利用環氧樹脂(DGEBA)為起始物，透過與二氧化碳的親核開環反應在常壓下催化製備而得環狀碳酸酯 Bis(cyclic carbonate)s，再使其與五種二胺: (1)親油脂肪族：乙二胺、十二烷二胺，(2)親水脂肪族：1,4-butanediol bis(3-aminopropyl) ether，(3) 芳香族：間位苯二甲基二胺進行聚合反應，形成在主鏈段上懸掛羥基的聚胺基甲酸酯 (Hydroxyl PU)，並利用其PU主鏈段上懸掛的高反應性羥基作改質。在本論文中，利用原來親油性Hydroxyl PU主鏈段上懸掛的羥基經由與琥珀酸酐(Maleic anhydride)的半酯化(Half-esterification Reaction)反應後，使PU在側鏈上懸掛具有強極性的羧酸基，其可作為聚胺酯分子中的內乳化劑，羧酸基能在水相中自身解離產生離子或加入適量鹼使之中合，使聚氨酯高分子能夠穩定分散於水中，即所謂水性PU分散液(Aqueous-based Polyurethane Dispersion)。 最後，在水性PU分散液加入各種比例的常溫架橋型架橋劑 TMPTA-AZ 與PU鏈段上的羧酸基反應形成三維網狀交聯結構，以提升乾膜後的各項物理性質、熱性質和機械性質。並與傳統使用異氰酸鹽製程的PU6331製成的乾膜作各性質的比較與探討。 Bis(cyclic carbonate)s were prepared by the reaction of bis (epoxide) and atmospheric pressure of CO2 in the presence of Lithium Bromide as catalyst at 100℃ in high yield. Polymerization between bis(cyclic carbonate)s and four different kinds of diamine that were ethylenediamine, 1,12-diaminododecane, 1,4-butanediol bis(3-aminopropyl) ether ,and m-xylyenediamine in N,N-dimethylacetamide (DMAc) afforded corresponding poly( hydroxyurethane)s. The pendent hydroxyl groups of hydroxyl-PU were very reactive and could be easily modified from multifarious synthesis. In this report, half-esterification between these pendent hydroxyl groups of hydroxyl-PU and maleic anhydride could lead to new pendent groups, carboxylic groups. These highly polar carboxylic groups in the side chain of PU could play the role of internal emulsifier. They had self-dissociation ability in the water or were neutralized first by appropriate amount of base. Then, PU bearing carboxylic group could dispersed steadily in the water, named aqueous-based polyurethane dispersion. Addition of different ratios of bridging reagent TMPTA-AZ into above dispersion would lead to cross-linking net structure because of the reaction between carboxylic group and aziridine group of TMPTA-AZ. At last, Compare the properties of physics, thermal stability, dynamic mechanics between various PU film from different diamine and PU6331 with or without curing reagent TMPTA-AZ.
