邓剑如 刘思萌 张平安 李通情

摘   要：以聚己二酸一缩二乙二醇酯（PADG）、异佛尔酮二异氰酸酯（IPDI）和1，4-丁炔二醇（BD）通过聚加成反应，合成分子中含多个活性炔基的线性聚氨酯树脂，并利用红外和拉曼光谱进行表征. 以三羟甲基丙烷三（3-巯基丙酸酯）（TTMP）为交联剂，制备系列巯基-炔紫外光固化聚氨酯薄膜（F-SAPU）及涂层（C-SAPU）. 根据扩链参数、硬段质量分数、固化参数和光引发剂参数对巯基-炔紫外光固化树脂合成及固化进行配方设计. 结果表明，通过调节配方参数，F-SAPU的拉伸强度、断裂伸长率分别在0.48 ～5.32 MPa和106%～172%内灵活可调，玻璃化转变温度在-10.1～26.9 ℃内灵活可调;探究了不同硬段质量分数对C-SAPU涂层性能的影响，当硬段质量分数为45%时，涂层性能最优.

关键词：聚氨酯;点击化学;UV光固化;分子结构

中图分类号：O631                                   文献标志码：A

Preparation and Property Study of Sulfhydryl-Alkynyl UV Curing Polyurethane

DENG Jianru?，LIU Simeng，ZHANG Pingan，LI Tongqing

（College of Chemistry and Chemical Engineering，Hunan University，Changsha  410082，China）

Abstract：Multiple alkynyl linear polyurethane resins（MAPU） were synthesized by polyaddition reaction using polyethylene adipate diethylene glycol（PADG），isophorone diisocyanate（IPDI） and 1，4-butynediol（BD）. The molecular structures of resins were characterized by Fourier transform infrared spectra and Raman spectra. Series of sulfhydryl-alkynyl UV curing polyurethane films（F-SAPU） and coatings（C-SAPU） were prepared using trimethylolpropane tris（3-mercaptopropionate）（TTMP） as a crosslinking agent. The synthetic and curing process of sulfhydryl-alkynyl UV curing resins were designed according to formulation parameters such as chain extension parameters，mass fraction of hard segment，curing parameters and photoinitiator parameters. The results showed that the tensile strength and elongation at break of F-SAPU were flexibly adjustable from 0.48 MPa to 5.32 MPa and 106% to 172%，respectively，and the glass transition temperature was in the range of -10.1 ℃ to 26.9 ℃ when changing the formulation parameters. In addition， the effect of mass fraction of hard segment on the performance of C-SAPU was explored. When mass fraction of hard segment was 45%，the coating had optimal performance.

Key words：polyurethane;click chemistry;UV curing;molecular structure

聚氨酯固化體系多基于异氰酸根与活泼氢反应，但异氰酸根易与水作用，固化配方及材料性能受到环境湿度的严重制约[1]. 巯基-炔加成反应是一种新型的点击反应，具有反应条件温和、反应快速、不受水影响等特点[2-3]. 一般的巯基-炔点击反应遵循自由基加成机理，巯基由光化学引发或热催化引发后，经历与三键、双键两个反应过程，其中巯基与三键的反应为决速步[4-7]. 由于炔基是双官能度，因此易于制备高交联密度的交联网络结构聚合物[3]，在聚合物合成与应用中具有广阔的前景.

Liu等[8]利用1，7-辛二炔与1，6-己二硫醇或四（3-巯基丙酸）季戊四醇酯，通过紫外光引发巯基-炔点击聚合制……