醇溶性蓖麻油基聚氨酯树脂的制备及性能研究
|
摘要
目前,在胶粘剂领域中存在溶剂型胶粘剂、水性胶粘剂和无溶剂型胶粘剂三大类,国内复合包装材料用胶粘剂普遍使用的是用乙酸乙酯为溶剂的聚氨酯胶粘剂,但酯溶性聚氨酯具有一定毒性和强烈的刺激性,对人体和环境造成很大的危害；水性聚氨酯乳液环保性能好,但其乳液中或多或少会存在的异氰酸酯基团以及剧毒的游离TDI、MDI等芳香族异氰酸酯分子。而且水挥发慢,影响生产效率,在塑料、铝箔等材料使用上适应性差；而无溶剂热熔胶粘剂设备投资成本过大,都难以在近期推广。随着市场对软包装的原材料安全性能要求的提高,醇溶性聚氨酯胶粘剂就应运而生。本课题以绿色环保的乙醇为溶剂,它能够较好的平衡水性胶粘剂与溶剂型胶粘剂的缺点,在节约成本方面也具有很大的优势。
本文第一章介绍了聚氨酯胶粘剂的原料选择和其分类,讨论了影响粘接强度的主要因素,并对醇溶性聚氨酯胶粘剂与其他类型聚氨酯胶粘剂的性能进行对比,突出其优点;另外又分别介绍了蓖麻油改性聚氨酯、纳米材料改性聚氨酯、环氧树脂改性聚氨酯的机理使用、实验方法和研究现状。
本文第二章以蓖麻油部分代替聚酯(醚)多元醇合成醇溶性聚氨酯树脂,红外分析表明蓖麻油已与聚氨酯反应,使聚氨酯从线形分子链转变成三维立体结构,蓖麻油的加入,使得聚氨酯胶的剥离强度得到明显提高,但当添加量超过7.5wt%后,样品的剥离强度增幅变小,其拉伸强度先增加后逐渐变小,而断裂伸长率不断减小；聚氨酯软硬段的最高热失重温度也得到增加；综合比较,添加10wt%的样品,大大改善了聚氨酯的传统特性,可以获得综合性能良好的醇溶性聚氨酯树脂。
本文第三章仍以蓖麻油部分替代聚醚多元醇N210制备醇溶性聚氨酯预聚体,以有机硅氧烷(KH550)充当有机-无机网络的偶联剂,对纳米二氧化硅进行表面改性,制备了疏水性纳米二氧化硅粒子,将其在机械搅拌和超声场作用下均匀分散到聚氨酯溶液中,结果表明：随着纳米二氧化硅含量的不断增加,黏度增长缓慢,拉伸强度有所增大,而断裂伸长率降低,PU膜的吸水率降低。当纳米二氧化硅含量继续加大时,材料的硬度和剥离强度都有所下降。综合比较,添加2wt%的样品,综合性能较好。
本文第四章在原制备的纳米二氧化硅改性聚氨酯基础上,选择丙酸为环氧树脂的开环起始剂参与开环反应,使得环氧基团开环成为羟基基团,引入聚氨酯基体中。结果表明：环氧树脂添加量的引入,使SiO2-PU复合材料的拉伸强度得到提高,断裂伸长率的有所下降,硬度一直呈上升趋势；当环氧树脂添加量为8wt%时,硬段最大热失重温度从344℃提高至356℃,软段最大热失重温度从389℃增至391℃；在此基础上引入2wt%的纳米Si02后,硬段最大热失重温度从356℃提高至363℃,软段最大热失重温度从391℃增至394℃。此时材料的耐热性能最好。
At present, there are solvent-based, water-based adhesives and solvent-free adhesive in the adhesive field. The composite packaging materials commonly used to use polyurethane adhesive with ethyl acetate as the solvent, but the ester-soluble polyurethane has some toxicity and strong irritant and cause great harm to humans and the environment. Compared to ester-soluble one, waterborne polyurethane has good environmental performance, but there will be more or less the isocyanate groups exited in highly toxic free aromatic isocyanate molecules such as TDI, MDI etc. Meanwhile, water volatile slowly, which impact on productivity, and waterborne adhesive has poor adaptability in materials such as plastic, aluminum foil. Hot melt adhesive without solvents cost too large in equipment investment, so it is difficult to develop in the near future. With the improvement of the market for flexible packaging raw materials security performance requirements, the alcohol-soluble polyurethane adhesive came into being. In this topic, ethanol-soluble polyurethanes were prepared, which balance water-based adhesives and solvent-based adhesive, and has a great advantage in cost savings.
The first chapter introduces the polyurethane adhesive materials selection and classification of the main factors affecting the bonding strength, and alcohol-soluble polyurethane adhesives and other types of polyurethane adhesives for performance comparison, highlighting its advantages; introduced grate The mechanism of sesame oil modified polyurethane, nano-materials-modified polyurethane, epoxy-modified polyurethane, the use of experimental methods and research status.
The second chapter introduces castor oil part instead of the polyester(ether) polyol synthesis of alcohol-soluble polyurethane resin, infrared analysis showed that castor oil reaction with the polyurethane, the polyurethane into three-dimensional structure from a linear molecular chain, castor oil added, making The peel strength of the polyurethane adhesive has been markedly improved, but the addition of more than7.5wt%, the increase in peel strength of the sample is smaller, its tensile strength increases first and then gradually smaller, while the elongation at break decreasing; polyurethane soft and hard section of the highest weight loss temperatures increase; comprehensive comparison, adding10wt%of the samples has greatly improved the traditional characteristics of the polyurethane, you can get good performance of the alcohol-soluble polyurethane resin.
The third chapter is still the castor oil a partial substitute for the preparation of polyether polyols N210alcohol-soluble prepolymer of organosiloxane (KH550) to act as organic-inorganic network coupling agents, surface modification of nano-silica, hydrophobic nano-silica particles are prepared, in the mechanical agitation and ultrasonic field dispersed into the polyurethane solution, the results show that:With the increasing of the nano-silica content, viscosity, slow growth, the tensile strength has increases, while the breaking elongation, lower water absorption of PU film. When the nano-silica content continue to increase the hardness and peel strength have declined. Comprehensive comparison, adding2wt%of the samples is very well.
The fourth chapter introduces the original preparation of nano-silica modified polyurethane base, propionic acid is involved in ring opening reaction of epoxy ring opening initiator, the hydroxyl groups makes the epoxy groups of open-loop, the introduction of the polyurethane matrix. The results showed that:the introduction of epoxy to add the amount of SiO2-composites the tensile strength increased, fracture elongation declined, the hardness has been an upward trend; adding8wt%of epoxy resin After the hard segment weight loss temperatures from344℃to356℃, the soft segment weight loss temperature increased from389℃to391℃; On this basis, the introduction of2wt%of nano-SiO2, the hard segment weight loss temperatures from356℃to363℃, the soft segment of maximum weight loss temperature increased from391℃to394℃. The heat-resistant properties of the material is well.
本文第一章介绍了聚氨酯胶粘剂的原料选择和其分类,讨论了影响粘接强度的主要因素,并对醇溶性聚氨酯胶粘剂与其他类型聚氨酯胶粘剂的性能进行对比,突出其优点;另外又分别介绍了蓖麻油改性聚氨酯、纳米材料改性聚氨酯、环氧树脂改性聚氨酯的机理使用、实验方法和研究现状。
本文第二章以蓖麻油部分代替聚酯(醚)多元醇合成醇溶性聚氨酯树脂,红外分析表明蓖麻油已与聚氨酯反应,使聚氨酯从线形分子链转变成三维立体结构,蓖麻油的加入,使得聚氨酯胶的剥离强度得到明显提高,但当添加量超过7.5wt%后,样品的剥离强度增幅变小,其拉伸强度先增加后逐渐变小,而断裂伸长率不断减小；聚氨酯软硬段的最高热失重温度也得到增加；综合比较,添加10wt%的样品,大大改善了聚氨酯的传统特性,可以获得综合性能良好的醇溶性聚氨酯树脂。
本文第三章仍以蓖麻油部分替代聚醚多元醇N210制备醇溶性聚氨酯预聚体,以有机硅氧烷(KH550)充当有机-无机网络的偶联剂,对纳米二氧化硅进行表面改性,制备了疏水性纳米二氧化硅粒子,将其在机械搅拌和超声场作用下均匀分散到聚氨酯溶液中,结果表明：随着纳米二氧化硅含量的不断增加,黏度增长缓慢,拉伸强度有所增大,而断裂伸长率降低,PU膜的吸水率降低。当纳米二氧化硅含量继续加大时,材料的硬度和剥离强度都有所下降。综合比较,添加2wt%的样品,综合性能较好。
本文第四章在原制备的纳米二氧化硅改性聚氨酯基础上,选择丙酸为环氧树脂的开环起始剂参与开环反应,使得环氧基团开环成为羟基基团,引入聚氨酯基体中。结果表明：环氧树脂添加量的引入,使SiO2-PU复合材料的拉伸强度得到提高,断裂伸长率的有所下降,硬度一直呈上升趋势；当环氧树脂添加量为8wt%时,硬段最大热失重温度从344℃提高至356℃,软段最大热失重温度从389℃增至391℃；在此基础上引入2wt%的纳米Si02后,硬段最大热失重温度从356℃提高至363℃,软段最大热失重温度从391℃增至394℃。此时材料的耐热性能最好。
At present, there are solvent-based, water-based adhesives and solvent-free adhesive in the adhesive field. The composite packaging materials commonly used to use polyurethane adhesive with ethyl acetate as the solvent, but the ester-soluble polyurethane has some toxicity and strong irritant and cause great harm to humans and the environment. Compared to ester-soluble one, waterborne polyurethane has good environmental performance, but there will be more or less the isocyanate groups exited in highly toxic free aromatic isocyanate molecules such as TDI, MDI etc. Meanwhile, water volatile slowly, which impact on productivity, and waterborne adhesive has poor adaptability in materials such as plastic, aluminum foil. Hot melt adhesive without solvents cost too large in equipment investment, so it is difficult to develop in the near future. With the improvement of the market for flexible packaging raw materials security performance requirements, the alcohol-soluble polyurethane adhesive came into being. In this topic, ethanol-soluble polyurethanes were prepared, which balance water-based adhesives and solvent-based adhesive, and has a great advantage in cost savings.
The first chapter introduces the polyurethane adhesive materials selection and classification of the main factors affecting the bonding strength, and alcohol-soluble polyurethane adhesives and other types of polyurethane adhesives for performance comparison, highlighting its advantages; introduced grate The mechanism of sesame oil modified polyurethane, nano-materials-modified polyurethane, epoxy-modified polyurethane, the use of experimental methods and research status.
The second chapter introduces castor oil part instead of the polyester(ether) polyol synthesis of alcohol-soluble polyurethane resin, infrared analysis showed that castor oil reaction with the polyurethane, the polyurethane into three-dimensional structure from a linear molecular chain, castor oil added, making The peel strength of the polyurethane adhesive has been markedly improved, but the addition of more than7.5wt%, the increase in peel strength of the sample is smaller, its tensile strength increases first and then gradually smaller, while the elongation at break decreasing; polyurethane soft and hard section of the highest weight loss temperatures increase; comprehensive comparison, adding10wt%of the samples has greatly improved the traditional characteristics of the polyurethane, you can get good performance of the alcohol-soluble polyurethane resin.
The third chapter is still the castor oil a partial substitute for the preparation of polyether polyols N210alcohol-soluble prepolymer of organosiloxane (KH550) to act as organic-inorganic network coupling agents, surface modification of nano-silica, hydrophobic nano-silica particles are prepared, in the mechanical agitation and ultrasonic field dispersed into the polyurethane solution, the results show that:With the increasing of the nano-silica content, viscosity, slow growth, the tensile strength has increases, while the breaking elongation, lower water absorption of PU film. When the nano-silica content continue to increase the hardness and peel strength have declined. Comprehensive comparison, adding2wt%of the samples is very well.
The fourth chapter introduces the original preparation of nano-silica modified polyurethane base, propionic acid is involved in ring opening reaction of epoxy ring opening initiator, the hydroxyl groups makes the epoxy groups of open-loop, the introduction of the polyurethane matrix. The results showed that:the introduction of epoxy to add the amount of SiO2-composites the tensile strength increased, fracture elongation declined, the hardness has been an upward trend; adding8wt%of epoxy resin After the hard segment weight loss temperatures from344℃to356℃, the soft segment weight loss temperature increased from389℃to391℃; On this basis, the introduction of2wt%of nano-SiO2, the hard segment weight loss temperatures from356℃to363℃, the soft segment of maximum weight loss temperature increased from391℃to394℃. The heat-resistant properties of the material is well.
引文
[1]许戈文.水性聚氨酯材料[M].北京：化学工业出版社,2006.
[2]王武生,潘才元.交联聚氨酯水分散体的合成[J].高分子学报,2000,3(6)：319-324.
[3]王凌云,杨丽庭,王成双,等.植物油基绿色聚合物的研究进展[J].应用化工,2009,38(5)：724-728.
[4]戴震,李莉,张海龙,等.植物油改性水性聚氨酯的研究现状[J].中国涂料,2009,24(2)：16-18.
[5]韩昶,卿宁,郭凯敏.水性聚氨酯多元改性的研究进展[J].中国皮革,2009,38(1)：40-44.
[6]陈红梅,廖时勇,张爱民.提高水性聚氨酯耐水性的研究[J].中国胶粘剂,2009,18(1)：11-15.
[7]Sharma V,Kundu P P. Addition polymers from natural oils-A review[J]Prog Polym Sci,2006,31(11):983-1008.
[9]Yongsheng Lu,Yong Tao,Chun Pu Hu. Polyurethaneurea/Vinyl Polymer Hybrid Aqueous Dispersions Based on Renewable Material[J].Biomacromolecules, 2001,2:80-84.
[10]李学良,孙炜.蓖麻油改性的水性聚氨酯涂料的制备及其防蚀性能[J].广东化工,2010,37(5)：3-7.
[11]鲍俊杰,钟达飞,谢伟,等.内交联水性聚氨酯胶粘剂的研究[J].粘接,2006,27(3)：1-5.
[12]高明志,谢伟,许戈文.一种新型水性聚氨酯光油的制备及其性能探讨[J].中国皮革,2007,36(1)：15-17.
[13]杜娟,郝俊松,李再峰TMPDCO对封端型水性聚氨酯的改性研究[J].聚氨酯工业,2010,25(1)：38-41.
[14]曾小君,郁燕萍.新型非离子水性聚氨酯表面活性剂的制备及性能[J].高分子材料科学与工程,2008,24(3)：129-132.
[15]Stefan Oprea. Effect of the long chain extender on the properties of linear and castor oil cross-linked PEG-based polyurethane elastomers[J]. Journal of Materials Science,2011,46:2251-2258.
[16]王齐,傅和青.蓖麻油-丙烯酸酯改性的双组分水性聚氨酯胶粘剂研究[J].包装工程,2008,29(11)：91-93；124.
[17]陈为,杨隽,何蕾,等.蓖麻油聚氨酯防水涂料的制备与性能研究[J].涂料工业,2009,39(9)：29-31.
[18]Li A Y, Hu B N, Hu H X. Castor oil alkyd prepolymer prepared by two-component polyurethane coatings based research [J]. Coatings Industry 2006,36(1):21-23;62.
[19]李金玲,王宝辉,李莉,等.纳米改性水性聚氨酯的研究进展[J].涂料工业,2010,40(8)：70-74.
[20]Du H, Zhao Y H,Li Q F,et al. Synthesis and characterization of waterborne polyurethane adhesive from MDI and HDI[J]. Journal of Applied Polymer Science,2008,110(3):1396-1402.
[21]Tamai T, Pinenq P, Winnik M A. Effect of cross-linking on polymer diffusion in poly(butyl methacrylate-co-butyl acrylate) latex films[J]. Macromolecules,1999,32(19):6102-6110.
[22]Ch En Xc, You B, Zhou Sx, et a.l. Surface and interface characterization of nano-SiO2/polyester based polyurethane composite coating. Surf inter anal[J]. Surface and Interface An alysis,2003,(35):369-374.
[23]Oliver Wc, Pharr Gm. An improved technique determining hardness and elastic-modulus using load and displacement sensing indentation experiments[J]. JMater Res,1992,7(6):1564-1583.
[24]沈一丁,刘敏,赖小娟,等.水性聚氨酯／纳米Si02杂化材料的制备及性能研究[J].精细化工,2010,27(4)：318-322.
[25]凡永利,郑水蓉,侯锐钢.纳米Si02改性水性聚氨酯乳液的制备及性能研究[J].中国胶粘剂,20117,20(7)：24-27.
[26]郭建,章于川,吴兵.原位聚合法制备纳米二氧化硅／聚氨酯复合树脂[J].应用化学,2011,28(11)：1244-1249.
[27]石智；强,李赛,刘孝波.溶胶-凝胶法制备聚氨酯/二氧化硅杂化材料[J].四川大学学报(工程科学版),2004,36(3)：60-63.
[28]周树学,陈国栋,武利民.丙烯酸酯聚氨酯/Si02纳米复合涂层结构与形态对其耐刮伤性影响研究[J].涂料工业,2006,36(5)：1-4.
[29]王磊,沈一丁.水性聚氨酯/纳米二氧化硅杂化材料的制备及性能[J].高分子材料科学与工程,2011,27(6)：137-141.
[30]张胜文,姜思思,沈利亚.光固化水性聚氨酯/Si02纳米复合乳液的合成和膜性能[J].高分子材料科学与工程,2010,26(11)：9-12.
[31]Hirose M, Zhou J H, Nagai K. The structure and properties of acrylic-polyurethane-hybrid emulsions[J]. Progress in Organic Coatings,2000(38):27-34.
[32]Spinu M, Jackson C, Keating M Y, et a.l. Material design in poly(lactic acid) systems:block copolymers, star homo-and copolymers, and stereocom plexes[J]. Journal of Macromolecular Science, Part A:Pure and Applied Chemistry.1996,33(10):1497-1530.
[33]张武英.环氧硅烷外交联改性水性聚氨酷的研究[J].中国胶粘剂,2006,15(4)：13-16.
[34]Hegedu S C R, Kloiber K A. Aqueous acrylic polyurethane hybrid dispersion and their use in industrial coating[J]. Journal of Coatings Technology, 1996(9):37-43.
[35]Marcia C D, Fernanda, C Ou Tinho M B. Waterborne an ionic polyurethanes and polyols:influence of the chain extender on mechanical and adhesive properties[J]. Polymer Test ing,2000(19):939-945
[36]刘天亮,沈慧芳,吴银萍.环氧树脂对PUA复合乳液的改性研究[J].粘接,2009,25(6)：238-42.
[37]江峰,沈慧芳,陈焕钦.环氧树脂-水性聚氨酯-丙烯酸酯复合乳液的研究[J].粘接,2007,28(1)：20-23.
[38]孙胜霞,钱欣.环氧树脂改性双组份水性聚氨酯的研究[J].轻工机械,2007,25(3)：120-123.
[39]韩文松,李良波,孟平蕊.环氧树脂改性脂肪族水性聚氨酯的合成及其性能[J].聚氨酯工业,2007,22(4)：24-27.
[40]朱延安,张心亚,阎虹.环氧树脂改性水性聚氨酯乳液的制备[J].江苏大学学报自然学科类,2008,29(2)：164-168.
[41]胡巧玲,朱永群,付晏彬.光固化型聚氨酯／环氧树脂IPN的制备与表征[J].高分子材料科学与工程,1999,15(5)：172-175.
[42]黄洪,傅和青,邓艳文.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.
[1]Ramamurthi, S, V. Manohar, and V. V. S. Mani. Characterisation of fatty acid isomers in dehydrated castor oil by gas chromatography and gas chromatography mass spectrometry techniques[J]. Am. Oil Chem. Soc.1998,75(10):1297-1303.
[2]Saxena, P. K., S. R. Srinivasan, J. Hrouz. The effect of castor oil on the structure and properties of polyurethane elastomers [J]. Appl. Polym. Sci.1992,44(8), 1343-1347.
[3]何向东,李国防,郑新,等.磷酸化酯交换蓖麻油加脂剂制备及性能的研究[J].河南科学,2004,22(1)：45-49.
[4]靳东杰,刘治猛.用蓖麻油合成聚氨酯乳液的研究[J].林产化学与工业,2003,23(1)：34-38.
[5]Tran, N. B, J. Vialle, and Q. T. Pham. Castor oil-based polyurethanes.I:Structural characterization of castor oil nature of intact glycerides and distribution of hydroxyl groups[J]. Polymer,1997,38(10):2467-2473.
[6]Lal, K. and V. Carrick. Performance testing of lubricants based on high oleic vegetable oils[J]. Synth. Lubr,1994,11 (3):189-206.
[7]邬润德,朱林华,童筱莉.蓖麻油型聚氨酯/PS同步IPNs的协同效应研究[J]. 聚氨酯工业,2005,20(5)：11-15.
[8]Yunus, R, A. Fakhrul-Razi, T. L. Ooi. Lubrication properties of trimethylolpropane esters based on palm oil and palm kernel oils Eur[J]. Lipid Sci. Technol. 2004,106(1):52-60.
[9]Lligadas G, Ronda JC, Galia M. Synthesis and characterization of polyurethanes from epoxidized methyl oleate based polyether polyols as renewable resources[J] Polym Sci A Polym Chem,2006,44:634-645.
[10]范浩军,石碧.蓖麻油改性聚氨酯皮革涂饰剂的研究[J].精细化工,1996(13)：30-35.
[11]瞿金清,陈焕钦.蓖麻油水性聚氨酯树脂的合成与性能的研究[J].林产化学与工业,2004,24(3)：78-82.
[12]Xu Y, Petrovic Z, Das S. Morphology and properties of thermoplastic polyurethanes with dangling chains in ricinoleate-based soft segments[J]. Polymer,2008,49:4248-4258.
[13]Papadimtrakopoulos F, Sawa E, MacKnight WJ. Investigation of a monotropic liquid crystal polyurethane based on biphenol,2,6-tolylene diisocyanate, and a six methylene containing flexible spacer2, IR spectroscopic phase characterization[J]. Macromolecules,1992,25:4682-4691.
[14]李爱阳,胡波年,胡汉祥.蓖麻油制备醇酸预聚型双组分聚氨酯树脂涂料的研究[J].涂料工业,2006,36(1)：21-23.
[15]Czech P, Okrasa L, Boiteux G, Mechin F, Ulanski J. Polyurethane networks based on hyperbranched polyesters:synthesis and molecular relaxations[J]. Non Cryst Solids,2005,351(33):2735-2741.
[16]Oprea S. Effect of the diisocyanate and chain extenders on the properties of the cross-linked polyetherurethane elastomers [J]. Mater Sci,2008,43(15):5274-5281.
[1]王凌云,杨丽庭,王成双,等.植物油基绿色聚合物的研究进展[J].应用化工,2009,38(5)：724-728.
[2]戴震,李莉,张海龙,等.植物油改性水性聚氨酯的研究现状[JJ.中国涂料,2009,24(2)：16-18.
[3]张胜文,姜思思,沈利亚,等.光固化水性聚氨酯/Si02纳米复合乳液的合成和膜性能[J].高分子材料科学与工程,2010,26(11)：9-12.
[4]Yongshang Lu, Richard C.Larock. Soybean-oil-Based Waterborne Polyurethane Dispe-rsions:Effect of Polyol Functionality and Hard Segment Content on Properties[J]. Bioma cromolecules,2008,(9):3332-3340.
[5]胡国文.蓖麻油和环氧树脂改性水性聚氨酯-丙烯酸酯的合成与表征[J].精细化工,2011,28(8)：1-6.
[6]Sharma V, Kundu P P. Addition polymers from natural oils-A review[J]. Prog Polym Sci,2006,31(11):983-1008.
[7]Zhou Shuxue, Wu Lim in, Sun Jian, et al. The change of the properties of acrylic-based polyurethane via addition of nano-silica[J]. Progress in Organic Coatings,2002(45):33-42.
[8]Kishore K. Jena and K. V. S. N. Raju.Synthes is and characterization of hyperbranched polyurethane-urea/silica based hybrid coatings[J]. Industrial & Engineering Chemistry Research,2007,46(20):6408-6416.
[9]P.Ganga Raju Acharya; Smita Biswala; Sneha Mohapatraa,et al.The Syntheses and Characterization of Interpenetrating Polymer Networks (IPNs) Derived from Cardanol-Based Dye and Linseed Oil-Based Polyurethanes[J]. Polymer-Plastics Technology and Engineering.2010,49(11):1114-1120.
[10]王磊,沈一丁,赖小娟.水性聚氨酯/纳米二氧化硅杂化材料的制备及性能[J].高分子材料科学与工程.2011,27(6)：137-141.
[11]Yongshang Lu, Richard C, Larock. Synthesis and Properties of Grafted Latices from a Soybean Oil-Based Waterborne Polyurethane and Acrylics [J]. Journal of Applied Polymer Science,2011,(119):3305-3312.
[12]李学良,孙炜.蓖麻油改性的水性聚氨酯涂料的制备及其防蚀性能[J].广东化工,2010,37(5)：3-5.
[13]陈为,杨隽,何蕾,等.蓖麻油聚氨酯防水涂料的制备与性能研究[J].涂料工业,2009,39(9)：29-31.
[1]王春艳,朱传方,万婷,等.环氧改性脂肪族水性聚氨酯的合成与性能[J].应用化学,2006,23(04)：441-443.
[2]邓朝霞,叶代勇,魏丹,等.环氧改性水性聚氨酯的合成工艺及性能[J].涂料工业,2007,37(4)：37-40.
[3]王淑艳,曾黎明,赵庆美.聚氨酯-环氧树脂复合材料的研究进展[J].化工生产与技术,2008,15(1)：44-49.
[4]Dong An-jie, An Ying-li, Feng Sh-i you. Preparation and morphology studies o f core-shell type waterborne polyacry late-polyurethanem icrospheres[J]. Journal of Colloid and Interface Science,1999,214(1):118-122.
[5]Danie 1 BO, Sandipan D, P ing Zhang, et a.l. Synthesis and phase separation du ring film forma tion of novel methyl methacry late/n-buty lacry late/methacry lie acid (MMA/BA/MAA) hybridurethane/acry late colloidal dispersions[J]. Polymer, 2004,45(18):6235-6243.
[6]Wang C, Chu F, Gra illat C, et a.l. Hybrid polymer latexes:acrylics-polyurethane from miniemulsion polymerization:properties of hybrid latexes versus blends[J]. Polymer,2005,46(4):1113-1124.
[7]李玉玮,王静媛,粟宜明,等.聚氨酯/环氧树脂互穿网络聚合物阻尼性能的研究[JJ.中国塑料,1990,4(4)：26-30.
[8]Wang Z Y, Han E H, Ke W. In fluence of expandable graphite on fire resistance and water resistance of flame-retardant coatings[J]. Corrosion Science,2007,49 :2237-2253.
[9]Chuen-Sh Ii, Chon, Sheau-Horng, Ch In-Iwang. Preparation and characterization of the intumescent fire retardant coating with a new flam eretardant[J]. Advanced Power Technology,2009,20(4):169-176.
[2]王武生,潘才元.交联聚氨酯水分散体的合成[J].高分子学报,2000,3(6)：319-324.
[3]王凌云,杨丽庭,王成双,等.植物油基绿色聚合物的研究进展[J].应用化工,2009,38(5)：724-728.
[4]戴震,李莉,张海龙,等.植物油改性水性聚氨酯的研究现状[J].中国涂料,2009,24(2)：16-18.
[5]韩昶,卿宁,郭凯敏.水性聚氨酯多元改性的研究进展[J].中国皮革,2009,38(1)：40-44.
[6]陈红梅,廖时勇,张爱民.提高水性聚氨酯耐水性的研究[J].中国胶粘剂,2009,18(1)：11-15.
[7]Sharma V,Kundu P P. Addition polymers from natural oils-A review[J]Prog Polym Sci,2006,31(11):983-1008.
[9]Yongsheng Lu,Yong Tao,Chun Pu Hu. Polyurethaneurea/Vinyl Polymer Hybrid Aqueous Dispersions Based on Renewable Material[J].Biomacromolecules, 2001,2:80-84.
[10]李学良,孙炜.蓖麻油改性的水性聚氨酯涂料的制备及其防蚀性能[J].广东化工,2010,37(5)：3-7.
[11]鲍俊杰,钟达飞,谢伟,等.内交联水性聚氨酯胶粘剂的研究[J].粘接,2006,27(3)：1-5.
[12]高明志,谢伟,许戈文.一种新型水性聚氨酯光油的制备及其性能探讨[J].中国皮革,2007,36(1)：15-17.
[13]杜娟,郝俊松,李再峰TMPDCO对封端型水性聚氨酯的改性研究[J].聚氨酯工业,2010,25(1)：38-41.
[14]曾小君,郁燕萍.新型非离子水性聚氨酯表面活性剂的制备及性能[J].高分子材料科学与工程,2008,24(3)：129-132.
[15]Stefan Oprea. Effect of the long chain extender on the properties of linear and castor oil cross-linked PEG-based polyurethane elastomers[J]. Journal of Materials Science,2011,46:2251-2258.
[16]王齐,傅和青.蓖麻油-丙烯酸酯改性的双组分水性聚氨酯胶粘剂研究[J].包装工程,2008,29(11)：91-93；124.
[17]陈为,杨隽,何蕾,等.蓖麻油聚氨酯防水涂料的制备与性能研究[J].涂料工业,2009,39(9)：29-31.
[18]Li A Y, Hu B N, Hu H X. Castor oil alkyd prepolymer prepared by two-component polyurethane coatings based research [J]. Coatings Industry 2006,36(1):21-23;62.
[19]李金玲,王宝辉,李莉,等.纳米改性水性聚氨酯的研究进展[J].涂料工业,2010,40(8)：70-74.
[20]Du H, Zhao Y H,Li Q F,et al. Synthesis and characterization of waterborne polyurethane adhesive from MDI and HDI[J]. Journal of Applied Polymer Science,2008,110(3):1396-1402.
[21]Tamai T, Pinenq P, Winnik M A. Effect of cross-linking on polymer diffusion in poly(butyl methacrylate-co-butyl acrylate) latex films[J]. Macromolecules,1999,32(19):6102-6110.
[22]Ch En Xc, You B, Zhou Sx, et a.l. Surface and interface characterization of nano-SiO2/polyester based polyurethane composite coating. Surf inter anal[J]. Surface and Interface An alysis,2003,(35):369-374.
[23]Oliver Wc, Pharr Gm. An improved technique determining hardness and elastic-modulus using load and displacement sensing indentation experiments[J]. JMater Res,1992,7(6):1564-1583.
[24]沈一丁,刘敏,赖小娟,等.水性聚氨酯／纳米Si02杂化材料的制备及性能研究[J].精细化工,2010,27(4)：318-322.
[25]凡永利,郑水蓉,侯锐钢.纳米Si02改性水性聚氨酯乳液的制备及性能研究[J].中国胶粘剂,20117,20(7)：24-27.
[26]郭建,章于川,吴兵.原位聚合法制备纳米二氧化硅／聚氨酯复合树脂[J].应用化学,2011,28(11)：1244-1249.
[27]石智；强,李赛,刘孝波.溶胶-凝胶法制备聚氨酯/二氧化硅杂化材料[J].四川大学学报(工程科学版),2004,36(3)：60-63.
[28]周树学,陈国栋,武利民.丙烯酸酯聚氨酯/Si02纳米复合涂层结构与形态对其耐刮伤性影响研究[J].涂料工业,2006,36(5)：1-4.
[29]王磊,沈一丁.水性聚氨酯/纳米二氧化硅杂化材料的制备及性能[J].高分子材料科学与工程,2011,27(6)：137-141.
[30]张胜文,姜思思,沈利亚.光固化水性聚氨酯/Si02纳米复合乳液的合成和膜性能[J].高分子材料科学与工程,2010,26(11)：9-12.
[31]Hirose M, Zhou J H, Nagai K. The structure and properties of acrylic-polyurethane-hybrid emulsions[J]. Progress in Organic Coatings,2000(38):27-34.
[32]Spinu M, Jackson C, Keating M Y, et a.l. Material design in poly(lactic acid) systems:block copolymers, star homo-and copolymers, and stereocom plexes[J]. Journal of Macromolecular Science, Part A:Pure and Applied Chemistry.1996,33(10):1497-1530.
[33]张武英.环氧硅烷外交联改性水性聚氨酷的研究[J].中国胶粘剂,2006,15(4)：13-16.
[34]Hegedu S C R, Kloiber K A. Aqueous acrylic polyurethane hybrid dispersion and their use in industrial coating[J]. Journal of Coatings Technology, 1996(9):37-43.
[35]Marcia C D, Fernanda, C Ou Tinho M B. Waterborne an ionic polyurethanes and polyols:influence of the chain extender on mechanical and adhesive properties[J]. Polymer Test ing,2000(19):939-945
[36]刘天亮,沈慧芳,吴银萍.环氧树脂对PUA复合乳液的改性研究[J].粘接,2009,25(6)：238-42.
[37]江峰,沈慧芳,陈焕钦.环氧树脂-水性聚氨酯-丙烯酸酯复合乳液的研究[J].粘接,2007,28(1)：20-23.
[38]孙胜霞,钱欣.环氧树脂改性双组份水性聚氨酯的研究[J].轻工机械,2007,25(3)：120-123.
[39]韩文松,李良波,孟平蕊.环氧树脂改性脂肪族水性聚氨酯的合成及其性能[J].聚氨酯工业,2007,22(4)：24-27.
[40]朱延安,张心亚,阎虹.环氧树脂改性水性聚氨酯乳液的制备[J].江苏大学学报自然学科类,2008,29(2)：164-168.
[41]胡巧玲,朱永群,付晏彬.光固化型聚氨酯／环氧树脂IPN的制备与表征[J].高分子材料科学与工程,1999,15(5)：172-175.
[42]黄洪,傅和青,邓艳文.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.
[1]Ramamurthi, S, V. Manohar, and V. V. S. Mani. Characterisation of fatty acid isomers in dehydrated castor oil by gas chromatography and gas chromatography mass spectrometry techniques[J]. Am. Oil Chem. Soc.1998,75(10):1297-1303.
[2]Saxena, P. K., S. R. Srinivasan, J. Hrouz. The effect of castor oil on the structure and properties of polyurethane elastomers [J]. Appl. Polym. Sci.1992,44(8), 1343-1347.
[3]何向东,李国防,郑新,等.磷酸化酯交换蓖麻油加脂剂制备及性能的研究[J].河南科学,2004,22(1)：45-49.
[4]靳东杰,刘治猛.用蓖麻油合成聚氨酯乳液的研究[J].林产化学与工业,2003,23(1)：34-38.
[5]Tran, N. B, J. Vialle, and Q. T. Pham. Castor oil-based polyurethanes.I:Structural characterization of castor oil nature of intact glycerides and distribution of hydroxyl groups[J]. Polymer,1997,38(10):2467-2473.
[6]Lal, K. and V. Carrick. Performance testing of lubricants based on high oleic vegetable oils[J]. Synth. Lubr,1994,11 (3):189-206.
[7]邬润德,朱林华,童筱莉.蓖麻油型聚氨酯/PS同步IPNs的协同效应研究[J]. 聚氨酯工业,2005,20(5)：11-15.
[8]Yunus, R, A. Fakhrul-Razi, T. L. Ooi. Lubrication properties of trimethylolpropane esters based on palm oil and palm kernel oils Eur[J]. Lipid Sci. Technol. 2004,106(1):52-60.
[9]Lligadas G, Ronda JC, Galia M. Synthesis and characterization of polyurethanes from epoxidized methyl oleate based polyether polyols as renewable resources[J] Polym Sci A Polym Chem,2006,44:634-645.
[10]范浩军,石碧.蓖麻油改性聚氨酯皮革涂饰剂的研究[J].精细化工,1996(13)：30-35.
[11]瞿金清,陈焕钦.蓖麻油水性聚氨酯树脂的合成与性能的研究[J].林产化学与工业,2004,24(3)：78-82.
[12]Xu Y, Petrovic Z, Das S. Morphology and properties of thermoplastic polyurethanes with dangling chains in ricinoleate-based soft segments[J]. Polymer,2008,49:4248-4258.
[13]Papadimtrakopoulos F, Sawa E, MacKnight WJ. Investigation of a monotropic liquid crystal polyurethane based on biphenol,2,6-tolylene diisocyanate, and a six methylene containing flexible spacer2, IR spectroscopic phase characterization[J]. Macromolecules,1992,25:4682-4691.
[14]李爱阳,胡波年,胡汉祥.蓖麻油制备醇酸预聚型双组分聚氨酯树脂涂料的研究[J].涂料工业,2006,36(1)：21-23.
[15]Czech P, Okrasa L, Boiteux G, Mechin F, Ulanski J. Polyurethane networks based on hyperbranched polyesters:synthesis and molecular relaxations[J]. Non Cryst Solids,2005,351(33):2735-2741.
[16]Oprea S. Effect of the diisocyanate and chain extenders on the properties of the cross-linked polyetherurethane elastomers [J]. Mater Sci,2008,43(15):5274-5281.
[1]王凌云,杨丽庭,王成双,等.植物油基绿色聚合物的研究进展[J].应用化工,2009,38(5)：724-728.
[2]戴震,李莉,张海龙,等.植物油改性水性聚氨酯的研究现状[JJ.中国涂料,2009,24(2)：16-18.
[3]张胜文,姜思思,沈利亚,等.光固化水性聚氨酯/Si02纳米复合乳液的合成和膜性能[J].高分子材料科学与工程,2010,26(11)：9-12.
[4]Yongshang Lu, Richard C.Larock. Soybean-oil-Based Waterborne Polyurethane Dispe-rsions:Effect of Polyol Functionality and Hard Segment Content on Properties[J]. Bioma cromolecules,2008,(9):3332-3340.
[5]胡国文.蓖麻油和环氧树脂改性水性聚氨酯-丙烯酸酯的合成与表征[J].精细化工,2011,28(8)：1-6.
[6]Sharma V, Kundu P P. Addition polymers from natural oils-A review[J]. Prog Polym Sci,2006,31(11):983-1008.
[7]Zhou Shuxue, Wu Lim in, Sun Jian, et al. The change of the properties of acrylic-based polyurethane via addition of nano-silica[J]. Progress in Organic Coatings,2002(45):33-42.
[8]Kishore K. Jena and K. V. S. N. Raju.Synthes is and characterization of hyperbranched polyurethane-urea/silica based hybrid coatings[J]. Industrial & Engineering Chemistry Research,2007,46(20):6408-6416.
[9]P.Ganga Raju Acharya; Smita Biswala; Sneha Mohapatraa,et al.The Syntheses and Characterization of Interpenetrating Polymer Networks (IPNs) Derived from Cardanol-Based Dye and Linseed Oil-Based Polyurethanes[J]. Polymer-Plastics Technology and Engineering.2010,49(11):1114-1120.
[10]王磊,沈一丁,赖小娟.水性聚氨酯/纳米二氧化硅杂化材料的制备及性能[J].高分子材料科学与工程.2011,27(6)：137-141.
[11]Yongshang Lu, Richard C, Larock. Synthesis and Properties of Grafted Latices from a Soybean Oil-Based Waterborne Polyurethane and Acrylics [J]. Journal of Applied Polymer Science,2011,(119):3305-3312.
[12]李学良,孙炜.蓖麻油改性的水性聚氨酯涂料的制备及其防蚀性能[J].广东化工,2010,37(5)：3-5.
[13]陈为,杨隽,何蕾,等.蓖麻油聚氨酯防水涂料的制备与性能研究[J].涂料工业,2009,39(9)：29-31.
[1]王春艳,朱传方,万婷,等.环氧改性脂肪族水性聚氨酯的合成与性能[J].应用化学,2006,23(04)：441-443.
[2]邓朝霞,叶代勇,魏丹,等.环氧改性水性聚氨酯的合成工艺及性能[J].涂料工业,2007,37(4)：37-40.
[3]王淑艳,曾黎明,赵庆美.聚氨酯-环氧树脂复合材料的研究进展[J].化工生产与技术,2008,15(1)：44-49.
[4]Dong An-jie, An Ying-li, Feng Sh-i you. Preparation and morphology studies o f core-shell type waterborne polyacry late-polyurethanem icrospheres[J]. Journal of Colloid and Interface Science,1999,214(1):118-122.
[5]Danie 1 BO, Sandipan D, P ing Zhang, et a.l. Synthesis and phase separation du ring film forma tion of novel methyl methacry late/n-buty lacry late/methacry lie acid (MMA/BA/MAA) hybridurethane/acry late colloidal dispersions[J]. Polymer, 2004,45(18):6235-6243.
[6]Wang C, Chu F, Gra illat C, et a.l. Hybrid polymer latexes:acrylics-polyurethane from miniemulsion polymerization:properties of hybrid latexes versus blends[J]. Polymer,2005,46(4):1113-1124.
[7]李玉玮,王静媛,粟宜明,等.聚氨酯/环氧树脂互穿网络聚合物阻尼性能的研究[JJ.中国塑料,1990,4(4)：26-30.
[8]Wang Z Y, Han E H, Ke W. In fluence of expandable graphite on fire resistance and water resistance of flame-retardant coatings[J]. Corrosion Science,2007,49 :2237-2253.
[9]Chuen-Sh Ii, Chon, Sheau-Horng, Ch In-Iwang. Preparation and characterization of the intumescent fire retardant coating with a new flam eretardant[J]. Advanced Power Technology,2009,20(4):169-176.