有机硅改性水性UV磺酸盐型聚氨酯乳液的研制  

Preparation of Silicone Modified Waterborne UV-Curing Polyurethane Emulsion with Sulfonate

作　　者：张祥龙 刘珠 欧阳雨鸣 李燕 强娜 熊前程 刁贵强 刘嘉怡 朱茵 沈琪力 郭永华 易玥 肖定书 ZHANG Xianglong;LIU Zhu;OU-YANG Yuming;LI Yan;QIANG Na;XIONG Qiancheng;DIAO Guiqiang;LIU Jiayi;ZHU Yin;SHEN Qili;GUO Yonghua;YI Yue;XIAO Dingshu(Guangdong Provincial Education Department Development Team of Advanced Material Coating and Surface Interface Technology,Huizhou Engineering Technology Research Center of Advanced Coating Materials,Dayawan Chemical Engineering Research Institute of Huizhou University,School of Dayawan Chemical and New Materials,School of Chemistry and Materials Engineering,Huizhou University,Huizhou 516007,China;Guangdong Libang Chang Runfa Technology and Materials Co.,Ltd.,Huizhou 516200,China;Guangdong Honeycomb Nanomaterials Co.,Ltd.,Huizhou 516229,China)

机构地区：[1]惠州学院大亚湾化工新材料学院,惠州学院大亚湾化工研究院,惠州学院化学与材料工程学院,广东省教育厅先进材料涂层与表界面技术开发团队,惠州市先进涂层材料工程技术研究中心,广东惠州516007 [2]广东立邦长润发科技材料有限公司,广东惠州516200 [3]广东省蜂巢纳米材料有限公司,广东惠州516229

出　　处：《有机硅材料》2024年第4期6-14,共9页Silicone Material

基　　金：广东省科技创新战略专项资金(“攀登计划”专项资金)(pdjh2022b0502,pdjh2023b0502);广东省普通高校青年创新人才类项目(2022KQNCX081);惠州市社会发展领域科技计划项目(2022CQ010006);大亚湾科技计划项目(2020020001);惠州学院教授、博士启动项目(2020JB051);大学生创新创业训练计划项目(S202110577033,S202110577034,202210577006);2022年惠州学院中青年教师南方科技大学访学计划([2022]21号)。

摘　　要：以3种不同羟值的聚酯磺酸型二元醇(BY-3303、BY-3305及BY-3306)为磺酸盐软段,羟基硅油PMX0156为有机硅软段,异佛尔酮二异氰酸酯(IPDI)为硬段,1,4-丁二醇(BDO)为扩链剂,制得系列有机硅改性水性磺酸盐型聚氨酯丙烯酸酯乳液(SWPUA)。系统研究了异氰酸酯与羟基的物质的量比(R值)、磺酸盐基含量及有机硅含量对SWPUA乳液外观、粒径、储存稳定性、热储稳定性以及固化后漆膜的硬度、附着力、吸水率、水接触角与力学性能的影响。结果表明,通过红外及核磁验证了胺酯化反应成功合成了SWPUA;当磺酸盐聚酯二元醇选用BY-3303且BY-3303、PMX0156与BDO物质的量比为1.5∶0.3∶1.0、R值为1.3时,制得的SWPUA外观为乳白泛蓝乳液,固含量约为40%,具有较低黏度和粒径,黏度(涂4#杯)为96 s,粒径为312 nm且储存稳定性与热储稳定性较佳;该条件下,SWPUA漆膜的综合性能较佳,铅笔硬度为1H、附着力达4B级、水接触角为93.2°、吸水率为2.43%、拉伸强度为8.14 MPa、断裂伸长率为327.47%。SWPUA还可在30 s内快速交联成型,引入有机硅链段一定程度上克服了氧阻聚,提高了双键转化率,转化率可达93%。A silicone-modified sulfonated waterborne polyurethane acrylate(SWPUA)emulsion with different sulfonate groups,silicone and R values(mole ratio of isocyanate to hydroxyl)was prepared by the three sulfonate polyester diols(i.e.BY-3303,BY-3305 and BY-3306)as sulfonated soft segment,hydroxysilicone oil PMX0156 as silicone soft segment,isoferone diisocyanate(IPDI)as hard segment,and 1,4-butanediol(BDO)as chain extender.The influence of value R,sulfonate and silicone on the appearance,particle size,storage stability and thermal storage stability of SWPUA emulsion were explored,as well as the hardness,adhesion,water absorption,water contact angle and mechanical strength of the UV-cured SWPUA film were also studied.It was confirmed by FIIR and 1 H NMR that SWPUA was successfully synthesized by amine esterification.When BY-3303 was selected as sulfonate polyester diol,and the mole ratio of BY-3303,PMX0156 and BDO was 1.5∶0.3∶1.0,value R was 1.3,the prepared SWPUA was a milky pan-blue emulsion,with solid content of 40wt%,low viscosity and particle size,i.e.,viscosity(No.4 Cup)of 96 s,a particle size of 312 nm,and good storage stability and thermal storage stability.Under this condition,SWPUA coating film has good comprehensive performance,with a hardness of 1H,adhesion of grade 4B,water contact angle of 93.2°,water absorption of 2.43%,tensile strength of 8.14 MPa,and elongation at break of 327.47%.SWPUA can also be quickly crosslinked in 30 s,and the silicone chain segments can overcome the oxygen inhibition and improve the double bond conversion rate up to 93%.

关 键 词：UV固化 有机硅改性 磺酸盐 水性聚氨酯 乳液 

分 类 号：TQ264.12[化学工程—有机化工] TQ323.8