Preparation and properties of poly(silicone‐co‐acrylate)/montmorillonite nanocomposite emulsion

Poly (silicone‐co‐acrylate)/montmorillonite nanocomposite emulsion were prepared by in situ intercalative emulsion polymerization of acrylate and organosilicone, in the presence of organic modified montmorillonite (OMMT) with different OMMT contents (0, 0.5, 1, 1.5, and 2 wt %). The nanocomposite emulsions were characterized with X‐ray diffraction (XRD), laser light scattering, fourier transform infrared (FTIR), rheological measurements, surface tension, drying speed, and water absorption property. Results showed that OMMT could improve the properties of emulsion, in other words, the properties of nanocomposite emulsion were better when compared with those of the silicone–acrylate emulsion. The properties of nanocomposite emulsion containing 1 wt % OMMT was the best one, and obtained the following advantages: smaller particle size, faster drying speed, shorter curing time, smaller surface tension, bigger apparent viscosity, and improved resistant water by the incorporation of OMMT. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3963–3970, 2006     

Preparation and characterization of water-based polyurethane–acrylic hybrid nanocomposite emulsion based on a new silane-containing acrylic macromonomer

A new silane-containing acrylic macromonomer, maleimidedoethoxybutoxydimethylsiloxy butyl acrylate (MEBDMSBA), based on maleic anhydride (MA), ethanolamine (EA), 1,4-butanediol (BDO), dichlorodimethylsilane (DCDMS), and acrylic acid (AA) has been synthesized for formulation of waterborne polyurethane (WPU). Also a series of new silane-containing WPU, methyl methacrylate (MMA), MEBDMSBA, and montmorillonite (MMT) with organically modified montmorillonite (OMMT) content (1.25 wt%) hybrid nanocomposites have been successfully prepared by the emulsion polymerization in the presence of a WPU dispersion, using ammonium peroxodisulfate (APS) as an initiator. The WPU dispersion has been synthesized by a polyaddition reaction of isophorone diisocyanate (IPDI) on polypropylene glycol (PPG-1000) and dimethylol propionic acid (DMPA) as chain extender. The monomer was characterized by Fourier transformer infrared spectroscopy (FTIR), elemental analysis, proton (¹H NMR), and carbon (¹³C NMR) nuclear magnetic resonance spectroscopes, respectively. The nanocomposite emulsions were also characterized using Fourier transform infrared spectroscopy (FTIR) and laser light scattering. Thermal properties of the copolymers were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The OMMT was characterized by FTIR and X-ray diffraction (XRD). The morphology of copolymers was investigated by scanning electron microscopy (SEM) and transition electron microscopy (TEM), and then the effects of silane concentrations on the water absorption ratio were examined. Results showed that OMMT could improve the properties of emulsion; in other words, the properties of nanocomposite emulsion were better when compared with those of the silane–acrylate emulsion.     

Synthesis and characterization of a novel silicone containing vinylic macromonomer and its uses in the preparation of poly (silicone‐co‐styrene‐co‐butylacrylate) with montmorillonite nanocomposite emulsion

A new silicone containing macromonomer, 4‐(methacrylamido) phenoxy polymethylhydrosiloxane (4‐MPMHS) with a vinyl group, was successfully synthesized. Then poly (silicone‐co‐styrene‐co‐butylacrylate) with montmorillonite, P (Si‐co‐St‐co‐BA) with MMT nanocomposite emulsion was prepared by in situ intercalative emulsion polymerization of styrene (St), butyl acrylate (BA), and 4‐MPMHS, in the presence of organic modified montmorillonite (OMMT) with different OMMT contents (0, 0.5, 1.0, 1.5, and 2 wt %). Potassium persulphate (KPS) was used as an initiator and sodium lauryl sulfoacetate (SLSA) and nonyl phenol ethylene oxide—40 U (NP‐40) were used as anionic and nonionic emulsifiers, respectively. The resulting macromonomer was characterized by elemental analysis, Fourier transformer infrared (FT‐IR), proton (¹H NMR), and carbon (¹³C NMR) nuclear magnetic resonance spectroscopes. The OMMT was characterized by FT‐IR and X‐ray diffraction (XRD). The nanocomposite emulsions were characterized by using Fourier Transform infrared spectroscopy (FT‐IR), laser light scattering, and surface tension method. Thermal properties of the copolymers were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) and then the effects of OMMT percent on the water absorption ratio and drying speed were examined. Results showed that OMMT could improve the properties of emulsion. In other words, the properties of nanocomposite emulsions were better when compared with those of the silicone‐acrylate emulsion. The property of nanocomposite emulsion containing 1 wt % OMMT was the best one, and the following advantages were obtained: smaller particle size, faster drying speed, smaller surface tension, and improved water resistance by the incorporation of OMMT. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

天然松香改性苯丙乳液的制备及其性能研究

以苯乙烯(St)、甲基丙烯酸甲酯(MMA)、丙烯酸-2-乙基己酯(2-EHA)、丙烯酸-2-羟基乙酯(HEA)和丙烯酸(AA)为反应单体,利用天然松香乳液作为改性剂,通过乳液聚合的方式制备了松香-苯丙复合乳液。研究了乳化剂用量、引发剂用量、松香乳液用量和单体配比对乳液性能的影响。并通过TGA、DLS、TEM对所制备的复合乳液进行了表征。结果表明:当乳化剂用量为单体质量的5%、引发剂用量为单体质量的0.8%、松香乳液用量为单体质量的30%、m(硬单体)∶m(软单体)=2.5∶1时,制得的乳液呈白色泛蓝光,粒径为131 nm。成膜后,漆膜光滑透明,硬度(1H)、耐水性(接触角97.05°)和附着力(1级)等性能良好。     

Synthesis of N-(2 amino benzothiazole) methacylamide monomer and its copolymers for antimicrobial coating application by RAFT polymerization

Monomer with thiazole moiety was synthesized and copolymerized with butyl acrylate and methyl methacrylate by reversible addition fragmentation chain transfer emulsion polymerization. The chain transfer agent was synthesized using N-ethyl piperazine, carbon disulfide, and ethyl 2-bromoisobutyrate. The wt% of monomer was varied from 3, 5, 7, 9, and 12 respectively. A antimicrobial activities of monomer and its copolymers were screened against E. coli, B. subtilis, C. albicans, and Aspergillus niger microorganisms. The synthesized monomer and chain transfer agent were characterized by ¹H NMR, FTIR, and mass spectral analysis, whereas emulsion copolymers were characterized for their molecular weight, particle size, and FTIR analysis.     

Synthesis of fiber crosslinking cationic latex and its effect on surface properties of paper

Series of fiber cross-linking cationic latexes containing both epoxy and quaternary ammonium groups were synthesized in the presence of styrene/butyl acrylate/steary methacrylate/dimethyl amino ethyl methacrylate/epichlorohydrin (SBSDE). The chemical structure and composition of SBSDE were confirmed by ¹H nuclear magnetic resonance spectrum (¹H NMR), Fourier transforms infrared (FTIR), gel permeation chromatography (GPC) analyses. Latexes were subsequently used as sizing agents and surface properties (water resistance, surface strength, burst strength, whiteness, and tensile strength) of paper were examined and compared. Results revealed that SBSDE was a potential candidate for emulsion polymerization. Monomer ratio, initiator type, and SBSDE content determined the properties of latexes and strongly affected the sizing performance. The superior surface sizing agent was obtained by using 2,2-azobisisobutyronitrile as the initiator, when the concentration of SBSDE was 8.5 wt%, the butyl acrylate (BA)/styrene (St) ratio was 0.85.     

纳米粒子种类对PMMA／纳米复合材料性能的影响

研究了胶体SiO2、粉体SiO2、有机改性蒙脱土OMMT等不同纳米粒子种类对纳米复合材料性能的影响,通过红外光谱、X射线衍射、热重分析和动态力学性能等测试手段对复合材料进行了分析表征。结果表明,OMMT和胶体SiO2与聚甲基丙烯酸甲酯（PMMA）的复合效果最好;OMMT的加入对复合材料的热性能有一定提高,而胶体和粉体SiO2的加入提高了复合材料的储能模量。     

核-壳结构含氟丙烯酸酯乳液的合成与表征

A fluorine-containing polyacrylate copolymer emulsion was synthesized by a seed emulsion polymerization method, in which methyl methacrylate （MMA） and butyl acrylate （BA） were used as main monomers and hexafluorobutyl methacrylate （HFMA） as fluorine-containing monomer. The structure and properties were characterized by Fourier transform infrared spectrum （FT-IR）, transmission electron microscopy （TEM）, particle size analysis, X-ray photoelectron spectroscopy （XPS）, contact angle （CA）, differential scanning calorimetry （DSC） and thermogravimetry （TG） analysis. The FTIR and TEM results showed that HFMA was effectively involved in the emulsion copolymerization, and the formed emulsion particles had a core-shell structure and a narrow particle size distribution. XPS and CA analysis revealed that a gradient concentration of fluorine existed in the depth profile of fluorine-containing emulsion film which was richer in fluorine and more hydrophobic in one side. DSC and TG analysis also showed that a clear core-shell structure existed in the fluorine-containing emulsion particles, and their film showed higher thermal stability than that of fluorine-free emulsion.     

Synthesis of allyl ether and benzyl methacrylate functionalized silane monomers for application in acrylate/montmorillonite nanocomposite emulsion

Abstract

Allyl trimethylsiloxybutyl ether (ATE) and 3-(trimethylsiloxy) benzylmethacrylate (TBM), tow novel silane involving monomers were successfully synthesized. Then, by in situ intercalative emulsion polymerization of styrene (St), butyl acrylate (BA), ATE and TBM, poly (silane-co-styrene-co-butylacrylate)/montmorillonite, P (Si-co-St-co-BA)/OMMT nanocomposite emulsions were prepared. The structures of monomers were clarified by the FT-IR, ¹H-NMR, and ¹³?C-NMR spectroscopic techniques and nanocomposites by FT-IR. The results indicated that addition of OMMT improved the thermal and morphological properties of emulsions and among the samples tested, the modified nanocomposites which were prepared by intercalating 1?wt% OMMT showed the most desirable effect. It was also demonstrated by TEM that OMMT addition causes some clusters or agglomerated particles into the polymer matrix and the most OMMT layers are dispersed homogeneously.     

Preparation and characterization of porous acrylate terpolymer nanocomposite for removal of diesel oil from artificial seawater

The present work deals with the preparation of magnetic acrylate terpolymer nanocomposite by emulsion polymerization. This nanocomposite was applied for the removal of diesel oil from artificial seawater by magnetic separation. Magnetic terpolymer nanocomposite was characterized by Fourier transform infrared (FTIR) spectra, X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Specific surface area and pore size distribution were measured by the Brunauer–Emmett–Teller (BET) method. Contact angle (CA) measurement showed superhydrophobic properties of magnetic acrylate nanocomposite. Kinetics and isothermal studies indicate that oil sorption fits the second-order kinetic model and the Langmuir isotherm. Magnetic acrylate terpolymer can be regenerated for six cycles.     

环氧树脂改性含氟丙烯酸酯/有机蒙脱土复合乳液的研究

以丙烯酸六氟丁酯(HFBM)为功能性单体,有机蒙脱土为改性剂,甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)和丙烯酸(AA)为主要单体,采用乳液聚合法合成了含氟丙烯酸酯/有机蒙脱土(PFA/OMMT)复合乳液,并用环氧树脂乳液对其进行共混改性,探讨了环氧树脂的环氧值和用量对共混乳液所成漆膜性能的影响.结果表明:环氧值越小...     

纳米SiO2/聚氨酯-含氟丙烯酸酯杂化乳液的合成与表征

采用种子乳液聚合法,以聚氨酯（PU）乳液为种子（在聚合过程中为壳相）,甲基丙烯酸甲酯（MMA）、丙烯酸丁酯（BA）、甲基丙烯酸十二氟庚酯（DFMA）和γ-甲基丙烯酰氧丙基三甲氧基硅烷（KH-570）改性的纳米SiO₂组成的混合物为核相,合成了具有核壳结构的纳米SiO₂/聚氨酯-含氟丙烯酸酯（SiO₂/FPUA）复合乳液。考察了纳米SiO₂和DFMA用量对乳液聚合过程及乳胶膜性能的影响。通过傅里叶红外光谱（FT-IR）、接触角（CA）、透射电子显微镜（TEM）、热重（TG）、差示扫描量热仪（DSC）和力学性能测试（MPT）等表征乳液的结构形态、乳胶膜的表面性能和综合性能。结果表明：乳胶粒子呈现“反相核壳”结构,以聚丙烯酸酯（PA）相为核,PU相为壳;由于纳米SiO₂和DFMA的协同作用,涂膜的疏水性和综合性能得到了较大的提高。     

核壳型含氟丙烯酸酯乳液的合成及表征

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、甲基丙烯酸六氟丁酯(HFMA)等为主要原料,采用多步乳液聚合法,合成了具有核壳结构的含氟丙烯酸酯乳液。实验结果表明,主要单体质量比m(MMA)∶m(BA)=45∶55,核壳单体质量比为6∶4,含氟单体质量分数为7%,乳化剂质量分数为3%~4%时,制备得到的含氟丙烯酸乳胶粒子具有软核/硬壳结构,粒径为120 nm,乳胶膜吸水率为7%。通过傅里叶红外光谱法(FTIR)对乳液结构进行表征,结果表明,含氟单体参与了有效聚合;差示量热扫描(DSC)和热重分析法(TG)分析结果表明,聚合物存在两个玻璃化温度(-10.2℃和58.4℃),且热分解温度比不含氟的聚合物提高了59℃;接触角测试结果表明,当w(HFMA)≥7%时,乳胶膜正面与水的接触角为98.2,°说明所合成的核壳结构含氟丙烯酸酯乳液中有机氟富集于壳层,涂膜的耐热、疏水性良好。     

核壳型丙烯酸酯乳液的制备与性能研究

采用甲基丙烯酸甲酯／丙烯酸丁酯作复合单体,丙烯酸为功能单体,通过预乳化半连续种子乳液聚合工艺合成了核壳型丙烯酸酯乳液,讨论了反应温度、乳化剂用量、核壳单体质量比以及丙烯酸加入量对乳液性能以及漆膜力学性能的影响,并用TEM对乳胶粒子进行了表征。结果表明：采用预乳化半连续滴加法,当复合乳化剂SDS与OP-10质量比为2：1且总用量为4％,核、壳层中甲基丙烯酸甲酯与丙烯酸丁酯的质量比分别为3：7和4：1,核壳总单体质量比为1：1,丙烯酸质量分数为4％,核层和壳层反应温度分别为70℃和80％时,可以合成黏度适中、乳胶粒粒径分布均匀、稳定性好和漆膜力学性能优良的核壳型丙烯酸酯乳液。     

色粉纸用自交联丙烯酸树脂乳液的合成及性能

根据色粉纸表面固砂的性能要求,以丙烯酸丁酯(BA)、甲基丙烯酸异辛酯(EHMA)为软单体、丙烯酸甲酯(MA)、甲基丙烯酸甲酯(MMA)为硬单体,丙烯酸羟丙酯(HPA)为交联单体,甲基丙烯酸(MAA)、甲基丙烯酸缩水甘油酯(GMA)作为功能单体,采用半连续种子乳液聚合法,制备了具有核壳结构的水性丙烯酸酯树脂乳液(WSAE-G),进一步将其作为色粉纸表面固砂用黏合剂和成膜剂.讨论了GMA用量对乳液粒径、稳定性和黏度等的影响.利用DLS和TEM对乳液乳胶粒子的大小及形貌进行了表征,使用TG、DSC以及万能材料试验机对胶膜的性能进行了测试.对固砂产品表面进行SEM测试.结果表明:GMA用量为1％(以混合单体总质量为基准,下同)时,乳液粒径为142.4 nm,PDI为0.063,乳液分散稳定指数(TSI)为0.162287.TEM显示,乳液具有清晰的核壳结构.胶膜拉伸强度达9.057 MPa.制得的色粉纸层间结合力为244.9 J/m2,所形成的固砂层均匀、磨砂性较好且不易掉砂.     

Controlled preparation and properties of acrylic acid epoxy-acrylate composite emulsion for self-crosslinking coatings

A stable epoxy-acrylate composite latex was successfully prepared through emulsion polymerization of modified epoxy acrylic (EPAC) oligomer with acrylate monomer. The EPAC oligomer was obtained using active acrylic acid (AA) to react with epoxy resin. And by regulating the reaction degree of the active hydrogen of AA and epoxide group, there is the acquisition of terminal double bond that gives EPAC reactivity, together with the partial retention of the epoxide group that enables self-crosslinking during film formation. The structural conformation of the oligomer was ascertained by Fourier transform infrared (FTIR) spectroscopy. The factors influencing the stability of the epoxy-acrylate composite latex were investigated. The epoxy-acrylate composite latex was the most stable when methyl acrylic acid was 1.5 wt% and modified EPAC oligomer was 15 wt% of the total monomer weight. The morphology and property of the composite latex films were characterized by scanning electron microscopy, transmission electron microscopy (TEM), and temperature-modulated differential scanning calorimetry (TOPEM-DSC). The results confirm that there is successful emulsion copolymerization between modified EPAC oligomer and acrylate monomer. TEM show that the particles of epoxy-acrylate composite have a core-shell structure, and there is no free epoxy resin. The FTIR and TOPEM-DSC results reveal that the copolymer emulsion possesses self-crosslinking ability. During film formation, self-crosslinking reaction occurs between epoxide groups with carboxyl groups, giving exothermal phenomena. The thermal stability as well as the corrosion resistance of the films was analyzed. The results show outstanding thermal stability as well as corrosion resistance attributable to the crosslinking reticulation structure. It is envisaged that the epoxy-acrylate composite latex has great potential in the development of high-performance aqueous coatings.     

Radiation synthesis and characterization of styrene/acrylic acid/organophilic montmorillonite hybrid nanocomposite for sorption of dyes from aqueous solutions

Organophilic montmorillonite (OMMT) was synthesized by cationic exchange reaction of Na⁺‐MMT and vinyl benzyl triethyl ammonium chloride (VBTAC) as a reactive organic modifier in an aqueous solution. A series of styrene (St)/acrylic acid (AA)/OMMT nanocomposite hydrogel containing different wt% of OMMT was synthesized through in situ polymerization using γ‐ray. The samples were characterized using Fourier transform infrared (FTIR), X‐ray powder diffraction (XRD), and transmission electron microscope (TEM), whereas thermal stability was examined by thermogravimetric analysis (TGA). The adsorption capacity and rate for both Acid Green B (anionic) and Maxilon C.I. Basic (cationic) dye including adsorption kinetics and isotherm were investigated at 30°C. TEM measurements showed spherical nanosized particles of average diameter 30–40 nm and XRD suggested the formation of exfoliated nanocomposite. TGA measurements showed that the addition of OMMT did not enhance the thermal stability where the onset temperature of the degradation for all samples was around 125°C. The effect of some important parameters on dye adsorption such as solution pH, initial dye concentration, and contact time was investigated. The equilibrium data obtained in batch experiments were correlated to Langmuir and Freundlich isotherm equations. Results showed that the adsorption of Acid Green B fitted well to the Langmuir model while the adsorption pattern of Maxilon C.I. Basic followed the Freundlich isotherm, which suggests heterogeneity of the adsorption sites on the nanocomposite. POLYM. COMPOS., 35:2353–2364, 2014. © 2014 Society of Plastics Engineers     

桐油酸改性含环氧基团聚丙烯酸酯乳液的制备

摘要：以丙烯酸丁酯（BA）、甲基丙烯酸甲酯（MMA）、丙烯酸羟乙酯（HEA）为主要单体，桐油酸和甲基丙烯酸缩水甘油酯（GMA）为功能性单体，采用半连续乳液聚合法制备了一系列桐油酸改性含环氧基团聚丙烯酸酯乳液（简称改性聚丙烯酸酯乳液）。通过FTIR表征胶膜的结构，同时测定了胶膜的力学性能、耐酸耐碱性等。结果表明：当桐油酸添加量（以MMA、BA、HEA、GMA的总质量为基准）为4%时，随着GMA含量（即GMA的质量占总丙烯酸单体质量的百分数，下同）的增加，胶膜铅笔硬度增大，耐水、耐酸碱性能增强，拉伸强度增大，热稳定性增加，胶膜附着力增加。当GMA含量为12%时，胶膜铅笔硬度为4H，涂在马口铁上的胶膜在5%的盐酸溶液中浸泡144 h无变化，在5%的氢氧化钠溶液浸泡72 h无变化，24 h的吸水率为3.31%，附着力为0级。     

Synthesis and characterization of rutile titanium dioxide/polyacrylate nanocomposites for applications in ultraviolet light‐shielding materials

Rutile titanium dioxide (TiO₂)/poly(methyl methacrylate‐acrylic acid‐butyl acrylate) nanocomposites were synthesized via seeded emulsion polymerization and characterized by Fourier transmission infrared, dynamic light scattering, X‐ray diffraction, ultraviolet–visible (UV–vis) spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis to study their UV‐shielding property. The effects of the nanoseed types, surfactant concentrations, and functional monomer amounts on the polymerization conversion, particle size, emulsion stability, and morphologies of the resulting nanocomposites were investigated. The dependence of UV‐shielding performance on the nanoparticle content and dispersion was also explored. The optimized results are obtained with 2 wt% of TiO₂ nanoparticles addition, and the effectiveness of UV shielding is significantly increased by using the synthesized rutile nano‐TiO₂/polyacrylates, for which the nanocomposite coating with a thickness of 200 μm could block up to 99.99% of UV light (≤350 nm) as confirmed by UV–vis spectrometry. POLYM. COMPOS., 36:8–16, 2015. © 2014 Society of Plastics Engineers     

含磷丙烯酸酯乳液的制备及性能研究

以甲基丙烯酸酯基烷氧基磷酸酯（PAM-100）、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸等为单体,采用预乳化半连续乳液聚合法制备了含磷丙烯酸酯共聚乳液。研究了PAM-100用量对单体转化率、乳液稳定性和乳胶粒粒径及分布的影响,并通过红外光谱（FT-IR）和微型燃烧量热分析（MCC）对乳胶膜的结构及性能进行表征。结果表明：PAM-100的加入有利于提高乳液聚合的稳定性及乳胶膜阻燃性能。与纯丙乳液相比,当PAM-100用量为10wt%时,含磷丙烯酸酯共聚乳液的乳胶粒表面Zeta电位绝对值由34.6mV提高至41.3mV,粒径由169nm下降至132nm;同时,含磷丙烯酸酯乳胶膜热释放速率峰值（pHRR）由391.1W/g下降至333.3W/g,到达pHRR的时间由264s推迟至300s。