Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3307
標題: Phosphorus-Containing Interpenetrating Polymer Networks Based on Maleimides and Epoxies: Synthesis and Thermal Properties
含磷雙馬來醯胺、環氧樹脂網狀互穿材料之製備及其熱性質分析
作者: 羅庚生
Lo, Geng-Sheng
關鍵字: bismaleimide;含磷雙馬來醯胺;IPN;epoxy;phosphorus-containing;LOI;char yield;網狀互穿結構;環氧樹脂;含磷;極限氧指數值;焦炭殘餘量
出版社: 化學工程學系
摘要: 
Epoxy resins, with characteristics of toughness, low shrinkage on cure, excellent attachment to many substrates and good alkali resistance, are widely used in casting, adhesive, lamination and encapsulation. However, as organic materials, one of the main drawbacks of the epoxy resins in many applications is their flammability. Moreover, higher thermal resistance is also needed for encapsulation materials. To meet higher thermal resistance and flame retardation requirements for epoxy materals, interpenetrating polymer networks (IPN) based on a phosphorus-containing maleimide and epoxy are thus prepared. First, a phosphorus-containing bismaleimide, 3,3'-bis(maleimidophenyl) phenylphosphine oxide (BMPPPO), was synthesized from triphenylphosphine oxide. In contrast to most known phosphours-containing polymers, the incorporation of BMPPPO into poly(bismaleimide) enhanced the polymers' glass transition temperatures. Thermal stability and char yields at high temperature region over 700 ℃ were also improved. As a result, the flame retardant properties of the poly(bismaleimide)s leveled up.
Two types of IPNs were studied in this work. The phosphorus-containing maleimide BMPPPO was cured simultaneously along with diglycidyl ether of bisphenol A- daminodiphenylmethane (DDM) and o-cresol novolac epoxy (CNE)-DDM, respectivley. For all of the IPNs, glass transition temperatures (Tg) increase with increasing phosphorus content. This is due to the fact that three rigid phenyl rings are covalently bound to P(O). Moreover, high char yields in TGA analysis and large LOI values indicate that these phosphorus-containing IPNs are capable of exhibiting superb flame retardant properties.

雙馬來醯胺(Bismaleimide)近來被重視的原因在於其優越的熱性質及易處理加工性能,基於以上之優點,故本研究特別選擇合成新型含磷雙馬來醯胺,來作為反應型難燃劑。
本研究主要分為兩大部分,第一部分為合成含磷雙馬來醯胺單體,我們採用市售TPPO(triphenyl phosphine oxide)經由硝化反應後得到含磷雙硝基化合物,再經由還原反應得到含磷雙胺基化合物,最後加入馬來酸酐經亞醯胺化反應即得我們所欲合成之含磷雙馬來醯胺單體。此種方法直接將磷團基導入高分子之重複單位中,可提高單位磷含量,另外,原料取得容易、合成步驟簡單、成本低等優點,使得此種單體極具商業化之潛力,並進一步行自身聚合反應製備含磷高分子,由結果顯示我們所合成之含磷雙馬來醯胺(BMPPPO)較市售之雙馬來醯胺(BMDM)玻璃轉移溫度增加70℃左右,而在空氣中之焦炭殘餘量增加54%之多,表示熱性質及難燃性質皆有顯著提昇。
第二部分為應用之探討,本研究是將所合成之含磷雙馬來醯胺當作難燃劑與改質劑使用,與常用市售之雙馬來醯胺、雙胺化合物及環氧樹脂摻合製備一系列難燃複合材料,共有以下兩種型態:(一)網狀互穿型含磷雙馬來醯胺/雙胺化合物/BE188難燃材料,(二)網狀互穿型含磷雙馬來醯胺/雙胺化合物/CNE200難燃材料,對其作熱性質分析。結果顯示玻璃轉移溫度皆隨磷含量之增加而增加,原因在於雙馬來醯胺結構中有三個堅硬之苯環共價鍵結於磷團基上,使分子鏈不易運動所致。另外由於磷團基會在低溫處裂解形成焦炭保護層,導致難燃材料熱裂解溫度隨磷含量增加而降低,而焦炭殘餘量卻隨之增加的現象產生。在極限氧指數質方面,亦隨磷含量之增加而增加(32∼45),表現出優異之難燃性質。
URI: http://hdl.handle.net/11455/3307
Appears in Collections:化學工程學系所

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