近年来,颜德岳等基于A2型单体二丙烯酸酯及BB2'型单体二胺化合物合成了多种端胺基超支化聚(酯-胺),并对反应机理及聚合物结构进行了系统研究,结果表明,由于B与B’活性差异,反应首先生成AB2’型和B4’型中间体,进一步聚合得到可溶性产物.我们基于A1型单体三丙烯酸酯与B2型单体二胺化合物合成了端丙烯酸酯基超支化聚(酯-胺).在这些体系中,由于官能团反应活性高,难以控制反应程度.另外,由于超支化聚合物不能直接用作结构材料,其在涂料、粘合剂等领域的应用多基于末端官能团的固化反应.但通常由于官能团在分子表面密集分布,部分先反应官能团所形成的网络结构会对剩余官能团产生屏蔽作用,使官能团总的反应程度降低并影响材料的物化性能,如何改善末端官能团的反应性已成为此类聚合物应用的关键.
n-Dodecylamine was used as reaction terminator to control the molecular structures of amine terminated hyperbranched poly(ester-amine) s ( HPEA ) synthesized from phthalicdiglycol diacrylate and 1- ( 2-aminoethyl ) piperazine at molar ratio of 1 : 1 by Michael addition reaction. From the ^1H-NMR spectra of HPEA, the degree of branching increased and the amino active hydrogen content decreased with prolonging the reaction time. HPEA were further cured with β-glycidyloxylpropyl trimethoxysilane under ambient condition. The highest gel content and best mechanical properties of the cured coatings at active hydrogen and epoxy group stoichiometric ratio of 1 : 1 can be attributed to-the stepwise curing process, involving the fast reaction between amino active hydrogen and epoxy groups, and the slow hydrolysis and self-condensation of methoxysilane groups.