基于二氧化碳共聚物的紫外光固化高分子材料的制备与性能  

Synthesis and Property of CO_(2) Copolymerbased UV-curable Polymer

作　　者：王征文 高凤翔 曹瀚[2] 刘顺杰 王献红 王佛松[1,2] WANG Zhengwen;GAO Fengxiang;CAO Han;LIU Shunjie;WANG Xianhong;WANG Fosong(School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026,China;CAS Key Laboratory of Polymer Ecomaterials,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China)

机构地区：[1]中国科学技术大学应用化学与工程学院,合肥230026 [2]中国科学院长春应用化学研究所,中国科学院生态环境高分子材料重点实验室,长春130022

出　　处：《高等学校化学学报》2022年第7期105-112,共8页Chemical Journal of Chinese Universities

基　　金：国家重点研发计划项目(批准号:2021YFD1700700);国家自然科学基金(批准号:51988102)资助.

摘　　要：普通低分子量的二氧化碳共聚物由于预聚体中含有较多的亲水性端羟基,在紫外光辐照下不能交联而降低材料的耐水性.为降低亲水性端羟基对材料耐水性的影响,本文利用锌钴双金属氰化物(Zn-Co DMC)催化剂实现了CO_(2)与4-乙烯基环氧环己烷、环氧环己烷的三元无规共聚,制备出分子量在40000以上,含C=C双键的脂环族聚碳酸酯;采用四(3-巯基丙酸)季戊四醇酯为固化剂,基于紫外光诱导的双键-巯基点击反应制备了紫外光固化高分子材料.研究发现,在5.0 mJ/cm^(2)的紫外光辐照剂量下即可制备出高透明硬化涂层,在可见光(400~750 nm)波段内透光率达到97.5%,铅笔硬度达到3H,对马口铁等基体附着力达到0级.值得指出的是,该紫外光固化薄膜的玻璃化转变温度超过110℃,与双酚A型环氧树脂相当,而且不含苯环等结构,具有更优异的耐紫外光老化性能.To overcome the strong hydrophilicity of terminal hydroxyl group from low molecular weight prepolymer,high molecular weight(>40000)CO_(2) copolymer was synthesized through the terpolymerization of CO_(2),cyclohexene oxide and 4-vinyl-1,2-cyclohexene oxide using Zn-Co double metal cyanide as catalyst.The thiol-ene click chemistry was then carried out using pentaerythritol tetra(3-mercaptopropionate)as curing agent under suitable dosage of ultraviolet light irradiation.A highly transparent film could be obtained at an irradiation dose of 5.0 mJ/cm^(2),whose transmittance at visible light(400-750 nm)reached 97.5%,with pencil hardness of 3H and adhesion of 5B on tinplate surface by cross-cut test in ASTM D3359.It is noteworthy that the film has glass transition temperature over 110℃,well comparable with bisphenol A type epoxy resin,while it has the specific advantage of UV-resistance since it is aromatic ring free.

关 键 词：二氧化碳共聚物 巯基-双键点击反应 紫外光固化高分子 

分 类 号：O632[理学—高分子化学]