氧代氮代苯并環己烷單體之設計合成及其高性能熱固性聚合物之研究

Design and Synthesis of Novel Benzoxazine Monomers and Characterization of Their High Performance Thermosets

周進義(Ching-I Chou)

指導教授 ： 劉英麟

中原大學/工學院/化學工程學系/博士(2008年)

https://doi.org/10.6840/cycu200900060

摘要

本研究以具有不同官能基之一級胺類、甲醛與苯酚或雙酚Ａ為反應物，合成出五種新穎之氧代氮代苯并[1]環己烷(benzoxazine)單體((3-phenyl-3,4-dihydro-2H-6-(N-maleimido)-1,3-benzoxazine, HPM-ABz; 3-furfuryl-3,4-dihydro-2H-1,3-benzoxazine, P-FBz; bis(3-furfuryl-3,4-dihydro-2H-1,3-benzoxazine)isopropane, BPA-FBz; 6-fluoro-3-furfuryl-3, 4-dihydro-2H-1,3-benzoxazine, 4-FP-FBz; 1,3-bis(3-aminopropyl)tetramethyldisiloxane benzoxazine, P-BATMSBz ) ，經由傅利葉轉換紅外線光譜儀(FT-IR)、氫核磁共振儀(1H-NMR)與元素分析(Elemental analysis)確認單體之化學結構，證明成功地合成五個高純度的單體；進而以BPA-FBz與雙(4-馬來醯亞胺基苯)甲烷(DDM-BMI)為單體，利用狄爾斯-阿爾德反應(Diels Alder reaction)製備出主鏈含有氧代氮代苯并環
己烷的可交聯線性高分子(PBz)。
第一部分以N-(4-羥基苯基)馬來醯亞胺[N-(4-hydroxyphenyl) maleimide, HPM]、甲醛及苯胺為反應物合成出具有馬來醯亞胺官能基之氧代氮代苯并環己烷單體HPM-ABz。HPM-ABz具有良好的有機溶劑溶解度，其熔點約為52~55℃；HPM-ABz具有兩階段的熱聚合反應，第一階段熱聚合反應為馬來醯亞胺之聚合反應，第二階段為氧代氮代苯并環己烷的熱開環反應。經過完全聚合後，Poly(HPM-ABz)具有204℃之高玻璃轉移溫度、優異的
熱安定性及難燃自熄特性。
第二部份以2-呋喃甲胺(Furfurylamine)為起始物，製備了P-FBz、4FP-FBz與BPA-FBz 三個含呋喃官能基之氧代氮代苯并環己烷的單體；BPA-FBz與P-FBz於開環聚合中形成之Mannich bridge網狀結構有效地提昇聚氧代氮代苯并環己烷聚合物之交聯密度與熱安定性(Thermal stability)；Poly(P-FBz)與Poly(BPA-FBz)具有大於300℃之玻璃轉移溫度(Glass transition temperature)、高的焦炭生成率(Char yield)與具有31之極限氧指數(Limited oxygen index, LOI)的難燃性特質，Poly (P-FBz)與Poly(BPA-FBz)之介電常數(Dk=3.21~3.39)與機械性質[3.0~3.9 GPa的儲存模數(Storage modulus)與37.7~45.4ppm之低熱膨脹係數( Low coefficient of thermal expansion, Low CTE)]均較其他聚氧代氮代苯并環己烷為優；4FP-FBz具有低之介電常數(Dk=2.7)，以其作為降低介電常數之反應型改質劑，與P-FBz混成，證實可有效地降低Poly(P-FBz)的介電常數。
第三部分以苯酚、甲醛與1,3-雙(3-氨丙基)四甲基二矽氧烷[1,3-bis (3-aminopropyl)tetramethyldisiloxane, BATMS]為反應物，合成出含矽氧烷雙官能基之氧代氮代苯并環己烷單體P-BATMSBz，Poly (P-BATMSABz)具有高的起始裂解溫度（354℃）、高的焦炭生成率（55％）以及較佳的韌性(Toughness)與難燃特質。進一步以P-BATMSBz改質P-FBz形成高分子共聚合物， 證明P-BATMSBz 為一高性能之改質劑，能同步提昇聚氧代氮
代苯并環己烷的玻璃轉移溫度與韌性。
第四部分則以具有雙呋喃官能基之BPA-FBz與雙(4-馬來醯亞胺基苯)甲烷為單體，經由狄爾斯-阿爾德反應製備出主鏈含氧代氮代苯并環己烷的可交聯線性高分子PBz，PBz經由熱處理後得到一交聯高分子PBz-R，PBz-R具有優良的熱性質及機械性質，而以相同之單體混摻所得之交聯高分子
PBz/BMI-BR其性質較PBz-R為差，特別在韌性方面。
本研究聚焦在聚氧代氮代苯并環己烷性質之改善，以終端需求之概念，利用分子設計觀點，將不同功能性的分子基團導入氧代氮代苯并環己烷的分子結構中，以提昇其加工易製性、熱安定性、電氣性質與材料特性，從研究結果顯示：本論文為聚氧代氮代苯并環己烷之改質作了相當程度之貢獻：(1)將具有可聚合的馬來醯亞胺導入聚氧代氮代苯并環己烷，提昇聚氧代氮代苯并環己烷的交聯密度，另可改善馬來醯亞胺之吸濕性，(2)從經濟與環保之概念將呋喃分子基團導入氧代氮代苯并環己烷的分子結構中，大幅提昇聚氧代氮代苯并環己烷的性質，(3)以矽氧烷與氟元素導入氧代氮代苯并環己烷單體作為反應型之改質劑，可有效地改善聚氧代氮代苯并環己烷的韌性與介電性質，(4)結合有機反應方法與高分子合成觀點，以狄爾斯-阿爾德反應製備出主鏈含有氧代氮代苯并環己烷之聚合物，進一步經由熱處理可得到一韌性高分子材料，為聚氧代氮代苯并環己烷開啟了另一個改質的方法。

關鍵字

氧代氮代苯并環己烷 ； ?喃 ； ?性 ； 難燃性

並列摘要

Abstract
In this study, five novel benzoxazine monomers (3-phenyl-3,4-di- hydro-2H-6-(N-maleimido)-1,3-benzoxazine, HPM-ABz; 3-furfuryl-3,4- dihydro-2H-1,3-benzoxazine, P-FBz; bis(3-furfuryl-3,4-dihydro-2H-1,3- benzoxazine)isopropane, BPA-FBz; 6-fluoro-3-furfuryl-3, 4-dihydro-2H- 1,3-benzoxazine, 4-FP-FBz; 1,3-bis(3-aminopropyl)tetramethyl-disiloxane- benzoxazine, P-BATMSBz ) were synthesized using functional primary amines (N-(4-hydroxyphenyl)maleimide; furfurylamine; 1,3-bis(3-amino- propyl)tetramethyldisiloxane, BATMS) as raw materials. The chemical structures of these benzoxazine mononmers were characterized with FT-IR, 1H NMR, and elemental analysis. Furthermore, a high molecular weight polymer (PBz) possessing reactive benzoxazine groups in the mainchain was prepared through the Diels-Alder reaction using BPA-FBz and a bismale-imide (BMI) as
monomers.
First, HPM-ABz was prepared from N-(4-hydroxyphenyl)maleimide, formaldehyde, and aniline. HPM-ABz showed a melting point of 52–55℃and good solubility in common organic solvents. HPM-ABz showed a two stage process of thermal polymerization. The first stage arose from the polymerization of maleimide groups, and the second one was the ring-opening reaction of benzoxazine groups. Fusible polymaleimides with a Tg of around 100 °C could be obtained by thermally polymerizing HPM-Ba at 130 °C. Further polymerizing the polymaleimides at 240 °C resulted in a completely cured resin showing a Tg at 204 °C. Good thermal stability and self-extinguishing behavior was observed with the cured polybenzoxazine
resins.
Second, furan-containing benzoxazine monomers, P-FBz, BPA-FBz, and 4FP-FBz were prepared using furfurylamine as a raw material. Formation of furfurylamine Mannich bridge networks in the polymerizations of P-FBz and BPA-FBz increased the cross-linking densities and thermal stability of the resulting polybenzoxazines. P-FBz and BPA-FBz- based polymers also exhibited high glass transition temperatures above 300℃, high char yields, and low flammability with a limited oxygen index value of 31. The dielectric (Dk3.21–3.39) and mechanical properties (high storage modulus of 3.0–3.9 GPa and low coefficient of thermal expansion of 37.7– 45.4 ppm) of the P-FBz and BPA-FBz-based polymers were superior or comparable to other polybenzoxazines. 4FP-FBz used for polybenzo- xazine modification by means of formation of benzoxazine hybridation with P-FBz. Poly(4FP-FBz) showed low dielectric constant(2.7), and 4FP-FBz incorporation showed significant
effect on lowering the dielectric constant of polybenzoxazine.
Third, a silicon-containing benzoxazine P-BATMSBz was prepared from 1, 3-bis(3-aminopropyl)tetramethyldisiloxane, BATMS, formaldehyde, and aniline. P-BATMSBz used for polybenzoxazine modification by means of formation of benzoxazine copolymers with P-FBz. P-BATMSBz incorporation exhibited significant effect on toughening polybenzoxazines. It is therefore demonstrated that P-BATMSBz is a high performance modifier to
simultaneously enhance the Tg and toughness of polybenzoxazines.
Fourth, a high molecular weight polymer (PBz) possessing reactive benzoxazine groups in the mainchain was prepared through the Diels-Alder reaction using BPA-FBz and a bismaleimide (BMI) as monomers. The polymer PBz was further thermally cross-linked to result in a high performance polymer (PBz-R), which exhibits high glass transition temperature of 242 oC, good thermal stability, high mechanical strength, and great flexibility. Another cross-linked polymer curing from the mixture of BPA-FBz and BMI was also prepared. However, the properties of PBz-BR is not as good as what observed
with PBz-R.
In this work, we focused on improving the properties of polybenzo- xazine. Utilizing the molecular design introduced different functional groups into a series of polybenzoxazines in order to fit the requirement of end use, and to enhance their processability easily, thermal stability, electrical and physical properties. In this study, it was demonstrated that we made contribution to improve the properties of polybenzoxazine as described below:(1) introducing the polymerizable maleimide group into the polybenzoxazine to enhance the crosslink density and reduce the water absorbance of polymaleimide, (2) using economic and ecological furan compound as a raw material in synthesis, to obtain high performance polybenzoxazines, (3) introducing the fluorine and siloxane into the polybenzoxazines as modifier to enhance the toughness and reduce Dk of polybenzoxazines, (4) combining the organic reaction and polymer synthesis, we reported a new approach(using Diels-Alder reaction) for
synthesizing polymers having benzoxazine in the main chain.

並列關鍵字

Benzoxazine ； furan ； toughness ； flame retardance

參考文獻

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