三聚体改性及高固含量水性聚氨酯
|
摘要
随着世界各国对环保以及国民身体健康的重视,溶剂型涂料使用受到限制,水性涂料因其具有环保、物美价廉、技术日益成熟等优势,已经成为全球涂料发展的一个主导方向,越来越受到人们的重视。水性聚氨酯涂料以其环保、高性能、分子结构和大小可灵活调整等优点,日益成为研究和应用的热点和重点。然而,传统水性聚氨酯涂料存在易黄变、固含量低、耐水性差等缺点,因此需要对其进行有效的改性。
本文以己二异氰酸酯(HDI)三聚体、甲苯二异氰酸酯(TDI)、聚醚二元醇(N220)、1,4-丁二醇(BDO)、二羟甲基丙酸(DMPA)、环氧树脂(E-20),甲基丙烯酸甲酯(MMA)等为原料,采用丙酮法合成了性能稳定、耐黄变的丙烯酸酯改性水性聚氨酯分散体(PUA)。研究了NCO/OH(初)摩尔比、NCO/OH(总)摩尔比、HDI三聚体/TDI摩尔比、DMPA含量、E-20含量、MMA含量等因素对水性PUA分散体性能的影响。确定的最优配比如下:NCO/OH(初)摩尔比为11～13,NCO/NCO(总)摩尔比为1.2～1.4,HDI三聚体/TDI摩尔比为10.5%左右,DMPA/PU百分比为6%～7%,E-20/PU的百分比为3%～5%,MMA/PU的百分比为20%。
此外,本文还以聚酯二元醇(PBA)和N220、HDI、异佛尔酮二异氰酸酯(IPDI)、BDO、DMPA、E-20等为原料合成了高固含量低粘度的WPU分散体,该分散体的固含量在45%以上。研究表明,采用分子量为2000的聚酯作为软段,当NCO/OH(总)摩尔比为1.35～1.50、聚醚/聚酯比例为1:4、HDI/IPDI摩尔比为1:3、采用冰水分散易制得高固含量低粘度的WPU分散体,该分散体具有假塑性流体的特征。
通过傅立叶红外光谱(FT-IR)、马尔文粒度仪、差热扫描量热仪(DSC)、原子力显微镜(AFM)、透射电镜(TEM)、扫描电镜(SEM)、热重分析(TG)和最低成膜温度测试等对HDI三聚体复合改性的WPUA和高固含量低粘度的WPU分散体进行了表征,结果表明HDI三聚体复合改性的WPUA分散体具有明显的核壳结构,以丙烯酸酯为核,聚氨酯为壳;而高固含量的WPU分散体具有良好的耐热性和耐低温性能。
With the increasing attention on environmental protection and health, solvent-borne coatings will be restricted because of its emission of Volatile Organic Compound (VOC) and its pollution to environment. Waterborne coatings are becoming the development trends of coatings technology. Because of its environment-protection, excellent properties, flexible design of molecular structure and molecular weight, the self-emulsified waterborne polyurethane coatings have become one of the hot spots and key points in the present coatings industry. However, because of some shortcomings, such as the yellowing, low solid content, low hardness and bad water-resistance, the self-emulsified waterborne polyurethane coatings need to be modified effectively.
A series of waterborne polyurethane (WPU) dispersions and waterborne polyurethane-acrylate (WPUA) hybrid dispersions were prepared and characterized. Their main materials were 1, 6-hexamethylene diisocyanate (HDI) trimer, toluene diisocyanate (TDI), polyether binary alcohol (N220), 1, 4-butanediol (BDO), dimethylol propionic acid (DMPA), epoxy resin (E-20), methyl methacrylate (MMA). The effect factors on dispersion properties and film properties, such as the initial and total mole rate of NCO/OH, HDI trimer/TDI mole ratio, dimethylol propionic acid (DMPA) contents, epoxy resin (E-20) contents, and methyl methacrylate (MMA)/polyurethane (PU) mass ratio, had been investigated. The optimal technological parameters of preparation of the polyurethane-acrylate (PUA) dispersion were as the following condition. The initial mole ratio of NCO/OH was 11~13.The total mole ratio of NCO/OH was 1.2~1.4.And the HDI trimer/TDI mole ratio was 10.5%. The contents of DMPA, E-20, MMA were about 6.0~7.0%, 3.0~5.0%, 30%, respectively.
In addition, a series of waterborne polyurethane (WPU) dispersions with high solid content and low viscosity were prepared and characterized. Their main materials were polyester diols (PBA), polyether binary alcohol (N220), 1, 6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1, 4-butanediol (BDO), dimethylol propionic acid (DMPA) and epoxy resin (E-20). The solid content of the dispersions were about 45%. When the molecular weight of polyester diols was 2000, the NCO/OH (total) molar ratio was 1.35 ~ 1.50, polyether/polyester mass ratio was 1:4, HDI/IPDI molar ratio was 1:3, the WPU dispersions with high solid content and low viscosity were easily prepared.
The WPU and WPUA dispersions were characterized by Fourier Transform Infrared (FTIR), Malvern Laser Particle Analyser, Different Scanning Calorimeter (DSC), Atomic Force Microscopy (AFM), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), and TG analyser and Minimum Filming Temperature (MFT). The TEM images show the particles of WPUA have obvious spherical core–shell structure. The TG and MFT analysis show excellent heat resistance and low temperature performance of the WPU dispersions with a high solid content.
本文以己二异氰酸酯(HDI)三聚体、甲苯二异氰酸酯(TDI)、聚醚二元醇(N220)、1,4-丁二醇(BDO)、二羟甲基丙酸(DMPA)、环氧树脂(E-20),甲基丙烯酸甲酯(MMA)等为原料,采用丙酮法合成了性能稳定、耐黄变的丙烯酸酯改性水性聚氨酯分散体(PUA)。研究了NCO/OH(初)摩尔比、NCO/OH(总)摩尔比、HDI三聚体/TDI摩尔比、DMPA含量、E-20含量、MMA含量等因素对水性PUA分散体性能的影响。确定的最优配比如下:NCO/OH(初)摩尔比为11～13,NCO/NCO(总)摩尔比为1.2～1.4,HDI三聚体/TDI摩尔比为10.5%左右,DMPA/PU百分比为6%～7%,E-20/PU的百分比为3%～5%,MMA/PU的百分比为20%。
此外,本文还以聚酯二元醇(PBA)和N220、HDI、异佛尔酮二异氰酸酯(IPDI)、BDO、DMPA、E-20等为原料合成了高固含量低粘度的WPU分散体,该分散体的固含量在45%以上。研究表明,采用分子量为2000的聚酯作为软段,当NCO/OH(总)摩尔比为1.35～1.50、聚醚/聚酯比例为1:4、HDI/IPDI摩尔比为1:3、采用冰水分散易制得高固含量低粘度的WPU分散体,该分散体具有假塑性流体的特征。
通过傅立叶红外光谱(FT-IR)、马尔文粒度仪、差热扫描量热仪(DSC)、原子力显微镜(AFM)、透射电镜(TEM)、扫描电镜(SEM)、热重分析(TG)和最低成膜温度测试等对HDI三聚体复合改性的WPUA和高固含量低粘度的WPU分散体进行了表征,结果表明HDI三聚体复合改性的WPUA分散体具有明显的核壳结构,以丙烯酸酯为核,聚氨酯为壳;而高固含量的WPU分散体具有良好的耐热性和耐低温性能。
With the increasing attention on environmental protection and health, solvent-borne coatings will be restricted because of its emission of Volatile Organic Compound (VOC) and its pollution to environment. Waterborne coatings are becoming the development trends of coatings technology. Because of its environment-protection, excellent properties, flexible design of molecular structure and molecular weight, the self-emulsified waterborne polyurethane coatings have become one of the hot spots and key points in the present coatings industry. However, because of some shortcomings, such as the yellowing, low solid content, low hardness and bad water-resistance, the self-emulsified waterborne polyurethane coatings need to be modified effectively.
A series of waterborne polyurethane (WPU) dispersions and waterborne polyurethane-acrylate (WPUA) hybrid dispersions were prepared and characterized. Their main materials were 1, 6-hexamethylene diisocyanate (HDI) trimer, toluene diisocyanate (TDI), polyether binary alcohol (N220), 1, 4-butanediol (BDO), dimethylol propionic acid (DMPA), epoxy resin (E-20), methyl methacrylate (MMA). The effect factors on dispersion properties and film properties, such as the initial and total mole rate of NCO/OH, HDI trimer/TDI mole ratio, dimethylol propionic acid (DMPA) contents, epoxy resin (E-20) contents, and methyl methacrylate (MMA)/polyurethane (PU) mass ratio, had been investigated. The optimal technological parameters of preparation of the polyurethane-acrylate (PUA) dispersion were as the following condition. The initial mole ratio of NCO/OH was 11~13.The total mole ratio of NCO/OH was 1.2~1.4.And the HDI trimer/TDI mole ratio was 10.5%. The contents of DMPA, E-20, MMA were about 6.0~7.0%, 3.0~5.0%, 30%, respectively.
In addition, a series of waterborne polyurethane (WPU) dispersions with high solid content and low viscosity were prepared and characterized. Their main materials were polyester diols (PBA), polyether binary alcohol (N220), 1, 6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1, 4-butanediol (BDO), dimethylol propionic acid (DMPA) and epoxy resin (E-20). The solid content of the dispersions were about 45%. When the molecular weight of polyester diols was 2000, the NCO/OH (total) molar ratio was 1.35 ~ 1.50, polyether/polyester mass ratio was 1:4, HDI/IPDI molar ratio was 1:3, the WPU dispersions with high solid content and low viscosity were easily prepared.
The WPU and WPUA dispersions were characterized by Fourier Transform Infrared (FTIR), Malvern Laser Particle Analyser, Different Scanning Calorimeter (DSC), Atomic Force Microscopy (AFM), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), and TG analyser and Minimum Filming Temperature (MFT). The TEM images show the particles of WPUA have obvious spherical core–shell structure. The TG and MFT analysis show excellent heat resistance and low temperature performance of the WPU dispersions with a high solid content.
引文
[1]曾少敏,刘丹,姚畅,等.高度支化水性聚氨酯的合成及性能[J].高分子材料科学与工程, 2009, 25(11):5-8
[2] Pathak S.S., Sharma A., Khanna A.S.. Value addition to waterborne polyurethane resin by silicone modification for developing high performance coating on aluminum alloy[J]. Progress in Organic Coatings, 2009, 65(2):206-216
[3] Lee S.K., Kim B.K.. High solid and high stability waterborne polyurethanes via ionic groups in soft segments and chain termini[J]. Journal of Colloid and Interface Science, 2009, 336(1):208-214
[4] Zhang C.Y., Zhang X.Y., Dai J.B., et al. Synthesis and properties of PDMS modified waterborne polyurethane–acrylic hybrid emulsion by solvent-free method[J]. Progress in Organic Coatings, 2008, 63(2):238-244
[5]许戈文.水性聚氨酯材料[M].北京:化学工业出版社, 2007:6-8
[6]田伟,王芳,汤克勇,等.脂肪族水性聚氨酯涂饰剂的研制[J].皮革科学与工程, 2006, 16(3):9-11
[7]李书卿,申屠勇敢,韩茂清,等.水性聚氨酯涂饰剂的性能分析[J].皮革科学与工程, 2007, 17(1):48-53
[8]刘方方,黄文杰,顾丽敏. PVC手套用水性聚氨酯涂饰剂[J] .聚氨酯工业, 2007,22(2):5-7
[9]陈红.水性聚氨酯涂料技术进展[J].涂料工业, 2006, 36(3):47-51
[10]陈珀丽,刘经梅,张之涵,等.聚氨酯涂料技术在中国的发展[J].涂料工业, 2007, 37(5):49-51
[11]于良民,王秀娟.水性聚氨酯的改性及水性聚氨酯涂料[J].热固性树脂, 2007, 22(4):44-46
[12] Ishiyama, Massaki, Matuura, et al. Aqueous dispersion of an aqueous hydrazine-terminated polyurethane[P]. US: 5700867, 1997
[13]陆冬贞.我国聚氨酯胶粘剂发展概况与展望[J].聚氨酯, 2007, (5):68-78
[14]叶青萱.水性聚氨酯胶粘剂技术进展[J].聚氨酯, 2006, (7):74-77
[15] Guo W.J., Fu H.Q., Huang H., et al. Waterborne polyurethane adhesive modified by rosin for laminated package films[J]. Packaging Engineering, 2007, 48(1):33-34
[16]修玉英,冯青,罗钟瑜.水性聚氨酯在织物整理中的应用[J].纺织导报, 2006,(2):82-85
[17]朱明杰.新型含短氟碳链水性聚氨酯的合成及在棉织物上的应用[D].上海:东华大学硕士学位论文, 2007
[18] Dvorchak, Michael J. Using high performance twocomponent waterborne polyurethane woodcoatings[J]. Journal of Coatings Technology, l997, 69(866):47-52
[19] Kim B.K., Kim T.K., et al. Aqueous dispersion of polyurethane anionomers from MDI/IPDI, PCL, BD and DMPA[J]. Journal of Applied Polymer Science, 1994, 53:371-374
[20] Chen Y., Chen T.L.. Aqueous dispersion of polyurethane antinomies: Effects of counteraction[J]. Journal of Applied Polymer Science, 1992, 46:435-439
[21] Lienert H.J., Schuster H., Schafer K.. Stabilized Aqueous Solution of a Bisulphite Blocked Polyisocyanate[P]. US:3984365, 1976
[22]胡国文,沈慧芳,杨清峰,等.聚氨酯-丙烯酸酯复合乳液的合成与表征[J].华南理工大学学报(自然科学版), 2007, 5(06):64-70
[23] Melchiors M., Leichlingen. Method of Producing Oxidative drying Urethane-Modified Polyester Dispersions and Their Use[P].US: 6620893, 2003
[24] Liu W., Rende T.. Waterborne oil-modified urethane resins[J]. Paint & Coatings Industry, 1999, (17):33-36
[25] Markus A, Schafheutle. Oxidativelydrying polyurethane Dispersions[P]. US:6359060, 2002
[26] Douglas A. Blocked IsocyanidesⅢPart B Use and Applications of Blocked isocyanates[J]. Progress in Organic Coatings, 2001, (41):3-7
[27] Wicks D.A., Wicks Z.W.. Review blocked isocyanides. Progress in Organic Coating, 2001, (41):81-83
[28]刘春华,方治奇.环氧树脂改性水性聚氨酯-丙烯酸酯的初步研究[J].聚氨酯工业, 2000, 15(3):23.
[29] Zheng W., Wong S.C., Sue H.J.. Transport behavior of PMMA/expandedgraphite nanocomposites[J]. Polymer, 2002, 43(25):6767-6773
[30]瞿金清,陈焕钦.环氧改性水性聚氨酯涂料的合成与性能研究[J].高校化学工程学报, 2002, 16(5):570-574
[31]瞿金清,陈焕钦.聚氨酯-聚丙烯酸酯复合乳液的研究[J].中国皮革, 2004, 33(5): 7-8
[32]罗建光,赖国隆.环氧树脂改性水性聚氨酯的研究[J].涂料工业, 2002, 32(12): 1-3
[33] Pulat M., Senvar C.. Structural and surface properties of polyurethane membranes of different porosities[J]. Polymer Testing, 1995, 14(2):115-120
[34]丁浩.塑料工业实用手册[M].北京:化学工业出版社, 1995:381-382
[35]吴培熙,张留成.聚合物共混改性[M].北京:中国轻工业出版社, 1995:310-311
[36] Parmar R., Patel K., Parmar J.. High-performance waterborne coatings based on epoxy-acrylic-graft-copolymer-mdified polyurethane dispersions[J]. Polym Int, 2005, (54): 488-494
[37]姜守霞,孙威,周照毅.环氧改性水性聚氨酯涂料的合成研究[J].应用化工, 2003, 32(5):7-21
[38]吴晓青,卫晓利,邱圣军.环氧树脂改性水性聚氨酯的合成工艺和性能研究[J].应用基础与工程科学学报, 2006, (6):153-159.
[39]黄洪,傅和青,邓艳文,等.环氧树脂与丙烯酸酯复合改性水性聚氨酯的合成研究[J].高校化学工程学报, 2006, (4):583-587.
[40] Karta A..Water-dispersable Air-drying Coatings[P]. US:5104737, 1991
[41] Okamoto Y., Hasegawa Y., Yoshino F.. Urethane/acrylic composite polymer emulsions[J]. Progress in Organic Coatings, 1996, 29(1): 175-182
[42] Okamoto Y., Hasegawa Y., Yoshino F.. Urethane/acrylic composite polymer emulsions[J]. Progress in organic coatings, 1996, (29):175-182
[43] Mequanint K., Sanderson R.. Nano-structure phosphorus-containing polyurethane dispersions:synthesis and crosslinking with melamine formaldehyde resin[J]. Polymer, 2002, 43(19):5341-5346
[44] Kim H., Shin J.S., Cheong I.W., et al. Seeded emulsion polymerization of methyl methacrylate using aqueous polyurethane dispersion: effect of hard segment on grafting efficiency[J]. Colloids and surfaces A: physicochemical and engineering aspects, 2002, 207(3):169-176
[45]张旭东,瞿金清,陈焕钦.制备聚氨酯-丙烯酸酯复合乳液的物料与工艺[J].现代化工, 2003, 23(2):15-18
[46] Santacesaria E., Serio M.D., Russo A., et al. Kinetic and catalytic aspects in the hydrogen peroxide production via anthraquinone[J]. Chemical engineering science, 1999, (54):2799-2806
[47] Alder H., Jahny K.,Bimbrich V.B.. Polyurethane macromers-new building blocks foracrylic hybrid emulsion with outstanding performance[J]. journal of Applied Polymer Science, 2000, 78(1):67-80
[48] Hirosea M, Kadowaha et al. Introduction of covalently bonded phosphorus into aqueous based polyurethane system via post curing reaction[J]. Progress in organic Coatings, l997, 31(1): 157-169
[49] Gooch J.W., Dong H., et al. Polyurethane ac-rylate or vinyl type polymeric material for coating optical fibers based on a fluorinated diol[J]. Journal of applied polymer Science, 2000, 76(1):105-114
[50] Boudreaux C.J., et al. Air curable water-borne urethane-acrylic hybrids[J]. European Coatings journal, 1999, (6):30-35
[51]王武生,曾俊,阮德礼,等.纳米级水基聚氨酯微凝胶环氧硅氧烷交联成膜机理[J].高分子材料科学与工程, 2001, 17(3):102-105.
[52]黄洪,傅和青,邓艳文,等.环氧树脂与丙烯酸酯复合改性水性聚氨酯的合成研究[J].高校化学工程学报, 2006, 20(4):583-587
[53]黄洪,谢筱薇,傅和青.多重改性水性聚氨酯乳液的合成及性能[J].华南理工大学学报(自然科学版), 2006, 34(8):46-50
[54]侯孟华,刘伟区,黎艳.有机硅蒙脱土复合改性水性聚氨酯的研究[J].功能高分子学报, 2005, 18(1):89-93
[55]王春会.环氧树脂及无机纳米改性水性聚氨酯的研究[D].天津:天津科技大学, 2006
[56]邱少君,甘孝贤,王吉贵,等. HDI三聚体合成研究[J].聚氨酯工业, 1998, 13(2):17-20
[57] Robin J., Blind A.. Purification of Isocyanurate Group-containing Polyisocyanates[P]. FR:2607499, 1988
[58] Robin J., Blind A.. Purification and Isolation of Polyol -polyurethanes by Extraction with Supercritical Carbon Dioxide[P]. FR:2629086, 1989-09-29
[59]李绍雄,刘益军.聚氨脂胶粘剂[M].北京:化学工业出版社, 1998:120
[60] Shindo M. Properties of HDI Trimer for Coating Systerns[J]. Polym Mater Sci Eng, 1983, (49):169-173
[61] Houze E.C., Vasta A.. Acrylic Polyurethane Coating Composition[P]. US: 4503175, 1985
[62]阮家声,刘红莲. TDI三聚体的合成研究[J].黎明化工, 1997, (4):24
[63] Kaoru U., Oyabunorio., Yabunorio A.. Iso-cyanurate Polyisocyanates as Curing Agentsfor Two- Component Polyurethane Compositions[P]. DE: 3810908, 1988
[64] Houze E.C., VASTA J.A.. Acrylic Polyurethane Coating Composition[P]. US: 4503175, 1985
[65] Shindom. Properties of HDI Trimer for Coating Systems[J]. Polym Mater Sci Eng, 1983, (49):169-173
[66] Sheffer M.W., Martin K., Parkerson H., et al. Aqueous Polyurethane Coatings with Improved Resistance to Sontan Lotion[p]. JP:97998303, 1997
[67] Byoung U.A., Su K.L., Sang K.L., et al. UV curable polyurethane dispersions from polyisocyanate and organosilane[J]. Progress in Organic Coatings, 2008, (4):258-264.
[68] HaiN I., Jeremy L.D, Pauline R.T, et a.l Cycloaliphatic polyester-based high-solid polyurethane coatings[J]. Progress in Organic Coating, 2002, (45):49-58
[69] Temtchenko T., Turri S., Novelli S., et al. New developments in per-fluoropolyether resins technology: high solid and durable polyure-thanes for heavy duty and clear OEM coatings[J]. Progress in Organic Coating, 2001, (43):75-84
[70]瞿金清,陈焕钦.高固含量水性聚氨酯分散体的合成[J].化工学报, 2003, 54(6): 868~871
[71]卫晓利,张发兴,肖忠良,等.高固含量低黏度聚氨酯微乳液的制备及性能研究[J].高分子学报, 2009, (1):28-34
[72]盛茂桂,邓桂琴.新型聚氨酯树脂涂料生产技术与应用[M].广州:广东科技出版社, 2001:38-40
[73]王武生,曾俊,阮德礼.水乳型聚氨酯与丙烯酸树酯结构性能比较[J].中国皮革, 1996, 25(5):26-31
[74] Fabrice S.M., Laurent C., CavailléJ.Y.. Mechanical properties of high density polyurethane foams:ⅡEffect of the filler size[J]. Composites Science and Technology, 2006, 66(15):2709-2718
[75] Saw,L.K.,Brooks B.W.. Different dispersion regions during the phase inversion of an ionomeric polymer-water system[J]. Collid and interface Sci, 2003, 257(1):163-172
[76] Saw L.K., Brooks B.W.. Catastrophic phase inversion in region II of an ionomeric polymer-water system[J]. Collid and interface Sci, 2004, 279(1):235-243
[77]梁宗军,沈亚,奚惠兰,等.水性聚氨酯的相转变过程[J].上海大学学报(自然科学版), 2005, 11(2):178-182
[78] Mequanint K., Sanderson R., Pasch H.. Phosphated polyurethane-acrylic dispersions:synthesis, rheological properties and wetting behaviour[J]. Polymer, 2002, 43(19): 5341-5346
[79] Kim I., Hyuk, et al. Seeded emulsion polymerization of methyl methacrylate using aqueous polyurethane dispersion: effect of hard segment on grafting efficiency[J]. Colloids and surfaces A: physicochemical and engineering aspects, 2002, 207(3):169-176
[80]李克友,耿克斌,朱弼忠.种子乳液共聚合聚氨酯-聚丙烯酸酯胶乳离子的“反相核壳”结构[J].合成橡胶工业, 1998, 21(3):158-160
[81] Swarup S., Natesh A., Fortune N.E., et al. Aqueous urethane/acrylic resins with branched chain extension and coating compositions made therefrom[P]. US: 5854332, 1998
[82] Tien C.F., Man C.L., Snyder J.M., et al. Low temperature self-crosslinking aqueous dispersions of urethane-vinyl polymers for coating applicaions[P]. US: 5977215, 1998
[83] Oshita S., Iwaizumi K., Sugiyama I.. Aqueous dispersion of urethane vinyl composite resin[P]. US: 5652291, 1997
[84]董岸杰,冯士有,万同,孙多先.水性丙烯酸-聚氨酯微乳液的制备及粒子形态[J].应用化学, 1998, 15(1):101-103
[85] Dobert J., Birnbrich B.V., Gobel A., et al. Aqueous polymer/polyurethane resin binder vehicle dispersions and the production thereof and coating media and the use thereof[P]. US: 6001924, 1999
[86]罗强,修玉英,谢禹.水基聚氨酯原料的选择[J].化学与粘合, 2001, (2):75-80
[87]黄世强,孙争光,李盛彪.环保胶黏剂[M].北京:化学工业出版社, 2003:213-216
[88]徐培林,张淑琴.聚氨酯材料手册[M].北京:化学工业出版社, 2002:156-157
[88]许戈文.水性聚氨酯材料[M].北京:化学工业出版社,2006。
[89]卢秀萍,王文杰.交联水性聚氨酯的制备及性能研究[J].聚氨酯工业, 2006, 21(4):18-21
[90]瞿金清,李佩妍,陈焕钦.甲基丙烯酸甲酯与水性聚氨酯的共聚反应[J].华南理工大学报:自然科学版, 2004, 32(8):54-58
[91]傅献彩,沈文霞,姚天扬.物理化学[M].北京:高等教育出版社, 1991:234-236
[92] Lovell P.A., Aasser E.. Emulsion polymerization and emulsion polymers[M]. John Wily & Sons Ltd, 1997:59-121
[93] Son S.H.,Lee H.J.,Kim J.H.. Effects of carboxyl groups dissociation and dielectric constant on particle size of polyurethane dispersion[J]. Colloids and SurfacesA:Physicochemical and Engineering Aspects, 1998, 133(3):295-301
[94]孙东成,王玉香. HDI-IPDI型高固含量水性聚氨酯分散体的合成及微观形态[J].高分子材料科学与工程, 2007, 23(3):59-62
[95] Yonek K.P., Berezkin Y.. Aqueous polyurethane dispersions containing non-cyclic diisocyanates and a process for their preparation[P]. US: 6147155, 2000.
[96]党晓容,方洁珠,袁荞龙,等.负离子型聚氨酯离聚体水分散过程的相反转[J].合成橡胶工业, 2005, 28(5):345-349
[97] Eckerley S.T., Rudin A.. Mechanism of formation from polymer latexes[J]. Journal of Coatings Technology, 1990, 62(780):89-99.
[2] Pathak S.S., Sharma A., Khanna A.S.. Value addition to waterborne polyurethane resin by silicone modification for developing high performance coating on aluminum alloy[J]. Progress in Organic Coatings, 2009, 65(2):206-216
[3] Lee S.K., Kim B.K.. High solid and high stability waterborne polyurethanes via ionic groups in soft segments and chain termini[J]. Journal of Colloid and Interface Science, 2009, 336(1):208-214
[4] Zhang C.Y., Zhang X.Y., Dai J.B., et al. Synthesis and properties of PDMS modified waterborne polyurethane–acrylic hybrid emulsion by solvent-free method[J]. Progress in Organic Coatings, 2008, 63(2):238-244
[5]许戈文.水性聚氨酯材料[M].北京:化学工业出版社, 2007:6-8
[6]田伟,王芳,汤克勇,等.脂肪族水性聚氨酯涂饰剂的研制[J].皮革科学与工程, 2006, 16(3):9-11
[7]李书卿,申屠勇敢,韩茂清,等.水性聚氨酯涂饰剂的性能分析[J].皮革科学与工程, 2007, 17(1):48-53
[8]刘方方,黄文杰,顾丽敏. PVC手套用水性聚氨酯涂饰剂[J] .聚氨酯工业, 2007,22(2):5-7
[9]陈红.水性聚氨酯涂料技术进展[J].涂料工业, 2006, 36(3):47-51
[10]陈珀丽,刘经梅,张之涵,等.聚氨酯涂料技术在中国的发展[J].涂料工业, 2007, 37(5):49-51
[11]于良民,王秀娟.水性聚氨酯的改性及水性聚氨酯涂料[J].热固性树脂, 2007, 22(4):44-46
[12] Ishiyama, Massaki, Matuura, et al. Aqueous dispersion of an aqueous hydrazine-terminated polyurethane[P]. US: 5700867, 1997
[13]陆冬贞.我国聚氨酯胶粘剂发展概况与展望[J].聚氨酯, 2007, (5):68-78
[14]叶青萱.水性聚氨酯胶粘剂技术进展[J].聚氨酯, 2006, (7):74-77
[15] Guo W.J., Fu H.Q., Huang H., et al. Waterborne polyurethane adhesive modified by rosin for laminated package films[J]. Packaging Engineering, 2007, 48(1):33-34
[16]修玉英,冯青,罗钟瑜.水性聚氨酯在织物整理中的应用[J].纺织导报, 2006,(2):82-85
[17]朱明杰.新型含短氟碳链水性聚氨酯的合成及在棉织物上的应用[D].上海:东华大学硕士学位论文, 2007
[18] Dvorchak, Michael J. Using high performance twocomponent waterborne polyurethane woodcoatings[J]. Journal of Coatings Technology, l997, 69(866):47-52
[19] Kim B.K., Kim T.K., et al. Aqueous dispersion of polyurethane anionomers from MDI/IPDI, PCL, BD and DMPA[J]. Journal of Applied Polymer Science, 1994, 53:371-374
[20] Chen Y., Chen T.L.. Aqueous dispersion of polyurethane antinomies: Effects of counteraction[J]. Journal of Applied Polymer Science, 1992, 46:435-439
[21] Lienert H.J., Schuster H., Schafer K.. Stabilized Aqueous Solution of a Bisulphite Blocked Polyisocyanate[P]. US:3984365, 1976
[22]胡国文,沈慧芳,杨清峰,等.聚氨酯-丙烯酸酯复合乳液的合成与表征[J].华南理工大学学报(自然科学版), 2007, 5(06):64-70
[23] Melchiors M., Leichlingen. Method of Producing Oxidative drying Urethane-Modified Polyester Dispersions and Their Use[P].US: 6620893, 2003
[24] Liu W., Rende T.. Waterborne oil-modified urethane resins[J]. Paint & Coatings Industry, 1999, (17):33-36
[25] Markus A, Schafheutle. Oxidativelydrying polyurethane Dispersions[P]. US:6359060, 2002
[26] Douglas A. Blocked IsocyanidesⅢPart B Use and Applications of Blocked isocyanates[J]. Progress in Organic Coatings, 2001, (41):3-7
[27] Wicks D.A., Wicks Z.W.. Review blocked isocyanides. Progress in Organic Coating, 2001, (41):81-83
[28]刘春华,方治奇.环氧树脂改性水性聚氨酯-丙烯酸酯的初步研究[J].聚氨酯工业, 2000, 15(3):23.
[29] Zheng W., Wong S.C., Sue H.J.. Transport behavior of PMMA/expandedgraphite nanocomposites[J]. Polymer, 2002, 43(25):6767-6773
[30]瞿金清,陈焕钦.环氧改性水性聚氨酯涂料的合成与性能研究[J].高校化学工程学报, 2002, 16(5):570-574
[31]瞿金清,陈焕钦.聚氨酯-聚丙烯酸酯复合乳液的研究[J].中国皮革, 2004, 33(5): 7-8
[32]罗建光,赖国隆.环氧树脂改性水性聚氨酯的研究[J].涂料工业, 2002, 32(12): 1-3
[33] Pulat M., Senvar C.. Structural and surface properties of polyurethane membranes of different porosities[J]. Polymer Testing, 1995, 14(2):115-120
[34]丁浩.塑料工业实用手册[M].北京:化学工业出版社, 1995:381-382
[35]吴培熙,张留成.聚合物共混改性[M].北京:中国轻工业出版社, 1995:310-311
[36] Parmar R., Patel K., Parmar J.. High-performance waterborne coatings based on epoxy-acrylic-graft-copolymer-mdified polyurethane dispersions[J]. Polym Int, 2005, (54): 488-494
[37]姜守霞,孙威,周照毅.环氧改性水性聚氨酯涂料的合成研究[J].应用化工, 2003, 32(5):7-21
[38]吴晓青,卫晓利,邱圣军.环氧树脂改性水性聚氨酯的合成工艺和性能研究[J].应用基础与工程科学学报, 2006, (6):153-159.
[39]黄洪,傅和青,邓艳文,等.环氧树脂与丙烯酸酯复合改性水性聚氨酯的合成研究[J].高校化学工程学报, 2006, (4):583-587.
[40] Karta A..Water-dispersable Air-drying Coatings[P]. US:5104737, 1991
[41] Okamoto Y., Hasegawa Y., Yoshino F.. Urethane/acrylic composite polymer emulsions[J]. Progress in Organic Coatings, 1996, 29(1): 175-182
[42] Okamoto Y., Hasegawa Y., Yoshino F.. Urethane/acrylic composite polymer emulsions[J]. Progress in organic coatings, 1996, (29):175-182
[43] Mequanint K., Sanderson R.. Nano-structure phosphorus-containing polyurethane dispersions:synthesis and crosslinking with melamine formaldehyde resin[J]. Polymer, 2002, 43(19):5341-5346
[44] Kim H., Shin J.S., Cheong I.W., et al. Seeded emulsion polymerization of methyl methacrylate using aqueous polyurethane dispersion: effect of hard segment on grafting efficiency[J]. Colloids and surfaces A: physicochemical and engineering aspects, 2002, 207(3):169-176
[45]张旭东,瞿金清,陈焕钦.制备聚氨酯-丙烯酸酯复合乳液的物料与工艺[J].现代化工, 2003, 23(2):15-18
[46] Santacesaria E., Serio M.D., Russo A., et al. Kinetic and catalytic aspects in the hydrogen peroxide production via anthraquinone[J]. Chemical engineering science, 1999, (54):2799-2806
[47] Alder H., Jahny K.,Bimbrich V.B.. Polyurethane macromers-new building blocks foracrylic hybrid emulsion with outstanding performance[J]. journal of Applied Polymer Science, 2000, 78(1):67-80
[48] Hirosea M, Kadowaha et al. Introduction of covalently bonded phosphorus into aqueous based polyurethane system via post curing reaction[J]. Progress in organic Coatings, l997, 31(1): 157-169
[49] Gooch J.W., Dong H., et al. Polyurethane ac-rylate or vinyl type polymeric material for coating optical fibers based on a fluorinated diol[J]. Journal of applied polymer Science, 2000, 76(1):105-114
[50] Boudreaux C.J., et al. Air curable water-borne urethane-acrylic hybrids[J]. European Coatings journal, 1999, (6):30-35
[51]王武生,曾俊,阮德礼,等.纳米级水基聚氨酯微凝胶环氧硅氧烷交联成膜机理[J].高分子材料科学与工程, 2001, 17(3):102-105.
[52]黄洪,傅和青,邓艳文,等.环氧树脂与丙烯酸酯复合改性水性聚氨酯的合成研究[J].高校化学工程学报, 2006, 20(4):583-587
[53]黄洪,谢筱薇,傅和青.多重改性水性聚氨酯乳液的合成及性能[J].华南理工大学学报(自然科学版), 2006, 34(8):46-50
[54]侯孟华,刘伟区,黎艳.有机硅蒙脱土复合改性水性聚氨酯的研究[J].功能高分子学报, 2005, 18(1):89-93
[55]王春会.环氧树脂及无机纳米改性水性聚氨酯的研究[D].天津:天津科技大学, 2006
[56]邱少君,甘孝贤,王吉贵,等. HDI三聚体合成研究[J].聚氨酯工业, 1998, 13(2):17-20
[57] Robin J., Blind A.. Purification of Isocyanurate Group-containing Polyisocyanates[P]. FR:2607499, 1988
[58] Robin J., Blind A.. Purification and Isolation of Polyol -polyurethanes by Extraction with Supercritical Carbon Dioxide[P]. FR:2629086, 1989-09-29
[59]李绍雄,刘益军.聚氨脂胶粘剂[M].北京:化学工业出版社, 1998:120
[60] Shindo M. Properties of HDI Trimer for Coating Systerns[J]. Polym Mater Sci Eng, 1983, (49):169-173
[61] Houze E.C., Vasta A.. Acrylic Polyurethane Coating Composition[P]. US: 4503175, 1985
[62]阮家声,刘红莲. TDI三聚体的合成研究[J].黎明化工, 1997, (4):24
[63] Kaoru U., Oyabunorio., Yabunorio A.. Iso-cyanurate Polyisocyanates as Curing Agentsfor Two- Component Polyurethane Compositions[P]. DE: 3810908, 1988
[64] Houze E.C., VASTA J.A.. Acrylic Polyurethane Coating Composition[P]. US: 4503175, 1985
[65] Shindom. Properties of HDI Trimer for Coating Systems[J]. Polym Mater Sci Eng, 1983, (49):169-173
[66] Sheffer M.W., Martin K., Parkerson H., et al. Aqueous Polyurethane Coatings with Improved Resistance to Sontan Lotion[p]. JP:97998303, 1997
[67] Byoung U.A., Su K.L., Sang K.L., et al. UV curable polyurethane dispersions from polyisocyanate and organosilane[J]. Progress in Organic Coatings, 2008, (4):258-264.
[68] HaiN I., Jeremy L.D, Pauline R.T, et a.l Cycloaliphatic polyester-based high-solid polyurethane coatings[J]. Progress in Organic Coating, 2002, (45):49-58
[69] Temtchenko T., Turri S., Novelli S., et al. New developments in per-fluoropolyether resins technology: high solid and durable polyure-thanes for heavy duty and clear OEM coatings[J]. Progress in Organic Coating, 2001, (43):75-84
[70]瞿金清,陈焕钦.高固含量水性聚氨酯分散体的合成[J].化工学报, 2003, 54(6): 868~871
[71]卫晓利,张发兴,肖忠良,等.高固含量低黏度聚氨酯微乳液的制备及性能研究[J].高分子学报, 2009, (1):28-34
[72]盛茂桂,邓桂琴.新型聚氨酯树脂涂料生产技术与应用[M].广州:广东科技出版社, 2001:38-40
[73]王武生,曾俊,阮德礼.水乳型聚氨酯与丙烯酸树酯结构性能比较[J].中国皮革, 1996, 25(5):26-31
[74] Fabrice S.M., Laurent C., CavailléJ.Y.. Mechanical properties of high density polyurethane foams:ⅡEffect of the filler size[J]. Composites Science and Technology, 2006, 66(15):2709-2718
[75] Saw,L.K.,Brooks B.W.. Different dispersion regions during the phase inversion of an ionomeric polymer-water system[J]. Collid and interface Sci, 2003, 257(1):163-172
[76] Saw L.K., Brooks B.W.. Catastrophic phase inversion in region II of an ionomeric polymer-water system[J]. Collid and interface Sci, 2004, 279(1):235-243
[77]梁宗军,沈亚,奚惠兰,等.水性聚氨酯的相转变过程[J].上海大学学报(自然科学版), 2005, 11(2):178-182
[78] Mequanint K., Sanderson R., Pasch H.. Phosphated polyurethane-acrylic dispersions:synthesis, rheological properties and wetting behaviour[J]. Polymer, 2002, 43(19): 5341-5346
[79] Kim I., Hyuk, et al. Seeded emulsion polymerization of methyl methacrylate using aqueous polyurethane dispersion: effect of hard segment on grafting efficiency[J]. Colloids and surfaces A: physicochemical and engineering aspects, 2002, 207(3):169-176
[80]李克友,耿克斌,朱弼忠.种子乳液共聚合聚氨酯-聚丙烯酸酯胶乳离子的“反相核壳”结构[J].合成橡胶工业, 1998, 21(3):158-160
[81] Swarup S., Natesh A., Fortune N.E., et al. Aqueous urethane/acrylic resins with branched chain extension and coating compositions made therefrom[P]. US: 5854332, 1998
[82] Tien C.F., Man C.L., Snyder J.M., et al. Low temperature self-crosslinking aqueous dispersions of urethane-vinyl polymers for coating applicaions[P]. US: 5977215, 1998
[83] Oshita S., Iwaizumi K., Sugiyama I.. Aqueous dispersion of urethane vinyl composite resin[P]. US: 5652291, 1997
[84]董岸杰,冯士有,万同,孙多先.水性丙烯酸-聚氨酯微乳液的制备及粒子形态[J].应用化学, 1998, 15(1):101-103
[85] Dobert J., Birnbrich B.V., Gobel A., et al. Aqueous polymer/polyurethane resin binder vehicle dispersions and the production thereof and coating media and the use thereof[P]. US: 6001924, 1999
[86]罗强,修玉英,谢禹.水基聚氨酯原料的选择[J].化学与粘合, 2001, (2):75-80
[87]黄世强,孙争光,李盛彪.环保胶黏剂[M].北京:化学工业出版社, 2003:213-216
[88]徐培林,张淑琴.聚氨酯材料手册[M].北京:化学工业出版社, 2002:156-157
[88]许戈文.水性聚氨酯材料[M].北京:化学工业出版社,2006。
[89]卢秀萍,王文杰.交联水性聚氨酯的制备及性能研究[J].聚氨酯工业, 2006, 21(4):18-21
[90]瞿金清,李佩妍,陈焕钦.甲基丙烯酸甲酯与水性聚氨酯的共聚反应[J].华南理工大学报:自然科学版, 2004, 32(8):54-58
[91]傅献彩,沈文霞,姚天扬.物理化学[M].北京:高等教育出版社, 1991:234-236
[92] Lovell P.A., Aasser E.. Emulsion polymerization and emulsion polymers[M]. John Wily & Sons Ltd, 1997:59-121
[93] Son S.H.,Lee H.J.,Kim J.H.. Effects of carboxyl groups dissociation and dielectric constant on particle size of polyurethane dispersion[J]. Colloids and SurfacesA:Physicochemical and Engineering Aspects, 1998, 133(3):295-301
[94]孙东成,王玉香. HDI-IPDI型高固含量水性聚氨酯分散体的合成及微观形态[J].高分子材料科学与工程, 2007, 23(3):59-62
[95] Yonek K.P., Berezkin Y.. Aqueous polyurethane dispersions containing non-cyclic diisocyanates and a process for their preparation[P]. US: 6147155, 2000.
[96]党晓容,方洁珠,袁荞龙,等.负离子型聚氨酯离聚体水分散过程的相反转[J].合成橡胶工业, 2005, 28(5):345-349
[97] Eckerley S.T., Rudin A.. Mechanism of formation from polymer latexes[J]. Journal of Coatings Technology, 1990, 62(780):89-99.