端羟基含氟丙烯酸酯接枝改性水性聚氨酯的性能研究

利用不同相对分子质量的端羟基含氟丙烯酸酯(FA)大分子改性水性聚氨酯得到一系列含氟丙烯酸酯改性水性聚氨酯(PUA)乳液.通过傅里叶红外光谱(IR)和透射电镜(TEM)分别表征了聚合物结构和聚合物乳液胶粒形态,通过吸水率、接触角,差示扫描量热(DSC),热重(TG)和拉伸强度测试研究了乳胶膜的性能.结果显示,PUA在耐水性、耐热性和力学性能等方面都有明显的提高.     

丙烯酸酯乳液改性的研究进展

文章就丙烯酸酯乳液改性的研究现状及其用途作了详细论述,重点介绍了有机硅改性丙烯酸酯乳液和聚氨酯改性的丙烯酸酯乳液(PUA)以及氟改性丙烯酸酯乳液的发展情况,并简要地对丙烯酸酯乳液改性的未来方向作了展望。     

含氟丙烯酸酯共聚物乳液的制备及复配研究

溶液型含氟丙烯酸酯共聚物在使用中会产生环境污染，近年来人们更加重视乳液型含氟丙烯酸酯共聚物的开发和应用，常采用的方法有2种：通过乳液聚合将含氟丙烯酸酯单体和其他烯类单体共聚，以及将含氟丙烯酸酯聚合物乳液和其他乳液通过共混和偶联进行复配，本文对这2种方法进行了综述。     

水性聚氨酯与丙烯酸酯共聚乳液的研究

用乳液聚合的方法 ,制备出了具有核壳结构的水性聚氨酯与丙烯酸酯共聚乳液 (PUA乳液 ) ,对PUA的性能进行了初步的研究。结果表明 ,丙烯酸酯的用量对吸水率、热性能和机械性能产生重要的影响     

丙烯酸酯改性水性聚氨酯乳液的制备及性能研究

采用物理共混和核-壳聚合法制备了丙烯酸酯改性水性聚氨酯(PU/PA,PUA)乳液,并对不同改性方法制得的乳液进行了研究。通过红外(FTIR)、透射电镜(TEM)、差示扫描量热(DSC)、热重分析(TGA)、耐水性和力学性能测试等研究了丙烯酸酯改性聚氨酯乳液及涂膜的结构与性能。结果表明具有核-壳结构的PUA乳液涂膜耐水性、耐热性和固含量较水性聚氨酯(PU)有明显的提高,力学性能稍有下降;PUA综合性能优于PU/PA。     

聚含氟丙烯酸酯/聚氨酯共聚物细乳液的制备及表征

以甲苯二异氰酸酯(TDI)和甲基丙烯酸羟乙酯(HEMA)为原料,合成了丙烯酸酯/聚氨酯(PUA)预聚体;采用细乳液聚合法,合成了聚含氟PUA细乳液。使用红外光谱(FT-IR)和核磁共振(1H-NMR)表征了PUA预聚体及共聚物的结构组成,用激光光散射粒度仪(PCS)分析了乳胶粒的粒径及其分布,并考察了氟单体用量对乳胶膜的吸水率和表面性能的影响。研究结果表明,乳胶粒的粒径随着PUA预聚体用量的增加而增大;当氟单体质量分数由0增至20%时,乳胶膜的吸水率由10.3%降至4.2%,表面自由能由34.89mJ/m2降至15.66mJ/m2,说明氟单体的加入较好地改善了乳胶膜的表面性能。     

聚氨酯－丙烯酸酯复合乳液制备方法的进展

综述了聚氨酯－丙烯酸酯(PUA)复合乳液的制备方法,主要包括共混交联法、核壳乳液聚合法、互穿聚合物网络( IPN)法、无皂乳液聚合法、微乳液聚合法和细乳液聚合法;介绍了这些制备方法的优势和应用范围,并展望了PUA复合乳液的发展前景.     

接枝型含氟丙烯酸酯改性水性聚氨酯的合成

通过溶液聚合的方法合成了端羟基含氟丙烯酸酯大分子,通过HNMR和FT-IR表征了大分子结构,并通过控制链转移剂SHCH2CH2OH用量和加入时间来控制分子量。并以此作为封端剂合成接枝型的含氟丙烯酸酯改性水性聚氨酯(PUA)。通过FT-IR表征了聚氨酯(PUA)的结构。     

聚氨酯-丙烯酸酯(PUA)复合乳液的研究进展

综述了聚氨酯-丙烯酸酯(PUA)复合乳液的制备方法,研究新进展及其应用.     

HEMA封端对PUA复合乳液性能的影响

采用甲基丙烯酸-β-羟乙酯(HEMA)对聚氨酯预聚体进行封端,合成含有双键的水性聚氨酯乳液,并制备了核壳接枝的聚氨酯-丙烯酸酯(PUA)复合乳液.通过对PUA复合乳液和涂膜性能测定,讨论了HEMA用量对PUA乳液和涂膜性能的影响.结果表明,随着HEMA用量增加,PUA复合乳液的稳定性和涂膜热稳定性得到了提高.当HEMA用量为75%时,PUA综合性能优良.     

细乳液聚合法制备含氟丙烯酸酯共聚物乳液的研究

通过细乳液聚合法制备含氟丙烯酸酯共聚物（FPA）乳液,采用红外光谱（ FT-IR）、透射电镜（TEM）、原子力显微镜（AFM）、热重分析仪（ TG）、扫描电镜和表面能谱（ SEM-EDS）等对聚合物进行表征,并考察了乳化剂与助乳化剂的物质的量比,氟单体用量和超声时间对乳液粒径的影响。结果表明,甲基丙烯酸六氟丁酯（ 6FA）、丙烯酸丁酯（ BA）、苯乙烯（ St）3种单体成功聚合,乳化剂与助乳化剂的物质的量比为 1.5∶1,超声时间为 60 min,氟单体用量为 10%时,乳液粒径最小且分布较窄,表面张力从 45.028 mN/m降至 33.399 mN/m,且乳胶膜粗糙度增加,热稳定性提高。     

细乳液聚合制备纳米SiO2／含氟丙烯酸酯复合乳液及其性能研究

采用溶胶-凝胶法,以正硅酸乙酯为前驱物,在丙烯酸酯单体为油相介质中原位生成纳米SiO2粒子,并通过细乳液聚合,制备出纳米Si02／含氟丙烯酸酯复合乳液。研究了含氟单体和SiO2的用量对复合乳胶膜性能的影响,并采用FT-IR,DSL等分析手段对产物进行了表征。结果表明：该乳液具有良好的稳定性,粒径分布较窄。当（甲基丙烯酸十二氟庚酯）FA与SiO2的用量分别为6％和5．5％时,乳胶膜表现出良好的疏水性能,对水的接触角达到了102．7°,吸水性降低到6．9％。     

氟代聚丙烯酸酯改性阳离子型聚氨酯乳液的制备

以丙烯酸十二氟庚酯(FA)、丙烯酸羟丙酯(HpAA)为单体,通过偶氮二异丁腈(AIBN)引发聚丙烯酸酯自由基在交联的聚氨酯预聚体中进行聚合,并用N-甲基二乙醇胺(MDEA)进行亲水基扩链,溶液聚合相转化法制得新型氟代聚丙烯酸酯改性阳离子型聚氨酯复合乳液(FPUA)。对聚合物结构、乳胶粒形态进行表征。结果表明,以丙酮为溶剂,n_(NCO)/n_(OH)=1.3,MDEA质量分数6.5%、FA质量分数为8%时能得到半透明蓝光、稳定性良好的核-壳结构乳液,FPUA胶膜拉伸强度为19 MPa,吸水率为6.9%,接触角为101°,产品的耐水性优良。     

Synthesis and properties of cationic polyurethane-fluorinated acrylic hybrid latexes by emulsifier-free emulsion polymerization and the solvent-free method

A series of cationic polyurethane-fluorinated acrylic hybrid latex (PUFA) have been synthesized by solvent-free method. In the method, vinyl monomers acted as dilution agent and the polyurethane (PU) having quaternary ammonium groups acted as macromolecular emulsifier without using any other solvent and surfactant. The structure and properties of PUFA were characterized by Fourier transform infrared spectroscopy (FT-IR), F¹⁹ nuclear magnetic resonance (F¹⁹ NMR), particle size distribution (PSD) analysis, transmission electron microscopy (TEM), contact angle (CA), surface free energy analysis, scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometry (EDS), and thermogravimetric (TG) analysis. The FT-IR, F¹⁹ NMR, and EDS confirmed that the FA monomer had been introduced into the chain of the PUFA hybrid polymer. The PSD analysis indicated the particles of PUFA were smaller than corresponding pure PU dispersion and narrower in particle size distribution. The CA and surface free energy analysis proved the PUFA hybrid latex film with fluorine possessed higher contact angle and lower surface free energy in contrast with the film without fluorine. The FPUA films exhibited good surface property which could be enhanced at higher annealing temperature. The EDS of PUFA confirmed the fluorine enrichment on the surface of PUFA. TG analysis suggested the PUFA hybrid latex film had a better thermal stability than pure PU.     

FA共聚物/SiO_2杂化薄膜的制备及表面性能的研究

以含氟丙烯酸酯(FA)共聚物乳胶粒为模板,四甲氧基硅烷(TMOS)为硅源,环境条件下仿生矿化制备得到核壳型FA共聚物/SiO2杂化纳米粒子,其中壳层由数十个纳米级的小SiO2粒子组成。进一步采用溶剂直接挥发法制备得到FA共聚物/SiO2杂化薄膜,结果证实无机SiO2粒子杂化可有效提高薄膜表层粗糙度,降低表面自由能,导致水滴静态接触角明显增加,并且一定范围内TMOS用量的增加和矿化反应时间的延长均有利于提高杂化薄膜的疏水、疏油性能。     

Synthesis and characterization of core‐shell particles containing a perfluoroacrylate copolymer rich in the shell

A simple synthetic method for preparing the core‐shell latex particles containing fluorinated shell was presented. Polymerization was achieved by a low‐sheer monomer‐starved emulsion polymerization process, thus facilitating mobility and subsequent polymerization of perfluoroacrylate (FA) along with methyl methacrylate (MMA) and n‐butyl acrylate (nBA) monomers. The structure and thermal behavior of the resulting perfluoroacrylate copolymer were investigated by FTIR, NMR, and DSC. Furthermore, PCS, TEM as well as SFM, were carried out to characterize the surface morphology of the particles. These studies illustrated that the incorporation of FA into MMA/nBA particle morphologies facilitated surface phase separation during coalescence, resulted in F‐containing film‐air interfaces. Thus, surface properties with a significant increase in the contact angles could be produced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Role of acrylic acid in the synthesis of core‐shell fluorine‐containing polyacrylate latex with spherical and plum blossom‐like morphology

The core‐shell fluorine‐containing polyacrylate latex was successfully synthesized by two‐stage semicontinuous emulsion copolymerization of methyl methacrylate (MMA), butylacrylate (BA), acrylic acid (AA), and dodecafluoroheptyl methacrylate (DFMA). The fluorine‐containing polyacrylate latex was characterized by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential, thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC). The effects of AA content on monomer conversion, polymerization stability, particle size, corsslinking degree, carboxyl groups distributions (latex surface, aqueous phase or buried in latex), as well as mechanical properties and water absorption rate of latex film were investigated. The obtained fluorine‐containing polyacrylate latex exhibited core‐shell structure with a particle size of 120–150 nm. The introduction of AA was beneficial for the increase of monomer conversion and the polymerization stability, and had little effects on the mechanical property of latex film. However, the hydrophilicity of AA made the water resistance of latex film get bad. With the increase of AA content, the carboxyl groups preferred to distribute on aqueous phase, and the possibility of homogeneous nucleation increased and more oligomers particles were formed. Moreover, the oligomers would distribute to the latex and continued to grow up, making the latex morphology changed from spherical to plum blossom‐like. The core‐shell latex had two T_g corresponding to the rubber polyacrylate core and hard fluorine‐containing polyacrylate shell, and the latex film possessed excellent thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42527.     

Double in-situ synthesis of polyacrylate/nano-TiO2 composite latex

Polyacrylate/nano-TiO₂ composite latex was prepared via double in-situ polymerization using acrylamide (AM), vinyl acetate (VAc), butyl acrylate (BA) and methyl methacrylate (MMA) as monomers, tetrabutyl titanate (Ti(OBu)₄) as precursor of TiO₂. The morphology, structure and distribution of composite latex were characterized by Transmission Electron Microscope (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Dynamic Light Scattering (DLS) and X-Ray Diffraction (XRD). The thermal stability, anti-yellowing and antibacterial properties of composite latex were also investigated. The results showed that nano-TiO₂ consisted in polyacrylate latex and it was located on the surface of latex particles. The average particle size of polyacrylate/nano-TiO₂ composite latex was 156.6 nm, which was bigger than that of pure polyacrylate (125.1 nm). The introduction of nano-TiO₂ improved the thermal stability, anti-yellowing and antibacterial properties of the latex film. At last, the polyacrylate/nano-TiO₂ composite latex was applied in leather finishing. Compared with polyacrylate latex, the properties of the leather finished by polyacrylate/nano-TiO₂ composite latex were enhanced: water vapor permeability increased by 58% and water uptake decreased by 3.52%.     

Particle size and morphology of poly[styrene‐co‐(butyl acrylate)]/nano‐silica composite latex

Nanocomposite latex with nano‐silica of varying particle sizes was prepared via in situ polymerization and investigated by submicron particle size analysis, transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier‐transform infrared spectrometry (FTIR) and Raman spectrometry. It was found that nanocomposite latex exhibited a core–shell structure with nano‐silica particles enwrapped, resulting in an increase in the latex particle size. The smaller the nano‐silica particles, the more were embedded in each latex particle. The increase in the particle size of latex depended not only on the particle size of nano‐silica, but also on the number of nano‐silica particles in each latex particle. Copyright © 2004 Society of Chemical Industry     

乳聚丁苯互穿网络型热塑性弹性体的制备

以丁苯胶乳为种子乳液,苯乙烯、甲基丙烯酸甲酯、丙烯腈或它们的混合物的硬单体,用氧化还原引发体系,经种子乳液聚合法同备出复合乳液,絮凝干燥后所得互穿聚合物网络可热塑性反复加工。考察了硬单体的种类和用量、交联剂的种类及用量、反复加工次数对聚合物力学性能的影响。用透射电子显微镜观察了乳胶粒微观形态,结果表明：用混合单体,聚合物力学性能较优,以３５份Ｓｔ＾＋ＭＭＡ为第二单体制备的聚合物的攫断伸长率为４００％,拉伸强度为９．３ＭＰａ,３００％定伸应力为７．６ＭＰ,撕裂强度为７３．９ｋＮ．Ｍ＾－１,邵尔Ａ型硬度为８４。