Polybenzoxazine/苯乙烯-馬來酸酐複合材料之硬化反應動力學及性質研究

A Study on Curing Kinetics and Characterization of Polybenzoxazine / Styrene-co-Maleic Anhydride Composite Materials

尤鈴雅(Ling-Ya Yu)

指導教授 ： 鄧道興

國立臺北科技大學/工程學院/有機高分子研究所/碩士(2013年)

https://doi.org/10.6841/NTUT.2013.00688

摘要

Polybenzoxazine因具有高Tg、低吸濕性、低介電常數及尺寸安定性佳等諸多優點，預期能廣泛應用於電子產業。
本研究以benzoxazine為基材與苯乙烯-馬來酸酐共聚物(SMA)共混，利用Fa單體oxazine ring打開所產生的羥基與SMA主鏈上的酸酐基反應形成酯鍵，以及因SMA酯化形成的羧基具有催化benzoxazine開環聚合及降低反應溫度的效果，藉由複合效應，提升polybenzoxazine / SMA複合材料的性質。
本研究分為三部分，首先以bisphenol F合成Fa單體，不同莫耳比例共聚合SMA，兩者皆利用傅立葉轉換紅外線光譜儀(FT-IR)及核磁共振光譜儀(NMR)分析鑑定官能基與結構，而SMA另藉由凝膠滲透層析儀(GPC)判定分子量大小及分布，示差掃描熱卡計(DSC)及熱重分析儀(TGA)進行熱性質分析，接枝率滴定確認共聚物中馬來酸酐含量的變化。
其次，將Fa單體混摻不同比例的SMA，其混摻物以FT-IR分析反應時分子結構的變化，旋轉式動態流變儀(MCR)分析反應時的黏度變化，並以動態DSC法研究Fa與Fa / SMA混摻物的硬化行為和反應動力學，探討添加SMA對整體系統的反應性是否有所差異。
最後，將混摻物經熱硬化後，探討不同SMA的添加比例對複合材料之性質影響及微相型態的變化，藉由DSC及TGA分析熱性質，動態機械分析儀(DMA)及熱機械分析儀(TMA)分析熱機械性質，並以掃描式電子顯微鏡(SEM)觀測試樣相分離的情形。

關鍵字

polybenzoxazine ； 苯乙烯-馬來酸酐 ； 交聯高分子 ； 反應動力學

並列摘要

Due to the high glass transition temperature (Tg), low moisture absorption, and low dielectric constant, as well as excellent dimensional stability, etc., polybenzoxazine will expected to be widely used in electronics industry.
In this study, benzoxazine monomer was cured with styrene-maleic anhydride (SMA) copolymer. Using the reaction between the hydroxyl group, which was formed via the ring-opening polymerization of oxazine ring, and the anhydride group of SMA copolymer occurred to form ester linkage; furthermore, the carboxyl group was formed via the esterification of SMA could decrease the curing temperature and catalyze the ring-opening polymerization of benzoxazine. By means of the synergistic effects would enhance performance of polybenzoxazine / SMA composite materials.
This experimental has subdivided into three parts. At first, we synthesized the Fa monomer by using bisphenol F, and copolymerized SMA copolymer by different feed mole ratios. Both were investigated the functional groups and chemical structures by FT-IR and NMR; besides, SMA were investigated the molecular weight and distribution by GPC; thermal properties by DSC and TGA, and evaluated MA content of copolymer by a titration method.
Secondarily, the Fa monomer was blended with SMA by various ratios. The blends were investigated the change of molecular structure as polymerization by FT-IR; the change of viscosity by MCR, and using dynamic DSC method to investigate the curing behavior and curing kinetics of Fa and Fa / SMA blends; explored the effect of reactivity of overall system by adding the SMA.
Finally, the blends were cured through the ring-opening polymerization to prepare composite materials (PFa / SMA), and explored the effect of characterization and morphology of composite materials by adding different ratios of SMA. The thermal properties of such composite materials were investigated by DSC and TGA. Its thermo-mechanical properties were investigated by DMA and TMA. In addition, its phase separation was observed by SEM.

並列關鍵字

polybenzoxazine ； styrene-maleic anhydride ； crosslinked polymer ； curing kinetics

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