多官能团单体对超支化聚酰胺酯光固动力学及其固化膜热性能的影响

以1，1，1-三羟甲基丙烷为核，4-N，N-（2-羟乙基）-4-酮丁酸为单体，按照 一定比例，合成理论上第二代羟端基超支化聚酰胺酯，再与丙烯酰氯反应获得丙烯 酸化超支化聚酰胺酯预聚物（HAPAE-2-A），它在光引发剂存在下经紫外光辐照可 以快速固化成膜。根据~1H NMR 谱测定所得产物的反应程度为85%。采用凝胶渗透 色谱和气相渗透法测定所得产物的分子量分布和数均分子量分别为2.16和1620 g/mol，与其理论分子量相比，其反应程度为89%，从而估算产物实际端基丙烯酸 酯双键数为10左右。采用光-差热分析仪研究HAPAE-2-A的反应动力学，发现当体系 中加入多官能团单体，如三羟甲基丙烷三丙烯酸酯、己二醇二丙烯酸酯和乙氧基一 缩二乙二醇丙烯酸酯时，多官能团单体的官能度及含量会对体系的最大光聚合反应 速率和不饱和双键的反应程度产生较大的影响。通过动态力学热性能测试发现 HAPAE-2-A光固化膜的玻璃态转化温度随多官能团单体的加入而提高。

Influences of Multifunctional Co-monomers on UV-Cure Kinetics of Hyperbranched Acrylated Polyamidester and the Thermal Properties of the Cured Films

The ultraviolet light curable hyperbranched aliphatic polyamidester (HAPAE-2-A) was synthesized based upon 4-N,N-di(2-hydroxyethyl)-4-ketobutyric acid as a AB 2 monomer, and 2-ethyl-2-(hydro~xy~methyl)-1,3-propanediol as a core molecule, then modified with acryloyl chloride. The molar mass and polydispersity of the polymer were measured by VPO and GPC as 1620 g/mol and 2.16, respectively. The reaction degree was obtained to be over 85% by 1H NMR. That is HAPAE-2-A obtained possesses, practically, an average of over 10.2 of the end double bonds in each molecule. The photopolymerization kinetics has been determined by Photo-DSC measurements. The results show that the addition of multi-functional comonomer with low viscosity can efficiently increase the maximum polymerization rate and the unsaturation conversion in the cured films, as well as raising glass transition temperature.