单组分水性聚氨脂的合成及性能研究
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摘要
聚氨酯指的是一类非常广的高分子聚合物，它的组成和结构能在一个非常大的范围内变动，因此它没有十分确定的结构性能模式。然而所有的聚氨酯都由相同的原理制备而成，因此，从纯化学的角度来说聚氨酯材料具有非常相似的化学组成，但是它同时也具有多种物理机械性能，被广泛的用于多种场合。
水性聚氨酯以水为分散介质，不含或只含极少的有机溶剂，对环境几乎没有污染，受到人们的青睐。目前已在涂层整理、皮革涂饰、胶粘剂、建筑涂料和木器等众多领域得到广泛应用。
本课题采用预聚体法合成了聚酯型和聚醚型单组分水性聚氨酯，并且引入内乳化机理，在合成聚醚型水性聚氨酯的基础上加入内交联剂进行改性。
首先，通过一系列平行实验对水性聚氨酯合成工艺进行了全面地考察。研究了合成原料的预处理、制备方法、制备温度、催化剂用量对合成水性聚氨酯的影响，进而得到合成水性聚氨酯的最佳工艺。
在参阅有关文献资料的基础上，确定合适的影响因子，利用正交实验合成了两个系列的聚酯型水性聚氨酯，一是用1，4-丁二醇扩链的，另一个系列是用乙二胺扩链。探索了DMPA用量对聚氨酯水分散体系乳液性能，以及对涂膜的拉伸强度、断裂伸长率、吸水率的影响，还考察了成盐度对乳液性能的影响以及二异氰酸酯与低聚二醇的比值对漆膜物理机械性能的影响。
在改性阶段，用聚醚多元醇合成了系列聚醚型水性聚氨酯，并在此基础上用三官能度的三羟甲基丙烷(TMP)作为内交联剂合成了一系列的改性水性聚氨酯。不但考察了交联剂TMP用量对涂膜力学性能与耐介质性能的影响，而且还研究了对水性聚氨酯影响较大的NCO／OH值对改性水性聚氨酯涂膜力学性能的影响。
最后，在分析和比较的基础上，得出合成具有最佳性能的水性聚氨酯的配方及反应条件，为工业化生产提供了依据。
Polyurethane is a very extensive class of polymers. Composition and structure can be varied within wide limits, consequently there is no definite property pattern. All polyurethane, however, are made by the same general principle. In spite of the multitude of aspects and features products base on the macromolecular polyurethane and the most versatile property patterns which can be tailor-made for the widest variety of applications, these products are chemically all very similar.
Waterborne polyurethane dispersions are popular because they are non-toxic, non-flammable and do not pollute air or water, at the same time, which can meet very demanding performance requirements. At present waterborne polyurethane coatings have been widely used in fabric finish, leather finish, high quality building coatings, coatings of wood and furniture .etc..
In this paper aqueous dispersions of anionic polyurethane(APU) were prepared using polyester and polyol. Based on the polyol waterborne polyurethane we carried out the modification by cross chain reagent.
Firstly, the synthesis techniques was fully researched with a series of parallel experiments test. The factors were considered, such as the method of preparation, the pretreatment to the raw materials, the temperature, the dosage of the catalyst. The relationship between the factors above and the sample's properties was researched.
According to the present information about it, the effect factors were obtained. The two series of polyester waterborne polyurethane were prepared. The impact of the dosage of DMPA to the properties of the waterborne polyurethane latex, and the film of rate of elongation, tensile-strength , water resistance was researched. We also considered the extent of neutralization and the ratio of TDI and PBAG
During the process of modification, we prepared a series of modified APU using the TMP which contains three function groups. The content of the TMP is the key factor which effects the properties of the APU. The ratio of NCO/OH was also researched in the aspect of the film's mechanism properties.
Finally, based on the comparison and analysis, we obtained the optimal prescription and the reaction condition which provides the theories for industrialization.
水性聚氨酯以水为分散介质，不含或只含极少的有机溶剂，对环境几乎没有污染，受到人们的青睐。目前已在涂层整理、皮革涂饰、胶粘剂、建筑涂料和木器等众多领域得到广泛应用。
本课题采用预聚体法合成了聚酯型和聚醚型单组分水性聚氨酯，并且引入内乳化机理，在合成聚醚型水性聚氨酯的基础上加入内交联剂进行改性。
首先，通过一系列平行实验对水性聚氨酯合成工艺进行了全面地考察。研究了合成原料的预处理、制备方法、制备温度、催化剂用量对合成水性聚氨酯的影响，进而得到合成水性聚氨酯的最佳工艺。
在参阅有关文献资料的基础上，确定合适的影响因子，利用正交实验合成了两个系列的聚酯型水性聚氨酯，一是用1，4-丁二醇扩链的，另一个系列是用乙二胺扩链。探索了DMPA用量对聚氨酯水分散体系乳液性能，以及对涂膜的拉伸强度、断裂伸长率、吸水率的影响，还考察了成盐度对乳液性能的影响以及二异氰酸酯与低聚二醇的比值对漆膜物理机械性能的影响。
在改性阶段，用聚醚多元醇合成了系列聚醚型水性聚氨酯，并在此基础上用三官能度的三羟甲基丙烷(TMP)作为内交联剂合成了一系列的改性水性聚氨酯。不但考察了交联剂TMP用量对涂膜力学性能与耐介质性能的影响，而且还研究了对水性聚氨酯影响较大的NCO／OH值对改性水性聚氨酯涂膜力学性能的影响。
最后，在分析和比较的基础上，得出合成具有最佳性能的水性聚氨酯的配方及反应条件，为工业化生产提供了依据。
Polyurethane is a very extensive class of polymers. Composition and structure can be varied within wide limits, consequently there is no definite property pattern. All polyurethane, however, are made by the same general principle. In spite of the multitude of aspects and features products base on the macromolecular polyurethane and the most versatile property patterns which can be tailor-made for the widest variety of applications, these products are chemically all very similar.
Waterborne polyurethane dispersions are popular because they are non-toxic, non-flammable and do not pollute air or water, at the same time, which can meet very demanding performance requirements. At present waterborne polyurethane coatings have been widely used in fabric finish, leather finish, high quality building coatings, coatings of wood and furniture .etc..
In this paper aqueous dispersions of anionic polyurethane(APU) were prepared using polyester and polyol. Based on the polyol waterborne polyurethane we carried out the modification by cross chain reagent.
Firstly, the synthesis techniques was fully researched with a series of parallel experiments test. The factors were considered, such as the method of preparation, the pretreatment to the raw materials, the temperature, the dosage of the catalyst. The relationship between the factors above and the sample's properties was researched.
According to the present information about it, the effect factors were obtained. The two series of polyester waterborne polyurethane were prepared. The impact of the dosage of DMPA to the properties of the waterborne polyurethane latex, and the film of rate of elongation, tensile-strength , water resistance was researched. We also considered the extent of neutralization and the ratio of TDI and PBAG
During the process of modification, we prepared a series of modified APU using the TMP which contains three function groups. The content of the TMP is the key factor which effects the properties of the APU. The ratio of NCO/OH was also researched in the aspect of the film's mechanism properties.
Finally, based on the comparison and analysis, we obtained the optimal prescription and the reaction condition which provides the theories for industrialization.
引文
[1] 山西省化工研究所编．聚氨酯弹性体手册．北京：化学工业出版社，2001
[2] 李绍雄，朱吕民．聚氨酯树脂．南京：江苏科技出版社，1993
[3] 王呸芬．水性聚氨酯分散体涂料的进展．上海涂料，1995，13(13)：1—6
[4] 吴建芬，孙建中，顾培韵．水性聚氨酯研究进展．高分子通报，1994，3：156—159
[5] 沈艳涛，周铭．水性聚氨酯涂料的研究现状与发展趋势．涂料工业，2002，1：27—30
[6] 颜俊，涂伟萍，杨卓如．水性聚氨酯研究进展．化工进展，2000，7：22—74
[7] C. A. Hawkins, A. C. Sheppard, T. G Wood. Rohm and Hass Company Recent advances in aqueous two-component systems for heavy-duty metal protection. Progress in Organic Coatings 1997, 32: 253-261
[8] 韦雨春．水性双组分聚氨酯涂料的研究进展．涂料技术2000，18(1)：12—15
[9] 平郑骅，汪长春编著．高分子世界．复旦大学出版社，2000
[10] 全锋．水性聚氨酯研究进展综述．光谱实验室，2000，17(1)：56—59
[11] 周后伟，葛义谦．水性聚氨酯涂料总述．涂料工业，2000，8：33—35
[12] 朱金华，文庆真，张宝真．聚氨酯防腐涂料综述．海军工程学院学报，1996，3：82—84
[13] 宣兆龙，易建政，杜仕国．水性聚氨酯涂料的研究进展．化工新型材料，2000，27(3)：20-22
[14] 杨昌跃，曹红菊，杨丽．水性聚氨酯木器漆胶膜物性的研究．聚氨酯工业，200116(4)：22-24
[15] H. H. Lou. Particulate Aqueous Polyurethane Dispersion and Process for Producing the Same. United States Patent, Patent Number: 5959003.
[16] 叶守富．汽车罩面漆用的新型水性双组份聚氨酯清漆．上海涂料，1996，133(3)：5-11
[17] 许戈文，刘玉龙．聚氨酯乳液成盐率与粘度关系的研究．精细化工，1996,13(2)：35—37
[18] Y. L. Duan. Water-based Polyurethanes for Footwear. United States Patent,
Patent Number: 5872182
[19] 孙文章．水性聚氨酯的制备及应用．上海化工，2001，(11)：23—26
[20] 李坚，周晓彤．非离子型水分散性聚氨酯的制备及性能研究．中国胶粘剂，2002，12(1)：26—29
[21] 阎福安．平均官能度与聚合度的关系及其在高分子设计中的应用．中国涂料，2002，3：25—26
[22] 阎福安．水性聚氨酯合成配方的设计与计算．皮革化工，2000，19(1)：1-3
[23] S. H. Guo. Two Component Aqueous Polyurethane Coatings. United States Patent, Patent Number: 5973073
[24] 周善康，许一婷，庄志强．软段PEG含量对水性聚氨酯涂膜结晶性的影响．厦门大学学报(自然科学版)，2000，39(3)：348—351
[25] C. Fallon. Waterbome Polyurethane Dispersions. European Patent Application, Publication Number: 0373617
[26] D. Dleterich, Polyurethane Division, Research, Bayer AG, 5090 leverkusen(F. R. G) Aqueous emulsion, dispersions and solutions of polyurethanes; synthesis and properties Progress in Organic Coatings,1981,9:281-340
[27] 杨文堂，王家汉．水性聚氨酯树脂制备研讨．皮革化工，1999，16(1)：25-27
[28] 徐峰．水性聚氨酯树脂和涂料．化学建材，1994，(3)：127-130
[29] 应燕，魏欣．水性聚氨酯．安徽化工，1997，4：1-4
[30] 刘剑洪，逢艳，李伦军．聚氨酯合成反应动力学研究．深圳大学学报(理工版)，1994，11(3-4)：40-44
[31] 刘建薪，华载文，华东．水溶性封端型聚氨酯丝绸整理剂的研制．印染助剂，2002，19(3)：9-12
[32] 刘芳，吴小华，贾德民．水性聚氨酯的交联改性技术．合成橡胶工业，2001，24(1)：60-62
[33] 周炳才，孙大庆．聚氨酯乳液皮革涂试剂生产中的-NCO含量的控制方法．皮革化工，1994，3：15-17
[34] 王雪晨．阴离子型聚氨酯乳液的合成．合成橡胶工业，1994，17(5)：274-276
[35] 王旭，戚莉．不同聚醚对聚氨制成膜性能的影响研究．皮革科学与工程，2002，12(1)：23-25
[36] R. E. Tirpak, P. H. Markusch Mobay corp. Aqueous Dispersions of crosslinked polyurethanes. The waterborne &solids coatings Symposium, in New Orleans,LA, Feb, 14.1985
[37] V. J. Tramontano, M. E. Thomas and R. D. Coughlin. Synthesis and Coating Properties of Novel Waterborne Polyurethane Dispersions. Progress in Organic Coatings,1985,10:290-320
[38] 鹿秀山，郝广杰，郭天瑛．水性聚氨酯乳化过程中相转变的研究．高分子学报，2001，3：320-323
[39] 胡津晰，孙多先．软段含羧基的水性聚氨酯相反转过程研究．聚氨酯工业，2002，17(4)：20-23
[40] 曾俊，王武生，阮德礼．新型水性聚氨酯涂料．上海涂料，1999，4：3-5
[41] D. Y. Chao, W. J. Kuo. Study of synthesis and physical properties offire-resistant polyurethane monomer[J]. Journal of Applied Polymer Science, 1998, 67(1): 19-26.
[42] X. Wei, Q. He. Synthesis and properties of polyoxyethylate damine polyurethane monomer [J].Joumal of Applied Polymer Science, 1998, 67(13):2179-2185.
[43] G E. Snow. Waterborne Polyurethane Having Film Properties Comparable to Rubber. United States Patent. Patent Number: 6017997
[44] 陈家华，汤嘉陵，杨昌跃．聚氨酯水乳液皮革涂饰剂性能与结构的关系．精细化工，1995，12：16-21
[45] K. Noll, P. Josef. Water-dispersed Polyurethanes. United State Patent, Patent Number: 4190566
[47] W. Anderle. Plasticized Waterborne Polyurethane Dispersions and Manufacturing Process. PCT, International Application Number: PCT/US01/22578
[48] W. R. Grace. Waterborne Polyurethane Polymers. UK Patent Application, Patent Number: GB2048289
[2] 李绍雄，朱吕民．聚氨酯树脂．南京：江苏科技出版社，1993
[3] 王呸芬．水性聚氨酯分散体涂料的进展．上海涂料，1995，13(13)：1—6
[4] 吴建芬，孙建中，顾培韵．水性聚氨酯研究进展．高分子通报，1994，3：156—159
[5] 沈艳涛，周铭．水性聚氨酯涂料的研究现状与发展趋势．涂料工业，2002，1：27—30
[6] 颜俊，涂伟萍，杨卓如．水性聚氨酯研究进展．化工进展，2000，7：22—74
[7] C. A. Hawkins, A. C. Sheppard, T. G Wood. Rohm and Hass Company Recent advances in aqueous two-component systems for heavy-duty metal protection. Progress in Organic Coatings 1997, 32: 253-261
[8] 韦雨春．水性双组分聚氨酯涂料的研究进展．涂料技术2000，18(1)：12—15
[9] 平郑骅，汪长春编著．高分子世界．复旦大学出版社，2000
[10] 全锋．水性聚氨酯研究进展综述．光谱实验室，2000，17(1)：56—59
[11] 周后伟，葛义谦．水性聚氨酯涂料总述．涂料工业，2000，8：33—35
[12] 朱金华，文庆真，张宝真．聚氨酯防腐涂料综述．海军工程学院学报，1996，3：82—84
[13] 宣兆龙，易建政，杜仕国．水性聚氨酯涂料的研究进展．化工新型材料，2000，27(3)：20-22
[14] 杨昌跃，曹红菊，杨丽．水性聚氨酯木器漆胶膜物性的研究．聚氨酯工业，200116(4)：22-24
[15] H. H. Lou. Particulate Aqueous Polyurethane Dispersion and Process for Producing the Same. United States Patent, Patent Number: 5959003.
[16] 叶守富．汽车罩面漆用的新型水性双组份聚氨酯清漆．上海涂料，1996，133(3)：5-11
[17] 许戈文，刘玉龙．聚氨酯乳液成盐率与粘度关系的研究．精细化工，1996,13(2)：35—37
[18] Y. L. Duan. Water-based Polyurethanes for Footwear. United States Patent,
Patent Number: 5872182
[19] 孙文章．水性聚氨酯的制备及应用．上海化工，2001，(11)：23—26
[20] 李坚，周晓彤．非离子型水分散性聚氨酯的制备及性能研究．中国胶粘剂，2002，12(1)：26—29
[21] 阎福安．平均官能度与聚合度的关系及其在高分子设计中的应用．中国涂料，2002，3：25—26
[22] 阎福安．水性聚氨酯合成配方的设计与计算．皮革化工，2000，19(1)：1-3
[23] S. H. Guo. Two Component Aqueous Polyurethane Coatings. United States Patent, Patent Number: 5973073
[24] 周善康，许一婷，庄志强．软段PEG含量对水性聚氨酯涂膜结晶性的影响．厦门大学学报(自然科学版)，2000，39(3)：348—351
[25] C. Fallon. Waterbome Polyurethane Dispersions. European Patent Application, Publication Number: 0373617
[26] D. Dleterich, Polyurethane Division, Research, Bayer AG, 5090 leverkusen(F. R. G) Aqueous emulsion, dispersions and solutions of polyurethanes; synthesis and properties Progress in Organic Coatings,1981,9:281-340
[27] 杨文堂，王家汉．水性聚氨酯树脂制备研讨．皮革化工，1999，16(1)：25-27
[28] 徐峰．水性聚氨酯树脂和涂料．化学建材，1994，(3)：127-130
[29] 应燕，魏欣．水性聚氨酯．安徽化工，1997，4：1-4
[30] 刘剑洪，逢艳，李伦军．聚氨酯合成反应动力学研究．深圳大学学报(理工版)，1994，11(3-4)：40-44
[31] 刘建薪，华载文，华东．水溶性封端型聚氨酯丝绸整理剂的研制．印染助剂，2002，19(3)：9-12
[32] 刘芳，吴小华，贾德民．水性聚氨酯的交联改性技术．合成橡胶工业，2001，24(1)：60-62
[33] 周炳才，孙大庆．聚氨酯乳液皮革涂试剂生产中的-NCO含量的控制方法．皮革化工，1994，3：15-17
[34] 王雪晨．阴离子型聚氨酯乳液的合成．合成橡胶工业，1994，17(5)：274-276
[35] 王旭，戚莉．不同聚醚对聚氨制成膜性能的影响研究．皮革科学与工程，2002，12(1)：23-25
[36] R. E. Tirpak, P. H. Markusch Mobay corp. Aqueous Dispersions of crosslinked polyurethanes. The waterborne &solids coatings Symposium, in New Orleans,LA, Feb, 14.1985
[37] V. J. Tramontano, M. E. Thomas and R. D. Coughlin. Synthesis and Coating Properties of Novel Waterborne Polyurethane Dispersions. Progress in Organic Coatings,1985,10:290-320
[38] 鹿秀山，郝广杰，郭天瑛．水性聚氨酯乳化过程中相转变的研究．高分子学报，2001，3：320-323
[39] 胡津晰，孙多先．软段含羧基的水性聚氨酯相反转过程研究．聚氨酯工业，2002，17(4)：20-23
[40] 曾俊，王武生，阮德礼．新型水性聚氨酯涂料．上海涂料，1999，4：3-5
[41] D. Y. Chao, W. J. Kuo. Study of synthesis and physical properties offire-resistant polyurethane monomer[J]. Journal of Applied Polymer Science, 1998, 67(1): 19-26.
[42] X. Wei, Q. He. Synthesis and properties of polyoxyethylate damine polyurethane monomer [J].Joumal of Applied Polymer Science, 1998, 67(13):2179-2185.
[43] G E. Snow. Waterborne Polyurethane Having Film Properties Comparable to Rubber. United States Patent. Patent Number: 6017997
[44] 陈家华，汤嘉陵，杨昌跃．聚氨酯水乳液皮革涂饰剂性能与结构的关系．精细化工，1995，12：16-21
[45] K. Noll, P. Josef. Water-dispersed Polyurethanes. United State Patent, Patent Number: 4190566
[47] W. Anderle. Plasticized Waterborne Polyurethane Dispersions and Manufacturing Process. PCT, International Application Number: PCT/US01/22578
[48] W. R. Grace. Waterborne Polyurethane Polymers. UK Patent Application, Patent Number: GB2048289