IPDI型水性聚氨酯的合成与性能研究
摘要
水性聚氨酯是以水为分散介质的二元胶体体系，它不仅具有溶剂型聚氨酯的耐低温、柔韧性好、粘接强度大的优良性能，而且具有不燃、气味小、不污染环境、节约能源、操作加工方便等优点。近年来，随着人们对环境保护意识的不断加强，加之有机溶剂价格高，因而水性聚氨酯取代溶剂型聚氨酯成为一种重要的发展方向。但由于国内生产水性聚氨酯所需的原料大都需要进口，所以价格昂贵，从而限制了水性聚氨酯的研究和应用。随着生产水性聚氨酯原料的国产化及生产品种和规模的不断扩大，原料价格逐渐降低，使得水性聚氨酯的研究和应用逐步趋于完善。
目前，国内水性聚氨酯研究所用的异氰酸酯原料大多集中在芳香族型；对脂肪族异氰酸酯的水性聚氨酯研究较少。随着人们生活水平的不断提高，对环保、健康及高性能产品的需要日益迫切，绿色化学品逐渐成为未来发展的主流，因而由更加环保的脂肪族异氰酸酯生产的水性聚氨酯产品，将成为顺应这
IPDI型水性聚氨酷的合成，j性能研究
1潮流的主要发展方向之一。
本实验选用脂肪族异佛尔酮二异氰酸醋(工S叩horone
〔liisoeyanate，简称IPDI)、聚四氢吠喃二醇
(polytetramethylene glyeol，简称PTMG)、二轻甲基丙酸
(Dihydroxymethyl malonie aeid，简称DMPA)等为主要原料，
采用阴离子自乳化法，合成了聚醚型水性聚氨醋乳液。通过对
乳液性能及胶膜性能的研究，结果发现:IPDI型水性聚氨酷胶
膜的耐光性明显优于甲苯二异氰酸酷(Toluene diisocyanate，
简称TDI)型;在保证乳液稳定性的前提条件下，应尽可能降低
DMPA含量更有利;n(NC0)/n(OH)为1.5:1时，得到水性聚氨酷
乳液及胶膜性能较佳;提高软段聚醚的分子量，将使乳液稳定
性及胶膜的拉伸强度减小，而断裂伸长率增加:且其胶膜的耐
介质性及耐热性都有所增强;另外，制备方法、催化剂种类和
川量、反应温度、反应时间、扩链剂用量、软段种类及中和度
等因素均对水性聚氨酷乳液及胶膜性能有一定影响。
Waterborne polyurethane is dispersible in water medium, which has not only the excellent properties of solvent-borne polyurethane with good resistance, great adhesion, as well as outstanding toughness combined with good flexibility, but also advantages of incombustibility, low- odor and environmental friendliness. The environmental regulation and the increasing concern of people' s environmental protection are leading to the replacement of solvent-borne polyurethane, and nowdays it is widely used in industries such as coatings or adhesives . But domestic research on it was limited by sorts of conditions, which is basically in primitive stage.
Now, many concentrationses of raw materials that uses of research of local waterbrone polyurethane are in the type of toluene diisocyanate;To the waterbrone polyurethane of the type aliphaic cliisocyanate research less. Along with the living level of people of continuously increase, demand environmental protection, health
and high performance product increasingly and urgently, the green chemicals gradually become the future development's main.current. A series of aliphatic waterborne polyurethanes were prepared from isophorone diisocyanate (IPDI), polyether and dimethylolpropanic acid (DMPA). The COOH groups were neutralized by triethylamine (TEA). The effects of soft-segment structure and molecular weight, DMPA amount, neutralizer on mechanical properties of the emulsion cast films were investigated. The experimental data showed that the mechanical properties of waterborne PU films depend heavily on the structure and molecular weight of soft segments. As the molecular weight of soft segments Increases, emulsion stable of waterborne PU films decrease, while elongation and tensile strength increase. DMPA amount also influences the mechanical properties of waterborne PU films. As DMPA amount increases, emulsion stable and tensile strength of waterborne PU films increase, while elongation and solvent-resistance decrease; therefo
re on condition that PU emulsion is stable, the content of DMPA should is possibly lower . As TEA amount increases also leads higher elongation. To compare TDI PU emulsion cast film, IPDI PU emulsion cast film is superior on
light-resistance.
目前，国内水性聚氨酯研究所用的异氰酸酯原料大多集中在芳香族型；对脂肪族异氰酸酯的水性聚氨酯研究较少。随着人们生活水平的不断提高，对环保、健康及高性能产品的需要日益迫切，绿色化学品逐渐成为未来发展的主流，因而由更加环保的脂肪族异氰酸酯生产的水性聚氨酯产品，将成为顺应这
IPDI型水性聚氨酷的合成，j性能研究
1潮流的主要发展方向之一。
本实验选用脂肪族异佛尔酮二异氰酸醋(工S叩horone
〔liisoeyanate，简称IPDI)、聚四氢吠喃二醇
(polytetramethylene glyeol，简称PTMG)、二轻甲基丙酸
(Dihydroxymethyl malonie aeid，简称DMPA)等为主要原料，
采用阴离子自乳化法，合成了聚醚型水性聚氨醋乳液。通过对
乳液性能及胶膜性能的研究，结果发现:IPDI型水性聚氨酷胶
膜的耐光性明显优于甲苯二异氰酸酷(Toluene diisocyanate，
简称TDI)型;在保证乳液稳定性的前提条件下，应尽可能降低
DMPA含量更有利;n(NC0)/n(OH)为1.5:1时，得到水性聚氨酷
乳液及胶膜性能较佳;提高软段聚醚的分子量，将使乳液稳定
性及胶膜的拉伸强度减小，而断裂伸长率增加:且其胶膜的耐
介质性及耐热性都有所增强;另外，制备方法、催化剂种类和
川量、反应温度、反应时间、扩链剂用量、软段种类及中和度
等因素均对水性聚氨酷乳液及胶膜性能有一定影响。
Waterborne polyurethane is dispersible in water medium, which has not only the excellent properties of solvent-borne polyurethane with good resistance, great adhesion, as well as outstanding toughness combined with good flexibility, but also advantages of incombustibility, low- odor and environmental friendliness. The environmental regulation and the increasing concern of people' s environmental protection are leading to the replacement of solvent-borne polyurethane, and nowdays it is widely used in industries such as coatings or adhesives . But domestic research on it was limited by sorts of conditions, which is basically in primitive stage.
Now, many concentrationses of raw materials that uses of research of local waterbrone polyurethane are in the type of toluene diisocyanate;To the waterbrone polyurethane of the type aliphaic cliisocyanate research less. Along with the living level of people of continuously increase, demand environmental protection, health
and high performance product increasingly and urgently, the green chemicals gradually become the future development's main.current. A series of aliphatic waterborne polyurethanes were prepared from isophorone diisocyanate (IPDI), polyether and dimethylolpropanic acid (DMPA). The COOH groups were neutralized by triethylamine (TEA). The effects of soft-segment structure and molecular weight, DMPA amount, neutralizer on mechanical properties of the emulsion cast films were investigated. The experimental data showed that the mechanical properties of waterborne PU films depend heavily on the structure and molecular weight of soft segments. As the molecular weight of soft segments Increases, emulsion stable of waterborne PU films decrease, while elongation and tensile strength increase. DMPA amount also influences the mechanical properties of waterborne PU films. As DMPA amount increases, emulsion stable and tensile strength of waterborne PU films increase, while elongation and solvent-resistance decrease; therefo
re on condition that PU emulsion is stable, the content of DMPA should is possibly lower . As TEA amount increases also leads higher elongation. To compare TDI PU emulsion cast film, IPDI PU emulsion cast film is superior on
light-resistance.
引文
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[2] Skeist Edit. Handbook of Adhesives, 1998,6:979
[3] 大村英正，高分子，1981，30(12)：888
[4] D.Dieterich, W. Keberle and R. Wust, J. Oil Colour Chem. Assoc, 1970, 53:363
[5] 王武生，阮德礼．水乳型聚氨酯皮革涂饰剂进展．精细化工，1991，8(6)：40
[6] ERDEM BEDRI (US); SCHROCK ALAN K (US); BHATTACHARJEE DEBKUMAR (US).Process for preparing aqueous dispersions of hybrid polyurethane particles. US Pat. US 2002177654. 2002-11-28
[7] 凌秀琴．水性聚氨酯的开发应用前景．广西化纤通讯．1999(2)：22
[8] R.E. Tirpak, P.H. Markusch, Synthesis and characterization of UV-curable waterborne polyurethane-acrylate ionomers for coatings J.Coat. Tech.,1986,58(7):49
[9] Ismail E A. Water-Soluble Polyurethane Resins as Emulsifiers in Emulsion Polymerization of Styrene: Nucleation and Particle Growth. J. Appl Polym Sci, 1998, 68:1531
[10] Kuo Y. M., Ku K. Y., J. Appl Polym Sci, 1998, 69:2097
[11] 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，2001：550
[12] K. Nachtkamp, J. Pedain. Process for the preparation of aqueous
polyurethane dispersions and solutions. US4269748.1981-5-26
[13]Chien-Hsin Yang, Shin-Min Lin and Ten-Chin Wen. Application of Statistical Experimental Stategies to the Process Optimization of Waterbrone Polyurethane. Polymer Engineering anf Science, 1995, 35 (8) : 722-730.
[14]D.Dieterich, Prog. org. Preparation and Properties of UV-Curable Polyurethane Acrylate ionomers. Coating, 1981,9:281
[15]J.S. Lee, B. K. Kim.Prog Org.Modification of Aqueous Polyurethane Dispersions via tetraphenylethane iniferters. Coat. 1995, 25 (4):311
[16]B.K. Kim, Y.M.Lee, T.M.S. Pure Appl. Chem. 1992,29(12) 1207
[17]Y. Chen and Y.L. Chen. J. Appl. Polym. Sci, 1992,46:435
[18]H.C.Lee, T.K.Kim, J. Poly. Sci. Poly. Chem. 1994,32:1983
[19]I.R. Rutger. Rheol. Acta, 1962,2:202
[20]Y. M. L, J. C. Lee, B. K. Kim. Polymer, 1994, 35(5):1095
[21]王念贵，邓丽娟．亲水基团含量和固含量对聚氨酯乳液的影响．聚氨酯工业，1998，13(3)：19
[22]B.K. Kim, T.K. Kim. J. Appl. Polym. Sci.,1991,43:393.
[23]李建宗，李士杰．国外水性聚氨酯研究进展．中国胶粘剂，1997，6(5)：44-50
[24]Yang W.P, Recent developments in polyurethane. Polym. Sci,1992,66:216
[25]前民主德国专利53675379
[26]D.Dieterich, W. Keberle and H. Witt, Polyurethane Ionomer. Angew, Chem Int. Ed, 1970, 9:4
[27]Dieterich D. Synthesis and Properties of Anionic Aqueous Polyurethane. Angew Makromol. Chem,1981,98:133
[28]D. Dieterich, and H. reiff, Urethane Sci Technol, 1976,4:12
[29]D.Dieterich, And org coat Sci Teeh Ser, 1979,1:55
[30]Wallon Alexandef (DE); Maempel Lothar (DE); Auchter Gerhard (DE); Seibert Horst(DE). Aqueous polyurethane dispersions. DE Pat,EP542073.1994-05-03
[31]S.P. Suskind, J. Appl. Polym. Sci, 1965,9:2451
[32]C.L. Milligan (US),S. Chaheston (US) and L. Kenneth (US).Water-dilutable polyurethanes .US Pat. US3412054. 1968-11-19
[33]O. Lorenz, F. Haulena and O. Kleben, Angew. Makromol.Chem,1973,33:115
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