Green Chemistry Approach to Synthesize Polyurea Elastomer

博士 === 國立中興大學 === 化學工程學系所 === 103 === 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 de...

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Main Authors: Wen Chen Pan, 潘玟蓁
Other Authors: Shenghong A. Dai
Format: Others
Language:en_US
Published: 2014
Online Access:http://ndltd.ncl.edu.tw/handle/00407604632870981823
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spelling ndltd-TW-103NCHU50630062017-06-25T04:37:53Z http://ndltd.ncl.edu.tw/handle/00407604632870981823 Green Chemistry Approach to Synthesize Polyurea Elastomer 以綠色化學程序製備聚尿素高分子彈性體 Wen Chen Pan 潘玟蓁 博士 國立中興大學 化學工程學系所 103 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. Shenghong A. Dai Ching Hsuan Lin 戴憲弘 林慶炫 2014 學位論文 ; thesis 72 en_US
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description 博士 === 國立中興大學 === 化學工程學系所 === 103 === 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.
author2 Shenghong A. Dai
author_facet Shenghong A. Dai
Wen Chen Pan
潘玟蓁
author Wen Chen Pan
潘玟蓁
spellingShingle Wen Chen Pan
潘玟蓁
Green Chemistry Approach to Synthesize Polyurea Elastomer
author_sort Wen Chen Pan
title Green Chemistry Approach to Synthesize Polyurea Elastomer
title_short Green Chemistry Approach to Synthesize Polyurea Elastomer
title_full Green Chemistry Approach to Synthesize Polyurea Elastomer
title_fullStr Green Chemistry Approach to Synthesize Polyurea Elastomer
title_full_unstemmed Green Chemistry Approach to Synthesize Polyurea Elastomer
title_sort green chemistry approach to synthesize polyurea elastomer
publishDate 2014
url http://ndltd.ncl.edu.tw/handle/00407604632870981823
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