Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/91529
標題: 以綠色化學程序製備聚尿素高分子彈性體
Green Chemistry Approach to Synthesize Polyurea Elastomer
作者: Wen Chen Pan
潘玟蓁
關鍵字: Polyurea Elastomer
Green Chemistry
Diphenyl Carbonate
Non-isocyanate Route
聚尿素高分子彈性體
綠色化學
碳酸二苯酯
非異氰酸鹽法
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摘要: 在致力於符合綠色程序之非異氰酸鹽法(NIR)製備聚尿素高分子彈性體(PUaE)的研究中,成功發展出具高度實用性的碳酸二苯酯(DPC)取代二元異氫酸鹽做為羰基化的試劑。將DPC與幾種代表性的二元胺在不同的進料順序及溶劑條件下進行酯交換聚合反應,順利合成具有相分離特性,機械性質優異且分子量高之聚尿素高分子產物。 NIR的研究發展中,開始時是藉由DPC與二元胺(MDA,HDA)合成並純化出高純度的二苯基二異氰酸酯而後以環丁砜(TMS)為溶劑並與長鏈及短鏈二元胺進行酯交換得到PUaE。在隨後的改進中,直接以一鍋化法在DPC與TMS溶液中依序加入三種不同二元胺,HDA、分子量2000的聚醚二元胺及異佛爾酮二元胺(IPDA)進而合成第二代的PUaE。最後,簡單地使用DPC其熔融狀態下進行開發的無VOC溶劑的酯交換反應。成功的關鍵在於添加二元胺的時機與順序,使得DPC可先形成二苯基二異氰酸酯中間體,再藉由從溶液中移除phenol而順利合成高分子量之聚尿素高分子。而後,利用ESA (3-[(2-aminoethyl) amino]-1-propane sulfonic acid sodium salt) 或APTES ((3-Aminopropyl) triethoxysilane) 取代部分鏈延長劑,順利將最終產物水性化,擴展產物利用的方便性。 本研究所提出優化的NIR聚尿素高分子膜具有0.6以上的固有黏度,15~30 MPa抗張強度及拉伸率超過400%以上的表現,其中以藉由熔融法所合成出的NS-P7表現優異的分子量及Td高於315 ℃的熱穩定性。另外,我們亦藉由AFM來觀察並確定產物中軟硬鏈段清楚的相分離。以上改進均是依照綠色化學及工業化量產的兩大目標逐步改進發展出全新NIR程序製備出性質優異之聚尿素高分子彈性體。
In an effort to develop green processes to produce elastomeric polyurethane-urea Elastomer (PUaE) through non-isocyanate routes (NIR), highly practical methods of utilizing diphenyl carbonate (DPC) instead of diisocyanate as the carbonylation agents have been developed. The trans-esterification of several representative aliphatic diamines with DPC under different combinations and solvents has resulted in new processes which produced segmented PUaEs with consistent high molecular weights and mechanical performances. In the evolution of our NIR process developments, it began with the preparation and isolation of pure bis-carbamates from diamines such methylene dianiline (MDA) or 1,6-hexamethylene diamine (HDA) with DPC which was followed by trans-esterifications with long-chained and short-chained diamines carried out in tetramethylene sulfone (TMS) solution leading to PUaEs. Then, in the subsequent improvement, a one-pot sequential addition of three different diamines, HDA, polypropylene ether diamine of 2,000 molecular weight, and isophorone diamine were added to DPC sequentially in TMS to form the second generation PUaEs. Finally, non-VOC solvent trans-esterification processes were developed simply using the pure DPC under its molten state. The key to the present successful development lies in the realization of timing and sequence of the diamine additions to form initial biscarbamate intermediates in-situ and then in shifting the equilibrium towards polyurea product formation by phenol removal from the solution so that high molecular weight polyurea could be formed favorably. Furthermore extension of the approach through replacing partial hard segment with water dispersants groups such as ESA (3-[(2-aminoethyl) amino]-1-propane sulfonic acid sodium salt) or APTES ((3-Aminopropyl) triethoxysilane) in making water-based PUaE also have been achieved. The optimized NIR polyurea films made in this study consistently have the ηinh of over 0.6, with high performance characteristics showing tensile strength ranges of 15~30 MPa and elongation exceeding 400 %. Ultra-high molecular weight of polyurea (NS-P7) and the highest heat properties with Td of > 315 ℃ was achieved in the melt-process. Well-defined soft- and hard-segment domains were observed for the products as determined by AFM. These new improved NIR processes to produce segmented poly-aliphatic ureas thereby comply fully with the principles of green chemistry using safe and readily available chemicals.
URI: http://hdl.handle.net/11455/91529
其他識別: U0005-2010201415585400
文章公開時間: 2017-10-27
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