聚醯亞胺複合材料及含磷雙馬來醯亞胺耐燃材料之製備與性質探討

Preparation and Properties of Polyimide Composites ＆Phosphorus-Containing Bismaleimide Flame Resistant Materials

湯仁忠(Jen-Chung Tang)

指導教授 ： 陳玉惠

中原大學/理學院/化學研究所/博士(2006年)

https://doi.org/10.6840/cycu200600680

摘要

摘 要

一般泛稱的聚醯亞胺(PI)被分類成縮合型(Condensation type)、加成型(Addition type)及改質型(Modification type)等三大類。由於聚醯亞胺(Polyimide)結構中含醯亞胺基(Imide group)，因此其分子鏈具有很強的分子間作用力及剛性，故聚醯亞胺具有極高的耐熱性、耐化學藥品性及機械等性質，而成為高性能電子工業材料之首選；然而，在實際應用上仍有改善空間。本研究分別對縮合型聚醯亞胺之玻璃轉移溫度、熱安定性、儲存模數、熱膨脹係數、介電常數及吸水率之改善，加成型聚醯亞胺加工溫度之降低，及含磷改質型雙馬來醯亞胺單體之合成與應用，加以探討研究，因此，將論文分為三部分。
本研究第一部分為針對聚醯亞胺材料，以物理混摻方式分散改質之奈米二氧化矽(SiO2-OA)於縮合型聚醯亞胺預聚合物(PAA)中，經熱環化反應，製備一系列不同SiO2-OA含量之奈米聚醯亞胺複合材料(PI/SiO2-OA)。其內容，除探討採用奈米SiO2-OA對所製備之PI /SiO2-OA奈米複合材料加工性的影響外，且評估奈米SiO2-OA對複合材料性質之熱穩定性，尺寸安定性、機械性質、介電常數及吸水率等性質之影響。結果顯示，添加SiO2-OA奈米粒子之PI/SiO2-OA奈米複合材料無論玻璃轉移溫度、熱安定性、儲存模數、熱膨脹係數、介電常數及吸水率都獲得改善，將有利與銅箔匹配及應用。
本研究第二部分係將加成型含磷雙馬來醯亞胺單體PBMI與商品化之雙馬來醯亞胺單體BMI混合，製備二成份系混成材料，期利用共熔特性，降低熔點及聚合溫度進而改善其加工溫度，並探討共熔組成對硬化樹脂耐熱性的影響。結果顯示，含20wt% PBMI含磷單體之PBMI與BMI混合物為一共熔混合體。此共熔混合體之熔點及最低聚合溫度均較PBMI與BMI單體為低，顯示PBMI之加入加大了加工窗口，可有效降低加工溫度。另，PBMI/BMI共聚合樹脂起始分解溫度隨PBMI重量比增加而下降，與用Coats-Redfern方程式計算所得之裂解活化能相符合。而使用Doyle’s提出之integral procedure decomposition temperature(IPDT)方法計算硬化樹脂之熱安定性結果發現，所有含PBMI單體的硬化樹脂皆有相對較高之IPDT值，IPDT在共聚合硬化樹脂中增加PBMI的含量其限氧指數(LOI)亦隨之提升。
本研究第三部分係將合成之含磷雙馬來醯亞胺單體PBMI3，與傳統環氧樹脂(DGEBA) 混摻，探討PBMI3之加入對樹脂硬化之反應熱、反應活化能、玻璃轉移溫度、耐燃性及對玻璃材質或鐵材質接着強度的影響。結果顯示，DGEBA/DDM/PBMI3摻合系統之交聯反應起始溫度約在110℃，且隨著PBMI3單體之添加其交聯反應最大放熱溫(Tmax)由154℃上升至177℃，而添加PBMI3對交聯系統之Ea影響不大，但對交聯反應熱而言，卻隨著添加PBMI3量之增加而下降。Tg點由不添加PBMI3之硬化環氧樹脂116 oC (EP0)上升至添加40wt%PBMI3之硬化環氧樹脂142 oC (EP40)。藉著添加含磷雙馬來醯亞胺PBMI3使得硬化後之環氧樹脂耐燃性提高，此現象由熱重量分析儀(TGA)及限氧指數(LOI)得到佐証。另外，以掃描式電子顯微鏡(SEM)觀察硬化後之環氧樹脂在斷裂面呈現相當均勻之結構，表示PBMI3與環氧樹脂之相容性非常好，在透光度及與鐵、玻璃等材質之接著強度亦表現優異。

關鍵字

耐燃材料 ； 複合材料 ； 聚醯亞胺 ； 含磷雙馬來醯亞胺

並列摘要

Abstract

Polyimides (PI) are known to possess good thermal-stability, mechanical strength and chemical resistance because of its strong intermolecular interaction and stiffness of imide group. Polyimides have been utilized in many high-tech fields. Nevertheless, there are spaces of improvement for application, especially used as electrical materials. In this thesis, the preparation and properties of PI composites and phosphorus-containing bismaleimide flame resistant materials were studied. for improvement of the properties of the condensation type, addition type and modification type PIs were studied
In the first part of this thesis, silica-containing PI nanocomposites were prepared and their properties were investigated. Hence, the commercial nano-sized silica (SiO2) was esterificated with oleic acid (OA), a relatively inexpensive and hydrophobic modifier, to make the particle’s surface hydrophobicly. The structure of the surface-modified silica (SiO2-OA) nanoparticles was confirmed with the FT-IR and EDS measurements. The SiO2-OA nanoparticles, then, were used to disperse in the poly(amic acid) solutions of a commercial polyimide (BPDA-PPD type) to prepare the PI/silica nanocomposite films. The results of the FT-IR, TGA, DMA, TMA, DSC, SEM, water absorption and dielectric constant measurements indicated that the as-prepared PI/silica nanocomposites exhibited significant improvements in the dynamic mechanical property, thermal stability, water resistance and thermal expansion.
Second part of this thesis aimed to prepare and study the properties of a hybrid composites based on a phosphonate-containing bismaleimide, PBMI, and a commercial bismaleimide, BMI. The phase diagram of the mixture system of PBMI and BMI was constructed from the result of the DSC measurements. It was found that the mixture with 20 wt% of PBMI formed a eutectic mixture. The eutectic mixture showed the lowest onset temperature of polymerization in the mixture system and its melting temperature was lower than the lower melting point of the monomers, indicating broader processing window in the molten state. The thermal behaviors of the cured resins of the mixture system were studied by DSC and TGA measurements. The initial degradation temperature was decreased with increasing PBMI content and well explained by the corresponding activation energies (Ea) evaluated by Coats-Redfern equation. All of the PBMI-containing cured resins showed very high IPDT values evaluated by Doyle’s proposition and the increasing orders of the char residues remained at 700 oC were consistent with the increasing orders of the corresponding IDPT values. The LOI value was significantly increased by increasing PBMI.
In the third part of this thesis, phosphorus-containing bismaleimide monomer, PBMI3, was prepared via imidization and condensation reaction. The structure of PBMI3 was confirmed by FTIR, NMR spectra and elemental analysis. The reaction kinetics of the mixtures of DGEBA/DDM/PBMI3 in various proportions was studied with DSC according to the method of Ozawa. It was found that with addition of PBMI3 into the DGEBA/DDM curing system, the apparent cured activation energies (Ea) were not much different with the Ea of the neat resin. However, the Tg increased from 116 oC (neat resin) to 142 oC for the sample with 40 phr of PBMI3 (EP40), and the enthalpy of the cured reaction was decreased with increasing the PBMI3 content. Besides, the char yield of the cured epoxy specimens increased with increasing PBMI3 due to the formation of the intumescent char materials during thermal decomposition, revealing an increase of flame retardant. The increase of LOI value with increasing the PMBI3 content confirmed its flame retardant efficiency. The SEM micrographs revealed that the phosphorus-containing bismaleimide cured epoxy resins had homogeneous fracture surface. Moreover, the cured epoxy resins showed high optical transparency and good adhesive strength to the glass and the stainless steel interface.

並列關鍵字

Polyimide ； Flame Resistant Materials ； Composites ； Phosphorus-Containing Bismaleimide

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