聚氨酯-聚丙烯酸酯复合乳液的研究进展

本文综述了聚氨酯-聚丙烯酸酯（PUA）复合乳液的合成方法，以及国内外为提高PUA复合乳液的性能所采取的措施，并指出了PUA复合乳液今后的主要发展方向。     

浅谈聚丙烯酸酯改性水性聚氨酯的方法

介绍了聚丙烯酸酯改性水性聚氨酯的几种主要方法,并指出了各自的优缺点及其应用范围。聚氨酯-丙烯酸酯(PUA)复合乳液能较好地克服单一的PU乳液、PA乳液各自的缺点,已经成为研制第3代新型水性聚氨酯的重要途径。     

阳离子水性聚氨酯/聚丙烯酸酯乳液的制备与性能研究

用聚醚二元醇、甲苯二异氰酸酯（TDI）、N–甲基二乙醇胺（N–MDEA）、乙酸为原料制备了阳离子水性聚氨酯乳液,然后向聚氨酯乳液中加入丙烯酸丁酯（BA）和引发剂进行自由基聚合制成阳离子水性聚氨酯/聚丙烯酸酯乳液。用旋转黏度计、FT–IR、电子万能（拉力）试验机对所制备的乳液黏度、膜的形态结构及力学性能进行了表征。结果表明,改性后的阳离子聚氨酯乳液综合性能明显提高。     

聚丙烯酸酯改性水性聚氨酯的制备及性能

以聚醚二元醇N210、甲苯二异氰酸酯(TDI)为主要原料,二羟甲基丙酸(DMPA)为亲水扩链剂,三乙胺为成盐剂按逐步聚合原理合成聚醚型水性聚氨酯(WPU);再经与Tg为–11℃或–33℃的聚丙烯酸酯(PA)的乳液反应或共混,制备了PA改性的WPU(PUA)共聚(共混)乳液。讨论了聚醚型WPU和Tg为–11℃或–33℃的PA的乳液的比例(m(WPU)∶m(PA))对PUA共聚乳液黏度以及PUA共聚(共混)薄膜的力学性能和耐溶剂性能的影响。     

环氧改性水性聚氨酯/聚丙烯酸酯的制备与性能

以聚己内酯二元醇(PCL 1000)、异佛尔酮二异氰酸酯(IPDI)、2,2-二羟甲基丁酸(DMBA)、甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)等为主要原料合成水性聚氨酯/聚丙烯酸酯乳液(WPUA),通过向WPUA中引入甲基丙烯酸缩水甘油酯(GMA)和可聚合乳化剂烯丙氧基羟丙基磺酸钠(AHPS),合成了稳定性好、固含量约为43%的可聚合乳化剂作用下的环氧改性聚氨酯/聚丙烯酸(EPUAS)复合乳液。采用FT-IR、TEM、XRD对改性前后乳液和涂膜结构进行了表征,探讨了GMA及AHPS在不同含量下对WPUA乳液及其涂膜性能的影响。实验表明:在GMA用量为5%(以丙烯酸单体总质量计,下同)、AHPS用量为2%时,乳液和涂膜的固含量、耐水性、硬度及机械性能等得到改善。     

酮肼交联水性聚氨酯/聚丙烯酸酯复合树脂的结构和性能研究

采用乳液聚合工艺,通过加入双丙酮丙烯酰胺(DAAM),合成了具有活性酮羰基的聚丙烯酸酯乳液;同时通过羟基酮将酮羰基引入聚氨酯分子中,经分散得到含活性酮羰基的聚氨酯树脂;将二者混合,并加入己二酰肼(ADH),得到酮肼交联水性聚氨酯/聚丙烯酸酯(PUA)复合树脂。通过红外光谱、动态力学分析和耐磨性等测定对涂膜结构和性能进行了表征和分析,并将其与常规水性聚氨酯/聚丙烯酸酯树脂等进行了比较。结果显示,酮肼交联的水性聚氨酯/聚丙烯酸酯树脂具有较好的性能。     

聚丙烯酸酯改性聚氨酯乳液的研究进展

综述了聚丙烯酸酯改性聚氨酯乳液的物理掺混法、嵌段共聚法、核壳共聚法、接枝共聚法和互穿聚合物网络共聚法的研究进展,并且结合实验对各种改性方法的优、缺点进行了讨论.     

单体含量对核壳结构聚氨酯-聚丙烯酸酯乳液性能影响

以水性聚氨酯（PU）为种子乳液,以丙烯酸酯（PA）为聚合性单体,采用种子乳液聚合法合成核壳结构聚氨酯-聚丙烯酸酯乳液（PUA）。研究了单体含量对乳液及胶膜性能的影响。实验结果表明：随着乙烯基单体含量的增加,乳液颜色加深,稳定性下降,胶膜的断裂伸长率降低,硬度和耐水性增加。当乙烯基单体和PU百分比（M／P）为25％时,乳液的稳定性大于12个月,胶膜的断裂伸长率为498％,硬度为0．64,吸水性为22．8％。红外光谱分析表明合成了PUA。     

聚氨酯-聚丙烯酸酯复合乳液合成工艺的研究

采用种子乳液聚合法制备了聚氨酯-聚丙烯酸酯(PUA)复合乳液。比较了4种不同合成工艺对PUA复合乳液性能的影响。试验结果发现，单体中和合成工艺的PUA复合乳液的贮存稳定性、机械性能和耐水性好，具有工艺简单、污染小、成本低的特点。     

室温交联单组分聚氨酯-聚丙烯酸酯乳液的合成

分别合成了带有端酰肼基的自乳化型聚氨酯乳液和带酮羰基侧链的聚丙烯酸酯乳液，将两种乳液混合复配成在室温下可长期稳定储存的乳液，应用时两种树脂的活性基团在室温发生交联反应得到聚氨酯交联的聚丙烯酸酯复合树脂。合成聚氨酯乳液的较好工艺是：反应温度约60℃，反应时间=6h，n（OH)／n(NCO)=0．85，W(—COOH)=3％，二羟甲基丙酸(DMPA)以丙酮提取法加入；分析了乳液的粒径分布和稳定性；用红外谱图证明在室温发生了交联反应 ；测试了复合树脂的某些机械性能和耐溶剂性。     

聚氨酯/丙烯酸酯复合乳液的制备方法及性能研究进展

介绍了近年来国内外聚氨酯/丙烯酸酯复合乳液制备方法：物理共混、种子乳液聚合法、原位聚合法等;评述了聚氨酯的结构、聚丙烯酸酯、引发剂以及制备方法等因素对复合乳液性能的影响;对目前常用的无机纳米粒子和交联等对聚氨酯/丙烯酸酯复合乳液改性方法进行了讨论;展望了该领域的发展趋势。     

聚氨酯/聚丙烯酸酯复合弹性体的力学性能研究

采用预聚体法合成了一系列聚氨酯／聚丙烯酸酯复合弹性体，研究了组成比例对PU／PA复合弹性体的力学性能的影响。结果表明：聚丙烯酸甲酯的比例在一定范围内时，可以较大程度地提高材料的力学强度和断裂伸长率，而将丙烯酸甲酯和甲基丙烯酸甲酯混合加入聚氨酯中，形成的复合弹性体的力学性能无明显改善。     

丙烯酸酯改性水性聚氨酯的研究进展

介绍了聚氨酯/丙烯酸酯(PUA)复合乳液的制备方法,包括物理共混、交联共混、复合乳液共聚、核/壳结构乳液共聚法及互穿聚合物网络(IPN)法等,同时从无机纳米粒子改性、氟改性、有机硅改性和环氧树脂(EP)改性等方面对改性PUA复合乳液的研究进展进行了概述。     

Structure and property characterization of nanograde core‐shell polyurethane/polyacrylate composite emulsion

Anionic aqueous polyurethane dispersion was synthesized through self‐emulsifing method from cycloaliphatic isophorone diisocyanate (IPDI) and dimethylolpropionic acid (DMPA). The carboxyl acid group in DMPA was used to make the polyurethane dispersible. The polyurethane/polyacrylate (PU/PA) composite particles were also prepared by seeded surfactant‐free emulsion polymerization; the cycloaliphatic polyurethane aqueous dispersion was used as seed particles. The structures and properties of the composite emulsion as well as the physical mixture of polyurethane dispersion and polyacrylate emulsion were characterized by FTIR, DSC, dynamic light scattering, TEM, X‐ray photoelectron spectroscopy (ESCA), and electronic tensile machine. The results showed that the synthesized PU/PA composite emulsion was found to form inverted core‐shell structure with polyacrylate as the core and with polyurethane as the shell, and its diameter of particles is in the range of nanograde, the crosslinking reaction was existed in composite emulsion. The intimate molecular mixing of crosslinking polymers are also claims to result in a superior balance of properties compared to physical blends of polyurethane dispersion and acrylate emulsion. The crosslinking mechanism of PU/PA composite emulsion was also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

水性聚氨酯/聚甲基丙烯酸甲酯杂化乳液的合成

用异佛尔酮二异氰酸酯(IPDI)、聚丙二醇(PPG)和二羟甲丙酸(DMPA)合成了水性聚氨酯分散体(WPU),讨论了PPG摩尔质量,NCO/OH及PPG/DMPA比例对WPU乳液和涂膜性能的影响。以WPU为种子与甲基丙烯酸甲酯进行乳液聚合制备杂化乳液,研究了不同PU/PMMA物质的量比例对杂化乳液及涂膜性能的影响,并采用TEM对WPU及杂化乳液粒子进行了表征。结果表明,在以PPG1000为原料,NCO与OH物质的量比为1.4∶1,PPG与DMPA物质的量比为1∶0.8条件下制备的WPU杂化乳液,随着PMMA比例增加,杂化乳液的稳定性和成膜性变差,聚合物膜断裂伸长率降低,但铅笔硬度、耐水性及耐乙醇性均得到了改善。     

Preparation and properties of reactive polyurethane polyacrylate blends based on carbonyl‐hydrazide reaction

A new reactive polyurethane/polyacrylate (PU/PA) blend was developed by mixing a core–shell polyacrylate latex containing keto groups in shell layer and a polyurethane dispersion incorporating multiple hydrazide groups which was synthesized by introducing the poly‐hydrazide groups into the end of the vinyl‐terminated polyurethane chains. Fourier transform infrared (FTIR) spectroscopy and gel permeation chromatography (GPC) results indicated that poly‐hydrazide groups had been incorporated in the polyurethane chains. Transmission electron microscopy (TEM) micrograph revealed that polyacrylate particles had a clear core–shell structure. The results of FTIR, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) indicated that the crosslinking reaction between two polymer systems had happened and crosslinking structure could effectively improve the compatibility between PA and PU. Thermogravimetric analysis (TGA) and mechanical tests results suggested that crosslinking structure could enhance the thermal stability and mechanical properties of blends. The influence of the PA content and the n(? CO? )/n(? NHNH₂) ratio on the hardness, water resistance, solvent resistance, and gel fraction of the blend films were comprehensively studied. The optimal PA content and n(? CO? )/n(? NHNH₂) ratio was 30% and 1.5:1 in this experiment, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44443.     

丙烯酸酯用量对溶胀-嵌段型水性聚氨酯性能的影响

以甲基丙烯酸甲酯（MMA）、丙烯酸正丁酯（BA）为单体,通过巯基乙醇链转移自由基无规共聚合成端羟基聚丙烯酸酯（PA-OH）,采用嵌段共聚法将PA-OH与水性聚氨酯（WPU）嵌段,通过预聚体分散法制得聚丙烯酸酯嵌段水性聚氨酯乳液（WPUA）,进而通过乳液聚合法制备了一系列以MMA/BA为单体的聚丙烯酸酯嵌段-溶胀水性聚氨酯复合乳液（WPUA-PA）,结果表明WPUA-PA中丙烯酸酯量最多可达到WPUA的240%,当丙烯酸酯量为WPUA的120%时WPUA-PA的性能最佳,此时乳液平均粒径为68 nm、粒径分布指数为0.174,胶膜拉伸强度为13.88 MPa、断裂伸长率为558.3%、吸水率为4.94%,且具有优异的乳液稳定性。     

水性纯丙乳液的合成及单体配比对乳液附着性能的影响

以甲基丙烯酸甲酯(MMA)、丙烯酸异辛酯(2-EHA)分别为硬单体、软单体,甲基丙烯酸(MAA)为功能单体,过硫酸铵(APS)为引发剂,十二烷基硫酸钠(SDS)、脂肪醇聚氧乙烯醚(AEO-9)为乳化剂,采用半连续种子乳液聚合方法合成单体配比不同的水性聚丙烯酸酯乳液。利用衰减全反射-傅立叶变换红外光谱、核磁共振氢谱、凝胶渗透色谱、热重分析和动态热机械分析层测定水性聚丙烯酸酯的结构及性能。结果表明：随着硬软单体比的减小,聚丙烯酸酯乳液的粒径约为100nm;聚丙烯酸酯共聚物的低分子量部分,数均分子量约为3万,重均分子量约为5万;乳液膜的热分解温度从327.5℃升高到343.5℃,玻璃化转变温度从21℃降至-3.5℃;乳液的表面张力从39.83mN/m降至36.71mN/m、界面张力从19.01mN/m降至4.87mN/m、接触角从62.6°降到27.8°,附着牢度从50%提高到95%,当硬软单体比为7：13时,乳液的润湿性最好,附着牢度最高,满足乳液在BOPP薄膜上的应用要求。说明提高聚合物中软单体含量有利于提高乳液的润湿性,从而提高乳液的附着力。     

双组分水性聚氨酯哑光清漆的制备

采用拜耳公司的水性羟基丙烯酸树脂乳液和聚异氰酸酯固化剂制备了一种聚氨酯哑光清漆.通过实验研究确定了两种羟基树脂组分的混拼比例为48.00％的Bayhydrol XP 2546和23.00％的Bayhydrol XP 2542,NCO与OH的摩尔比为1.6.讨论了消光剂加入量与漆膜光泽的变化关系,当消光剂的质量分数为2.4％时,所制备的聚氨酯哑光清漆具有硬度高,耐磨性与耐候性好,光泽低等特点,综合性能优异.     

Damping materials based on polyurethane/polyacrylate IPNs: dynamic mechanical spectroscopy,mechanical properties and multiphase morphology

Four kinds of polyurethane/polyacrylate interpenetrating polymer networks (crosslinked polyacrylate semi-IPNs, crosslinked polyurethane semi-IPNs, all-IPNs and all-IPNs with opposite charge groups) were synthesized by a simultaneous polymerization process. Their damping properties, mechanical properties and multiphase morphology were investigated by automatic torsional braid analysis, an Instron tester, small-angle X-ray scattering (SAXS) and tranmission electron microscopy (TEM). The results show that the attraction between positively charged groups and negatively charged groups improved the miscibility of the two components. When the weight ratio of polyurethane/polyacrylate was 1:2, the resulting IPN materials possessed better damping and mechanical properties, and the specific surface area reached a maximum. © 1999 Society of Chemical Industry