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標題: 磷系可交聯型聚醚醚酮及聚醯亞胺之合成與物性探討
Synthesis and properties of phosphinated crosslinkable poly(ether ether ketone)s and polyimides
作者: 王譽儒
Wang, Yu-Ru
關鍵字: 聚醚醚酮;poly(ether ether ketone)s;聚醯亞胺;polyimides
出版社: 化學工程學系所
引用: 參考文獻 [1] Kreuchumas, A. US Pat. 2822 351 [2] Johnson, R. N., Farnham, A. G.,Clendinning, R. A.,Hale, W. F., Merriam, C. N., J.Appl. Polym. Sci. Part A-1, 1967, 5, 2398., [3] Hergenrother PM, Jensen BJ, Havens SJ., Polymer 1988;29:358. [4] Baek, J. B., Tan, L. S., Polymer 2003;44:4135 [5] Singh,R., Hay, A. S., Macromolecules 1991;24:2637. [6] Singh,R., Hay, A. S., Macromolecules 1991;24:2640 [7] Uhrich, K. E., Hawker, C. J., Frechet, J. M. J., Macromolecules 1992;25:4583 [8] Srinivasan, S. Twieg, R. , L. Hedrick, J., Hawker, C. J.,Macromolecules 1996;29:8543 [9] Gong, Z.H., Leu, C. M., Wu, F.I., Shu, C.F., Macromolecules 2000;33:8527 [10] Wu, F.I., Shu, C.F., J PolymSci Part A: Polym. Chem.2001;39:2536 [11] Cho, S. Y., Chang, Y., Kim, J. S., Lee, S. C., Kim, C., Macromol. Chem. Phys. 2001; 202:263 [12] Hwang, H.J., Hsu, S. W., Wang, C.S., J Appl Polym Sci 2008;110:1180 [13] Lin, C. H., Chang, S. L., Wei, T. P.,Macromolecules 2011;212:455 [14] Lin, C. H., Chang, S. L., Cheng, P. W.,Polymer 2011;52:1249 [15] Fukuhara, T., Shibasaki, Y., Ando, S., Ueda, M.,Polymer 2004;45:843 [16] Barton, J.M., Chaplin, A., Hamerton, I., Howlin,B.J., Polymer.1999;40:843.
1.線性聚醚高分子是利用等莫耳比的雙酚單體與芳香族二鹵化物在鹼性環境下製備而得,但是線性聚醚高分子難以在其重複單元中留有可反應性酚基官能基。因此,本研究利用bisphenol A製備而成的聚醚醚酮(BPA-PEEK)與DOPO、Phenol在硫酸催化下成功以一步法合成出重複單元中留有酚基官能基之磷系聚醚(P1)。此酚基提供了一個可與環氧樹脂反應之反應點,因此,將P1各別與三種環氧樹脂共聚交聯可製備出具有可撓曲且透明的環氧樹脂固化物薄膜。我們製備出的熱固性材料具有高玻璃轉移溫度、較低的介電常數且其耐燃性達UL-94 VTM V-0等級。此具有柔韌性且擁有較高分子量的P1,於環氧樹脂熱固性材料方面至今仍鮮少被應用。
2.含丙烯基的雙酚單體(1)是利用DOPO、4-hydroxyacetophenone及2-allylphenol在甲基對苯磺酸(p-TSA)催化下以一步法反應製備而得。將雙酚單體與4-fluoronitrobenzene進行親核性取代反應後,利用Fe/HCl還原硝基而合成出含丙烯基的雙胺單體(3)。利用上述雙胺單體與二酸酐ODPA以m-cresol為溶劑在isoqunoline促進下進行縮合製備出具可撓曲性之聚醯亞胺(4)。此聚醯亞胺利用DSC掃描測試有放熱峰的存在,證實了其具有可交聯之特性。我們發現經300oC,1 h加熱交聯後的聚醯亞胺在熱性質與溶劑阻抗性上皆有顯著的提升。

1.Linear polyethers are generally prepared from equal molar of bisphenols and aromatic bishalides in the presence of base. Therefore, polyethers with a residual phenol group in the repeating unit are difficult to prepare. In this work, a phosphinated polyether (P1) with a phenol group in the repeating unit was prepared from a one-pot reaction of a BPA-based poly(ether ether ketone), poly(oxy-1,4-phenylenecarboneyl-1,4-phenyleneoxy-1,4-phenylene-isopropylidene-1,4-phenylene (BPA-PEEK), with 9,10-dihydro-oxa-10-phosphaphenanthrene-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 prepared from the curing of P1 with three epoxy resins. The resulting thermosets show high Tg (250 oC), moderate-to-low dielectric constant (3.01), and flame retardancy (UL-94 VTM V-0). The moderate-to-high molecular weight of P1 might be responsible for the flexibility, which is rarely seen in epoxy thermosets.
2.An allyl-containing diphenol (1), was prepared from a one-pot reaction of 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 4-hydroxyacetophenone, and 2-allylphenol in the presence of p-TSA. A allyl-containingdietheramine (3) was nucleophilic substitution of (1) with 4-fluoronitrobenzene, followed by the reduction of the dinitro groups by Fe/HCl. Flexible polyimide (4) with curable characteristic, as supported by the DSC exothermic peak, was prepared from the condensation of (3) and ODPA in m-cresol in the presence of isoqunoline. Thermal properties and solvent resistance of polyimide (4) was significant improved after thermal curing at 300 oC, 1h.
其他識別: U0005-0808201220383400
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