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研究生:鍾明智
研究生(外文):Ming-Chin Chung
論文名稱:含磷環氧樹脂與氰酸酯組成物之物性研究
論文名稱(外文):Studies on the Properties of Phosphorus-Containing Epoxy/Cyanate Compositions
指導教授:何宗漢何宗漢引用關係謝正悅謝正悅引用關係
指導教授(外文):Tsung-Han HoJeng-Yueh Shieh
學位類別:碩士
校院名稱:國立高雄應用科技大學
系所名稱:化學工程系碩士班
學門:工程學門
學類:化學工程學類
畢業學年度:94
語文別:中文
論文頁數:123
中文關鍵詞:含磷環氧樹脂難燃劑氰酸酯
外文關鍵詞:phosphorus-containing epoxy resinflame retardantcyanate ester
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環氧樹脂具有加工容易、黏著性佳、耐化學溶劑和耐酸鹼腐蝕,以及優異的電氣和機械特性等特性,因而廣用於電子工業。然而,傳統環氧樹脂的易燃性、高吸水性和高介電常數,且高溫下性能會變差使其無法滿足目前技術上的需求。
在本研究中,含磷環氧樹脂半固化物(phosphorus-containing advanced epoxy resin)由diglycidyl ether of bisphenol-A(DGEBA)分別與2-(6-oxido-6H-dibenz(c,e)(1,2)-oxaphosphorin-6-yl)-1,4-benzenediol (ODOPB或稱DOPOBQ)及 2-(6-oxido-6H-dibenz(c,e) (1,2)oxaphos-phorin-6-yl)- naphthalenediol(ODOPN或稱DOPONQ)所合成。另外,以丙二酚(Bisphenol-A, BPA)與DGEBA合成丙二酚環氧樹脂半固化物(Control advanced epoxy resin)作為比較。環氧樹脂半固化物各別添加Bisphenol-A dicyanate(BADCy)、Tetramethyl bisphenol-F dicyanate(TBFDCy)、Biphenol dicyanate(BIDCy)以及 Oxydiphenol dicyanate(ODDCy),經硬化過程後可得環氧樹脂/氰酸酯固化物。利用DSC、DMA、TMA、TGA、UL-94、吸水性及DEA來探討固化物的物性。結果顯示,含磷固化物的玻璃轉移溫度(Tg)隨磷含量的增加而下降,但比Control之系統高。固化物系統中有萘環結構存在時,玻璃轉移溫度會比含苯環結構的系統高,因堅硬的萘環結構會增加環氧樹脂主幹上鏈段旋動的困難。環氧樹脂混掺BIDCy之系統有最高之Tg,因聯苯的堅硬結構會限制住固化物鏈段的運動。於氮氣環境下,由於氰酸酯與含磷難燃劑相互補償的結果,其固化物的熱穩定性差異不大。在空氣下,熱裂解溫度隨著含磷量的增加而降低,但灰份殘餘量則會有明顯的增加。固化物的含磷量僅需2 %左右便可達到V-0等級。增加磷含量會導致固化物吸水性、介電常數和介電損失增大,其原因為強極性的OH基增加。含萘環結構的固化物,其吸水性、介電常數和介電損失會比含苯環的固化物低,主要歸因於萘環自由體積較大的緣故。以TBFDCy混掺之系統有最低的吸水性、介電常數及介電損失,因TBFDCy結構上具有四個龐大的甲基可有效的增加疏水性及自由體積。
Epoxy resins, with the characteristics of easy processability, good adhesion to various substrates, high chemical and corrosion resistance, and excellent electric and mechanical properties, are widely used in electronic application. However, the common epoxy resins cannot satisfy field applications, which have relatively poor performance at high temperatures, have high dielectric constants, and exhibit significant water absorption.
In this study, phosphorus-containing advanced epoxy resins were synthesized from diglycidyl ether of bisphenol-A(DGEBA) with 2-(6-oxido-6H-dibenz(c,e)(1,2)- oxaphosphorin-6-yl)- 1,4-benzenediol (ODOPB namely DOPOBQ) and 2-(6-oxido-6H- dibenz (c,e) (1,2)oxaphosphorin-6-yl)- naphthalenediol (ODOPN namely DOPONQ), respectively. In addition, Control advanced epoxy resins were synthesized from DGEBA with Bisphenol-A in order to compare.Epoxy/cyanate cured resins were prepared from phosphorus-containing advance epoxy resins and Control advance epoxy resin add Bisphenol A dicyanate (BADCy), Tetramethyl bisphenol F dicyanate (TBFDCy), Biphenol dicyanate (BIDCy) and Oxydiphenol dicyanate (ODDCy) through curing procedure, respectively. The properties of cured resins studied by differential scanning calorimetry(DSC), dynamic mechanical analysis (DMA), thermal mechanical analysis(TMA), thermal gravimetric analysis(TGA), UL-94 vertical, moisture absorption and Dielectric analysis(DEA).The resulting phosphorus-containing cured resins epoxy will decrease glass transition temperature (Tg) by increase phosphorus content, but Tgs higher than the Control systems. Introduction of rigid naphthalene structure into the epoxy backbone increased the difficulty of chain rotation, hence the Tgs were higher than benzene structure. Tgs of Epoxy/BIDCy system are highest than other due to the rigid biphenyl structure limited motion of chain. The thermal stability difference of the cured resins were very close in nitrogen atmosphere, owing to cyanate and phosphorus-containing flame retardant are complementary compositions. The thermal degradation temperatures is reduced with increase of phosphorus content, however, char yield is a marked increase in air atmosphere. An increase in the phosphorus content in the cured resins led to higher moisture absorption, dielectric constant and dielectric loss factor due to raise the strong polar OH group. The moisture absorption, dielectric constant and dielectric loss factor of naphthalene-containing cured resins are much lower than that of benzene-containing cured resins, which attribute to the more free volume of molecular structure of the naphthalene. The moisture absorption, dielectric constant of Epoxy/TBFDCy system are lowest than other, this is because four bulky methyl groups of TBFDCy structure can increase hydrophobicity and free volume effectively.
中文摘要 ------------------------------------------------------- i
英文摘要 ------------------------------------------------------- ii
誌謝 ------------------------------------------------------- iv
目錄 ------------------------------------------------------- v
Scheme ------------------------------------------------------- viii
表目錄 ------------------------------------------------------- ix
圖目錄 ------------------------------------------------------- xi
第一章、 緒論--------------------------------------------------- 1
1-1 前言--------------------------------------------------- 1
1-2 印刷電路板之種類與發展----------------------------------- 1
1-3 研究之目的及主要內容------------------------------------- 3
第二章、 原理與文獻回顧------------------------------------------ 6
2-1 環氧樹脂(Epoxy Resin)--------------------------------- 6
2-1-1 環氧樹脂簡介-------------------------------------------- 6
2-1-2 環氧樹脂硬化之流變行為與硬化劑---------------------------- 7
2-2 高分子燃燒與難燃劑(Flame Retardant)-------------------- 11
2-2-1 高分子的燃燒性質---------------------------------------- 11
2-2-2 難燃劑之簡介與原理-------------------------------------- 12
2-2-3 難燃劑之協同作用(Synergism)---------------------------- 14
2-2-4 難燃材料之測試方法--------------------------------------- 15
2-3 環氧樹脂之難燃化----------------------------------------- 18
2-4 氰酸酯(Cyanate Ester)--------------------------------- 23
2-4-1 氰酸酯簡介---------------------------------------------- 23
2-4-2 氰酸酯與環氧樹脂的反應機構-------------------------------- 26
2-5 電氣性質------------------------------------------------ 28
2-5-1 介電常數與介電損失--------------------------------------- 28
2-5-2 影響介電常數的原因--------------------------------------- 29
第三章、 實驗--------------------------------------------------- 30
3-1 材料與藥品---------------------------------------------- 30
3-2 實驗裝置圖---------------------------------------------- 32
3-3 實驗流程圖---------------------------------------------- 33
3-3-1 合成與鑑定---------------------------------------------- 33
3-3-2 物性測試流程-------------------------------------------- 33
3-4 儀器設備----------------------------------------------- 34
3-5 實驗步驟----------------------------------------------- 35
3-5-1 含磷雙酚化合物之合成------------------------------------- 35
3-5-2 環氧樹脂半固化物(advanced epoxy resins)之合成----------- 36
3-5-3 雙官能氰酸酯之合成--------------------------------------- 37
3-6 試片製備------------------------------------------------ 38
3-6-1 以DOPOBQ作為難燃劑之環氧樹脂/氰酸酯系統配方及硬化條件-------- 38
3-6-2 以DOPONQ作為難燃劑之環氧樹脂/氰酸酯系統配方及硬化條件-------- 38
3-7 結構鑑定與物性測試--------------------------------------- 39
第四章、 結果與討論---------------------------------------------- 46
4-1 單體之鑑定---------------------------------------------- 46
4-1-1 含磷雙酚化合物(DOPOBQ 與DOPONQ)之鑑定------------------- 46
4-1-2 含磷環氧樹脂半固化物之鑑定-------------------------------- 48
4-1-3 雙官能氰酸酯之鑑定--------------------------------------- 49
4-2 以DOPOBQ作為難燃劑之環氧樹脂/氰酸酯系統-------------------- 67
4-2-1 DSC分析------------------------------------------------ 67
4-2-2 DMA分析------------------------------------------------ 67
4-2-3 TMA分析------------------------------------------------ 68
4-2-4 TGA分析------------------------------------------------ 69
4-2-5 UL-94測試---------------------------------------------- 70
4-2-6 吸水性分析---------------------------------------------- 70
4-2-7 介電分析------------------------------------------------ 71
4-3 以DOPONQ作為難燃劑之環氧樹脂/氰酸酯系統-------------------- 89
4-3-1 DSC分析------------------------------------------------ 89
4-3-2 DMA分析------------------------------------------------ 89
4-3-3 TMA分析------------------------------------------------ 90
4-3-4 TGA分析------------------------------------------------ 90
4-3-5 UL-94測試---------------------------------------------- 91
4-3-6 吸水性分析---------------------------------------------- 91
4-3-7 介電分析----------------------------------------------- 92
4-4 難燃劑(DOPOBQ,DOPONQ)在固化物物性上的比較-------------- 110
4-4-1 DMA分析------------------------------------------------ 110
4-4-2 TMA分析------------------------------------------------ 110
4-4-3 TGA分析------------------------------------------------ 110
4-4-4 UL-94測試---------------------------------------------- 110
4-4-5 吸水性與介電分析---------------------------------------- 110
4-5 結論--------------------------------------------------- 117
第五章、 總結--------------------------------------------------- 118
參考文獻 ------------------------------------------------------- 119
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