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標題: 以綠色化學程序製備聚尿素高分子彈性體
Green Chemistry Approach to Synthesize Polyurea Elastomer
作者: Wen Chen Pan
關鍵字: Polyurea Elastomer
Green Chemistry
Diphenyl Carbonate
Non-isocyanate Route
引用: 1. Woods, G. and I. Polyurethanes, The ICI polyurethanes book. 1990: Published jointly by ICI Polyurethanes and Wiley. 2. Super, M.S., et al., High Performance RIM Elastomers and A Process for Their Production. 2004: United States. 3. Heimann, R.B., Plasma-spray coating: principles and applications. 2008: John Wiley & Sons. 4. Huang, W.B., et al., Study on mechanical properties aging of spray pure polyurea for hydraulic concrete protection. Advanced Materials Research, 2012. 374: p. 1325-1329. 5. Primeaux II, D., Polyurea spray technology in commercial applications. 60 years of polyurethanes: International symposium and exhibition. University of Detroit Mercy: January, 1998. 224238. 6. Fortun, K., Advocacy after Bhopal: Environmentalism, Disaster, New Global Orders. 2009: University of Chicago Press. 7. Process for the preparation of isocyanate. 1999: United States. 8. Irwin, C.F., Apparatus For Manufacure of Organic isocyanate. 1975: United States. 9. Anastas, P. and N. Eghbali, Green chemistry: principles and practice. Chem Soc Rev, 2010. 39(1): p. 301-12. 10. Anastas, P.T. and J.C. Warner, Green Chemistry: Theory and Practice. 2000: Oxford University Press. 11. Fauss, R., et al., NPR-Process for the preparation of N, O-disubstituted urethanes suitable as a starting material for the preparation of isocyanates. 1983: United States. 12. Wang, X.K., et al., A novel non‐phosgene process for the synthesis of methyl N‐phenyl carbamate from methanol and phenylurea: Effect of solvent and catalyst. Chinese Journal of Chemistry, 2004. 22(8): p. 782-786. 13. Ono, Y., Dimethyl carbonate for environmentally benign reactions. Catalysis Today, 1997. 35(1): p. 15-25. 14. Gao, J., et al., Non-phosgene synthesis of isocyanates based on CO2: Synthesis of methyl N''-phenyl carbamate through coupling route with lead compound catalysts. Catalysis Today, 2009. 148(3): p. 378-382. 15. Hutchins, S.M. and K.T. Chapman, A general method for the solid phase synthesis of ureas. Tetrahedron letters, 1994. 35(24): p. 4055-4058. 16. Versteegen, R.M., R.P. Sijbesma, and E.W. Meijer, Synthesis and characterization of segmented copoly(ether urea)s with uniform hard segments. Macromolecules, 2005. 38(8): p. 3176-3184. 17. Versteegen, R.M., et al., Properties and morphology of segmented copoly(ether urea)s with uniform hard segments. Macromolecules, 2006. 39(2): p. 772-783. 18. Tang, D., et al., Well-defined Biobased Segmented Polyureas Synthesis via a TBD-catalyzed Isocyanate-free Route. Macromol Rapid Commun, 2011. 19. Chen, H.-Y., et al., Synthesis and trans-ureation of N,N’-diphenyl-4,4′-methylenediphenylene biscarbamate with diamines: a non-isocyanate route (NIR) to polyureas. Journal of Polymer Research, 2012. 19(2). 20. Unverferth, M., et al., Renewable non-isocyanate based thermoplastic polyurethanes via polycondensation of dimethyl carbamate monomers with diols. Macromol Rapid Commun, 2013. 34(19): p. 1569-74. 21. Kreye, O., H. Mutlu, and M.A.R. Meier, Sustainable routes to polyurethane precursors. Green Chemistry, 2013. 15(6): p. 1431. 22. Yamazaki, N., T. Iguchi, and F. Higashi, The reaction of diphenyl carbonate with amines and its application to polymer synthesis. Journal of Polymer Science: Polymer Chemistry Edition, 1979. 17(3): p. 835-841. 23. Ubaghs, L., Isocyanate-free Synthesis of (Functional) Polyureas, Polyurethanes, and Urethane-containing Copolymers, Ph. D. in Dipolm-Chemiker. 2005, RWTH Aachen University. 24. Delebecq, E., et al., On the versatility of urethane/urea bonds: reversibility, blocked isocyanate, and non-isocyanate polyurethane. Chem Rev, 2013. 113(1): p. 80-118. 25. Kihara, N. and T. Endo, Synthesis and properties of poly (hydroxyurethane) s. Journal of Polymer Science Part A: Polymer Chemistry, 1993. 31(11): p. 2765-2773. 26. Figovsky, O.L. and L.D. Shapovalov. Features of reaction amino‐cyclocarbonate for production of new type nonisocyanate polyurethane coatings. in Macromolecular Symposia. 2002. Wiley Online Library. 27. Ochiai, B. and T. Endo, Carbon dioxide and carbon disulfide as resources for functional polymers. Progress in Polymer Science, 2005. 30(2): p. 183-215. 28. Aoyagi, N., Y. Furusho, and T. Endo, Convenient synthesis of cyclic carbonates from CO2 and epoxides by simple secondary and primary ammonium iodides as metal-free catalysts under mild conditions and its application to synthesis of polymer bearing cyclic carbonate moiety. Journal of Polymer Science Part A: Polymer Chemistry, 2013. 51(5): p. 1230-1242. 29. Diakoumakos, C.D. and D.L. Kotzev, Non-Isocyanate-Based Polyurethanes Derived upon the Reaction of Amines with Cyclocarbonate Resins. Macromolecular Symposia, 2004. 216(1): p. 37-46. 30. Brignou, P., et al., Polycarbonates Derived from Green Acids: Ring-Opening Polymerization of Seven-Membered Cyclic Carbonates. Macromolecules, 2010. 43(19): p. 8007-8017. 31. Thavonekham, B., A Practical Synthesis of Ureas from Phenyl Carbamates. Synthesis, 1997. 1997(10): p. 1189-1194. 32. Schwarzenbach, R.P., P.M. Gschwend, and D.M. Imboden, Environmental Organic Chemistry. 2005: John Wiley & Sons. 33. Water-based, Solvent-free or Low VOC, Two-component Polyurethane Coatings. 1996: United States. 34. Aqueous Coating Composition BAsed on Specific Two-component Polyurethanes and to a process for its production. 1991: United States. 35. Deepa, P. and M. Jayakannan, Solvent-free and nonisocyanate melt transurethane reaction for aliphatic polyurethanes and mechanistic aspects. Journal of Polymer Science Part A: Polymer Chemistry, 2008. 46(7): p. 2445-2458. 36. Lin, C.-H., Green Chemistry Synthesis of Intermediates for Polyurethane-urea, Ph. D. in Department of Chemical Engineering. 2008, National Chung Hsing University: Taiwan. 37. Neffgen, S., H. Keul, and H. Hocker, Cationic Ring-Opening Polymerization of Trimethylene Urethane:  A Mechanistic Study. Macromolecules, 1997. 30(5): p. 1289-1297. 38. Neffgen, S., H. Keul, and H. Hocker, Ring‐opening polymerization of cyclic urethanes and ring‐closing depolymerization of the respective polyurethanes. Macromolecular rapid communications, 1996. 17(6): p. 373-382. 39. Kušan, J., H. Keul, and H. Hocker, Cationic Ring-Opening Polymerization of Tetramethylene Urethane. Macromolecules, 2001. 34(3): p. 389-395. 40. Lebedev, B.V., et al., Thermodynamics of dimethylene urethane, of its ring-opening polymerization, and of poly(dimethylene urethane) between 0 and 335 K. Macromolecular Chemistry and Physics, 2000. 201(17): p. 2469-2474. 41. Lebedev, B., et al., Thermodynamics of Linear Poly(pentamethylene urethane) and Poly(hexamethylene urethane) in the Range from 0 to 450 K. Macromolecular Chemistry and Physics, 2004. 205(2): p. 230-240. 42. Qaroush, A.K., et al., Highly efficient isocyanate-free microwave-assisted synthesis of [6]-oligourea. Catalysis Science & Technology, 2013. 3(9): p. 2221. 43. Murray, R.J., Water-based adhesive. 1995, US Patent 5,395,879: United States. 44. Sacks, R., Water-based coating. 2006, US Patent 20,060,178,463: United States. 45. Argillier, J.-f.C.O., A. Audibert-hayet, and S. Zeilinger, Water-based foaming composition-method for making same. 2001, US Patent 6,172,010: United States. 46. Yang, X., P.C. Painter, and M.M. Coleman, Infrared and Thermal Analysis Studies of Transreations in Phenoxy-Polycarbonate Blends. Macromolecules, 1992. 25. 47. van der Schuur, M., B. Noordover, and R.J. Gaymans, Polyurethane elastomers with amide chain extenders of uniform length. Polymer, 2006. 47(4): p. 1091-1100. 48. Rashmi, B., et al., Development of bio-based thermoplastic polyurethanes formulations using corn-derived chain extender for reactive rotational molding. Express Polymer Letters, 2013. 7(10). 49. Pan, W.C., C.-H. Lin, and S.A. Dai, High-performance segmented polyurea by transesterification of diphenyl carbonates with aliphatic diamines. Journal of Polymer Science Part A: Polymer Chemistry, 2014. 52(19): p. 2781-2790. 50. Zastrow, A., et al., Aqueous Polyurethane-Polyurea dispersions. 2013: Taiwan. 51. Orliac, O., et al., Effects of various plasticizers on the mechanical properties, water resistance and aging of thermo-moulded films made from sunflower proteins. Industrial Crops and Products, 2003. 18(2): p. 91-100. 52. Chen, H.-Y., Non-phosgene Route to 4,4''-Methylenediphenyl Diisocyanate, Master in Department of Chemical Engineering. 2011, National Chung Hsing University: Taichung, Taiwan. 53. Lin, W.H., Non-Phosgene Route (NPR) to Aliphatic Diisocyanates through Diphenyl Biscarbamates, in 2014 Annual Meeting of the Polymer Society, Taipei. 2013: Taichung, Taiwan. 54. Pan, W.C., Synthesis of Polyurea and Polyurea Elastomers from DP-Biscarbamates and Diamines, Master in Department of Chemical Engineering. 2012, National Chung Hsing University: Taichung, Taiwan. 55. Mergelsberg, I., Globalization of green chemistry within the pharmaceutical industry-Advancements and opportunities, in 198th OMICS Group Conference. 2014: Philadelphia, USA. p. 31. 56. Kullman, E., Create, Grow, Sustain: How Companies Are Doing Well by Doing Good. 2013, Dupont.
摘要: 在致力於符合綠色程序之非異氰酸鹽法(NIR)製備聚尿素高分子彈性體(PUaE)的研究中,成功發展出具高度實用性的碳酸二苯酯(DPC)取代二元異氫酸鹽做為羰基化的試劑。將DPC與幾種代表性的二元胺在不同的進料順序及溶劑條件下進行酯交換聚合反應,順利合成具有相分離特性,機械性質優異且分子量高之聚尿素高分子產物。 NIR的研究發展中,開始時是藉由DPC與二元胺(MDA,HDA)合成並純化出高純度的二苯基二異氰酸酯而後以環丁砜(TMS)為溶劑並與長鏈及短鏈二元胺進行酯交換得到PUaE。在隨後的改進中,直接以一鍋化法在DPC與TMS溶液中依序加入三種不同二元胺,HDA、分子量2000的聚醚二元胺及異佛爾酮二元胺(IPDA)進而合成第二代的PUaE。最後,簡單地使用DPC其熔融狀態下進行開發的無VOC溶劑的酯交換反應。成功的關鍵在於添加二元胺的時機與順序,使得DPC可先形成二苯基二異氰酸酯中間體,再藉由從溶液中移除phenol而順利合成高分子量之聚尿素高分子。而後,利用ESA (3-[(2-aminoethyl) amino]-1-propane sulfonic acid sodium salt) 或APTES ((3-Aminopropyl) triethoxysilane) 取代部分鏈延長劑,順利將最終產物水性化,擴展產物利用的方便性。 本研究所提出優化的NIR聚尿素高分子膜具有0.6以上的固有黏度,15~30 MPa抗張強度及拉伸率超過400%以上的表現,其中以藉由熔融法所合成出的NS-P7表現優異的分子量及Td高於315 ℃的熱穩定性。另外,我們亦藉由AFM來觀察並確定產物中軟硬鏈段清楚的相分離。以上改進均是依照綠色化學及工業化量產的兩大目標逐步改進發展出全新NIR程序製備出性質優異之聚尿素高分子彈性體。
In an effort to develop green processes to produce elastomeric polyurethane-urea Elastomer (PUaE) through non-isocyanate routes (NIR), highly practical methods of utilizing diphenyl carbonate (DPC) instead of diisocyanate as the carbonylation agents have been developed. The trans-esterification of several representative aliphatic diamines with DPC under different combinations and solvents has resulted in new processes which produced segmented PUaEs with consistent high molecular weights and mechanical performances. In the evolution of our NIR process developments, it began with the preparation and isolation of pure bis-carbamates from diamines such methylene dianiline (MDA) or 1,6-hexamethylene diamine (HDA) with DPC which was followed by trans-esterifications with long-chained and short-chained diamines carried out in tetramethylene sulfone (TMS) solution leading to PUaEs. Then, in the subsequent improvement, a one-pot sequential addition of three different diamines, HDA, polypropylene ether diamine of 2,000 molecular weight, and isophorone diamine were added to DPC sequentially in TMS to form the second generation PUaEs. Finally, non-VOC solvent trans-esterification processes were developed simply using the pure DPC under its molten state. The key to the present successful development lies in the realization of timing and sequence of the diamine additions to form initial biscarbamate intermediates in-situ and then in shifting the equilibrium towards polyurea product formation by phenol removal from the solution so that high molecular weight polyurea could be formed favorably. Furthermore extension of the approach through replacing partial hard segment with water dispersants groups such as ESA (3-[(2-aminoethyl) amino]-1-propane sulfonic acid sodium salt) or APTES ((3-Aminopropyl) triethoxysilane) in making water-based PUaE also have been achieved. The optimized NIR polyurea films made in this study consistently have the ηinh of over 0.6, with high performance characteristics showing tensile strength ranges of 15~30 MPa and elongation exceeding 400 %. Ultra-high molecular weight of polyurea (NS-P7) and the highest heat properties with Td of > 315 ℃ was achieved in the melt-process. Well-defined soft- and hard-segment domains were observed for the products as determined by AFM. These new improved NIR processes to produce segmented poly-aliphatic ureas thereby comply fully with the principles of green chemistry using safe and readily available chemicals.
其他識別: U0005-2010201415585400
文章公開時間: 2017-10-27
Appears in Collections:化學工程學系所



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