自交联核壳丙烯酸乳液的构建及对水性油墨的影响  

Construction of self-crosslinking core-shell acrylic emulsions and their effect on water-based ink

作　　者：段仪豪 郑咏佳 郑熙熙 徐洪杰 王海花[1,2] 费贵强 DUAN Yihao;ZHENG Yongjia;ZHENG Xixi;XU Hongjie;WANG Haihua;FEI Guiqiang(College of Chemistry and Chemical Engineering,Shaanxi University of Science&Technology,Xi'an 710021,Shaanxi,China;Shaanxi Key Laboratory of Chemical Additives for Industry,Xi'an 710021,Shaanxi,China)

机构地区：[1]陕西科技大学化学化工学院,陕西西安710021 [2]陕西省轻化工助剂重点实验室,陕西西安710021

出　　处：《精细化工》2024年第9期2045-2054,共10页Fine Chemicals

基　　金：国家自然科学基金项目(21978164、22078189、22105120);陕西省教育厅产业化项目(19jC010);陕西省特支计划——科技创新人才项目;陕西省杰出青年科学基金项目(2021JC-046);陕西省高层次人才专项支持计划项目;陕西省创新支持计划项目(2021JZY-001);陕西省重点研发项目(2020GY-243);陕西省教育厅专项研究基金项目(20JK0535);国家高端外国专家项目(GDW20186100428);韩国人才库计划项目(2021H1D3A2A02082663)。

摘　　要：以丙烯酸(AA)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)、丙烯酸羟丙酯、甲基丙烯酸羟乙酯为单体,乙二醇二甲基丙烯酸酯(EGDMA)、甲基丙烯酸缩水甘油酯(GMA)为交联单体,采用两步乳液聚合法制备了自交联核壳丙烯酸乳液,以其为连接料制备了水性油墨。考察了核壳特性影响油墨耐水性和附着力的因素。利用TEM、FTIR、TG、DSC、光学接触角测量仪、万能试验机对自交联核壳丙烯酸乳液及其胶膜进行了表征,考察了壳层单体中GMA质量分数对乳液粒径、稳定性和油墨附着力、耐水性的影响。结果表明,核层中AA与壳层中AA的质量比(核壳AA比)对油墨附着力影响显著,核层中MMA与BA的质量比与壳层中MMA与BA的质量比之比(核壳软硬比)对油墨耐水性影响显著。自交联核壳丙烯酸乳液最佳配方为:核层混合单体与壳层混合单体的质量比(核壳质量比)2.00∶3.00、核壳软硬比3.00∶0.75、核壳AA比0.50∶2.50、内交联单体EGDMA用量0.75 g。当壳层单体中GMA质量分数为1.5%时,自交联核壳丙烯酸乳液平均粒径为112.2 nm,多分散性指数为0.108,胶膜最大热分解速率在409℃,核层与壳层的玻璃化转变温度分别为28.5和51.7℃,乳液分散稳定性最佳,胶膜吸水率为34.55%,油墨附着力为99%,耐水性达50次。Self-crosslinked core-shell acrylic emulsions were prepared by two-step emulsion polymerization with acrylic acid(AA),butyl acrylate(BA),methyl methacrylate(MMA),hydroxypropyl acrylate and hydroxyethyl methacrylate as monomers,ethylene glycol dimethacrylate(EGDMA)and glycidyl methacrylate(GMA)as cross-linking monomer,and further bonded to synthesize water-based ink.The influencing factors on the water resistance and adhesion of the ink were investigated.The self-crosslinked core-shell acrylic emulsions and their corresponding films were characterized by TEM,FTIR,TG,DSC,optical contact angle measuring instrument and universal test machine,while the effects of GMA mass fraction in shell monomers on emulsion particle size,stability,ink adhesion and water resistance were analyzed.The results indicated that the mass ratio of AA in core-layer to AA in shell-layer(core-shell acrylic acid ratio)showed a significant effect on the adhesion of ink,while the ratio of the mass ratio of MMA to BA in core-layer to the mass ratio of MMA to BA in shell-layer(core-shell softness/hardness ratio)showed a significant effect on the water resistance of ink.The optimal formulation of self-crosslinking core-shell acrylic emulsion was as follows:mass ratio of mixed monomers in core-layer to those in shell-layer(core-to-shell mass ratio)2.00∶3.00,core-to-shell softness ratio 3.00∶0.75,core-to-shell acrylic ratio 0.50∶2.50,and the amount of internal crosslinking monomer EGDMA 0.75 g.When the mass fraction of GMA in the shell-layer monomers was 1.5%,the self-crosslinked core-shell acrylic emulsion exhibited an average particle size of 112.2 nm,polydispersity index of 0.108,maximum thermal decomposition rate at 409℃,the glass transition temperatures of the core-layer and shell-layer of 28.5 and 51.7℃,respectively,optimal dispersion stability,latex film water absorption rate of 34.55%,ink adhesion of 99%,and water resistance of 50 times.

关 键 词：水性油墨 核壳结构 丙烯酸酯乳液 耐水性能 交联改性 

分 类 号：TQ628.5[化学工程—精细化工]