采用不同官能基的偶联剂合成了一系列在硬段中含有硅氧烷链段的水性聚氨酯(WPU)乳液。通过红外光谱、激光粒度仪、耐湿热老化试验、差示扫描量热和热失重等手段详细研究了偶联剂和扩链剂种类及n(扩链剂):n(偶联剂)对WPU乳液性能、粘接性能、耐湿热老化性能和胶膜热稳定性的影响。结果表明:当n(EDA):n(KH550)和n(EDA):n(KH580)为1:1时,WPU的乳液性能、粘接性能和耐湿热老化性能最佳。引入硅氧烷链段对WPU胶膜的微相分离产生影响,微相分离程度较好的WPU-EDA和WPU-550比其他两种热稳定性更好。
A series of waterborne polyurethane(WPU) emulsions containing siloxane groups in hard segment were synthesized by using coupling agents with different functional group instead of part chain extender.The effect of the coupling agent structure and n(ethyl diamine):n(coupling agent) on the emulsion properties,resistance to wet and heat aging properties of WPU,and thermal stability of WPU film were studied by FT-IR,laser particle size analyzer,resistance to wet and heat ageing test,differential scanning calorimeter(DSC) and thermo-gravimetric analysis (TG).The results showed that the emulsion performance,adhesion strength and thermo-moisture resistance of WPU were improved with the introducing coupling agent.The best result was acquired when n(EDA):n(KH550) and n(EDA):n(KH580) was 1:1.The introduction of siloxane chain into the hard segment could affect the microphase separation of WPU film,and WPU-EDA and WPU-550 with higher microphase separation showed better thermal stability than that of others.
[1] Ryu Y S,Lee Y H,Kim J S,et al.Preparation and properties of emulsifier-/solvent-free polyurethaneacrylic hybrid emulsions for binder materials:effect of the glycidyl methacrylate/acrylonitrile content[J].Journal of Applied Polymer Science,2017,134:1-9.
[2] Ma S,Chen C,Sablong R J,et al.Non-isocyanate strategy for anionicallystabilized water-borne polyurea dispersions and coatings[J].Journalof Polymer Science,Part A:Polymer Chemistry,2018,56:1078-1090.
[3] Li J,Gan L Z,Liu Y C,et al.Boron nitride nanosheets reinforced waterborne polyurethane coatings for improving corrosion resistance and antifriction properties[J].European Polymer Journal,2018,104:57-63.
[4] Athak S S,Sharm A A,Khanna A S.Value addition to waterborne polyurethane resin by silicone modification for developing high performance coating on aluminumalloy[J].Progress in Organic Coatings,2009,65(2):206-216.
[5] Kwak Y S,Kim E Y,Yoo B H,et al.Preparation and properties of waterborne poly(urethane-urea)s for adhesives:The effects of the 2,2-bis(hydroxylmethyl)propionic acid content on the properties[J].Journal of Applied Polymer Science,2004,94:1743-1751.
[6] Wu J H,Wang C H,Mu C D,et al.A waterborne polyurethane coating functionalized by isobornyl with enhanced antibacterial adhesion and hydrophobic property[J].European Polymer Journal,2018,108:498-506.
[7] Chang P R,Ai F J,Chen Y.Effect of starch nanocrystalgraft-polycaprolactone on mechanical properties of waterborne polyurethane-based nanocomposites[J].Journal of Applied Polymer Science,2009,111:619-627.
[8] Lee D K,Tsai H B,Yang Z D,et al.Polyurethane dispersions derived from polycarbonatediolsby a solvent-free process[J].Journal of Applied Polymer Science,2012,126:E275-E282.
[9] Alvarez G A,Fuensanta M,Orozco V H,et al.Hybrid waterborne polyurethane/acrylate dispersion synthesized with bisphenol A-glicidyl-methacrylate(bis-GMA) grafting agent[J].Progressin Organic Coating,2018,118:30-39.
[10] Shi R,Zhang X,Dai J.Synthesis of TDI-polyurethane/polyacrylate composite emulsion by solvent-free method and performances of the latex film[J].Journal Macromolecule Science,Part A:Pure Applied Chemistry,2013,50:350-357.
[11] Yi T,Ma G,Hou C,et al.Polyurethane-acrylic hybrid emulsions with high acrylic/polyurethane ratios:synthesis,characterization,and properties[J].Journal of Applied Polymer Science,2017,134:1-9.
[12] Yuan C,Wang J,Cui M,et al.Aqueous PUA emulsionprepared by dispersing polyurethane prepolymer in polyacrylate emulsion[J].Journal of Applied Polymer Science,2016,133:43203(1-9).
[13] Kim B S,Kim B K.Enhancement of hydrolytic stability and adhesion of waterborne polyurethanes[J].Journal of Applied Polymer Science,2005,97:1961-1969.
[14] Rahman M M,Kim H D,Lee W K.Preparation and characterization of waterbornepolyurethane/clay nanocomposite:effect on water vapor permeability[J].Journal of Applied Polymer Science,2008,110:3697-3705.
[15] Jiao L,ZhaoQ P,Yun G.Study on the morphology structure and properties of aqueous polyurethane modified bypoly(dimethyl siloxane)[J].Journal of Applied Polymer Science,2007,105:3037-3046.
[16] Yen M S,Tsai P Y.Study on polyethylene glycol/polydimethylsiloxane mixing soft-segment waterborne polyurethane from different mixing processes[J].Journal of Applied Polymer Science,2003,90:233-243.
[17] Liu N,Zhao Y H,Kang M Q,et al.The effects of the molecular weight and structure of polycarbonatediols on the properties of water-borne polyurethanes[J].Progress in Organic Coatings,2015,82:46-56.
[18] 赵雨花,刘娜,冯月兰,等.短链和长链交联剂对水性聚氨酯性能的影响[J].化学推进剂与高分子材料,2016,14(1):50-54.
[19] 赵雨花,冯月兰,亢茂青,等.丙烯酸酯改性蓖麻油基水性聚氨酯乳液的制备[J].化学推进剂与高分子材料,2016,14(3):53-58.
[20] 赵雨花,冯月兰,殷宁,等.汽车涂料用丙烯酸酯改性蓖麻油基水性聚氨酯无皂乳液研究[J].化学推进剂与高分子材料,2018,16(2):34-38.
基金资助
山西省科技重大专项(20181101012)