Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3911
標題: 新型異質雙官能基高分子中間體 4-異氰酸鹽-甲基-苯乙烯之合成及應用
Synthesis and Applications of 4-Vinylbenzyl Isocyanate - A Dual Functional Polymer Intermediate
作者: 黃漢斌
Huang, Han-Bin
關鍵字: Dual Functional Polymer Intermediate
異質雙官能基高分子中間體
4-Vinylbenzyl Isocyanate
4-異氰酸鹽-甲基-苯乙烯
出版社: 化學工程學系所
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摘要: 本研究將利用商業品4-氯-甲基-苯乙烯 (4-vinylbenzyl chloride,4-VBC) 為起始原料,經簡單的化學氨化反應成 4-胺基-甲基-苯乙烯 (4-vinylbenzyl amine,4-VBA),可再利用傳統之光氣法或胺酯之熱裂解法來合成 4-異氰酸鹽-甲基-苯乙烯 (4-vinylbenzyl isocyanate,4-VBI)。此異質雙官能基單體特色為分子內同時具有不飽和雙鍵 (Vinyl) 及異氰酸鹽官能基團 (-NCO),本研究中利用其異質官能基之反應獨立性,證實不飽和雙鍵以及異氰酸鹽基團這兩種不同反應機制的官能基,其自由基聚合及異氰酸鹽加成兩個反應皆可獨立進行,不會彼此相互影響,同時也將此中間體做進一步之應用。 第一種聚合方式,利用不飽和雙鍵官能基為反應優先,將苯乙烯和VBI行自由基共聚合反應生成其共聚物r-PS-PVBI,接著導入不同比例之壓克力單體羥乙基甲基丙烯酸酯 (2-hydroxyethyl methacrylate,HEMA) 與VBI單體上的異氰酸鹽官能基反應,生成側鏈上帶有HEMA官能基之聚苯乙烯高分子r-PS-PVBH,而最終的HEMA壓克力官能基又可以進行紫外光交聯固化反應進而提升其熱性質及硬度。 第二種聚合方式,以異氰酸鹽官能基為反應優先,利用VBI與三羥甲基丙烷 (Trimethylolpropane,TMP) 反應,合成具有三個VBI苯乙烯官能基之單體 (VBI-TMP),最後再利用紫外光/熱交聯固化形成網狀聚合物,藉以提升其熱性質及硬度,其固化前後之硬度可由8.7 sec提升至174 sec。 透過本研究,我們證實且了解此異質雙官能基中間體VBI之獨特性及應用性,未來可再進一步的針對結構與成本上之修正,使異質雙官能基中間體VBI可實際的應用在工業上之生產。
A simple synthetic scheme of 4-vinylbenzyl amine (4-VBA) has been successfully accomplished in this study using a commercially available 4-vinylbenzyl chloride (4-VBC) as the starting material. In the first step reaction, the chloride atom in 4-VBC was replaced by ammonia through the action of ammonia water (NH4OH) in dioxane solution. Subsequently, the 4-vinylbenzyl amine (4-VBA) could use phosgene or pyrolysis to get the 4-vinylbenzyl isocyanate (VBI) readily. Dual functional groups of 4-VBI with an isocyanate group and an active-vinyl group at the opposite ends of the VBI molecule are of significant application interests, since they could independently undergo additions/polymerizations in tandem to form polymers of diverse properties. In the first trial, a free-radical co-polymerization of 4-VBI with styrene was carried out and then was followed by the addition of 2-hydroxyethyl methacrylate (HEMA) to the obtained the random γ-PS-PVBI to consume the isocyanate in formation of urethane-acrylate functionalized graft-polymers. The acrylate groups in the graft-polymer could undergo UV-curing reaction to further strengthen its thermal properties and hardness. In the second trial, VBI was reacted first with trimethylolpropane (TMP) to form tri-functionalied vinylbenzyl urethane intermediates (VBI-TMP). The VBI-TMP can use its tri-functionalied vinylbenzyl group undergo UV/Thermal curing to get crosslinked polymer with highly thermal properties and hardness. Through this research, we demonstrated the importance and significant capability of dual functional polymer intermediates (4-VBI). With further structural and cost refinements, it is hoped that one of these products could be applied practically in the real world.
URI: http://hdl.handle.net/11455/3911
其他識別: U0005-1807201111432500
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-1807201111432500
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