Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/93418
標題: 含有不飽和雙鍵以及異氰酸酯的異質雙官能基高分子中間體之合成與應用
Synthesis and Application of Dual Functional Polymer Intermediates with Vinyl and Isocyanate Groups.
作者: Chien-Chang Chen
陳建彰
關鍵字: Dual-cure
UV Curing
isocyanate
vinyl
異質雙官能基
異氰酸酯
不飽和雙鍵
碳管改質
紫外光固化
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摘要: 分子內同時具有不飽和雙鍵(Vinyl)以及異氰酸酯基團(NCO)的異質雙官能基高分子中間體已於本研究中成功的被合成製備出,同時本研究也將此中間體當成交聯劑做進一步的應用。本研究同時證實不飽和雙鍵以及異氰酸酯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酯加成兩個反應皆可獨立進行,不會彼此相互影響,而最終所合成出的高交聯度高分子具有良好的表面硬度以及對於機械性質的提升。 在氰酸根置換法合成4-異氰酸鹽-甲基-苯乙烯(4-Vinylbenzyl Isocyanate,簡稱4-VBI)部分,以4-氯-甲基-苯乙烯(4-Vinylbenzyl Chloride,簡稱4-VBC)為起始原料,第一步先以碘化鉀在丙酮溶劑中,將4-VBC之氯原子置換成碘原子,形成4-碘-甲基-苯乙烯(4-Vinylbenzyl Iodide,簡稱4-VBIodide),接著在甲苯溶劑中,利用氰酸銀(AgCNO)與4-VBIodide反應製得4-VBI,其中,反應置換的效率極高,不但時間短暫,而且可得高達85%的產物。 本研究依照反應機制的不同而有兩種不同先後順序的聚合方式。第一種聚合方式,以乙烯官能基為反應優先的實驗,採用自由基聚合方式,合成苯乙烯和4-VBI的共聚物r-PS-PVBI,再以羥乙基甲丙烯酸酯(2-hydroxyethyl methacrylate,簡稱HEMA)的羥基與4-VBI單體上的異氰酸酯官能基反應,生成帶有HEMA側鍊的聚苯乙烯高分子r-PS-PVBH,而最終的HEMA壓克力官能基又可以進行紫外光固化進而提升機械性質。第二種聚合方式,以異氰酸酯官能基為反應優先的實驗,先將4-VBI單體與三羥甲基丙烷(Trimethylolpropane,簡稱TMP)反應,合成具有3個4-VBI乙烯官能基的單體(3-VBU-TMP),最後再透過紫外光固化完成最終反應,在此實驗意外地發現有別於一般Vinyl Ether紫外光固化的系統,4-VBI使用紫外光自由基固化法即可有效的快速交聯,固化前、後的硬度可由8.7 sec提升到174 sec。 在環形醯基尿素-壓克力合成策略部分,使用環形碳二亞胺(Macrocyclic Carbodiimide,簡稱MC-CDI)與帶有不飽和雙鍵的壓克力酸反應,形成環形醯基尿素-壓克力(Macrocyclic Acylurea Acrylate,簡稱MC-AU-A)中間體,其中環形醯基尿素可視為一隱性的異氰酸酯官能基,可藉由加熱再活化釋放出異氰酸酯官能基。本部分依照反應機制的不同也有兩種不同先後順序的聚合方式,而聚合順序的取決,端看反應最終所需的性質而定,如果對於表面硬度以及外觀平整有較高需求,則採用先行紫外光固化後高溫熱處理;如果是對於最終產物的熱穩定性有較高需求,則改採高溫熱處理程序先行後紫外光固化。此外,使用MC-AU-A(T2P192)導入常用之紫外光配方中,當MC-AU-A(T2P192)含量達27 %時有最佳化的硬度表現。 另外,利用本研究合成過程中的中間產物,環形碳二亞胺(T2P192-MC-CDI),對酸化奈米碳管進行環形醯基尿素化改質,此環形醯基尿素化奈米碳管在有機溶液中具有極佳的分散性,分散時間可達數月,其間碳管之間沒有聚集沈澱現象產生。此外,由於改質奈米碳管上的環形醯基尿素可視為一隱性的異氰酸酯官能基,可當成交聯劑使用,使複材成為交聯的高分子,而奈米碳管最終與複材有實質的化學鍵結,進而使奈米碳管嵌在複材上。而採用環形醯基尿素化奈米碳管的複材在機械性質方面,確實比採用未改質奈米碳管的複材有較好的表現。 透過本研究,我們證實以及瞭解此異質雙官能基中間體的重要性以及獨特性,未來將進一步的針對結構與成本上的修正,使本研究中的異質雙官能中間,可以實際的付諸於工業之生產與應用。
Two dual functional polymer intermediates with both vinyl and isocyanate functional groups have been successfully synthesized and studied as crosslinkers in this research. We demonstrated that the selective reaction and polymerization of either functionality, i.e. vinyl or isocyanate groups, can be exploited independently and sequentially in the formation of highly crosslinked polymers with high hardness and improved mechanical properties. In the synthesis of 4-vinylbenzyl isocyanate (4-VBI), the chlorine-atom of readily available 4-vinylbenzyl chloride (4-VBC) had to be replaced by iodine first through the action of potassium iodide (KI) in acetone solution to afford 4-vinylbenzyl iodide (4VBIodide) to enhance its reactivity. In the subsequent replacement step, 4-VBIodide was reacted with silver cyanate (AgCNO) in toluene solution to quickly afford 4-VBI in an overall yield of 85 %. Two polymerizations have been carried out to demonstrate the utility of 4-VBI. In the first experiment, 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 mechanical properties. In the second example, VBI was reacted first with trimethylolpropane (TMP) to form tri-functionalied vinylbenzyl urethane intermediates before carrying out the UV-curing reaction. It was surprised to see those vinyl group did crosslinked rapidly under UV-irridation to form polymers with their hardness from 8.7 sec. before the curing jumping to 174 sec. afterward. In the study of macrocyclic dual intermediates, our syntheses were based on addition of acrylic acid to the macrocylic carbodiimde (MC-CDI) in formation of acrylate-acylurea intermediates. Through this novel system, acrylate group were tested for its UV-curing ability, while the acylurea group was used as a latent isocyanate group that can release isocyanate upon heating. Again, we have studied two different reaction modes by either heating before UV-curing in the first case or by UV-curing before thermal treatment in the second case. Although the final results of those two processes will achieve about the same polymeric hardness of ~177 sec. in the final polymers, there are substantial differences in the physical natures of intermediates after the first stage treatment. For a better initial hardness and smooth surface, the dual curing processing appears to favor to start with the UV-irradiation. However, in achieving the final product’s thermal stability, the thermal curing in the initial step followed by the UV-irradiation has the advantages. Furthermore, in our co-polymerization study with MC-AU-A(T2P) and acrylate system, it revealed that at the content of only 27% for the MC-AU-A(T2P), the UV-curing formulation could achieve enhanced performances. In my final study, the dual intermediate concept has been applied to the functionalization of carbon nanotube (CNT) through addition of MC-CDI on to the carboxylic groups of CNT. This acylurea-functionalization of CNT was found to be a superior way of dispersing CNT in the organic media, so that the modified CNT stays in organic media for months without precipitation. Furthermore, the formed ringed acylurea groups attached to the modified CNT also can serve as latent reactive group capable to crosslinking polymers in formation of composites with chemically bonding to CNT. The modified CNT composite generally results in better mechanical properties than those with either pristine CNT or non-cured CNT composites. Through this research, we demonstrated the importance and significant capability of dual functional intermediates. 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/11455/93418
其他識別: U0005-0308201008361900
文章公開時間: 10000-01-01
Appears in Collections:化學工程學系所

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