Sun Miao, Yin Chunxiao, Gu Yanan, Li Yun, Xin Zhirong
School of Chemistry and Chemical Engineering, Yantai University, Yantai, PR China.
Des Monomers Polym. 2017 Jul 13;20(1):458-467. doi: 10.1080/15685551.2017.1351728. eCollection 2017.
A series of tertiary amine-based hyperbranched poly(amine-ester)s have been synthesized by Michael addition polymerization of trifunctional monomer, TMEA and difunctional monomer, diacylates in chloroform, and the resultant polymers were subsequently treated with mercaptoethenol or 1-dodecanethiol for improving stability in storage. The caption efficiency of mercaptoethanol is much better than that of 1-dodecanthiol. Kinetic study reveals that the thiol group is consumed faster than the acrylate group when the polymerization with feed molar ratio of diacrylate/TMEA = 2/1 was carried out. At initial polymerization, monomer conversion increases fast, but the molecular weights increase slowly and sharp increase of the molecular weight occurs at the final polymerization. The hyperbranched polymers were well characterized by H NMR spectra and TD-SEC, and DBs of the polymers obtained are between 0.6 and 0.82, as well as the molar ratios of diacrylate/TMEA in the hyperbranched polymers are between 1.60 and 1.82. The fluorescence efficiency and quantum yields of HypET20, HypHT24 and HypDT24 has the following sequence: HypET20 > HypHT24 > HypDT24.
通过三官能团单体三羟甲基乙烷三丙烯酸酯(TMEA)与二官能团单体二丙烯酸酯在氯仿中进行迈克尔加成聚合反应,合成了一系列基于叔胺的超支化聚(胺 - 酯),随后用巯基乙醇或1 - 十二烷硫醇处理所得聚合物,以提高其储存稳定性。巯基乙醇的封端效率远高于1 - 十二烷硫醇。动力学研究表明,当以二丙烯酸酯/ TMEA的进料摩尔比为2/1进行聚合反应时,硫醇基团的消耗速度比丙烯酸酯基团快。在初始聚合阶段,单体转化率快速增加,但分子量增加缓慢,而在聚合反应后期分子量急剧增加。通过核磁共振氢谱(H NMR)和体积排阻色谱(TD - SEC)对超支化聚合物进行了很好的表征,所得聚合物的支化度(DBs)在0.6至0.82之间,并且超支化聚合物中二丙烯酸酯/ TMEA的摩尔比在1.60至1.82之间。HypET20、HypHT24和HypDT24的荧光效率和量子产率具有以下顺序:HypET20 > HypHT24 > HypDT24。