端氟烷基超支化聚氨酯成膜剂的合成及表征

发布时间：2018-06-26 06:59

本文选题：阴/阳离子型水性聚氨酯 + 端氟烷基　；参考：《陕西科技大学》2017年硕士论文

【摘要】：针对水性聚氨酯耐水性差的缺陷,本文做了相关的改性研究,具体研究内容如下:首先,以异氟尔酮二异氰酸酯(IPDI)、聚己二酸丁二醇酯(CMA-1044)、1,4-丁二醇(BDO)和二羟甲基丙酸(DMPA)为原料采用丙酮法合成了-NCO封端的聚氨酯预聚体(PU);然后加入端羟基超支化聚合物进行改性,合成了超支化聚氨酯(HBPU);再通过接枝反应使全氟己基乙醇(S104)与HBPU反应制得一种新型端氟烷基超支化聚氨酯(HBPUF),最后经中和、加水分散即制得HBPUF乳液。用傅里叶红外光谱(FT-IR)、核磁共振波谱(NMR)、透射电镜(TEM)、纳米粒度仪、热重分析仪(TGA)、差示扫描量热仪(DSC)、X-射线衍射仪(XRD)、光电子能谱仪(XPS)、扫描电镜(SEM)、原子力显微镜(AFM)以及静态接触角测量仪等分别对乳液主组分的结构、乳胶粒形貌、粒径大小及分布、胶膜热性能、膜微观结构、膜表面化学组成、膜形貌以及膜疏水性进行研究。FT-IR、1H NMR及13C NMR结果证实所制备的HBPUF具有预期的结构。HBPUF乳液具有良好的稳定性,聚合物胶粒呈规则圆球状和核壳结构,在内部相对明亮的区域有微弱明暗交替的衍射环,说明HBPUF聚合物具有一定的结晶性。XPS分析表明,在成膜过程中氟碳链发生了明显的表面迁移,使得HBPUF膜的疏水性提高;HBPUF胶膜的接触角较PU胶膜提高了36.1°,吸水率较PU胶膜降低了125.2%。TGA分析表明,PU、HBPU以及HBPUF的热稳定性逐渐增强。DSC分析发现PU、HBPU和HBPUF均存在结晶熔融吸收峰,这表明这些聚合物中均存在一定程度上的结晶。XRD分析进一步说明了聚合物的结晶情况,与PU相比,由于超支化聚合物的引入,HBPU和HBPUF的结晶区出现了更小晶粒。SEM分析也验证了这一观点。AFM分析表明,PU膜存在微观相分离现象;由于超支化聚合物的引入,其交联作用导致链与链之间的卷曲或盘旋受阻,从而使HBPU膜微观精细形貌较为平滑;HBPUF中端氟烷基的表面迁移作用使其微观相分离非常显著,膜粗糙度大大增加。其次,以异氟尔酮二异氰酸酯(IPDI)、聚己二酸丁二醇酯(CMA-1044)、1,4-丁二醇(BDO)和N-甲基二乙醇胺(MDEA)为原料采用丙酮法合成了-NCO封端的聚氨酯预聚体(CPU);然后加入端羟基超支化聚合物进行改性,合成了超支化聚氨酯(CHBPU);再通过接枝反应使全氟己基乙醇(S104)与CHBPU反应制得一种新型端氟烷基超支化聚氨酯(CHBPUF),最后经中和、加水分散即制得CHBPUF乳液。用傅里叶红外光谱(FT-IR)、核磁共振波谱(NMR)、透射电镜(TEM)、纳米粒度仪、热重分析仪(TGA)、差示扫描量热仪(DSC)、X-射线衍射仪(XRD)、光电子能谱仪(XPS)、扫描电镜(SEM)、原子力显微镜(AFM)以及静态接触角测量仪等分别对乳液主组分的结构、乳胶粒形貌、粒径大小及分布、胶膜热性能、膜微观结构、膜表面化学组成、膜形貌以及膜疏水性进行研究。FT-IR、1H NMR以及13C NMR结果同样表明所制备的CHBPUF具有预期的结构。CHBPUF乳液由于MDEA的乳化能力较弱,稳定性不佳,外观呈乳黄色。XPS分析表明,在成膜过程中氟碳链发生了明显的表面迁移,使得CHBPUF膜的疏水性提高;CHBPUF胶膜的接触角较CPU胶膜提高了18.5°,CHBPUF胶膜的吸水率较PU胶膜降低了91.67%。TGA分析表明,CPU、CHBPU以及CHBPUF的热稳定性逐渐增强。DSC分析发现CPU、CHBPU和CHBPUF均存在结晶熔融吸收峰,这表明这些聚合物中均存在一定程度上的结晶。XRD分析结果进一步说明了聚合物的结晶情况,与CPU相比,由于超支化聚合物的引入,CHBPU和CHBPUF的结晶区出现了更小晶粒。SEM分析也验证了这一观点。AFM分析表明,CPU膜存在微观相分离现象;由于超支化聚合物的引入,其交联作用导致链与链之间的卷曲或盘旋受阻,从而使CHBPU膜微观精细形貌较为平滑;CHBPUF中端氟烷基的表面迁移作用使其微观相分离非常显著,膜粗糙度大大增加。
[Abstract]:In view of the defects of water borne polyurethane with poor water resistance, the relevant modification research was made in this paper. The specific research contents are as follows: first, the polyurethane prepolymer (PU) with -NCO sealing ends (PU) was synthesized by acetone method using isoflofarone diisocyanate (IPDI), polybutylene adipate (CMA-1044), 1,4- butanediol (BDO) and dimethy propionic acid (DMPA) as raw materials. After adding hydroxyl terminated hyperbranched polymer, the hyperbranched polyurethane (HBPU) was synthesized and a new type of terminated fluoroalkyl hyperbranched polyurethane (HBPUF) was prepared by reaction of graft reaction and HBPU. Finally, HBPUF emulsion was prepared by neutralization and water dispersion. The Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy were used. (NMR), transmission electron microscopy (TEM), nano particle size meter, thermogravimetric analyzer (TGA), differential scanning calorimeter (DSC), X- ray diffractometer (XRD), photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscope (AFM) and static contact angle measuring instrument, respectively, the morphology, size and distribution of latex particles, the size and distribution of the particle size, and the thermal properties of the film. The microstructure of the membrane, the chemical composition of the surface of the membrane, the morphology of the membrane and the hydrophobicity of the membrane have been studied. The results of.FT-IR, 1H NMR and 13C NMR confirm that the prepared HBPUF has the expected structural.HBPUF emulsion with good stability. The polymer particles are regular sphere and nuclear shell structure, and there is a weak light and dark alternate diffraction ring in the interior relatively bright region. It is indicated that the HBPUF polymer has a certain crystalline.XPS analysis, which shows that the fluorocarbon chain has obvious surface migration during the film forming process, which makes the hydrophobicity of the HBPUF film increase, the contact angle of the HBPUF film is 36.1 degrees higher than that of the PU film, and the water absorption rate is lower than that of the PU film by 125.2%.TGA segregation, and the thermal stability of PU, HBPU and HBPUF increases gradually. The strong.DSC analysis found that the crystallization and melting absorption peaks of PU, HBPU and HBPUF showed that there was a certain degree of crystallization.XRD analysis in these polymers to further illustrate the crystallization of the polymer. Compared with PU, the crystallization area of HBPU and HBPUF appeared in the crystallization region of HBPU and HBPUF, as compared with PU. .AFM analysis shows that there is a microscopic phase separation in the PU film. Because of the introduction of the hyperbranched polymer, the cross linking effect leads to the curl or circling between chain and chain, which makes the fine morphology of the HBPU film more smooth, and the surface migration of fluorine alkyl at the middle end of HBPUF makes the microscopic phase separation very significant and the film roughness is greatly increased. Secondly, the -NCO sealed polyurethane prepolymer (CPU) was synthesized with isoflolone diisocyanate (IPDI), polybutylene adipate (CMA-1044), 1,4- butanediol (BDO) and N- methyl two ethanolamine (MDEA) as raw materials, and then the hyperbranched polyurethane (CHBPU) was synthesized by adding hydroxy terminated hyperbranched polymers, and then graft copolymerization was made by grafting. The reaction made a new type of endoflurane based hyperbranched polyurethane (CHBPUF) prepared by the reaction of perfluorohexyl alcohol (S104) with CHBPU. Finally, the CHBPUF emulsion was produced by neutralization and water dispersion. Using Fourier infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), transmission electron microscopy (TEM), nano particle size instrument, thermogravimetric analyzer (TGA), differential scanning calorimeter (DSC), X-. Line diffractometer (XRD), photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM) and static contact angle measuring instrument, respectively, the structure of the main component of emulsion, the size and distribution of latex particles, the thermal properties of the film, the microstructure of the membrane, the chemical composition of the membrane surface, the morphology of the membrane and the hydrophobicity of the membrane,.FT-IR, 1H NMR The results of 13C NMR also show that the prepared CHBPUF has the expected structural.CHBPUF emulsion because of the weak emulsification capacity of MDEA, and the appearance of the emulsion yellow.XPS analysis shows that the fluorocarbon chain has obvious surface migration during the film forming process, which makes the hydrophobicity of the CHBPUF film improved, and the contact angle of the CHBPUF film is higher than that of the CPU film. The water absorption of CHBPUF film was lower than that of PU film by 91.67%.TGA analysis. The 91.67%.TGA analysis showed that the thermal stability of CPU, CHBPU and CHBPUF increased gradually by.DSC analysis and found that CPU, CHBPU and CHBPUF all had crystallization absorption peaks. This indicates that all of these polymers all have a certain degree of crystallization.XRD analysis results to further explain the polymer junction. As compared with CPU, compared with CPU, due to the introduction of hyperbranched polymers, smaller grain.SEM analysis appeared in the crystalline region of CHBPU and CHBPUF. The.AFM analysis showed that there was a microscopic phase separation in the CPU film. Because of the introduction of the hyperbranched polymer, the crosslinking of the chain and the curling or circling between the chain and the chain was hindered, so that CHBPU The microscopic morphology of the films is smoother. The surface migration of fluorinated alkyl groups in CHBPUF makes the microscopic phase separation very significant, and the roughness of the films increases greatly.
【学位授予单位】：陕西科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.2;TQ317

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