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標題: 磷系反應型聚醚碸之合成與物性探討
Synthesis and properties of phosphinated reactive poly(ether sulfone)s
作者: 陳俊瑞
Chen, Jui-Chun
關鍵字: 聚醚碸環氧樹脂;poly(ether sulfone)s;Epoxy
出版社: 化學工程學系所
引用: 1.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 2.Rao, V. L. Polymer Reviews 1999, 39, 655. 3.Yee, A. F.; Pearson, R. A. J Mater Sci 1986, 21, 2462. 4.Wang, C. S.; Shieh, J. Y. Polymer 1998, 39, 5819. 5.Hoffmann, T.; Pospiech, D.; Häußler, L.; Komber, H.; Voigt, D.; Harnisch, C.; Kollann, C.; Ciesielski, M.; Döring, M.; Perez-Graterol, R.; Sandler, J.; Altstädt, V. Macromol Chem Phys 2005, 206, 423. 6.H. R. Kricheldorf;L. Vakhtangishvili;D. Fritsch. J. Polym Sci Part A: Polymer Chemistry, 2002 , 40, 2967 7.Hsiao, S. H.; Lin, K. H. J. Polym Sci Part A: Polym Chem 2005, 43, 331. 8.Chung, C. L.; Yang, C. P.; Hsiao, S. H. J Polym Sci Part A: Polym Chem 2006, 44, 3092. 9.Chern, Y. T.; Tsai, J. Y. Macromolecules 2008, 41, 9556. 10.Chern, Y. T.; Tsai, J. Y.; Wang, J. J. J Polym Sci Part A: Polym Chem 2009, 47, 2443. 11.Chung, I. S.; Kim, S. Y. Macromolecules 2000, 33, 3190. 12.Kricheldorf, H. R.; Fna, S. C.; Vakhtangishvili, L.; Schwarz, G.; Fritsch, D. J Polym Sci Part A: Polym Chem 2005, 43, 6272. 13.Wu, S.; Hayakawa, T.; Kikuchi, R.; Grunzinger, S. J.; Kakimoto, M. Macromolecules 2007, 40, 5698. 14.Wu, S.; Hayakawa, T.; Kakimoto, M.; Oikawa, H. Macromolecules 2008, 41, 3481. 15.Kim, Y. H.; Anh, S. K.; Kim, H. S.; Kwon, S. K. J Polym Sci Part A: Polym Chem 2002, 40, 4288. 16.Liaw, D. J.; Liaw, B. Y. Macromolecules 1999, 32, 7248. 17.Lin, C.H., Lin, T.L., Chang, S.L., Dai, S.A., Cheng, R.J., Hwang, K.Y., Tu, A.P., and Su, W.C. J Polym Sci Part A: Polymer Chemistry 2008,46, 7898–7912. 18.Lin, C.H., Chang, S.L., and Wei, T.P. Macromol Chem Phys 2011,212, 455–464. 19.Aguilar-Veag, M.; Paul, D. R. J Polym Sci Part B: Polym Phys Ed 1993, 31, 1599. 20.Mathias, L. J.; Lewis, C. M.; Wiegel, K. N. Macromolecules 1997, 30, 5970. 21.Rama Rao, M.; Rao, V. L.; Radhakrishnan, T. S.; Ramachandran, S. Polymer 1992, 33, 2834. 22.Liu, Y. L.; Hsiue, G.. H.; Lee, R. H.; Chiu, Y. S. J Appl Polym Sci 1997, 63, 895. 23.Banks, M.; Ebdon, J. R.; Johnson, M. Polymer 1993, 34, 4547. 24.Liu, Y. L.; Hsiue, G. H.; Lee, R. H.; Chiu, Y. S. J Appl Polym Sci 1997, 63, 895. 25.Wang, C. S., Shieh, J. Y. Polymer 1998, 39, 5819. 26.Cai, S. X.; Lin, C. H. J Polym Sci Part A: Polym Chem 2005, 43, 2862. 27.Lin, C. H.; Cai, S. X.; Lin, C. H. J Polym Scs Part A: Polym Chem 2005, 43, 5971. 28.Lin, C. H.; Lin, T. L.; Chang, S. L.; Dai, S. H. A.; Cheng, R. J.; Hwang, K. Y.; Tu, A. P.; Su, W. C. J Polym Sci Part A: Polym Chem 2008, 46, 7898. 29.Kissinger, H. E. Anal Chem 1957, 29, 1702. 30.Ozawa, T. Bull Chem Soc Jpn 1965, 38, 1881. 31.Lin, C. H.; Yang, K. Z.; Leu, T. S.; Lin, C. H.; Sie, J. W. J Polym Sci Part A: Polym Chem 2006, 44, 3487.
本實驗是由DHBP (4,4''-Dihydroxybenzophenone)與DFDPS (4,4`-Difluorodiphenyl Sulfone)藉由親核取代反應縮合聚合成poly(ether sulfone)s (DHBP-PES)。再藉由DOPO、Phenol對DHBP-PES進行親核加成反應及親電子取代反應而成功得到P1,我們利用相同的方式加入 DOPO、Aniline對DHBP-PES來合成P2,然而在P2的和結果由NMR圖譜看到有反應不完全的現象,顯示高分子P2是不容易聚合的。另外本實驗亦從單體合成方向而製備高分子(P2),實驗藉由DHBP 與 DOPO、Aniline 先合成為單體(1)在與4,4`-Difluorodiphenyl Sulfone 進行親核性取代反應縮合聚合成,成功合成反應型聚醚碸 (P2)。由實驗結果顯示,導入DOPO結構的聚醚碸具有相當優異的熱穩定性,及玻璃轉移溫度,亦有相當優異的溶解特性,對日後業界加工提供新的應用方向。
將反應型聚醚碸(P1、P2)與環氧樹脂(DGEBA、CNE)進行部分交聯反應,以及(P2)與ODPA (Oxydiphthalicanhydride)進而製備出可塗佈易加工的交聯型聚醚碸,透過交聯反應可大幅提昇聚醚碸對有機溶劑的耐受性與提高熱穩定性。

Linear poly(ether sulfones) are generally prepared from equal molar of bisphenols and dihalides of diphenyl sulfone in the presence of base. Therefore, poly(ethers sulfones) with a residual phenol group in the repea ting unit are difficult to control. In this work, a phosphinate poly(ether su- lfone) (P1) with a phenol group in the repeating unit was prepared from a one-pot reaction of a 4,4''-dihydroxybenzophenone (DHBP)-based poly(e- ther sulfone), poly(oxy-1,4-phenylenecarbonyl-1,4-phenyleneoxy-1,4-ph- enylene-sulfonyl-1,4-phenylene (DHBP-PEEK), with 9,10-dihydro-oxa- 10-phosph aphenanthrene-10-oxide (DOPO) and phenol in the presence of H2SO4. The phenol linkages provide reacting cites with epoxy resins. Therefore, flexible and transparent films of epoxy thermosets can be pre- pared from the curing of P1 with epoxy resins, cresol novolac epoxy (C- NE) and diglycidyl ether of bisphenol A(DGEBA). A phosphinated pol- y(ether sulfone) (P2) with an amino group in the repeating unit was ate- mpted to prepare in a similar procedure except for the phenol is replaced by aniline. However, the reaction was not successfully. To achieve the go- al, a DOPO-diphenolaniline, 1,1-bis(4-hydroxyphenyl)-1-(4-aminopheny- l)-1-(6-oxido-6H -dibenz <1,2> oxaphosphorin-6-yl)ethane, was prepared from the one-pot reaction of DOPO, DHBP and aniline in the presence of H2SO4 . P2 can successfully be prepared from the nucleophi- lic substitution of DOPO-diphenolaniline and difluorodiphenylsulfone (DFDPS) in the presence of K2CO3. P1/CNE, P1/DGEBA, P2/CNE, P2/DGEBA thermosets all show flexibility. The moderate-to-high mole- cular weight of P1 might be responsible for the flexibility (toughness), which is rarely seen in the low molecular weight curing agent/epoxy thermosets. P2 is brittle, but flexible film can be achieved by reacting the amine with dianhydride ODPA. After imidization at 300 oC (1h), the resulting P2/ODPA displays a Tg value as high as 340 oC by dynamic mechanical mechanical analysis. The data show the power of crosslinking.
其他識別: U0005-0808201214152100
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