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研究生:周裕偉
研究生(外文):Yu Wei Chou
論文名稱:雙環戊二烯氰酸酯/benzoxazine及磷系氰酸酯/benzoxazine共聚合物之合成與物性
論文名稱(外文):Synthesis and properties of dicyclopentadiene-based cyanate ester/benzoxazine and phosphinated cyanate ester/benzoxazine copolymers
指導教授:林慶炫
指導教授(外文):Ching Hsuan Lin
口試委員:王志逢郭紹偉
口試委員(外文):Chih-Feng WangShiao-Wei Kuo
口試日期:2014-07-18
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學工程學系所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2014
畢業學年度:102
語文別:中文
論文頁數:81
中文關鍵詞:
外文關鍵詞:No
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雙環戊二烯苯酚(Dicyclopentadiene-phenol, DP)具有剛性脂肪族結
構,常用予提升材料熱性質、電氣性質等。本研究將其改質成氰酸酯材料 DPCY,並混摻用於改質雙官能Benzoxazine樹脂4,4’diaminodiphenyl ether-based benzoxazine (ODABz),使兩樹脂於固化過程中相互反應,而隨著 DPCY 導入有效降低固化物之介電常數。所得材料經測試,除表現出優異的電氣性質外,亦保有良好的熱性質、熱穩定性,並由於導入脂肪族結構,提升材料疏水性,製得多項性能提升的氰酸酯材料。
在阻燃性材料的發展中,磷系阻燃劑(DOPO)除具有絕佳的阻燃效果外,其剛性芳香族結構亦有提升熱性質與疏水性之功效,因此本研究設計以 DOPO 合成新型磷系四酚單體並進一步製備成氰酸酯樹脂後,改質雙官能 Benzoxazine 樹脂 ODABz 製得氰酸酯/Benzoxazine 共聚固化物,所得材料經測試表現出絕佳的阻燃效果,並且於熱性質、熱穩定性以及疏水性等皆有良好的性質表現,有效降低材料吸水性,獲得高性能低吸水材料。


Dicyclepentadiene-phenol (DP) has rigid aliphatic structure, commonly used in enhancing thermal property and dielectric property for materials. In the study, DP was modified into cyanate ester, DPCY, and blended with
bifunctional benzoxazine, 4,4’-diaminodiphenyl ether-based benzoxazine(ODABz). The two resins co-reacted when being cured. The dielectric constants were decreased by adding DPCY in to the thermosets. The resulting materials achieved great thermal properties, thermal stability, and
dielectric properties. The hydrophobicity of the materials was also decreased because of the aliphatic structures.
In the development of materials with flame-retardancy, DOPO has outstanding flame-retardancy, and increases thermal stability and hydrophobicity because of the rigid aromatic structures. The novel tetrafunctional phenolic monomers were synthesized by reacting with DOPO and further modified into cyanate esters. Blended with ODABz, the thermosets have great thermal properties, thermal stability, hydrophobicity,and flame -retardancy.


中文摘要 ............................................................................................................................i
Abstract ............................................................................................................................ii
第一章 緒論 .................................................................................................................... 1
第二章 文獻回顧 ............................................................................................................ 2
2-1 雙環戊二烯苯酚(Dicyclopentadiene-phenol, DCPD)簡介 ............................ 2
2-2 含磷難燃材料簡介 ............................................................................................ 3
2-3 氰酸酯簡介 ........................................................................................................ 7
2-4 氰酸酯與 Benzoxazine 樹酯簡介 .................................................................... 8
2-5 研究動機 .......................................................................................................... 16
第三章 實驗 .................................................................................................................. 17
3-1 實驗藥品與溶劑 ............................................................................................. 17
3-2 儀器設備 ......................................................................................................... 19
3-3 雙環戊二烯氰酸酯系列合成與鑑定 .............................................................. 22
3-3-1 DP 的合成與鑑定 ............................................................................................ 22
3-3-2 DPCY 的合成與鑑定 ...................................................................................... 25
3-4 含磷氰酸酯系列合成與鑑定 .......................................................................... 28
3-4-1 D2HB (1)合成與鑑定 ...................................................................................... 31
3-4-2 P-D2HB (2) 合成與鑑定 ................................................................................ 34
3-4-3 磷系四酚(3)合成與鑑定 .................................................................................. 37
3-4-4 磷系氰酸酯(4)合成與鑑定 ............................................................................. 40
第四章 性質分析與討論 .............................................................................................. 43
4-1 雙環戊二烯氰酸酯/ODABz 性質分析 ......................................................... 43
4-1-1 DSC 放熱峰探討 ............................................................................................. 43
4-1-2 FTIR 共聚反應機制探討 ................................................................................ 45
4-1-3 試片硬化條件 .................................................................................................. 53
4-1-4 共聚之熱性質分析 .......................................................................................... 54
4-1-5 共聚介電性質分析 .......................................................................................... 58
4-1-6 共聚吸水性測試 .............................................................................................. 60
4-2 含磷氰酸酯/ODABz 性質分析 ..................................................................... 61
4-2-1 DSC 放熱峰探討 ............................................................................................. 61
4-2-2 FTIR 共聚反應機制探討 ................................................................................ 63
4-2-3 試片硬化條件 .................................................................................................. 69
4-2-4 共聚熱性質分析 .............................................................................................. 70
4-2-5 共聚介電性質分析 .......................................................................................... 74
4-2-6 共聚吸水性測試 .............................................................................................. 76
4-2-7 共聚物之難燃測試 .......................................................................................... 77
第五章 結論 .................................................................................................................. 78
第六章 參考文獻 .......................................................................................................... 80


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