聚氨酯一聚丙烯酸酯共聚乳液的合成研究

以甲基丙烯酸β－羟乙酯封端的聚氨酯大分子单体与丙烯酸酯类单体进行乳液共聚，合成了以聚丙烯酸酯（PA）为主链、聚氨酯（PU）为侧链的接枝共聚物（PA－g－PU）乳液，用IR光谱和^1H NMR光谱对该聚氨酯大分子单体及PA－g－PU接枝共聚物进行了表征，并对影响聚氨酯－聚丙烯酸酯共聚合的因素进行了探讨。结果表明：聚氨酯大分子单体的加入对乳液聚合的速率造成较大的影响。该体系的表观活化自由能为99.39KJ/mol,Rp∝[I]^0.87,Rp∝[S]^0.12。     

聚氨酯/聚丙烯酸酯复合乳液粒子热力学平衡形态预测

以水性聚氨酯分散液为种子采用无皂乳液聚合新技术合成出了具有核壳结构的聚氨酯/聚丙烯酸酯（PU/PA）复合聚合物乳液。采用界面张力简化计算方法计算了聚合物与聚合物之间以及聚合物和水之间的界面张力,通过界面自由能变化最小的热力学判据对合成的复合乳液粒子的热力学平衡形态进行了预测。并利用透射电子显微镜观察和用接触角法测定的膜的表面极性对其进行了证实。结果表明：界面自由能变化的最小判据可以推广到PU/PA 体系,本文给出的界面张力的简化计算方法是可行的。     

大分子不饱和单体法合成具有核壳结构的丙烯酸酯/聚氨酯乳液及表征

采用丙烯酸酯（AC）对水性聚氨酯（WPU）进行改性,合成了接枝型丙烯酸酯/聚氨酯(PUA)复合乳液。 随着共聚物中丙烯酸酯质量分数的增加,乳液外观由透明变为不透明,乳液粒径随之增大、分布变宽。 TEM显示,PUA乳胶粒子呈现清晰的核壳结构,且形态规整,粒径分布在60~120 nm之间。 FTIR测试表明,随着丙烯酸酯质量分数的增加,聚氨酯(PU)硬段氢键化作用先增强后减弱,硬段的有序度逐渐降低。 DSC分析表明,当AC的质量分数低于75%时,PU、聚丙烯酸酯(PA)两组分相容性较好,只出现一个玻璃化转变温度,并且随着PA质量分数的增加逐渐升高。 PA质量分数的增加,使胶膜的最大热失重速率从363 ℃提高至412 ℃,吸水率从11.3%降低至5.7%,弹性模量从16.4 MPa提高至47.6 MPa,拉伸强度从9.0 MPa提高至23.7 MPa,断裂伸长率从365%提高至408%,同时乳液的粘度下降,干燥时间变短,胶膜的附着力变好。     

聚氨酯/聚丙烯酸酯复合乳液的研制进展

概述聚氨酯－聚丙烯酸酯复合乳液的制备方法。特别对聚氨酯－聚丙烯酸酯复合乳液共聚法作了较为系统的介绍和讨论。     

丙烯酸酯改性水性聚氨酯乳液的制备及性能研究

采用共聚的方法制备出丙烯酸酯改性的水性聚氨酯共聚乳液(PUA乳液),并对PUA乳液的制备方法和工艺、耐溶剂性、机械稳定性进行了初步的研究。结果表明,具有IPN结构的PUA乳液耐溶剂性、机械稳定性比水性PU有明显的提高。     

端羟基聚丙烯酸酯改性水性聚氨酯

将丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA)通过溶液自由基聚合,用巯基乙醇作为链转移剂调控合成了一定分子量的端羟基聚丙烯酸酯(PA),再与聚氨酯(PU)预聚体反应,在水中分散得到PA-PU-PA三嵌段共聚复合乳液。 采用FTIR和¹HNMR测试技术对共聚物结构进行了表征。 结果表明,随着PU与PA质量比的降低,共聚物中丙烯酸酯含量随之增加;PU软硬链段之间的氢键化作用减弱。 TEM显示,复合乳胶粒子形态均匀规整,并呈现明显的核壳结构。改性后的乳胶膜耐水、耐热性能均随着PU/PA质量比的减小而提高,吸水率由25%降低至5%,最大热失重温度由369 ℃提高至432 ℃。     

聚氨酯-丙烯酸酯杂化乳液结构与性能的影响

以聚四氢呋喃醚二醇（PTMG）、异氟尔酮二异氰酸酯（IPDI）、亲水单体二羟甲基丙酸（DMPA）,乙二胺为主要原料,制备了稳定的水性聚氨酯乳液.然后以苯乙烯（St）、丙烯酸丁酯（BA）为单体,过硫酸钾为引发剂,在不外加乳化剂的条件下,运用物理共混、化学复合和化学共聚三种方法对该水性聚氨酯乳液进行改性研究.用FTIR技术对聚氨酯-丙烯酸酯杂化乳液的结构进行了对比与表征;通过粘度测定、粒度分析、力学性能和耐水性能测试、DSC分析,研究了不同改性方法对乳液及其胶膜性能的影响.结果表明,化学共聚的改性方法对原水性聚氨酯的耐水性的改良效果最好,能够得到稳定且综合性能较优的聚氨酯-丙烯酸酯杂化乳液.     

丙烯酸羟乙酯对丙烯酸酯改性水性聚氨酯性能的影响

以异佛尔酮二异氰酸酯、二羟甲基丙酸和聚丙醚二醇等为聚氨酯原料, 丙烯酸丁酯、甲基丙烯酸甲酯、三羟甲基丙烷三丙烯酸酯为丙烯酸酯类单体, 丙烯酸羟乙酯(HEA)为聚氨酯和聚丙烯酸酯间的偶联剂合成了丙烯酸酯改性水性聚氨酯(PU-AC)乳液. 首先建立并验证了一种测定PU接枝率, 即PU与丙烯酸酯发生接枝的部分占PU总数的百分比的方法, 然后探讨了加入HEA后的反应温度和HEA用量对PU接枝率、PU-AC乳胶粒径、胶膜吸水率和交联度等性能的影响. 随着HEA与PU预聚体反应温度和HEA用量的提高, 体系中的最终残余NCO逐渐降低. 当HEA用量低于其加入前体系中残余NCO量时, 增加其用量使PU接枝率和PU-AC乳胶粒径逐渐增加; 当HEA用量大于体系残余的NCO量后继续增加其用量对PU接枝率和PU-AC乳胶粒径的影响不大. 胶膜吸水率随着HEA用量的增加而降低.     

单油酸三羟甲基丙烷酯改性水性聚氨酯

利用单油酸三羟甲基丙烷酯(TMPM)、异佛尔酮二异氰酸酯(IPDI)和聚氧化丙烯(PPG)等制备水性聚氨酯。采用透射电镜(TEM)、动态激光光散射(DLLS)、红外光谱(FT-IR)、热重分析(TGA)和表面张力仪表征了乳液胶束形态、产物结构及性能。结果表明:水性聚氨酯(PU)分子上引入脂肪侧链容易在水中形成规整的胶束,但TMPM改性的水性聚氨酯胶束粒径随TMPM含量的增加不断增大,当w(TMPM)=0.07时,乳液不稳定;脂肪侧链的引入降低了水性聚氨酯乳液的表面张力,表面张力随着反应体系中—NCO和—OH摩尔比的增大而降低,随交联度的增大先增加后减小;TMPM的引入可以提高胶膜的热稳定性。     

环氧改性水性聚氨酯乳液的制备及其膜性能

以聚己内酯二元醇(CAPA)为软段,异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)为硬段,环氧树脂E-44为大分子交联剂,经相转化法合成了一系列环氧树脂改性负离子水性聚氨酯(EPPU)自乳化乳液,并制备了改性水性聚氨酯的固化膜.通过FTIR、TGA及接触角、力学性能测试对聚合物结构及其膜性能进行了研究.通过原子力显微镜(AFM)观察膜表面形态和表面粗糙度.乳液粒径及粒径分布通过动态激光光散射法(DLLS)测定.FTIR分析表明环氧树脂的羟基和环氧基都参与了发应.TGA表明,环氧树脂的加入可以提高聚氨酯的热稳定性.随着w(E-44)增大,改性聚氨酯膜的拉伸强度得到改善,断裂伸长率减小.随着w(E-44)增大,乳液粒径增大,薄膜的接触角增大,改性后的PU膜表面光滑度下降,拒水性增强.     

Structure and properties of polyurethane/polyacrylate latex interpenetrating networks hybrid emulsions

Some new kinds of novel polyurethane (PU)/polyacrylate (PA) latex interpenetrating networks (LIPNs) were synthesized. Firstly PU dispersions were synthesized by self-emulsification polymerization. Then PU/PA LIPNs using PU dispersion as the seed were prepared by soap free emulsion polymerization. The effects of different PU/PA ratios, the blending method and the NCO/OH molar ratio of PU components on PU/PA LIPNs performance were also investigated. The structure and properties of PU/PA LIPNs such as mechanical properties, particle size, morphology of the surface were characterized by dynamic mechanical analysis, scanning electron microscopy, and dynamic light scattering. It was found that PU/PA LIPNs can markedly improve the water resistance and the mechanical properties of PU latex much more than those of PU/PA physical blends due to a great deal of interpenetrating and entangling between PU and PA latex. Moreover, the particle size of PU/PA LIPNs is related to the PA content and NCO/OH molar ratio of PU components: the higher the NCO/OH molar ratio in PU dispersions, the larger is the particle size of PU/PA LIPNs, and the average particle size of PU/PA LIPNs becomes larger with an increase in PA content.     

苯乙烯在阴离子型聚氨酯纳米水分散液中聚合过程的研究

采用自乳化法制备出阴离子聚氨酯纳米水分散液,以其作为乳化剂使苯乙烯单体在其中进行聚合,制备出不同聚苯乙烯与聚氨酯质量比的阴离子型PS/PU纳米复合物水分散液;对苯乙烯单体的聚合过程进行了研究;采用光子相关谱仪和透射电镜对其微观结构、粒径及其分布进行了测试,结果表明,该方法能够制备出稳定的具有核壳结构的PS/PU纳米复合物水分散液,但当苯乙烯单体浓度增大到一定程度(PS/PU质量比为50∶100)时,粒子不稳定而发生聚集.     

Luminescence techniques and characterization of the morphology of polymer latices. 3. An investigation of the microenvironments within stabilized aqueous latex dispersions of poly(n-butyl methacrylate) and polyurethane

Fluorescence techniques (including time-resolved anisotropy measurements, TRAMS) have been used to probe differences in morphology between two stabilized aqueous latex dispersions (poly(n-butyl methacrylate), PBMA, and polyurethane, PU). Use of the emission characteristics of probes such as pyrene and phenanthrene dispersed within particles reveals that the PU latices are more heterogeneous in nature: evidence exists, particularly from quenching measurements and TRAMS, that voids and channels of water permeate the PU structure, resulting in a relatively soft, open particle, swollen by ingress of the bulk aqueous phase. Fluorescence measurements indicate that PBMA colloids, however, are composed of relatively hard, hydrophobic particles. In addition, TRAMS are considered to be a valuable tool both for probing the morphological characteristics of such dispersions and in estimating the average particle size.     

软段含羧基的水性聚氨酯物性研究

合成了单官能团小分子物质封端的软硬段皆含羧基的脂环族水性聚氨酯(PU),研究了反离子种类、固含量、外加小分子盐/酸、pH值对水性PU的粘度、粒径、CMC和电导率的影响,同时,比较了不同软段分子量水性PU分散液pH临界值和CMC的差异.实验结果表明,随固含量升高,PU分散液体系粘度增大,当固含量为30wt%时,粘度比固含量20wt%的体系粘度增大约20倍;随小分子盐NaCl的加入,PU分散液电粘滞效应逐渐消失,电导率呈现先减小后增大的趋势,随NaCl的加入/软段分子量提高,PU分散体系的CMC值减小,钙离子对PU粒子扩散双电层的破坏作用更加明显.随pH值的增大,PU分散液体系粒径减小,电导率则升高,随软段分子量提高,pH临界值增大,PU分散体对外加小分子酸存在缓冲作用.     

The grafting of phthalic acid onto polyurethane copolymer and its impact on the surface hydrophilicity,tensile stress,and shape recovery properties

Phthalic acid (PA) was grafted onto polyurethane (PU) in the PA series due to its rigid aromatic structure and carboxyl groups, but PA was simply blended with PU in the control CPA series. The cross-link density and solution viscosity of the PA series notably increased with increasing PA content, and the same parameters of the CPA series did not increase. The maximum tensile stress of the PA series sharply increased due to the chemical cross-linking of the grafted PA, and the tensile strain at break slowly decreased with increasing PA content. The shape recovery of the PA series at 10?°C rapidly increased upon the grafting of PA; however, that of the CPA series decreased with increasing PA content. The hydrophilicity of PU was enhanced by the grafting of PA based on the water contact angle and water vapor permeation results. The low temperature flexibility of the PA series improved more than that of the CPA series under freezing conditions with increasing PA content due to the chemical cross-linking and steric and electrostatic repulsion between PU moieties. Overall, the grafted PA definitely increased the maximum tensile stress, shape recovery, and low temperature flexibility of PU.     

Graft copolymers of polyurethane with various vinyl monomers via radiation-induced miniemulsion polymerization: Influential factors to grafting efficiency and particle morphology

Graft copolymers of polyurethane (PU) with various vinyl monomers were synthesized through a one-pot but two-step miniemulsion polymerization process. Firstly, the polycondensation of isophorone diisocyanate (IPDI) with hydroxyl-terminated polybutadiene (HTPB) had been performed in aqueous miniemulsion at 40 °C in order to obtain PU dispersions. Consecutively, an in-situ graft copolymerization of the vinyl monomers with the synthesized PU was initiated by γ-ray radiation at room temperature. The grafting efficiency of PU with vinyl monomer (G_PU/monomer) was calculated from ¹H NMR spectra and the particle morphology of the final hybrid latex was observed by transmission electron microscopy (TEM). As there was no monomer transferring in miniemulsion system, homogenous hybrid particles would be synthesized provided that the monomer was miscible with PU, such as styrene. With the increase of the polarity of the monomer, the compatibility of PU with monomer decreased. G_PU/monomer varied as G_PU/styrene(37%)>G_{PU/butyl acrylate (BA)}(21%)>G_{PU/methyl methacrylate (MMA)}(12%). The proportion of homogeneous nucleation would increase as the hydrophilicity of the monomer increased. High temperature would destabilize the miniemulsion so as to result in a less grafting efficiency. Compared to the phase separation during the seeded emulsion polymerization, the miniemulsion polymerization method facilitated the preparation of homogeneous materials owing to its monomer droplet nucleation mechanism.     

Semibatch emulsion polymerization of methyl methacrylate using different polyurethane particles

Aqueous acrylic‐polyurethane (AC–PU) hybrid emulsions were prepared by semibatch emulsion polymerization of methyl methacrylate (MMA) in the presence of four polyurethane (PU) dispersions. The PU dispersions were synthesized with isophorone diisocyanate (IPDI), 1000 and 2000 molecular weight (MW) poly(neopentyl) adipate, 1000 MW polytetramethyleneetherglycol, butanediol (BD), and dimethylol propionic acid (DMPA). MMA was added in the monomer emulsion feed. We studied the effect of the use of different PU seed particles on the rate of polymerization, the particle size and distribution, the number of particles, and the average number of radicals per particle. The PU rigidity was controlled by varying the polyol chemical structure, the polyol MW (M_n), and by adding BD. The monomer feed rate was varied to study its influence on the process. It was observed that the PU particles that had been prepared with a higher MW polyol swelled better with MMA before the monomer‐starved conditions occurred. There seemed to be no significant discrepancies between the series with different PU seeds in the monomer‐starved conditions. The overall conversion depended on the monomer addition rate, and the polymerization rate acquired a constant value that was comparable to the value of the monomer addition rate. The instantaneous conversion increased slightly. The average particle size increased, and the total particle number in the reactor was constant and similar to the number of PU particles in the initial charge. The average number of radicals per particle increased. The differences between the system with a constant particle number and average number of radicals per particle and the system with a fixed radical concentration are discussed. The semibatch emulsion polymerization of MMA in the presence of PU particles studied was better compared to the system with a fixed radical concentration. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 844–858, 2005