环氧大豆油和硅氧烷改性水性聚氨酯胶黏剂

doi:10.3969/j.issn.0438-1157.2014.11.055

摘要/Abstract

摘要： 以环氧大豆油(ESO)与3-氨基丙基三乙氧基硅烷(KH550)双重交联改性水性聚氨酯(WPU).通过FTIR、TG、DSC、DMA、AFM、粒径分析仪、拉力试验机等仪器对改性的水性聚氨酯进行了表征.研究了ESO和KH550的含量对水性聚氨酯乳液、胶膜以及胶黏剂性能的影响.分析了KH550对水性聚氨酯结晶性能和微相分离的影响.研究发现,随着ESO与KH550的加入,水性聚氨酯乳液的性能得到改善,胶膜的吸水率先减小后增大,拉伸强度逐渐增大,断裂伸张率逐渐减小.水性聚氨酯胶黏剂对PVC的T-剥离强度先增大后减小.随着KH550含量的增加,热稳定性逐步改善,结晶性降低,软段与硬段相混合程度提高.当ESO为4%、KH550为2%(均为质量分数)时,水性聚氨酯胶黏剂的综合性能最好.

关键词: 环氧大豆油, KH550, 聚合物, 结晶性能, 力学性能, 粘接性能

Abstract: Waterborne polyurethane (WPU) modified by epoxy soybean oil (ESO) and 3-aminopropyltriethoxysilane (KH550) were synthesized. The properties of the modified WPU were characterized by FTIR, TG, DSC, DMA, AFM, particle size analyzer and tensile test machine. The effects of contents of ESO and KH550 on the properties of WPU emulsion, its film and adhesive strength were studied. And the effect of KH550 on the crystallinity and microphase separation of WPU was analyzed. With the increase of contents of ESO and KH550, the properties of WPU dispersion were improved, the water absorption of WPU film decreased first, and then increased. Tensile strength increased, while elongation at break decreased. The T-peel strength of the adhesive to PVC/PVC increased first, and then decreased. With increasing KH550 content, thermal stability of the WPU film was improved, crystallinity decreased, degree of mixing of soft segment phase and hard segment phase was enhanced. When the contents of ESO and KH550 were 4% and 2%(mass), respectively, the properties of WPU adhesive were perfect.

Key words: epoxy soybean oil, 3-aminopropyltriethoxysilane, polymers, crystallinity, mechanical property, adhesive property

中图分类号:

TQ323.8

何飞强, 傅和青, 周威. 环氧大豆油和硅氧烷改性水性聚氨酯胶黏剂[J]. 化工学报, 2014, 65(11): 4599-4606.

HE Feiqiang, FU Heqing, ZHOU Wei . Waterborne polyurethane adhesive modified by epoxy oil soybean and 3-aminopropyltriethoxysilane[J]. CIESC Journal, 2014, 65(11): 4599-4606.

参考文献 22

[1]	García-Pacios V, Colera M, Iwata Y, et al. Incidence of the polyol nature in waterborne polyurethane dispersions on their performance as coatings on stainless steel [J]. Progress in Organic Coatings, 2013, 76(12): 1726-1729
[2]	Orgiles-Calpena E, Aran-Ais F, Torró-Palau A M, et al. Addition of different amounts of a urethane-based thickener to waterborne polyurethane adhesive [J]. International Journal of Adhesion and Adhesives, 2009, 29(3): 309-318
[3]	Xu Gewen(许戈文). Waterborne Polyurethane Material(水性聚氨酯材料)[M]. Beijing: Chemical Industry Press, 2007
[4]	Sun D, Miao X, Zhang K, et al. Triazole-forming waterborne polyurethane composites fabricated with silane coupling agent functionalized nano-silica [J]. Journal of Colloid and Interface Science, 2011, 361(2): 483-490
[5]	Fu Heqing(傅和青), Huang Hong(黄洪), Zhang Xinya(张心亚), Chen Huanqin(陈焕钦). Preparation of epoxide-acylate-polyurethane hybrid dispersion [J]. Journal of Chemical Industry and Engineering(China)(化工学报), 2007, 58(2):495-500
[6]	Xia Y, Larock R C. Preparation and properties of aqueous castor oil-based polyurethane-silica nanocomposite dispersions through a sol-gel process [J]. Macromolecular Rapid Communications, 2011, 32(17): 1331-1337
[7]	Hang Xiaomin(杭晓敏), Hua Pinpin(华聘聘). The mechanism and kinetics study of formic acid - ethylene oil ring opening reaction [J]. Journal of Shanghai Jiao Tong University(上海交通大学学报), 1996, 30(7): 40-46
[8]	Guo Y, Hardesty J H, Mannari V M, et al. Hydrolysis of epoxidized soybean oil in the presence of phosphoric acid [J]. Journal of the American Oil Chemists' Society, 2007, 84(10): 929-935
[9]	Bakhshi H, Yeganeh H, Mehdipour-Ataei S, et al. Synthesis and characterization of antibacterial polyurethane coatings from quaternary ammonium salts functionalized soybean oil based polyols [J]. Materials Science and Engineering C, 2013, 33(1): 153-164
[10]	Seeni Meera K M, Murali Sankar R, Jaisankar S N, et al. Physicochemical studies on polyurethane/siloxane cross-linked films for hydrophobic surfaces by the sol-gel process [J]. The Journal of Physical Chemistry B, 2013, 117(9): 2682-2694
[11]	David D, Staley H. Analytical Chemistry of Polyurethane[M].New York: John Wiley&Sons Inc., 1969: 86-90
[12]	Zhang Dapeng(张大鹏), He Lifan(何立凡), Wang Haiqiao(王海侨), Li Xiaoyu(李效玉). Modification of waterborne polyurethane adhesives with a silane coupling agent [J]. Journal of Beijing University of Chemical Technology: Natural Science (北京化工大学学报:自然科学版), 2011, 38(5): 81-85
[13]	Rahman M M, Hasneen A, Lee W K, et al. Preparation and properties of sol-gel waterborne polyurethane adhesive [J]. Journal of Sol-gel Science and Technology, 2013, 67(3): 473-479
[14]	Zhou Wei(周威), Fu Heqing(傅和青), Yan Caibin(颜财彬), Chen Huanqin(陈焕钦). Synthesis and characterization of self-emulsified nano-SiO2/polyurethane-fluorinated polyacrylate hybird latexes and their films [J]. CIESC Journal (化工学报), 2013, 64(6): 2291-2299
[15]	Caki? S M, Risti? I S, Marinovi?-Cincovi? M, et al. The effects of the structure and molecular weight of the macrodiol on the properties polyurethane anionic adhesives [J]. International Journal of Adhesion and Adhesives, 2013, 41: 132-139
[16]	Chattopadhyay D K, Webster D C. Thermal stability and flame retardancy of polyurethanes [J]. Progress in Polymer Science, 2009, 34(10): 1068-1133
[17]	Yanagihara Y, Osaka N, Murayama S, et al. Thermal annealing behavior and structure development of crystalline hard segment domain in a melt-quenched thermoplastic polyurethane [J]. Polymer, 2013, 54(8): 2183-2189
[18]	McLean R S, Sauer B B. Tapping-mode AFM studies using phase detection for resolution of nanophases in segmented polyurethanes and other block copolymers [J]. Macromolecules, 1997, 30(26): 8314-8317
[19]	Schön P, Bagdi K, Molnár K, et al. Quantitative mapping of elastic moduli at the nanoscale in phase separated polyurethanes by AFM [J]. European Polymer Journal, 2011, 47(4): 692-698
[20]	Li Fan(李凡), He Yubing(贺余兵), Ye Lin(叶林). The synthesis and the damping property of polyester-based thermoplastic polyurethanes elastomer [J].Polymer Materials Science&Engineering(高分子材料科学与工程), 2007, 23(2): 198-202
[21]	Jiang L, Zhang C, Liu M, et al. Simultaneous reinforcement and toughening of polyurethane composites with carbon nanotube/ halloysite nanotube hybrids [J]. Composites Science and Technology, 2014, 91: 98-103
[22]	Malkappa K, Jana T. Simultaneous improvement of tensile strength and elongation: an unprecedented observation in the case of hydroxyl terminated polybutadiene polyurethanes [J]. Industrial & Engineering Chemistry Research, 2013, 52(36): 12887-12896