Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3709
標題: 藉由簡易方法合成新型環氧樹脂硬化劑與其高性能固化物之製作
Facile Preparation of Novel Epoxy Curing Agents and Their High-performance Thermosets
作者: 林宗立
Lin, Tsung-Li
關鍵字: Epoxy Curing Agents;環氧樹脂硬化劑
出版社: 化學工程學系所
引用: [1] 桓內弘著,賴耿揚譯,環氧樹脂應用實務,復漢出版社,1-3 ,1993 [2] 謝正悅,林慶炫,王春山,科學發展月刊,第28 卷第11 期,八十 九年九月 [3] Wang, C. S.; Berman, J. R.; Walker, L. L.; Mendoza,A. J Appl Polym Sci 1991, 43, 1315. [4] Wang, C. S.; Sun, Y. M.; Mendoza, A. Org PreprProc Int 1992, 24, 176. [5] Liu, Y. L.; Hsiue, G. H.; Chiu, Y. S. J Polym Sci Part A: Polym Chem 1997, 35, 565. [6] Shau, M. D.; Wang, T. S. J Polym Sci Part A: Polym Chem 1996, 34, 387. [7] Liu, Y. L. J Polym Sci Part A: Polym Chem 2002,40, 359. [8] Wang, C. S.; Lin, C. H. J Polym Sci Part A: Polym Chem 1999, 37, 3903. [9] Espinosa, M. A.; Galia` , M.; Ca` diz, V. J Polym Sci Part A: Polym Chem 2004, 42, 3516. [10] Shieh, J. Y.; Wang, C. S. Polymer 2001, 42, 7617. [11] Liu, W.; Varley, R. J.; Simon, G. P. J Appl Polym Sci 2004, 92, 2093. [12] Wang, C. S.; Lin, C. H. J Appl Polym Sci 1999,74, 1635. [13] Mikroyannidis, J. A.; Kourtides, D. A. J Appl Polym Sci 1984, 29, 197. [14] Liu, Y. L.; Hsiue, G. H.; Lee, R. H.; Chiu, Y. S.J Appl Polym Sci 1997, 63, 895. [15] Stokland, Jr. R. A.; Taylolr, R. I.; Thompson, L. E.; Patel P. B. 2005, 7, 851 [16] Lin, C. H.; Wang, C.S. Polymer 2001, 42, 1869 [17] Liu, Y. L. J. Polym. Sci., Part A: Polym. Chem. 2002, 40, 359 [18] Liu, Y. L.; Wu, C. S.; Hsu, K.Y. and Chang, T. C. J. Polym. Sci., Part A: Polym. Chem. 2002,40, 2329 [19] Cai, S. X. and Lin C. H. Lin, J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 2862 [20] Lin, C. H, Cai, S. X., Lin, C. H J. Polym. Sci., Part A: Polym. Chem. 2005, 43, 5971 [21] Annakurtty, K. S.; Kishore, K. Polymer, 29,756(1988). [22] Kishore, K.; Annakurtty, K. S.; Mallick, I. M. Polymer, 29, 762(1988). [23] Sato, M.; Yokoyama, M. Eur Polym J,16,79(1980). [24] Sato, M.; Yokoyama, M. J Polym Sci Part A:Polym Chem, 18, 2751(1980). [25] Sato, M.; Tada, Y.; Yokoyama, M. J Polym Sci Part A: Polym Chem, 19, 1037(1981).
摘要: 
本實驗藉由低成本且簡單的一步反應合成兩個難燃環氧樹脂硬化劑,9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl- tris(4-hydroxyphenyl)methane (1),與9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-yl-(4-aminophenyl)-bis(4-hydroxyphenyl)methane (2),藉由IR,高解析mass,X-rad單晶繞射與NMR鑑定其結構正確,並探討各種反應條件對產率與產物之結構的影響。由實驗結果推測此為SN1反應機制,另外我們也探討推電子基與拉電子基對於反應性的影響。我們將(1-2)做為環氧樹脂DGEBA,CNE和HP7200的硬化劑,並測試其硬化後的玻璃轉移溫度、熱裂解溫度、難燃性與吸水性,硬化後的環氧樹脂固化物相較於傳統的(DDM)硬化系統具有適當的Tg,熱穩定性與傑出的難燃性質。
另外我們利用o-cresol、2,6-Dimethylphenol 、o-Toluidine或2,6-Dimethylaniline做為第三個反應物原料合成一系列含有甲基的硬化劑(3-6) ,藉由IR,高解析mass,X-rad單晶繞射與NMR鑑定其結構正確,我們將(3-6)做為環氧樹脂DGEBA和HP7200的硬化劑,並測試其硬化後的玻璃轉移溫度、熱烈解溫度、難燃性與吸水性,含有甲基的環氧樹脂固化物比較不含甲基的(1-2)硬化系統,具有略低的Tg,適當的熱穩定性,較低的吸水性與傑出的難燃性質。

Two flame-retardant epoxy curing agents, 9,10-dihydro-9-oxa-10-
phosphaphenanthrene-10-yl- tris(4-hydroxyphenyl)methane (1) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl- (4-aminophenyl)-
bis(4-hydroxyphenyl)methane (2), were prepared by a facile, inexpensive and one-pot procedure. The structures of the curing agents were confirmed by IR, high-resolution mass, single crystal diffractogram and NMR spectra. The effects of the reaction conditions on the yield and the structure of the product were discussed. According to the experimental data, a SN1 mechanism was proposed. The effect of electron-donating and electron-withdrawing groups on the reactivity was also discussed. Compound 1 and 2 served as curing agents for diglycidyl ether of bisphenol A (DGEBA) , cresol novolac epoxy (CNE) and dicyclopentadiene epoxy(HP7200). Properties such as glass transition temperature, thermal decomposition temperature, flame retardancy, and moisture absorption of the resulting epoxy thermosets were evaluated. The glass transition temperature, thermal decomposition temperature, flame retardancy, and moisture absorption of the resulting epoxy thermosets were evaluated. The glass transition temperatures of epoxy thermosets are in the range of 171-220 oC. The flame retardancy increases with increasing phosphorus content and a UL-94 V0 grade can be a chieved with a phosphorus content of 1.5%.
We also synthesized another novel methyl-containing epoxy curing agents (3-6) by selected o-cresol, 2,6-Dimethylphenol, o-Toluidine, and 2,6-Dimethylaniline as the third reactant. The structure of the curing agents were confirmed by IR, high-resolution mass, single crystal diffractogram and NMR spectra. Compound 3-6 served as curing agents for diglycidyl ether of bisphenol A (DGEBA) and dicyclopentadiene epoxy(HP7200). Properties such as glass transition temperature, thermal decomposition temperature, flame retardancy, and moisture absorption of the resulting epoxy thermosets were evaluated. The methyl-containing epoxy thermosets show slightly lower Tg values, moderate thermostability , lower moisture absorption and excellent flame retardancy than (1-2) curing system.
URI: http://hdl.handle.net/11455/3709
其他識別: U0005-2607200818143600
Appears in Collections:化學工程學系所

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