-BA-MAA）] composite particles were synthesized by emulsion polymerization. The emulsifier concentration and molar concentration ratios of monomers exhibited a great influence on the morphology of the composite particles. The effects of operation variables, such as emulsifier concentration, initiator concentration, molar concentration ratios of monomers, co-emulsifier concentration, polymerization temperature on the kinetic features were also investigated. The TEM images, FTIR spectra and TG analysis indicated that the composite particles of TiO2/P（MMA BA-MAA） with smooth surface, good dispersibility and spherical core-shell structure were obtained. The kinetics data showed that under the conditions studied the rate equation for the whole reaction of coating polymerization was educed, and the apparent activation energy was 163.0 kJ · mol^-1, which suggested that the possible reaction mechanism could be ＂TiO2/surfactant＂ micelle nucleation and homogeneous coagulative nucleation mechanism of the emulsion polymerization ofMMA-BA-MAA. Thermal analysis showed that the thermal stability of composite particles was higher than that of copolymer particles formed under the same conditions. Compared with nano-TiO2, the measurements of ξ-potential and contact angles of composite particles indicated that the hydrophilicity composite particles decreased and the hydrophobicity increased.

关 键 词：TIO2 含甲基丙烯酸共聚物 复合粒子 乳液聚合 动力学 

分 类 号：TQ630.4[化学工程—精细化工]