水性热敏聚氨酯树脂设计、制备及热敏性能的研究
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摘要
热敏聚氨酯树脂是智能材料的一种,是精细高分子领域研究的热点。本文采用丙酮法制备了聚酯型水性热敏聚氨酯树脂、聚醚型水性热敏聚氨酯树脂、混合型水性热敏聚氨酯树脂三个系列的水性热敏聚氨酯树脂。确定了水性热敏聚氨酯树脂的合成单体和最佳合成工艺,并对三个系列的水性热敏聚氨酯树脂的透气量、玻璃化转变温度、接触角、力学性能进行检测与表征。
通过以上的研究工作,发现羟基硅油可以作为聚氨酯分子软段结构的扩链剂,羟基硅油的含量的变化可以改变聚氨酯树脂的软段与硬段的比例,从而改变聚氨酯树脂的玻璃化转变温度,所以羟基硅油可以作为玻璃化转变温度调节剂,使水性聚氨酯树脂具有热敏性。1,4-丁二醇扩链剂对聚酯、聚醚、混合型聚氨酯树脂的玻璃化转变温度作用与羟基硅油相反,两种扩链剂的结合可以制备性能优异的水性热敏聚氨酯树脂。实验证明:聚酯型水性热敏聚氨酯树脂热敏性能优异,但较脆;聚醚型水性热敏聚氨酯树脂热敏性能并不突出,但树脂柔软;混合型水性热敏聚氨酯树脂综合性能优异,其最佳工艺参数为:1,4-丁二醇占多元醇的摩尔比为1;羟基硅油占多元醇的摩尔比0.08;活化温度为:60℃.
Thermal polyurethane resin which is hotspot in the fine polymer field is a kind of intelligent materials. The paper prepared polyester-type, polyether-type and mix-type water-based water-based thermal polyurethane resin. The monomer and the best synthesis process of water-based thermal polyurethane resin was identified. And the water vapor permeability, gass tansition temperature, contact angle, Tensile strength of three series of water-based thermal polyurethane resin were tested and characterized.
Through the research work, the ratio between hard segment and soft segment of polyurethane resin can been altered by the content of hydroxyl silicone oil which used as chain extender of soft segment molecular structure of polyurethane. The glass transition temperature of the polyurethane resin can been changing with the the ratio between its hard segment and soft segment, thereby hydroxyl silicone oil as the regulator of the glass transition temperature make water-based polyurethane resins with thermosensitive. The variation of glass transition temperature of the polyester, polyether and mixed polyurethane resin was contrary compare with join 1,4 - butanediol and silicon oil as chain extender. Combined with the two kinds of chain extenders can prepared excellent performanced thermal water-based polyurethane resin. Results show: Polyester-type thermal water-based polyurethane resin has excellent thermal performance, but more brittle; polyether-type thermal water-based polyurethane resin is not has an outstanding thermal properties, but soft; mixed-type thermal water-based polyurethane resin has excellent comprehensive performance, the most Optimal parameters: 1,4 - butanediol accounts for the molar ratio of polyol by 1; hydroxyl silicone oil accounts for the molar ratio of polyol by 0.08; activation temperature: 60℃.
通过以上的研究工作,发现羟基硅油可以作为聚氨酯分子软段结构的扩链剂,羟基硅油的含量的变化可以改变聚氨酯树脂的软段与硬段的比例,从而改变聚氨酯树脂的玻璃化转变温度,所以羟基硅油可以作为玻璃化转变温度调节剂,使水性聚氨酯树脂具有热敏性。1,4-丁二醇扩链剂对聚酯、聚醚、混合型聚氨酯树脂的玻璃化转变温度作用与羟基硅油相反,两种扩链剂的结合可以制备性能优异的水性热敏聚氨酯树脂。实验证明:聚酯型水性热敏聚氨酯树脂热敏性能优异,但较脆;聚醚型水性热敏聚氨酯树脂热敏性能并不突出,但树脂柔软;混合型水性热敏聚氨酯树脂综合性能优异,其最佳工艺参数为:1,4-丁二醇占多元醇的摩尔比为1;羟基硅油占多元醇的摩尔比0.08;活化温度为:60℃.
Thermal polyurethane resin which is hotspot in the fine polymer field is a kind of intelligent materials. The paper prepared polyester-type, polyether-type and mix-type water-based water-based thermal polyurethane resin. The monomer and the best synthesis process of water-based thermal polyurethane resin was identified. And the water vapor permeability, gass tansition temperature, contact angle, Tensile strength of three series of water-based thermal polyurethane resin were tested and characterized.
Through the research work, the ratio between hard segment and soft segment of polyurethane resin can been altered by the content of hydroxyl silicone oil which used as chain extender of soft segment molecular structure of polyurethane. The glass transition temperature of the polyurethane resin can been changing with the the ratio between its hard segment and soft segment, thereby hydroxyl silicone oil as the regulator of the glass transition temperature make water-based polyurethane resins with thermosensitive. The variation of glass transition temperature of the polyester, polyether and mixed polyurethane resin was contrary compare with join 1,4 - butanediol and silicon oil as chain extender. Combined with the two kinds of chain extenders can prepared excellent performanced thermal water-based polyurethane resin. Results show: Polyester-type thermal water-based polyurethane resin has excellent thermal performance, but more brittle; polyether-type thermal water-based polyurethane resin is not has an outstanding thermal properties, but soft; mixed-type thermal water-based polyurethane resin has excellent comprehensive performance, the most Optimal parameters: 1,4 - butanediol accounts for the molar ratio of polyol by 1; hydroxyl silicone oil accounts for the molar ratio of polyol by 0.08; activation temperature: 60℃.
引文
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[4]肖孟辉.单组分水性聚氨酯的合成及性能研究[D]. 2003, 11.
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[7]中国聚氨酯工业协会水性聚氨酯专业委员会.水性聚氨酯发展概况[J].涂料综述, 21-27
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[9]姚明.烷羟基硅油改性水性聚氨酯的合成和性能研究[D]. 2006, 6.
[10]李绍雄,刘益君.聚氨酯胶粘剂[M].化工工业出版社, 2006, 383.
[11]王文杰,卢秀萍.阴离子水性聚氨酯内乳化剂的研究进展[J].聚氨酯工业, 2005, 20(4): 6-10.
[12]李莉,刘好,李智华等.阳离子水性聚氨酯综述[J].中国胶黏剂, 2007, 16(11): 45-48.
[13]何君学.改性纳米二氧化硅—阴离子水性聚氨酯复合研究[D]. 2004, 1.
[14]王爱东.单组分常温自交联水性聚氨酯的合成和性能研究[D]. 2005, 5.
[15]张蒲.水性聚氨酯的交联改性研究进展[J].涂料技术与文摘. 5-7, 11.
[16]杜明,赵毅磊,徐鑫.水性聚氨酯的交联改性研究[J].化学与黏合, 2007, 29(1): 49-51, 74
[17]刘芳,吴小华,贾德民.水性聚氨酯的交联改性技术[J].合成橡胶工业, 2001, 24(1): 60-62.
[18]韩文松,郭连波,李良波.内交联型水性聚氨酯的合成及其性能研究[J].化学建材, 2006, 22(6): 7-9.
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[20] CHEN GUANAN, CHEN KANNAN. Self-curing Behaviors of Single Pack Aqueous based Polyurethane System [J]. Journal of Applied Polymer Science, 1997, 63(12): 1609.
[21] AUGUSTIN T C, LAWRENE E K, RONAID TW, et al. Internal Crosslinking Increase Stability [J]. Modern Paint and Coatings,1996, 86(5): 49.
[22] MarekW. Urban, ClaudiaL. Interfacial Studies Of Crosslinked Urethanes: Part IV. Substrate Effect on Film Formation in Polyester Waterborne Polyurethanes[J]. 1999, 71(896): 73
[23] M.W. Urban, C.L. Allison, et al. Interfacial Studies Of Crosslinked Urethanes: Part III. Substrate-Property Relationships in Polyester Waterborne Polyurethanes[J]. 1999, 71(888): 75
[24]许戈文.水性聚氨酯材料[M].化学工业出版社, 85-92.
[25]杨金花.高稳定性聚酯型阴离子水性聚氨酯乳液的合成及改性研究[D].
[26]朱春凤,陈钢进.羟基硅油改性水基聚氨酯的合成及性能[J].精细化工, 2004, 21(8): 608-611
[27]杨清峰,瞿金清,陈焕钦.有机硅改性水性聚氨酯的研究进展[J].涂料技术与文摘, 2004, 25(6): 1-5
[28]陈精华,刘伟区,宣宜宁等.氨基硅油改性聚氨酯弹性体材料的研究[J].化学建材, 2003, 6, 20-22, 25
[29] L.J. Matienzo. F.D. Egitto. Transformation of poly(dimethylsiloxane) into thin surface films of SiOx by UV/ozone treatment. Part II: segregation and modification of doped polymer blends[J].Mater Sci. 2006, 41: 6374-6384
[30]聂桂平,丁超.智能材料与产品设计[J].东华大学学报(自然科学版), 2008, 34(3): 362-265
[31]魏凤春,张恒,张晓.智能材料的开发与应用[J].河南科技学院学报, 2005, 25(3): 89-94
[32] Feng Long Ji, Jin Lian Hu, Ting Cheng Li, et al. Morphology and shape memory effect of segmented polyurethanes. PartI: With crystalline reversible phase[J]. Polymer, 2007, 48: 5133-5145
[33] S. Mondal, J.L. Hu. Free volume and water vapor permeability of dense segmented polyurethane membrane[J]. Membrane Science, 2006, 280: 427-432
[34] Z.F. Wanga, B.Wanga, N.Qia, et al. Free volume and water vapor permeability properties in polyurethane membranes studied by positrons[J]. Materials Chemistry and Physics, 2004, 88: 212-216
[35] S. Mondal, J.L. Hu. Water vapor permeability of cotton fabrics coated with shape memory polyurethane[J]. Carbohydrate Polymers, 2007, 67: 282–287
[36] Chia-Yen Lin, Ken-Hsuan Liao, Cheng-Feng Su, et al. Smart temperature-controlled water vapor permeable polyurethane film[J]. Journal of Membrane Science, 2007, 299: 91-96
[37] Hu Zhou, Yi Chen, Haojun Fan, et al. The polyurethane/SiO2 nano-hybrid membrane with temperature sensitivity for water vapor permeation[J]. Journal of Membrane Science, 2008, 318: 71-78
[38] Horii, F., Maruyarna, Hayashi, et al., Moisture-permeable water-proof fabric and its production, Japan patent, 1992, Unitika Ltd; Mitsubishi heavy industrial Ltd., Bairon KK; Maeda Kasei KK;.
[39] Hayashi, S., Ishikawa, N., and Giordano, C.; J. coated Fabrics. 1993, 23: 74-83
[40] Gibson, P., In The Fiber Society Annual Technical Conference. Natick, MA. USA,2002
[41] Ding. X.M., Hu. J. L.. Hu. C. P.. et al., In The Fiber Society Annual Technical Conference. Natick, MA. USA, 2002
[42] Ding. X.M., Hu. J. L.. Hu. C. P.. et al., In The Research Institute Symposium. In Memory of Dr. Bernie Miller. Princeton, NJ, USA, 2002
[43] Ding. X.M., Hu. J. L.. Hu. C. P.. et al., In Material Research Society 2002 Fall Meeting. Boston, Massachusetts. USA, 2002
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