有机硅/聚氨酯改性醇溶性聚丙烯酸酯复膜胶的研究
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摘要
在环保要求日趋严格的今天,对化工产品的环保性能提出了新的挑战,绿色化工、低碳化工是未来的发展趋势。在包装行业也不例外,随着包装行业的发展,复膜胶的需求量也与日俱增。目前,在复膜胶领域中主要有溶剂型胶粘剂和水基胶粘剂两种,但更多的仍使用溶剂型胶粘剂,这主要是因为水基胶粘剂存在表面张力大、固含量低、干燥速度慢、粘接强度不够等尚未得到很好解决的一些问题,而溶剂型胶粘剂多数使用对环境及人体有害的溶剂。为平衡这一矛盾,本文以绿色环保的乙醇为溶剂,合成出了一种环保型胶粘剂,它能够较好的平衡水性胶粘剂与溶剂型胶粘剂的缺点。
本文第一章介绍了醇溶性聚丙烯酸酯及聚氨酯的研究现状以及目前常用的改性方法,指出了各自的优缺点和以后的发展趋势；然后分别介绍了单、双组分复膜胶的研究现状,复膜胶的粘接机理以及影响粘接强度的因素。
本文第二章以丙烯酸乙酯为主要单体,配合以自制的醇溶性单体以及功能性丙烯酸酯单体,合成了醇溶性聚丙烯酸酯胶粘剂,该胶粘剂醇溶性良好,为淡黄色透明的粘稠液体。其后用有机硅进行了改性,并将改性好的胶液涂覆于经电晕处理的薄膜上研究该胶对薄膜的粘接性能,初步探讨了影响粘接性能的因素,实验测定了单体的转化率、胶膜的吸水率,并用DSC、TG、SEM对胶膜的其它性能进行了表征。结果表明,有机硅的加入降低了单体的转化率、增加了胶膜的吸水率、一定程度上降低了聚合物的玻璃化转变温度、提高了聚合物的耐热性,并最终提高了胶粘剂对塑料薄膜的粘接性能。扫描电镜表明,有机硅的过量加入不是成比例的提高胶粘剂的粘接性能,而是降低了粘接性能。
本文第三章用聚氨酯对醇溶性聚丙烯酸酯复膜胶进行了改性,实验合成了-种单组分聚丙烯酸酯-聚氨酯复膜胶。本章通过一种较新颖的设计思路,合成了一种梳状结构的聚合物,解决了常规接枝共聚中聚氨酯的加入量极为有限的问题。该胶粘剂既具有刚性的聚丙烯酸酯主链又具有柔性的聚氨酯侧链,能更好的提高胶粘剂的粘接性能。具体方法是用聚醚多元醇和异氰酸酯合成出聚氨酯预聚体,然后用含双键的丙烯酸酯单体进行封端,通过控制加入量得到单双键封端的聚氨酯预聚体,再将其与丙烯酸酯单体在乙醇中共聚,最终得到梳状结构的聚合物。实验用核磁、红外表征了聚氨酯预聚体的结构；红外分峰表明,聚氨酯的加入增强了聚氨酯与聚丙烯酸酯间的氢键相互作用,这对提高二者的相容性起到了一定的作用；热分析表明,聚氨酯的加入降低了聚合物的玻璃化转变温度,提高了聚合物在低温区域的耐热性；T型剥离强度表明,聚氨酯的加入在一定程度上提高了胶粘剂的剥离强度。
本文第四章合成了一种双组分聚丙烯酸酯-聚氨酯胶粘剂。首先合成了含环氧功能基团的醇溶性聚丙烯酸酯,将它作为双组分胶粘剂中的主剂；然后合成出氨基封端的聚醚型聚氨酯作为固化剂,通过调节二者的比例来得到满足不同要求的胶粘剂。实验用核磁、红外表征了主剂与固化剂的结构,研究了主剂、固化剂的不同配比对胶粘剂力学性能、耐水、耐热性以及粘接性能的影响。结果表明,该胶粘剂的力学性能、粘接强度、耐热性等性能不仅与固化剂的比例有关还与所加的聚氨酯的结构有关。此外,该胶粘剂成膜性好,固化后不收缩,粘接性能优异,是理想的双组分胶粘剂。
With the development of the environmental protection rules, chemical industry also full of challenges. Green and low carbon chemical industry will become the developing trend. Consequently, the packing industry is also included. With the big market demanding of the packing industry, the laminating adhesives also developed rapidly. Though the water-based laminating adhesive was exist at present, the solvent-based adhesive remain widely used because of its excellent properties comparing with the disadvantages which the water-based adhesive have, such as high surface tension, low solid content, low drying speed and so on. So the problem that most of solvents are bad to the health and environment is not solved. To the solution, this paper has got a kind of environmental friendly adhesive which was synthesize in alcohol solvent. It can keep the balance between water-based adhesives and solvent-based adhesives.
At the beginning of the paper, current research situation and modification methods of alcohol soluble polyacrylate and polyurethane were reviewed, and the developing trend was also discussed. Then the adhesion mechanism and influence factors of adhesion strength of the laminating adhesive were introduced.
In the second chapter, a kind of well alcohol soluble, transparent, yellow and viscidity solution was get from ethyl acrylate as a main alcohol soluble monomer, functional acrylate and self-synthesized monomer by free radical polymerization. This adhesive was cast on the plastic film to testing the adhesion properties after modified by siloxane. The influence factors of adhesion were roughly researched. The overall conversion rate, water absorption rate were tested. Other properties were also conferred by DSC, TG and SEM. The result shows that the incorporation of siloxane lowered the overall conversion rate of monomer, water resistance and the Tg of polymer, but improved heat resistance and adhesion strength. SEM shows that when the siloxane content surpassed a proper amount, the improving of adhesion strength was not ratio with the contents of siloxane but decreasing when the contents of siloxane surpass a proper amount.
In the third chapter, one-pot polyacrylate-polyurethane adhesives were also got. For the one-pot adhesive, a new designed method was used to getting a comb liked structure. Here, single double carbon bond blocked polyurethane pre-polymer was got firstly, then, it was used to copolymerize with the acrylate monomers. At last, we get the comb liked copolymers. The contents of the polyurethane were improved greatly comparing with the multi double carbon bond blocked polyurethane. This adhesive has a rigidity polyacrylate main chain and a soft polyurethane side chain which can improve the adhesion strength dramatically. In this experiment, the structure of polyurethane pre-polymer was confirmed by HMR, and the peak decomposition of IR shows that the incorporation of polyurethane can improve the hydrogen bond interaction between polyurethane and polyacrylate. Thermal analysis indicated that the Tg of the polymer was lowered, heat resistance and T peel off strength were improved due to the introducing of polyurethane.
In the fourth chapter, two-pot polyacrylate-polyurethane adhesive was got in the following method. The main agent of alcohol soluble polyacrylate with epoxy group was got firstly. Then the polyurethane with ethyl ammine blocked was got as the curing agent. Different kinds of adhesives were got by adjusting the ratio of the two components. NMR and IR were used to confirming the structure of the main agent and curing agent. Influence of different ratio of main agent and curing agent on the mechanical properties, water absorption rate, heat resistance and adhesion strength was researched. The result shows that these properties were not only related with the ratio between main agent and curing agent, but also related with the structure of the polyurethane. Besides these, the adhesive has good film formation properties, and not shrinks during the curing process.
本文第一章介绍了醇溶性聚丙烯酸酯及聚氨酯的研究现状以及目前常用的改性方法,指出了各自的优缺点和以后的发展趋势；然后分别介绍了单、双组分复膜胶的研究现状,复膜胶的粘接机理以及影响粘接强度的因素。
本文第二章以丙烯酸乙酯为主要单体,配合以自制的醇溶性单体以及功能性丙烯酸酯单体,合成了醇溶性聚丙烯酸酯胶粘剂,该胶粘剂醇溶性良好,为淡黄色透明的粘稠液体。其后用有机硅进行了改性,并将改性好的胶液涂覆于经电晕处理的薄膜上研究该胶对薄膜的粘接性能,初步探讨了影响粘接性能的因素,实验测定了单体的转化率、胶膜的吸水率,并用DSC、TG、SEM对胶膜的其它性能进行了表征。结果表明,有机硅的加入降低了单体的转化率、增加了胶膜的吸水率、一定程度上降低了聚合物的玻璃化转变温度、提高了聚合物的耐热性,并最终提高了胶粘剂对塑料薄膜的粘接性能。扫描电镜表明,有机硅的过量加入不是成比例的提高胶粘剂的粘接性能,而是降低了粘接性能。
本文第三章用聚氨酯对醇溶性聚丙烯酸酯复膜胶进行了改性,实验合成了-种单组分聚丙烯酸酯-聚氨酯复膜胶。本章通过一种较新颖的设计思路,合成了一种梳状结构的聚合物,解决了常规接枝共聚中聚氨酯的加入量极为有限的问题。该胶粘剂既具有刚性的聚丙烯酸酯主链又具有柔性的聚氨酯侧链,能更好的提高胶粘剂的粘接性能。具体方法是用聚醚多元醇和异氰酸酯合成出聚氨酯预聚体,然后用含双键的丙烯酸酯单体进行封端,通过控制加入量得到单双键封端的聚氨酯预聚体,再将其与丙烯酸酯单体在乙醇中共聚,最终得到梳状结构的聚合物。实验用核磁、红外表征了聚氨酯预聚体的结构；红外分峰表明,聚氨酯的加入增强了聚氨酯与聚丙烯酸酯间的氢键相互作用,这对提高二者的相容性起到了一定的作用；热分析表明,聚氨酯的加入降低了聚合物的玻璃化转变温度,提高了聚合物在低温区域的耐热性；T型剥离强度表明,聚氨酯的加入在一定程度上提高了胶粘剂的剥离强度。
本文第四章合成了一种双组分聚丙烯酸酯-聚氨酯胶粘剂。首先合成了含环氧功能基团的醇溶性聚丙烯酸酯,将它作为双组分胶粘剂中的主剂；然后合成出氨基封端的聚醚型聚氨酯作为固化剂,通过调节二者的比例来得到满足不同要求的胶粘剂。实验用核磁、红外表征了主剂与固化剂的结构,研究了主剂、固化剂的不同配比对胶粘剂力学性能、耐水、耐热性以及粘接性能的影响。结果表明,该胶粘剂的力学性能、粘接强度、耐热性等性能不仅与固化剂的比例有关还与所加的聚氨酯的结构有关。此外,该胶粘剂成膜性好,固化后不收缩,粘接性能优异,是理想的双组分胶粘剂。
With the development of the environmental protection rules, chemical industry also full of challenges. Green and low carbon chemical industry will become the developing trend. Consequently, the packing industry is also included. With the big market demanding of the packing industry, the laminating adhesives also developed rapidly. Though the water-based laminating adhesive was exist at present, the solvent-based adhesive remain widely used because of its excellent properties comparing with the disadvantages which the water-based adhesive have, such as high surface tension, low solid content, low drying speed and so on. So the problem that most of solvents are bad to the health and environment is not solved. To the solution, this paper has got a kind of environmental friendly adhesive which was synthesize in alcohol solvent. It can keep the balance between water-based adhesives and solvent-based adhesives.
At the beginning of the paper, current research situation and modification methods of alcohol soluble polyacrylate and polyurethane were reviewed, and the developing trend was also discussed. Then the adhesion mechanism and influence factors of adhesion strength of the laminating adhesive were introduced.
In the second chapter, a kind of well alcohol soluble, transparent, yellow and viscidity solution was get from ethyl acrylate as a main alcohol soluble monomer, functional acrylate and self-synthesized monomer by free radical polymerization. This adhesive was cast on the plastic film to testing the adhesion properties after modified by siloxane. The influence factors of adhesion were roughly researched. The overall conversion rate, water absorption rate were tested. Other properties were also conferred by DSC, TG and SEM. The result shows that the incorporation of siloxane lowered the overall conversion rate of monomer, water resistance and the Tg of polymer, but improved heat resistance and adhesion strength. SEM shows that when the siloxane content surpassed a proper amount, the improving of adhesion strength was not ratio with the contents of siloxane but decreasing when the contents of siloxane surpass a proper amount.
In the third chapter, one-pot polyacrylate-polyurethane adhesives were also got. For the one-pot adhesive, a new designed method was used to getting a comb liked structure. Here, single double carbon bond blocked polyurethane pre-polymer was got firstly, then, it was used to copolymerize with the acrylate monomers. At last, we get the comb liked copolymers. The contents of the polyurethane were improved greatly comparing with the multi double carbon bond blocked polyurethane. This adhesive has a rigidity polyacrylate main chain and a soft polyurethane side chain which can improve the adhesion strength dramatically. In this experiment, the structure of polyurethane pre-polymer was confirmed by HMR, and the peak decomposition of IR shows that the incorporation of polyurethane can improve the hydrogen bond interaction between polyurethane and polyacrylate. Thermal analysis indicated that the Tg of the polymer was lowered, heat resistance and T peel off strength were improved due to the introducing of polyurethane.
In the fourth chapter, two-pot polyacrylate-polyurethane adhesive was got in the following method. The main agent of alcohol soluble polyacrylate with epoxy group was got firstly. Then the polyurethane with ethyl ammine blocked was got as the curing agent. Different kinds of adhesives were got by adjusting the ratio of the two components. NMR and IR were used to confirming the structure of the main agent and curing agent. Influence of different ratio of main agent and curing agent on the mechanical properties, water absorption rate, heat resistance and adhesion strength was researched. The result shows that these properties were not only related with the ratio between main agent and curing agent, but also related with the structure of the polyurethane. Besides these, the adhesive has good film formation properties, and not shrinks during the curing process.
引文
[1]熊林,王建营,延玺.丙烯酸酯胶粘剂研究进展[J].中国胶粘剂,2001,11(3) ： 47-53.
[2]大森英三.功能性丙烯酸树脂[M].北京：化学工业出版社,1993,3.
[3]周雍鑫,周俊等.胶粘剂粘接技术实用问答[M].北京：机械工业出版社.1998,78-81.
[4]邹文俊.一种醇溶性树酯的制备方法[P].CN1737021：2006-2-22.
[5]农兰平,唐国成.鞋材用聚丙烯酸酯乳液及其醇溶性港宝的研制[J].塑料工业,2005,33(5)62-65.
[6]刘旭,谢顶杉,吴佳等.新型醇溶性干式复合胶[J].化学工程师,2008,(5)：11-13.
[7]徐艳,孙燕,孟跃中.三元丙烯酸酯共聚物的合成及醇溶性复膜胶的研制[J].粘接,1998, (1)：7-11.
[8]王金山,秦宏伟,段洪东等.高性能醇溶性复膜胶的研制[J].青岛科技大学学报,2003,24(4)：347-351.
[9]倪丽琴.醇溶性纸塑复膜胶的研制[J].橡塑资源利用,2007(5)：3-7.
[10]周艳,张永强,丁正学等.醇溶性纸品上光涂料的研制[J].胶体与聚合物,2004,23(4)：21-22.
[11]阚成友,孔祥正,袁青.有机硅改性丙烯酸酯聚合物研究进展[J].高分子材料科学与工程,2000,26(4)：1-4.
[12]龚兴宇,范晓东.有机硅-丙烯酸酯共聚复合乳液的结构、形态及性能[J].高分子材料科学与工程,2004,20, (2)：140-144.
[13]柯跃虎,文秀芳,杨卓如.有机硅-丙烯酸酯共聚乳液的合成研究[J].涂料工业,2004,34(5)：32-36.
[14]刘敬芹,张力,朱志博.有机硅改性丙烯酸酯乳液的合成[J].应用化学,2002,19(6)：569-573.
[15]徐瑞芬,佘广为.原位聚合法制备纳米TiO2/有机硅改性丙烯酸酯复合乳液[J].有机硅材料,2003,17(6)：11-14.
[16]毛淑才,沈慧芳,瞿金清.聚四氟乙烯改性聚丙烯酸酯乳液的制备与表征[J].现代化工,2004,24(4)：31-34.
[17]邱俊英,程艳玲,郭小丽等.有机氟硅改性丙烯酸酯共聚物乳液的研究涂料工业,38(8)：37-39.
[18]杨卫疆,王镛先.环氧树脂-丙烯酸酯IPN材料的合成与表征[J].高分子材料科学与工程,1998,14(1)：24-27.
[19]张洁,瞿金清,张心亚等.环氧改性苯丙乳液的合成及性能[J].涂料技术与文摘年,25,(2)：24-29.
[20]周其华.醇溶性聚氨酯胶粘剂的开发与应用[J].中国包装报,2003-04-07.
[21]付勇.醇溶性聚氨酯双组分粘合剂及其制备工艺[P]CN1970672：2007-5-30.
[22]王鑫,戴震,许体文等.醇溶性聚氨酯胶粘剂的合成与性能研究[J].中国胶粘剂,2008,17(1)：20-23.
[23]王士财,李丙霞,楼涛等.丙烯酸乙酯改性水性聚氨酯涂料的研制[J].聚氨酯工业,2007,22(4)：38-41.
[24]侯孟华,刘伟区,陈精华等.氨基硅油改性水性聚氨酯涂料的研究[J].化学建材,2004,(3)：23-26.
[25]Wan-Chao Jiang, Yangen Huang, Guo-tuan Gu, et al. A novel waterborne polyurethane containing short fluoroalkyl chains:Synthesis、 characterization and its application on cotton fabrics surface[J]. Applied Surface Science,2006, (253): 2304-2309.
[26]H. Pan, D. Chen. Preparation and characterization of waterborne polyurethane/ attapulgite nanocomposites[J]. European Polymer Journal,2007, (43):3766-3772.
[27]Nair P D, Jayabalam M, Krishramurthy V N. Polyurethane-polyacrylamide IPNs. I. synthesis and characterization[J]. J Polym Sci Part A:Polym Chem,1990,28 (13):3775-3786.
[28]Yu Shu-Huei, Mi Fwu-Long, Shyu Shin-Shing, et al. Miscibility, mechanical characteristic and platelet adhesion of 6-O-carboxymethylchitosan/polyurethane semi-IPN membranes [J]. Journal of Membrane Science,2006,276 (1-2):68-80
[29]崔锦峰,杨保平,张应鹏等.自交联型水性聚氨酯涂料的研制[J].兰州理工大学学报,2005,31(3)：72-75.
[30]张武英.环氧硅烷外交联改性水性聚氨酯的研究[J].中国胶粘剂,2006,15(4)：13-16.
[31]李克友,耿克斌,朱弼忠.种子乳液共聚合聚氨酯-聚丙烯酸酯胶乳粒子的“反相核-壳”结构[J].合成橡胶工业,1998,21(3)：158-160.
[32]Hirose M, Kadowak. The Structure and properties of core-shell type acrylic-polyurethanehybrid aqueous emulsions[J]. Progress in Organic Coatings, 1997,31 (1-2):157-169.
[33]Zanetti-Ramos B, Lemos-Senna E, Soldi V, et al. Polyurethane nanoparticles from a natural polyol via Minni-emulsion technique[J]. Polymer,2006,47 (24): 8080-8087.
[34]杨建军,吴庆云,张建安等.水性聚氨酯-含硅丙烯酸酯织物涂层胶的辐射聚合及其性能研究[J].涂料工业,2006,6(36)：15-19.
[35]华明扬.汽车、鞋用水性聚氨酯硅氧烷透气涂层胶的制备方法：CN101186798[P].2008-5-28
[36]Kohjiya S, Ikeda Y, Takesako S ea al. Drug release behavior from polyurethane gel[J]. Reactive Polymers,1991, (15):165-175.
[37]Lai Y C, Baccei L J.Novel polyurethane hydrogels for biomedical applications[J] Journal of Applied Polymer Science,1991,42(12):3173-3179.
[38]Petrini P, Fare S, Piva A, et al.Design synthesis and properties of polyurethane hydrogels for tissue engineering[J].Journal of Materials Science:Materials in Medicine.2003(14):683-686.
[39]Landrock, Arthur H. Adhesives Technology Handbook[M]. Park Ridge:Noyes Publications,1985,4.
[40]向明,蔡燎原,张季冰.胶粘剂基础与配方设计[M].北京：化学工业出版社,2002,17.
[41]Mgaya Alexander P, Ramalingam Balasubramaniam. Adhesive useful for film laminating applications[P]WO2007047513,2007-04-26.
[42]邹友思,许锐,蒋卓君等.一种双组分醇溶性聚氨酯复膜胶的制备方法[P]CN101407709：2009-4-15.
[43]王齐,傅和青.双组分水性丙烯酸酯复膜胶的研究[J].粘接,2009,2(30)：39-42.
[44]Voss Peter A, Rolando Thomas E. Aqueous laminating adhesive composition and a method of using thereof [P]US6235384,2001-05-22.
[45]梁文庆,唐宏科,孙夏.丙烯酸酯类乳液型纸塑复膜胶的研究进展[J].胶体与聚合物,2009,27(2)：44-47.
[1]刘旭,谢顶杉,钟本和等.环氧改性醇溶性丙烯酸酯干式复膜胶的研制[J]中国胶粘剂,2008,17(6)：34-36.
[2]付勇.醇溶性聚氨酯双组分粘合剂及其制备工艺[P]CN1970672：2007-5-30.
[3]邹文俊.一种醇溶性树酯的制备方法[P].CN1737021：2006-2-22.
[4]Sonnenschein M. F., Webb S. P., Wendt B. L. Poly(acrylate/siloxane) hybrid adhesives for polymers with low surface energy. International Journal of Adhesion & Adhesives,2008,28 (3):126-134.
[5]Vitry S., Mezzino A., Gauthier C. et al. Hybrid copolymer latexes cross-linked with methacryloxy propyl trimethoxy silane. Film formation and mechanical properties[J]. C R Chimie,2003,6(11):1285-1293.
[6]Horgnies M., Darque-Ceretti E., Combarieu R.. Adhesion of pressure sensitive adhesives to automotive coatings:influence of topcoat composition[J]. J Adhes Sci Technol,2004,18 (9):1047-1061.
[7]Esfandeh M., Mirabedini S.M., Pazokifard S., Tari M.. Study of silicone coating adhesion to an epoxy undercoat using silane compounds Effect of silane type and application method[J]. Colloids and Surfaces A:Physicochem. Eng. Aspects,2007, 302(1):11-16.
[1]Maandi, Eerik. Bonding system having adherence to low energy surfaces[P]. US6632908,2002-3-12.
[2]Sonnenschein M F, Webb S. P, Kastl P E et al. Mechanism of Trialkylborane Promoted Adhesion to Low Surface Energy Plastics[J].Macromolecules,2004,37 (21):7974-7978.
[3]Sonnenschein M F, Webb S P, Kastl P E et al. Poly(acrylate/siloxane) hybrid adhesives for polymers with low surface energy[J]International Journal of Adhesion & Adhesives,2008,28(3),126-134.
[4]Esfandeh M, Mirabedini S M, Pazokifard S et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects[J] 2007,302(1-3):11-16.
[5]Wang Chunpeng, Chu Fuxiang, Jin Liwei. Polyurethane-acrylate hybrid latexes from miniemulsion polymerization:effect of end groups on structure and properties[J].Polymers for Advanced Technologies,2009,20(3):319-326.
[6]Huybrechts J, Bruylants P, Vaes A et al. Surfactant-free emulsions for waterborne, two-component polyurethane coatings[J].Progress in Organic Coatings,2000,38, (2): 67-77.
[7]付勇.醇溶性聚氨酯双组分粘合剂及其制备工艺[P]CN1970672：2007-5-30.
[8]邹文俊.一种醇溶性树酯的制备方法[P].CN1737021：2006-2-22.
[9]Baron A, Cloutet E, Cramail H et al. Relationship between Architecture and Adhesive Properties of Macromolecular Materials[J]. Macromolecular Chemistry and Physics, 2003,204(13):1616-1620.
[10]Baron A, Rodriguez-Hernandez J, Papon E. Relationship Between Architecture and Adhesion in Polyurethane-Based Copolymers[J].Macromolecular Chemistry and Physics,2005,206(23):2381-2389.
[11]陈洪亮,陈红艳.醇溶性聚氨酯胶粘剂几大优点[J].中国包装报,2003-3-24.
[12]Sebenik U, Krajnc M. Semibatch emulsion polymerization of methyl methacrylate using different polyurethane particles[J]. Journal of Polymer Science Part B:Polymer Physics,2005,43(4):844-858.
[13]Athawale V D, Kulkarni M A. Preparation and properties of urethane/acrylate composite by emulsion polymerization technique[J].Progress in Organic Coatings, 2009,65(3):392-400.
[14]Wu Limin, You Bo, Li Dan. Synthesis and characterization of urethane/acrylate composite latex [J] Journal of Applied Polymer Science,2002,84(8):1620-1628.
[15]Subramani S, Cheong I W, Kim J H. Chain extension studies of water-borne polyurethanes from methyl ethyl ketoxime/caprolactam-blocked aromatic isocyanates[J]. Progress in Organic Coatings,2004:328-338.
[16]David D J, Stanley H E. Wiley-Interscience, New York,1969.
[17]Reddy, G. V. R.; Devi, N. G.; Panda, J. J Appl Polym Sci 2007,105,3391-3402.
[18]Xu G, Shi W F. Synthesis and characterization of hyperbranched polyurethane acrylates used as UV curable oligomers for coatings[J].Progress in Organic Coatings 2005,52(2):110-117.
[19]Amelie Baron, Juan Rodriguez-Hernandez, Eric Papon. Relationship Between Architecture and Adhesion in Polyurethane-Based Copolymers [J]. Macro-molecular Chemistry and Physics,2005,206(23):2381-2389.
[20]Hu Y S,Tao Y, Hu C P. Polyurethaneurea/Vinyl Polymer Hybrid Aqueous Dispersions Based on Renewable Material[J]. Biomacromolecules,2001,2 (1):80-84.
[21]Wen Ten-Chin, Wang Yeong-Jyh, Tsung-Tien Cheng et al.The effect of DMPA units on ionic conductivity of PEG-DMPA-IPDI waterborne polyurethane as single-ion electrolytes[J]. Polymer,1999,40 (14):3979-3988.
[22]Wen Ten-Chin, Wu Ming-Sieng. Spectroscopic Investigations of Poly (oxy-propylene) glycol-Based Waterborne Polyurethane Doped with Lithium Perchlorate[J]. Macromolecules,1999,32(8):2712-2720.
[23]Macros-Fernandez A, Lozano A E, Gonzalez L,Hydrogen Bonding in Copoly(ether-urea)s and Its Relationship with the Physical Properties. Macromolecules,1997,30 (12):3584-3592.
[24]Zhang Hongtao, Huang He, Cao Jianhua. Concentrated Emulsion Copoly-merization of a-DoubleBond-Containing Polyurethane/Styrene Initiated by Redox System[J]. Journal of Applied Polymer Science,2004,94, (l,):1-8.
[25]Kukanja D, Golob J, Zupancic-Valant A et al. The structure and properties of acrylic-polyurethane hybrid emulsions and comparison with physical blends[J].2000, 78(1):67-80.
[1]Chai Shuling, Tan Huimin. Structure and Property Characterization of Nanograde Core-shell Polyurethane/Polyacrylate Composite Emulsion[J].Journal of Applied Polymer Science,2008,107(6):3499-3504.
[2]Rharbi Y, Yekta A, Mitchell A. Winnik. Energy Transfer Studies of Interpenetrating Polymer Networks Characterizing the Interface in Polyacrylate-Polyurethane IPNs[J].Macromolecules,1999,32(10),3241-3248.
[3]Chai Shuling, Martin Ming Jin. Morphology and Particle Size of Nanograde Polyurethane/Polyacrylate Hybrid Emulsions[J].Journal of Applied Polymer Science,2009,114, (4):2030-2035.
[4]Jie Yang, Mitchell A. Winnik. Polyurethane-Polyacrylate Interpenetrating Networks Morphology Studies by Direct Nonradiative Energy Transfer Experiments[J]. Macromolecules 1996,29(22),7055-7063.
[5]Tien; Mao Chao-Fong, Snyder Chung-Ling, et al. Low temperature self-crosslinking aqueous urethane-vinyl polymers for coating applications US5521246,1996-5-28.
[6]冯海波,卿宁核壳交联结构水性聚氨酯的合成研究皮革化工,2005,22(1)：21-25.
[2]大森英三.功能性丙烯酸树脂[M].北京：化学工业出版社,1993,3.
[3]周雍鑫,周俊等.胶粘剂粘接技术实用问答[M].北京：机械工业出版社.1998,78-81.
[4]邹文俊.一种醇溶性树酯的制备方法[P].CN1737021：2006-2-22.
[5]农兰平,唐国成.鞋材用聚丙烯酸酯乳液及其醇溶性港宝的研制[J].塑料工业,2005,33(5)62-65.
[6]刘旭,谢顶杉,吴佳等.新型醇溶性干式复合胶[J].化学工程师,2008,(5)：11-13.
[7]徐艳,孙燕,孟跃中.三元丙烯酸酯共聚物的合成及醇溶性复膜胶的研制[J].粘接,1998, (1)：7-11.
[8]王金山,秦宏伟,段洪东等.高性能醇溶性复膜胶的研制[J].青岛科技大学学报,2003,24(4)：347-351.
[9]倪丽琴.醇溶性纸塑复膜胶的研制[J].橡塑资源利用,2007(5)：3-7.
[10]周艳,张永强,丁正学等.醇溶性纸品上光涂料的研制[J].胶体与聚合物,2004,23(4)：21-22.
[11]阚成友,孔祥正,袁青.有机硅改性丙烯酸酯聚合物研究进展[J].高分子材料科学与工程,2000,26(4)：1-4.
[12]龚兴宇,范晓东.有机硅-丙烯酸酯共聚复合乳液的结构、形态及性能[J].高分子材料科学与工程,2004,20, (2)：140-144.
[13]柯跃虎,文秀芳,杨卓如.有机硅-丙烯酸酯共聚乳液的合成研究[J].涂料工业,2004,34(5)：32-36.
[14]刘敬芹,张力,朱志博.有机硅改性丙烯酸酯乳液的合成[J].应用化学,2002,19(6)：569-573.
[15]徐瑞芬,佘广为.原位聚合法制备纳米TiO2/有机硅改性丙烯酸酯复合乳液[J].有机硅材料,2003,17(6)：11-14.
[16]毛淑才,沈慧芳,瞿金清.聚四氟乙烯改性聚丙烯酸酯乳液的制备与表征[J].现代化工,2004,24(4)：31-34.
[17]邱俊英,程艳玲,郭小丽等.有机氟硅改性丙烯酸酯共聚物乳液的研究涂料工业,38(8)：37-39.
[18]杨卫疆,王镛先.环氧树脂-丙烯酸酯IPN材料的合成与表征[J].高分子材料科学与工程,1998,14(1)：24-27.
[19]张洁,瞿金清,张心亚等.环氧改性苯丙乳液的合成及性能[J].涂料技术与文摘年,25,(2)：24-29.
[20]周其华.醇溶性聚氨酯胶粘剂的开发与应用[J].中国包装报,2003-04-07.
[21]付勇.醇溶性聚氨酯双组分粘合剂及其制备工艺[P]CN1970672：2007-5-30.
[22]王鑫,戴震,许体文等.醇溶性聚氨酯胶粘剂的合成与性能研究[J].中国胶粘剂,2008,17(1)：20-23.
[23]王士财,李丙霞,楼涛等.丙烯酸乙酯改性水性聚氨酯涂料的研制[J].聚氨酯工业,2007,22(4)：38-41.
[24]侯孟华,刘伟区,陈精华等.氨基硅油改性水性聚氨酯涂料的研究[J].化学建材,2004,(3)：23-26.
[25]Wan-Chao Jiang, Yangen Huang, Guo-tuan Gu, et al. A novel waterborne polyurethane containing short fluoroalkyl chains:Synthesis、 characterization and its application on cotton fabrics surface[J]. Applied Surface Science,2006, (253): 2304-2309.
[26]H. Pan, D. Chen. Preparation and characterization of waterborne polyurethane/ attapulgite nanocomposites[J]. European Polymer Journal,2007, (43):3766-3772.
[27]Nair P D, Jayabalam M, Krishramurthy V N. Polyurethane-polyacrylamide IPNs. I. synthesis and characterization[J]. J Polym Sci Part A:Polym Chem,1990,28 (13):3775-3786.
[28]Yu Shu-Huei, Mi Fwu-Long, Shyu Shin-Shing, et al. Miscibility, mechanical characteristic and platelet adhesion of 6-O-carboxymethylchitosan/polyurethane semi-IPN membranes [J]. Journal of Membrane Science,2006,276 (1-2):68-80
[29]崔锦峰,杨保平,张应鹏等.自交联型水性聚氨酯涂料的研制[J].兰州理工大学学报,2005,31(3)：72-75.
[30]张武英.环氧硅烷外交联改性水性聚氨酯的研究[J].中国胶粘剂,2006,15(4)：13-16.
[31]李克友,耿克斌,朱弼忠.种子乳液共聚合聚氨酯-聚丙烯酸酯胶乳粒子的“反相核-壳”结构[J].合成橡胶工业,1998,21(3)：158-160.
[32]Hirose M, Kadowak. The Structure and properties of core-shell type acrylic-polyurethanehybrid aqueous emulsions[J]. Progress in Organic Coatings, 1997,31 (1-2):157-169.
[33]Zanetti-Ramos B, Lemos-Senna E, Soldi V, et al. Polyurethane nanoparticles from a natural polyol via Minni-emulsion technique[J]. Polymer,2006,47 (24): 8080-8087.
[34]杨建军,吴庆云,张建安等.水性聚氨酯-含硅丙烯酸酯织物涂层胶的辐射聚合及其性能研究[J].涂料工业,2006,6(36)：15-19.
[35]华明扬.汽车、鞋用水性聚氨酯硅氧烷透气涂层胶的制备方法：CN101186798[P].2008-5-28
[36]Kohjiya S, Ikeda Y, Takesako S ea al. Drug release behavior from polyurethane gel[J]. Reactive Polymers,1991, (15):165-175.
[37]Lai Y C, Baccei L J.Novel polyurethane hydrogels for biomedical applications[J] Journal of Applied Polymer Science,1991,42(12):3173-3179.
[38]Petrini P, Fare S, Piva A, et al.Design synthesis and properties of polyurethane hydrogels for tissue engineering[J].Journal of Materials Science:Materials in Medicine.2003(14):683-686.
[39]Landrock, Arthur H. Adhesives Technology Handbook[M]. Park Ridge:Noyes Publications,1985,4.
[40]向明,蔡燎原,张季冰.胶粘剂基础与配方设计[M].北京：化学工业出版社,2002,17.
[41]Mgaya Alexander P, Ramalingam Balasubramaniam. Adhesive useful for film laminating applications[P]WO2007047513,2007-04-26.
[42]邹友思,许锐,蒋卓君等.一种双组分醇溶性聚氨酯复膜胶的制备方法[P]CN101407709：2009-4-15.
[43]王齐,傅和青.双组分水性丙烯酸酯复膜胶的研究[J].粘接,2009,2(30)：39-42.
[44]Voss Peter A, Rolando Thomas E. Aqueous laminating adhesive composition and a method of using thereof [P]US6235384,2001-05-22.
[45]梁文庆,唐宏科,孙夏.丙烯酸酯类乳液型纸塑复膜胶的研究进展[J].胶体与聚合物,2009,27(2)：44-47.
[1]刘旭,谢顶杉,钟本和等.环氧改性醇溶性丙烯酸酯干式复膜胶的研制[J]中国胶粘剂,2008,17(6)：34-36.
[2]付勇.醇溶性聚氨酯双组分粘合剂及其制备工艺[P]CN1970672：2007-5-30.
[3]邹文俊.一种醇溶性树酯的制备方法[P].CN1737021：2006-2-22.
[4]Sonnenschein M. F., Webb S. P., Wendt B. L. Poly(acrylate/siloxane) hybrid adhesives for polymers with low surface energy. International Journal of Adhesion & Adhesives,2008,28 (3):126-134.
[5]Vitry S., Mezzino A., Gauthier C. et al. Hybrid copolymer latexes cross-linked with methacryloxy propyl trimethoxy silane. Film formation and mechanical properties[J]. C R Chimie,2003,6(11):1285-1293.
[6]Horgnies M., Darque-Ceretti E., Combarieu R.. Adhesion of pressure sensitive adhesives to automotive coatings:influence of topcoat composition[J]. J Adhes Sci Technol,2004,18 (9):1047-1061.
[7]Esfandeh M., Mirabedini S.M., Pazokifard S., Tari M.. Study of silicone coating adhesion to an epoxy undercoat using silane compounds Effect of silane type and application method[J]. Colloids and Surfaces A:Physicochem. Eng. Aspects,2007, 302(1):11-16.
[1]Maandi, Eerik. Bonding system having adherence to low energy surfaces[P]. US6632908,2002-3-12.
[2]Sonnenschein M F, Webb S. P, Kastl P E et al. Mechanism of Trialkylborane Promoted Adhesion to Low Surface Energy Plastics[J].Macromolecules,2004,37 (21):7974-7978.
[3]Sonnenschein M F, Webb S P, Kastl P E et al. Poly(acrylate/siloxane) hybrid adhesives for polymers with low surface energy[J]International Journal of Adhesion & Adhesives,2008,28(3),126-134.
[4]Esfandeh M, Mirabedini S M, Pazokifard S et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects[J] 2007,302(1-3):11-16.
[5]Wang Chunpeng, Chu Fuxiang, Jin Liwei. Polyurethane-acrylate hybrid latexes from miniemulsion polymerization:effect of end groups on structure and properties[J].Polymers for Advanced Technologies,2009,20(3):319-326.
[6]Huybrechts J, Bruylants P, Vaes A et al. Surfactant-free emulsions for waterborne, two-component polyurethane coatings[J].Progress in Organic Coatings,2000,38, (2): 67-77.
[7]付勇.醇溶性聚氨酯双组分粘合剂及其制备工艺[P]CN1970672：2007-5-30.
[8]邹文俊.一种醇溶性树酯的制备方法[P].CN1737021：2006-2-22.
[9]Baron A, Cloutet E, Cramail H et al. Relationship between Architecture and Adhesive Properties of Macromolecular Materials[J]. Macromolecular Chemistry and Physics, 2003,204(13):1616-1620.
[10]Baron A, Rodriguez-Hernandez J, Papon E. Relationship Between Architecture and Adhesion in Polyurethane-Based Copolymers[J].Macromolecular Chemistry and Physics,2005,206(23):2381-2389.
[11]陈洪亮,陈红艳.醇溶性聚氨酯胶粘剂几大优点[J].中国包装报,2003-3-24.
[12]Sebenik U, Krajnc M. Semibatch emulsion polymerization of methyl methacrylate using different polyurethane particles[J]. Journal of Polymer Science Part B:Polymer Physics,2005,43(4):844-858.
[13]Athawale V D, Kulkarni M A. Preparation and properties of urethane/acrylate composite by emulsion polymerization technique[J].Progress in Organic Coatings, 2009,65(3):392-400.
[14]Wu Limin, You Bo, Li Dan. Synthesis and characterization of urethane/acrylate composite latex [J] Journal of Applied Polymer Science,2002,84(8):1620-1628.
[15]Subramani S, Cheong I W, Kim J H. Chain extension studies of water-borne polyurethanes from methyl ethyl ketoxime/caprolactam-blocked aromatic isocyanates[J]. Progress in Organic Coatings,2004:328-338.
[16]David D J, Stanley H E. Wiley-Interscience, New York,1969.
[17]Reddy, G. V. R.; Devi, N. G.; Panda, J. J Appl Polym Sci 2007,105,3391-3402.
[18]Xu G, Shi W F. Synthesis and characterization of hyperbranched polyurethane acrylates used as UV curable oligomers for coatings[J].Progress in Organic Coatings 2005,52(2):110-117.
[19]Amelie Baron, Juan Rodriguez-Hernandez, Eric Papon. Relationship Between Architecture and Adhesion in Polyurethane-Based Copolymers [J]. Macro-molecular Chemistry and Physics,2005,206(23):2381-2389.
[20]Hu Y S,Tao Y, Hu C P. Polyurethaneurea/Vinyl Polymer Hybrid Aqueous Dispersions Based on Renewable Material[J]. Biomacromolecules,2001,2 (1):80-84.
[21]Wen Ten-Chin, Wang Yeong-Jyh, Tsung-Tien Cheng et al.The effect of DMPA units on ionic conductivity of PEG-DMPA-IPDI waterborne polyurethane as single-ion electrolytes[J]. Polymer,1999,40 (14):3979-3988.
[22]Wen Ten-Chin, Wu Ming-Sieng. Spectroscopic Investigations of Poly (oxy-propylene) glycol-Based Waterborne Polyurethane Doped with Lithium Perchlorate[J]. Macromolecules,1999,32(8):2712-2720.
[23]Macros-Fernandez A, Lozano A E, Gonzalez L,Hydrogen Bonding in Copoly(ether-urea)s and Its Relationship with the Physical Properties. Macromolecules,1997,30 (12):3584-3592.
[24]Zhang Hongtao, Huang He, Cao Jianhua. Concentrated Emulsion Copoly-merization of a-DoubleBond-Containing Polyurethane/Styrene Initiated by Redox System[J]. Journal of Applied Polymer Science,2004,94, (l,):1-8.
[25]Kukanja D, Golob J, Zupancic-Valant A et al. The structure and properties of acrylic-polyurethane hybrid emulsions and comparison with physical blends[J].2000, 78(1):67-80.
[1]Chai Shuling, Tan Huimin. Structure and Property Characterization of Nanograde Core-shell Polyurethane/Polyacrylate Composite Emulsion[J].Journal of Applied Polymer Science,2008,107(6):3499-3504.
[2]Rharbi Y, Yekta A, Mitchell A. Winnik. Energy Transfer Studies of Interpenetrating Polymer Networks Characterizing the Interface in Polyacrylate-Polyurethane IPNs[J].Macromolecules,1999,32(10),3241-3248.
[3]Chai Shuling, Martin Ming Jin. Morphology and Particle Size of Nanograde Polyurethane/Polyacrylate Hybrid Emulsions[J].Journal of Applied Polymer Science,2009,114, (4):2030-2035.
[4]Jie Yang, Mitchell A. Winnik. Polyurethane-Polyacrylate Interpenetrating Networks Morphology Studies by Direct Nonradiative Energy Transfer Experiments[J]. Macromolecules 1996,29(22),7055-7063.
[5]Tien; Mao Chao-Fong, Snyder Chung-Ling, et al. Low temperature self-crosslinking aqueous urethane-vinyl polymers for coating applications US5521246,1996-5-28.
[6]冯海波,卿宁核壳交联结构水性聚氨酯的合成研究皮革化工,2005,22(1)：21-25.