TiO_(2)/有机硅溶胶改性含氟苯丙乳液的制备及性能表征  

Preparation and Characterization of TiO_(2)/Organic Silica Sol Modified Fluorinated Poly(styrene-acrylate)Emulsion

作　　者：史书源 安秋凤[1] 邱甲云 SHI Shuyuan;AN Qiufeng;QIU Jiayun Shaanxi(Provincial Key Laboratory of Light Chemical Additives,School of Chemistry and Chemical Engineering,Shaanxi University of Science and Technology,Xi'an 710021,China)

机构地区：[1]陕西科技大学化学与化工学院,陕西省轻化工助剂重点实验室,西安710021

出　　处：《材料导报》2023年第8期234-241,共8页Materials Reports

基　　金：陕西省重点研发计划项目(2020ZDLGY13-11);国家科技部重点研发计划项目(2017YFB0307700)。

摘　　要：为改善含氟苯丙乳液的疏水性、热稳定性及力学性能,以钛酸丁酯(TBT)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)为原料,通过溶胶-凝胶法制备出TiO_(2)/有机硅溶胶(TS),并将其与丙烯酸丁酯(BA)、苯乙烯(ST)、甲基丙烯酸十二氟庚酯(G04)及其他丙烯酸类功能单体作为主要原料,通过半连续加料法及种子乳液聚合,制备出一种TiO_(2)/有机硅溶胶改性的含氟苯丙乳液(TS-BHSAG)。探讨了不同TS含量对乳液转化率的影响,利用FTIR、纳米粒度仪、稳定性分析仪、XPS、XRD、SEM、AFM、TGA表征研究了乳液及乳胶膜的结构组成及应用性能。结果表明,当TS含量逐渐增加时,乳液转化率及稳定性呈持续下降趋势;随着TS含量增加,乳液平均粒径从55.58 nm增至106.16 nm;FTIR及XPS结果显示,TS-BHSAG乳胶膜中形成了Si-O-Si、Si-O-Ti、CF2键,证实TS被初步合成,且其与G04一起被引入聚合物中;XRD结果表明,TS是以无定形相分散于丙烯酸树脂基体中;通过SEM与AFM观察到,TS纳米粒子在乳胶膜表面构成峰状粗糙结构,增强了乳液的疏水性能;TGA结果表明,在热失重为10%及50%时,TS-BHSAG的热分解温度分别为380.59℃、415.39℃,在600℃时,乳胶膜的残余质量分数从4.78%增加到8.56%;当TS添加量为3%时,TS-BHSAG乳胶膜的接触角为121°,附着力为1级,耐冲击性能为50 cm,硬度为2H,吸水率为6.1%。In order to improve the hydrophobicity,thermal stability and mechanical properties of the fluorine-containing styrene-acrylic emulsion,Using butyl titanate(TBT)and γ-methacryloyloxypropyltrimethoxysilane(KH-570)as raw materials,TiO_(2)/organosilica sol(TS)was prepared by sol-gel method.With butyl acrylate(BA),styrene(ST),dodecafluoroheptyl methacrylate(G04)and other acrylic functional monomers as the main raw materials through semi-continuous feeding method and seed emulsion polymerization,a fluorine-containing styrene-acrylic emulsion(TS-BHSAG)modified by TiO_(2)/organosilicon sol was prepared.The effects of different TS contents on the emulsion conversion were discussed.The structure composition and application properties of the emulsion and latex film were studied by FTIR,nanometer particle size analyzer,stability analyzer,XPS,XRD,SEM,AFM,and TGA.The results show that when the TS content gradually increased,the emulsion conversion rate and stability showed a continuous downward trend.As the TS content increase,the average particle size of the emulsion increased from 55.58 nm to 106.16 nm.FTIR and XPS results show that Si-O-Si,Si-O-Ti,CF_(2) bonds were formed in the TS-BHSAG latex film,confirming the fact that preliminary synthesis of TS has been achieved,and it has been introduced into the polymer with G04.XRD results show that TS was dispersed in the acrylic resin matrix in an amorphous phase.It was observed by SEM and AFM that TS nanoparticles formed a peak-like rough structure on the surface of the latex film,which enhanced the hydrophobicity.TGA results show that when the thermal weight loss is 10% and 50%,the thermal decomposition temperatures of TS-BHSAG are 380.59℃ and 415.39℃,while at 600℃ the residual content increased from 4.78% to 8.56%.When the amount of TS added is 3%,the contact angle of the TS-BHSAG latex film is 121°,the adhesion is grade 1,the impact resistance is 50 cm,the hardness is 2H,and the water absorption rate is 6.1%.

关 键 词：TiO_(2)/有机硅改性 乳液聚合 含氟苯丙乳液 疏水性 热稳定性 

分 类 号：O63[理学—高分子化学]