摘要
本论文的工作集中在聚醚型水性聚氨酯/丙烯酸六氟丁酯(WPU/F6BA)复合乳液的制备和性能研究上。主要成果总结如下:
1、基于异佛尔酮二异氰酸酯的聚醚型聚氨酯乳液的制备及性能研究
以异佛尔酮二异氰酸酯(IPDI)、聚醚二元醇(PPG,Mn=1000)和二羟甲基丙酸(DMPA)为主要原料,制备了水性聚氨酯乳液(WPU)。用红外分析仪(FT-IR)、粘度测试仪、激光粒度分析仪(LPA)等手段研究了NCO/OH摩尔比(R)、DMPA的含量对乳液相转变、粘度、稳定性、膜机械性能和耐介质性能的影响。结果表明:随R值的增加,乳液的粘度升高、粒径增大、相转变点延后、稳定性下降以及膜的拉伸强度增加,断裂伸长率降低,耐水性增加;随DMPA用量的增加,乳液的粘度下降、粒径减小、相转变点后延、膜的断裂伸长率增加、拉伸强度降低和耐水性降低。综上因素可得,R=1.5且wt%(DMPA)= 7%的聚氨酯预聚体(PU-1)经离子化得到的WPU的综合性能优良,为进一步的改性提供较好前提。
2、甲基丙烯酸-β羟丙酯(HPMA)对PUA复合乳液性能的影响
采用HPMA、PU-1反应形成了双键封端的聚氨酯大分子单体(PUL)。利用其自乳化的特点,将其与苯乙烯(St)、丙烯酸丁酯(BA)单体共聚,制备了聚氨酯/丙烯酸酯的复合乳液(PUA)。用FT-IR、TGA、TEM等手段研究了其结构、热性能、粒子大小形态和HPMA含量对PUA乳液涂膜性能的影响。结果表明:随着HPMA含量的增加, PUA复合乳液的稳定性和涂膜的热稳定性都得到了提高,但PUA膜吸水率呈先降后升的趋势。综上因素可得,大分子单体中HPMA的含量为75%( PUL-1)时,PUA综合性能较好。
3、水性PU/F6BA的复合乳液(FPUL)制备及性能研究
采用无皂乳液聚合,将PUL-1与F6BA共聚反应得到FPUL。用FT-IR、DSC、TEM等手段研究了其结构、热性能、形态和粒子大小。结果表明:FPUL的的软段和硬段的玻璃化温度分别为6.5℃,43.8℃,玻璃化温度有明显变化,壳平均厚度约为131nm,核厚度约为237nm。当F6BA的质量分数为50%时,FPUL复合膜的表面能降低到11.56mJ·m~(-2)。
4、水性PU/ F6BA/BA/St的复合乳液(FPUA)的制备及性能研究
采用无皂乳液聚合,PUL-1与F6BA、BA和St共聚反应制得FPUA。采用FT-IR, DSC、TGA、LPA、TEM等手段对产物进行了表征。结果表明,FPUA的软段和硬段的玻璃化温度分别为-1.8℃,37.0℃,耐热性能有所提高,其平均粒径为1.43μm,分布较均一,壳厚度约为975nm,核厚度约为425nm。FPUA复合膜的表面性能随着氟单体含量的增加而下降,当氟单体含量占总量20.8%时,降低到23.87mJ·m~(-2)。
In this thesis, we focused on the preparation and characterization of polyether waterborne polyurethane / hexafluorobutly acrylate composite latexes.
The main contents were summarized as follows:
1. Investigation on Synthesis and Characterization of polyether waterborne polyurethane Latexes based on IPDI (WPU)
WPU were synthesized with DMPA,IPDI and PPG as the main raw materials. The effects on the emulsion phase transiton, viscosity, stability, membrane mechanical properties and resistance to medium performance of the WPU were studied by FT-IR, viscosity testers and LPA and so on. The results showed that with increasing the value of R, the dispersions viscosity, the average particle size, tensile strength of the WPU films and the resistance to water increased, while the phase transition point delayed, the dispersions stability and the tensile elongation was decreased. With the content of DMPA increasing, the effects were quite opposite in the addition of the phase transition point. Through the ionization of the PU-1 in which the value of R was 1.5 and the content of DMPA was 7wt%, the WPU overall performance was excellent, which provided a better prerequisite for subsequent modification based on comprehensive consideration of the above performance.
2. Effect of HPMA on the Properties of PUA composite Latexes
Double bond-end capped Polyurethane macromonomers (PUL) were synthe- -sized with PU-1 and HPMA. Through emulsifier-free emulsion polymerizati on of PUL, butyl acrylate (BA) and styrene (St), the PUA hybrid latexes were prepared. The structures, the thermal properties, the dimension and morphology of PUA latexes were studied by FT-IR, TGA and TEM.The results showed that HPMA can successfully provide the bridge of PU, PA copolymerization. The average thicknesses of the PA, PU layer of PUA latexes particles with even distribution were 290nm and 105nm, respectively. As HPMA increased, the stability and thermal stability of PUA membranes were enhanced, while water absorption of PUA film was falling, following by the rising trend. When the content of HPMA is 75% (PUL-1), the overall performance of PUA latexes were excellent.
3. Investigation on Synthesis and Characterization of FPUL composite latexes
Through emulsifier-free emulsion polymerization of PUL-1 and F6BA, the FPUL composite latexes were prepared. The structures, the thermal properties, the dimension and morphology of FPUL latexes were studied by FT-IR, TGA and TEM. The results showed that the glass transition temperatures of the soft and hard segment were respectively 6.5℃, 43.8℃. The layer size of the core and the shell of FPUL were about 237nm and 131nm, respectively. The surface free energies of FPUL films reached 11.56mJ·m~(-2) at 50% F6BA.
4. Investigation on Synthesis and Characterization of FPUA styrene composite latexes
Through emulsifier-free emulsion polymerization of PUL-1, F6BA, BA and St, the FPUA composite latexes were prepared and characterized by FT-IR, TGA, DSC, LPA and TEM. The results showed that the glass transition temperatures of the soft and hard segment were respectively -1.8℃, 37.0℃. The heat resistance of FPUA was more excellent. The size of the core-shell particles was about 1.43μm and distribution was even. The layer size of the core and the shell -were about 425nm and 975nm, respectively. The surface free energies of FPUA films decreased with increasing of F6BA and reached 23.87mJ·m~(-2) at 20.8% (mass) F6BA.
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