馬來醯胺-氧代氮代苯并環己烷之合 成、聚合及硬化樹脂研究

Synthesis and properties of benzoxazine with maleimide functional group, polybenzoxazine resin curing study

游俊盟(Juin-Meng Yu)

指導教授 ： 劉英麟

中原大學/工學院/化學工程研究所/碩士(2005年)

https://doi.org/10.6840/cycu200500323

摘要

摘 要
本研究首先以N-(4-hydroxyphenyl)maleimide, formaldehyde,及aniline作為原料合成出帶有馬來醯胺官能基之氧代氮代苯并環己烷單體3-phenyl-3-4-dihydro-2H-6-(N-maleimido)-1,3-benzoxazine(HPM-
Ba)，經由FT-IR、1H-NMR、及元素分析確認其化學結構。導入maleimide於Benzoxazine結構中，可藉由該官能基可聚合的特性，以提升Polybenzoxazine的玻璃轉移溫度和熱性質，另一方面，藉由碳碳雙鍵的導入來提升整體的聚合度。在微掃描卡計（DSC）中，HPM-Ba具有兩個明顯放熱峰，顯示其有兩階段的熱聚合反應，本文以控溫FT-IR追蹤發現，第一階段熱聚合反應為馬來醯胺上碳碳雙鍵聚合反應，第二階段為benzoxazine 開環反應。經過完全熟化後，HPM-Ba-Ⅱ具有高玻璃轉移溫度（204℃）、在氮氣下具有高起始裂解溫度（330℃）及高焦炭殘餘量（50%）。
其後，本研究以摻混的方式將具有不同官能基的馬來醯胺單體與3,4-dihydro-3-phenyl-2H-1,3-benzoxazine（PPA）摻混硬化形成共聚合物，以微掃描卡計（DSC）探討在不同官能基催化下的反應性，發現除了benzoxazine的開環反應外，連馬來醯胺碳碳雙鍵聚合反應亦被催化。本研究發現，benzoxazine開環反應後會形成一中間體iminium ion，此中間體與具非飽和鍵物質有很強反應性，因而影響碳碳雙鍵反應溫度。在摻混系統中，具有羧酸基的系統有最低的反應溫度，及最高的玻璃轉移溫度（224℃），所有摻混系統的高分子，皆具有高Tg（最高可達224℃）、良好的熱穩定性、高焦炭殘餘量（最高可達52%）、及低重量損失速率，但是卻具有低的起始裂解溫度，主要是因為iminium ion易與非飽和鍵反應，與另一benzoxazine單體反應的速度較慢，所以造成benzoxazine該部分的聚合度較差，所以會具有較低的起始裂解溫度，經由TGA-GC-MS收集200~400℃區間裂解所產生的氣體，經分析發現產物苯胺為主要產物，係由Polybenzoxazine上Mannich bridge的裂解，唯有在HPM-Ba-Ⅱ中，會有較多二級及三級胺，是因為maleimide拉電子效應形成Schiff base，隨後較易斷裂出二級及三級胺。

關鍵字

馬來醯胺 ； 氧代氮代苯并環己烷

並列摘要

Abstract
In this study, a maleimide-containing benzoxazine monomer, 3-phenyl-3-4-dihydro-2H-6-(N-maleimido)-1,3-benzoxazine (HPM-Ba), was prepared with using N-(4-hydroxyphenyl)maleimide, formaldehyde, and aniline as starting materials. The chemical structure of HPM-Ba was confirmed by FT-IR, 1H-NMR, and Elemental Analysis measurements. A two-stage thermal polymerization was observed with HPM-Ba under heat, in which the first stage was the reaction of maleimide groups and the second one was the ring-opening reaction of benzoxazine groups. The reaction scheme was demonstrated with differential scanning calorimetry (DSC) and thermal-stage FT-IR observation. The completely cured P-HPM-Ba-Ⅱ polymer exhibited a high glass-transition temperature of 204℃, good thermal stability about 330,℃and self-extinguishing behavior .
In addition, cured polymers were also obtained from the blends of 3,4-dihydro-3-phenyl-2H-1,3-benzoxazine（PPA）and various maleimide compounds. The effect of pendent groups of maleimide derivates on the polymerization scheme of the monomer blends were studied by DSC. The ring-opening polymerization of benzoxazine groups was catalyzed by the acidic –OH and –COOH groups in maleimides. The catalytic effects were directly observed with DSC measurements and the reaction scheme was confirmed with TGA-GC/MS measurements on the evolved gases in degradation. Meanwhile, the polymerization maleimide group was also catalyzed with benzoxazine groups. These catalytic effects shifted the polymerization of the monomer blends toward low temperatures. Therefore, polymers from PPA and P-cpm (maleimide with carboxylic acid group) showed the lowest polymerization temperature and the highest glass-transition temperature（224 ℃）among the cured polymers. It was concluded that combination of maleimide and benzoxazine resulted in high performance thermosets, both in processing and properties.

並列關鍵字

polybenzoxazine ； maleimide ； benzoxazine

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