臺灣博碩士論文加值系統

本研究是探討環氧樹脂與含磷硬化劑的硬化反應動力學以及熱裂解與難燃等性質。分別將將含磷雙酚硬化劑，2-6(-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-
yl)-1,4-naphthalenediol (ODOPN) 以及酚醛型硬化劑Phenol Novolac(PN)與鄰-甲酚醛多環性環氧樹脂o-Cresol Novolac Epoxy (CNE)進行硬化聚合反應，以示差掃瞄熱卡計DSC進行動態掃瞄求得最大放熱峰值(Tp)，再以小澤法(Ozawa method)計算硬化活化能。
將兩種硬化劑ODOPN與PN混摻，以0/100、25/75、50/50、75/25、100/0比例均勻混合再與環氧樹脂(CNE)進行固化，以動態黏彈機械分析儀DMA測其玻璃轉移溫度。利用熱重量損失分析儀TGA探討含磷環氧樹脂的熱裂解溫度及殘餘量與含磷量之間的關係，發現700℃時的殘餘量均隨著磷含量增加而增加，但熱裂解溫度有向低溫提前的趨勢。並利用小澤法(Ozawa method)計算熱裂解活化能，顯示含磷量越多的含磷環氧樹脂其裂解活化能越低。再利用限氧指數測試儀測試含磷環氧樹脂限氧指數LOI值，隨著磷含量增加，其限氧指數LOI值越高，難燃程度越好。

In this paper, discussions of the kinetics in curing reaction of epoxy resin with a curing agent containing phosphorus, and the thermal degradation behavior, flame-retardant property of the cured epoxy resins.
The curing reaction of a o-Cresol Novolac Epoxy (CNE) coupled with a curing agent containing phosphorus, 2-6(-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-naphthalenediol
(ODOPN) was conducted to obtain an epoxy resin containing phosphorus in main chain. The kinetic parameters, activation energy of the curing reaction were obtained by DSC analysis.
The glass transition temperature of the phosphorus content in cured phosphorus epoxy resins was measured by DMA. The thermal degradation behavior of cured phosphorus epoxy resins with different content of phosphorus was examined by TGA analysis. The residue in 700℃ by TGA was increased, and the degradation temperature will decrease by increasing phosphorus contents. The thermal degradation energy of cured phosphorus epoxy resins was estimated by Ozawa method, the energy was decreased by increasing phosphorus content in cured phosphorus epoxy resins. The flame-retardant property of cured phosphorus epoxy resin was measured by LOI. The LOI value was increased by increasing phosphorus content in cured phosphorus epoxy resins.

摘要‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧Ⅲ
誌謝‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧Ⅴ
目錄‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧Ⅵ
表目錄‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧Ⅷ
圖目錄‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧Ⅸ
第一章　序論‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧1
1.1前言‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧1
1.2環氧樹脂簡介‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧1
第二章　文獻回顧與原理‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧5
2.1環氧樹脂特性‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧5
2.2高分子難燃劑之重要性‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧9
2.3高分子難燃劑的開發‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧9
2.4高分子燃燒的因素‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧11
2.5高分子的燃燒機構‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧12
2.6高分子難燃劑的選擇‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧14
2.7難燃劑阻燃原理‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧16
2.8燃燒特性之測試‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧20
2.9環氧樹脂硬化反應動力學‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧21
2.10環氧樹脂裂解動力學‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧24
第三章　實驗‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧26
3.1材料與藥品‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧26
3.2儀器設備‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧27
3.3實驗方法‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧28
第四章　結果與討論‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧33
4.1DSC分析硬化劑之硬化反應活性‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧33
4.2硬化動力學求反應活化能‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧33
4.2.1動態法Ⅰ(Kissinger’s method) ‧‧‧‧‧‧‧‧‧‧‧‧‧33
4.2.2動態法Ⅱ(Ozawa’s method) ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧34
4.3自我催化反應模式(autocatalytic kinetic model) ‧‧‧‧‧‧35
4.4DMA分析‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧36
4.5難燃性分析TGA、LOI‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧36
4.5.1含磷環氧樹脂裂解活化能分析‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧37
4.5.2LOI值分析‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧37
第五章　結論‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧38
第六章　參考文獻‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧40

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