Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3581
標題: 非光氣法合成2,2-bis(4-isocyanatophenyl)propane及其在耐黃變型聚胺酯之應用研究
Non-phosgene route to 2,2-bis(4-isocyanatophenyl)propane and its application in non-yellowing PU
作者: 鐘子惠
CHung, Tzu-Hui
關鍵字: Non-phosgene route
耐黃變
non-yellowing
PU
聚胺酯
非光氣法
出版社: 化學工程學系所
引用: 1.D. Randall, S. Lee, The Polyurethanes book; John Wiley: New York, 2000. 2.N. E. House, C. J. Kolaskie, U.S.Patent 5,349,077 2000. 3.C. S. Schollenberger, H. Scott , G. R. Moore, Rubber Word 1958, 4, 549. 4.J. E. Kresta, 60 Years of Polyurethanes; Technomic Pub.: Lancaster, Pa., 1998. 5.山西省化工研究所,聚氨酯彈性體手冊,化學工業出版社,2001年。 6.張豐志,應用高分子手冊,五南圖書,2003年。 7.Y. M. Jeon, NIKE FOOTWEAR RSL, 1997. 8.凃耀國,張德展,謝淳仁,大葉學報,第九卷,第二期,47頁,2000年。 9.D.C. Allport, D.S. Gilbert, S.M. Outterside, MDI and TDI:a safety, health and the environment, John Wiley: New York, 2003. 10.中鼎月刊,第28期,312頁,2003年。 11.H. Hellbach, F. Merger, F. Towae, U.S. Patent 4,596,679 1984. 12.G. Bohmholtd, W. Heitmann, P. Kirechner, U.S. Patent 5,360,931 1993. 13.Zajacek, G. John, Fuger, E. Karl, U.S. Patent 3,895,054 1975. 14.Fukuoka, Shinsuke, Chono; Masazumi, Watanabe, Tomonari, Kohno, Masashi, U.S. Patent 4,547,322 1985. 15.溫建勝,含羰基的化合物在一元醇及二元醇醇化反應之研究,國立中興大學化學工程學系,台中,2001年 16.C. E. Hoyle, K. J. Kim, Y. G. No, G. L. Nelson, J. Appl. Polym. Sci. 1987, 34, 763. 17.J. L. Gardette, J. Lemaire, Makromol. Chem. 1982, 183, 2415. 18.T. Servay, R. Voelkel, H. Schmiedberger, Polymer 1999, 41, 5247. 19.R. P. Singh, N. S. Tomer, S. V. Bhadraiah, Polymer Degradation and Stability. 2001, 73, 443. 20.Ciba Value beyond chemistry. 2006 Ciba Specialty Chemicals. 19 May 2006 <http://www.cibasc.com/>. 21.A. J. Corson, J. Org. Chem. 1958, 23, 544. 22.K. Inoue, U.S. Patent 4,594,459. 23.J. V. Crivello, A. J. Ramdas, J. Master. Sci. Pure Appl. 1992, A29, 753. 24.K. K. Sun, U.S.Patent 4,177,211, 1979. 25.A. J. Caruso, J. L. Lee, J.Org.Chem. 1997, 62, 1058. 26.W. F. Chen, H. Y. Lin and S. A. Dai, Org. Lett. 2004, 6, 2341. 27.G. A. Hiegel, T. J. Hogenauer, Synthetic Communications 2005, 35, 2091. 28.M. Avram, G. D. Mateescu, Spectroscopie Information; Dound: Paris, 1970.
摘要: 本研究以Bisphenol A(BPA)為起始原料,在強酸及苯胺基甲酸甲基酯(Methyl N-phenylcarbamate,MPC)之作用下,經除酚-烷交換反應(De-phenol Transalkylation)後,可以得到雙胺酯基化合物Dimethyl 4,4''-isopropyliden bis(phenylcarbamate)(DM-MDI bis-carbamate),再將其經由高溫熱裂解的方式即可得到新型的芳香族二元異氰酸鹽單體2,2-bis (4-isocyanatophenyl)propane(DM-MDI)。以此非光氣路徑可兼顧環保免用光氣,並以極為簡捷的程序合成此較MDI更具抗氧化及自由基作用的聚胺酯(PU)中間體。 在除酚-烷交換反應中,發現以原料莫爾比例為1:5:2.5(BPA:MPC:MSA),在減壓蒸餾下反應,同時控制反應溫度低於90℃,該反應條件可將酚順利從反應混合物中移除,以促進反應完成,而獲得雙胺酯基化合物DM-MDI bis-carbamate,其產率為75%。而在第二步驟的熱裂解反應中,在3wt %二苯醚溶液中,控制反應溫度在254℃,經反應5-6小時即得到DM-MDI,經濃縮及純化後主產物之產率為61%。 本實驗進一步運用DM-MDI合成新型耐黃變聚胺酯高分子,以混合不同莫爾比例(10%、20%、40%、100%)的DM-MDI及MDI作為製備PU的原料,由測試結果顯示,均勻分散10-20 mole%的DM-MDI於PU產品時,產物之耐黃變能力有明顯的提升,並且也能保有芳香族PU的良好性能。
In my research, Bisphenol A(BPA)was used a raw material and was treated with Methyl N-phenylcarbamate(MPC)under strong acidic condition to effect a “De-phenol Trans-alkylation Reaction” in formation of Dimethyl 4,4''-isopropyliden bis(phenylcarbamate)(DM-MDI bis-carbamate)as the first step. In the subsequent step, its corresponding 2,2-bis(4-isocyanatophenyl)propane(DM-DMI)was obtained from the DM-MDI bis-carbamate by thermolysis in high dilution. This non-phosgene synthetic route appears to be more straightforward and environmentally friendly than that of the known process in the literature. In this de-phenol trans-alkylation reaction of BPA, we found that optimum condition for the mole ratio of BPA, MPC to MSA is 1:5:2.5 at 90℃ under full vacuum. Under the condition, phenol was readily fractionated from the reaction mixture without the contamination of MPC. The highest yield of DM-DMI bis-carbamate achieved so far has been 75%. Thermolysis of DM-DMI bis-carbamate was carried out in ~3wt % solution of diphenyl ether at 254℃ for 5-6 hours, and the yield of DM-MDI is 61% after purification. We prepared a number of polyurethanes based on DM-MDI mixed in various mole ratios with MDI/DM-MDI(10/90、20/80、40/60、0/100)to find out their physical performances. At the mixing ratios of 10-20 mole% of DM-MDI to MDI, we found that those PU products exhibited enhanced resistant to oxidation and yellowing while maintains mechanical properties comparable to the MDI based PU product.
URI: http://hdl.handle.net/11455/3581
其他識別: U0005-2407200616282900
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-2407200616282900
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