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dc.contributorShenghong A. Daien_US
dc.contributor.authorWen Chen Panen_US
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dc.description.abstract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。zh_TW
dc.description.abstractIn 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.en_US
dc.description.tableofcontentsContents Abstract i 摘要 iii Contents v List of Figures vii List of Tables x CH1. Introduction 1 1.1 Description:PUaE and Green Chemistry 1 1.2 Non-isocyanate Route 4 1.3 Non-isocyanate Rout (NIR) via Melt-polymerization Process 10 CH2. Experimental Section 14 2.1 Materials 14 2.2 Instruments 15 2.3 Experiments 17 2.3.1 Different methods to synthesize segmented polyurea elastomer from DPC in TMS as a solvent (Method 1~4) 17 Method 1: one-step process 17 Method 2: two-step process with hard segment prepared first 19 Method 3: two-step process with soft segment prepared first 21 Method 4: three-step process 22 2.3.2 Synthesis of polyurea elastomer through non-isocyanate route under non-solvent condition 24 One-step process via melt-polymerization 24 Three-step process via melt-polymerization 26 2.3.3 Synthesis of water-based polyurea elastomer through non-isocyanate route 28 2.3.3 Synthesis of water-based polyurea elastomer through sol-gel reaction 30 CH3. Results and Discussions 34 3.1 Different methods to synthesize segmented polyurea from DPC in TMS as a solvent. (Method 1~4) 34 3.1.1 FT-IR monitoring of polymerization 34 3.1.2 Polyurea isolation and general characteristics 36 3.1.3 GPC analyses (Method 1~4) 38 3.1.4 Formulation and process optimization for segmented polyurea 41 3.1.5 Phase separation analysis by AFM 46 3.2 Synthesis of polyurea elastomer through non-isocyanate route under non-solvent condition 48 3.2.1 Formulation and properties of NS-PUaE and NS-SPUaE 48 3.2.2 GPC, DSC and AFM Analyses of PUaE 55 3.2.3 Optimization of WBPU formulations based on DPC as the carbonylation intermediate. 59 CH4. Conclusion 66 Reference 69 List of Figures Fig.1. Synthesis of polyurea from DTBTC and diamines 4 Fig.2. The influence of hydrogen bond on polyurea. 5 Fig.3. Flow temperature of blockcopoly(ether urea)s. 5 Fig.4. Synthesis of polyurea from DPC and MDA by Yamazaki. 6 Fig.5. Catalyzed synthesis of biscarbamate with different segment lengths 7 Fig.6. NIR to polyurethane from cyclocarbonates 8 Fig.7. Non-phosgene / Non-isocyanate route from our study 9 Fig.8. Melt trans-urethane process 11 Fig.9. Three melting-NIR to synthesize PU 11 Fig.10. [6]-oligourea is synthesized via non-solvent and non-isocyanate method 11 Fig.11. Method 1:One-pot Process 18 Fig.12. Method 2:Two steps process by adding hard segment first 20 Fig.13. Method 3:Two steps by adding soft segment first 21 Fig.14. Method 4:Three-steps process 23 Fig.15. Synthesis of NS-PUaE by one-step process 25 Fig.16. Synthesis of NS-SPUaE by three-step process 27 Fig.17. synthesis of water-based polyurea (WB-PUaE) 29 Fig.18. Synthesis of water-based polyurea through sol-gel process 31 Fig.19. Monitoring Method 3 by FT-IR 35 Fig.20. GPC of P1~P3 and P10 39 Fig.21. Graphic Models of Polyureas made from Method1~4. 43 Fig.22. Monitoring of Method 4 by FT-IR 43 Fig.23. 1H-NMR of crude product is made by Method 4 in the early stage of HDA addition. S: Residual TMS as a reaction solvent. 44 Fig. 24. 1H-NMR of SPUaE(P11) synthesized via Method 4 (400MHz, DMSO-d6). 44 Fig.25 AFM of P1 47 Fig.26 AFM of P2 47 Fig.27 AFM of P3 47 Fig.28 AFM of P10 47 Fig.29. Monitoring One-step process by FT-IR 49 Fig.30. Monitoring of three-step process by FT-IR 49 Fig.31. Dried NS-P5 can be identified by 1H-NMR (400MHz, DMSO-d) 51 Fig.32. Comparison of thermal stability between the samples from one-step and three-step process through TGA (N2, 10 ℃/min) 52 Fig.33. Comparison of mechanical properties between the samples from one-step and three-step process 53 Fig.34. Comparison of different methods through GPC 56 Fig.35. The influences of ED-2003, D-2000 and methods on samples in 1st heating scan of DSC. 57 Fig.36 AFM of NS-P6 58 Fig. 37 AFM of NS-P2 58 Fig. 38 AFM of WB-P1 58 Fig. 39 AFM of WB-P9 58 Fig.40. Monitoring of water-based process by FT-IR 62 Fig.41. Dried WB-P1 can be identified by 1H-NMR (400MHz, DMSO-d) 62 Fig.42. Mechanical properties; the influences of components and methods on tensile strength 63 Fig.43. Sol-gel mechanism 63 Fig.44. Dried WB-P11 can be identified by 1H-NMR (400 MHz, DMSO-d). There are some residual DPC. 64 List of Tables Table 1. Formulation of Method 1~3 18 Table 2. Formulation of Method 4 23 Table 3. Formulation of one-step process 25 Table 4. Formulation of three-step process 27 Table 5. Formulation of water-based process 29 Table 6. Formulation of sol-gel process 31 Table 7. Sample code list 32 Table 8. Comparison yields, thermal properties and mechanical properties via Method 1~3 among different proportions of hard segment. 37 Table 9. Analyses of GPC and inherent viscosity 40 Table 10. Comparison the type of hard and soft segments in Method 4 45 Table 11. The average of surface roughness of polyurea elastomer 47 Table 12. Comparison of thermal, mechanical properties, viscosity and solubility via one-step and three-step of non-solvent route among different components. 54 Table 13. Analyses of GPC 57 Table 14. The average surface roughness of polyurea elastomer 58 Table 15. Comparison of thermal, mechanical properties and solubility via water-based non-solvent route between different components. 65zh_TW
dc.subjectPolyurea Elastomeren_US
dc.subjectGreen Chemistryen_US
dc.subjectDiphenyl Carbonateen_US
dc.subjectNon-isocyanate Routeen_US
dc.titleGreen Chemistry Approach to Synthesize Polyurea Elastomeren_US
dc.typeThesis and Dissertationen_US
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