甲基丙烯酸(2,3-環碳酸酯)縮水甘油酯之合成與應用

本研究以二氧化碳與甲基丙烯酸縮水甘油酯( Glycidyl methacrylate )做為起始物，透過親核加成反應形成一端帶有壓克力基而另一端為五環碳酸酯之中間體，(2-oxo-1,3-dioxolan-4yl)methyl methacrylate， 簡稱ODMA ，並將其與五種不同官能基數的一級胺進行反應，形成在主鏈段上懸掛羥基的PU壓克力前聚物（Hydroxyl-PU-acylate oligomers），並利用壓克力基上之雙鍵進行紫外光交聯( UV-Curing )或熱交聯( Thermal-Curing )反應，經由非異氰酸鹽方式製備具網狀結構之高硬度壓克力聚胺酯產物(Polyurethane)。 在第一步合成ODMA步驟中，以四級胺鹽做為催化劑，並探討催化劑的選擇、用量、反應的溫度與壓力及ODMA之純化方式，建立合成ODMA之最佳化條件；經由實驗結果得知，在高壓(8atm)低催化劑(10 wt%)及溫和溫度(80℃)反應下可使ODMA產率高達97%。 第二步實驗中利用四種不同胺類：(1)單官能胺基-Butylamine (2) 雙官能胺基-Diethylenetriamine與Triethylenetetramine (3)三官能胺基-tris(2-aminoethyl)amine 與Jeffamine T403 與ODMA進行親核加成反應，形成主鏈上有壓克力胺基甲酸酯鍵(urethane)以及在側鏈上帶有官能性羥基的寡聚物，再利用壓克力基上之雙鍵進行紫外光交聯或熱交聯使之形成網狀結構聚胺酯，並探討交聯前後之硬度變化及熱性質，其中以ODMA-TEA-2GMA(A4U2-802)效果最佳，經紫外光/熱交聯後之硬度分別可高達212.6與215 sec，已接近玻璃硬度，顯示單體上壓克力官能基密度及數目具正面決定性的影嚮。 依此法所合成之非異氰酸酯聚氨酯從分子結構上比起傳統聚氨酯分子具有更佳的耐化學性、耐水解性及抗滲透性。因此經由本實驗研究，不僅可將CO2做一有效利用，更可透過非異氰酸鹽的方式高速形成帶有聚胺酯官能基之化合物，亟其符合目前綠色化學之趨勢。 英文摘要 This research utilizes carbon dioxide and glycidyl methacrlate (GMA) as the raw materials to synthesize 2-oxo-1,3-doxolan-4yl)methyl methacrylate (ODMA) through a nucleophilic addition reaction. ODMA was then reacted with five aliphatic amines with different primary amine groups to differentiate the utility of hydroxyl urethane-acrylate oligomers through ring-opening reaction of ODMA at the cyclic carbonate sites. Furthermore, these PU-acyrlate oligomers were cured under UV or thermally in formation of crosslinked PU-acrylates. In the ODMA preparation, we have studied the optimal conditions by varying catalyst kind and concentration. In the meantime, reaction temperature, CO2 pressure and isolation procedures also have been screened and optimized. It was found that ODMA yield of 97% was achieved at 80℃ under 8 atm of CO2 pressure with TBAB as the catalyst at 10 wt%. In my subsequent study, five different amine compounds including butylamine, diethylene triamine, triethylenetetraamine, tri(2-aminoethyl)amine, and Jeffamine T403 were reacted with ODMA in formation of different acrylate urethane oligomers all possessing hydroxyl group on the side chains. These oligomers were independently subjected to UV or heat treatment to promote their crosslinkings at the acryl ate groups to find out product properties. Among the tested oligomers, it was found that OMDA-TEA-2GMA gave rise to the best overall results showing hardness of 212.6 and 215 sec (in Tendulum Hardness Rocker test) under UV and thermal treatments respectively. The hardness was close to those of glasses indicating the positive impact of high acrylate groups in PU chains for crosslinking From our study, it was found that this non-isocyanate approach of PU making have some distinct advantages over the conventional PU synthesis with poly-isocyanates due to dealing with safer and more stable polymer intermediates in our case. Moreover, the processes seem greener for using carbon dioxide as one of the key raw material with rapid curing process in formation of polyurethane acrylates