胶粒为“Salami”结构的PMMA/SiPUA乳液与膜性能研究  

Investigation on Properties of PMMA/SiPUA Latexes with “Salami” Structural Particles and Their Coating Films

作　　者：孙静[1] 王海利[1] 丁瑜秋[1] 方华高[1,2] 杨善中[1,2] 丁运生[1,2] 

机构地区：[1]合肥工业大学化学与化工学院 [2]先进功能材料与器件安徽省重点实验室,合肥230009

出　　处：《高分子学报》2016年第11期1572-1578,共7页Acta Polymerica Sinica

基　　金：国家高技术研究发展计划项目(863计划;项目号2015AA033903);安徽省重点科技攻关项目(项目号1301021016);中国航空工业集团产学研项目(项目号cxy2012HFGD24)资助

摘　　要：采用两步法,先以六亚甲基二异氰酸酯(HDI)、聚醚二元醇(N210)、端羟丙基硅油(HPMS)、端羟基丙烯酸树脂(PA-OH)为主要原料,合成了含硅聚氨酯-丙烯酸酯(Si PUA)种子乳液,然后在Si PUA乳胶粒内引入甲基丙烯酸甲酯(MMA),通过原位自由基共聚合,构筑了以Si PUA为壳,聚甲基丙烯酸甲酯(PMMA)为多核的"Salami"结构乳胶粒(PMMA/Si PUA).FTIR和DSC测试表明,聚氨酯、有机硅与丙烯酸酯发生反应,并确认了PMMA的生成;TEM结果显示,PMMA/Si PUA乳胶粒子具有"Salami"结构;随着Si PUA中HPMS含量的增加,PMMA/Si PUA乳胶粒子的粒径先增加后减小,粒径分布则从单峰窄分布变化到双峰宽分布,其乳液涂膜的水接触角呈现先增加后减小的趋势,但膜的吸水率则逐渐减小;与Si PUA相比,PMMA/Si PUA涂膜的透明性有一定下降,相分离程度增加;动态流变测试显示,PMMA/Si PUA涂膜中PMMA的存在,提高了其模量和黏度.当Si PUA中HPMS含量为10 wt%,核/壳质量比m(PMMA)/m(Si PUA)=0.5时,PMMA/Si PUA乳液的粒径较小,且为单峰分布,其涂膜的耐水性和耐高温性能较好.A series of waterborne latexes with hybrid panicles composed of poly（methyl methacrylate） and silicone-containing polyurethane acrylate （PMMA/SiPUA） were successfully prepared via a two-step procedure. Waterborne SiPUA latexes were firstly synthesized to serve as seeds, and methyl methacrylate （MMA） was then introduced into SiPUA latexes to form polymeric cores by in situ radical polymerization. The results of Fourier transform infrared spectrometry （FTIR） and differential scanning calorimeter （DSC） confirm the polymerization of MMA occurred inside SiPUA latex particles. Transmission electron microscopy （TEM） observation showed ＂Salami＂ morphology in the hybrid latex particles,where PMMA and SiPUA acted as the dispersed core and the outer continuous shell, respectively. With increased HPMS content in the latex of SiPUA,the average size of latex panicles of PMMA/SiPUA increased at first and then decreased. Meanwhile, the particle size distribution changed from a narrow unimodal to a wide bimodal distribution. The surface water contact angle of PMMA/SiPUA coating films was found to increase first and then to decrease with increasing HPMS in SiPUA, however, the water absorption of PMMA/SiPUA films showed monotonic decrease with increasing HPMS in SiPUA. Atom force microscopy （AFM） reveals that the surface roughness changes little with the presence of HPMS. With introduction of PMMA in the modified PU,phase separation occurred,which led to the reduction of transparency in PMMA/SiPUA latex films. Rheologieal measurement of PMMA/SiPUA latexes demonstrated the reinforcement effect of PMMA to their films, showing increased modulus and viscosity. When the mass ratio of PMMA/SiPUA and HPMS content in SiPUA were 0.5 wt% and 10 wt% , respectively, the average particle size of PMMA/SiPUA latex reached a minimum, and the size distribution exhibited a narrow unimodal distribution. Therefore, introduction of PMMA into SiPUA, leading to the formation of ＂Salami＂ structure in the latex particles

关 键 词：含硅聚氨酯 端羟基丙烯酸酯 聚甲基丙烯酸甲酯 “Salami”结构 膜性能 

分 类 号：TQ316.334[化学工程—高聚物工业]