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.     

聚氨酯-聚甲基丙烯酸甲酯核壳乳液的制备研究

以甲苯二异氰酸酯(TDI)、聚丙二醇(PPG)和二羟甲基丙酸(DMPA)等为原料,甲基丙烯酸甲酯(MMA)为活性稀释剂,合成阴离子聚氨酯乳液(WPU),并进一步在WPU乳液存在下进行MMA单体的乳液聚合,制得了聚氨酯-聚甲基丙烯酸甲酯核壳乳液(PUA)。通过透射电镜分析证明了核壳结构的存在,讨论了MMA、PPG、N-甲基吡咯烷酮(NMP)含量对乳液性能的影响。结果表明,MMA和PPG-400用量增加,并适量使用NMP溶剂,可有效改善WPU涂膜硬度及耐水性。     

复合改性水性聚氨酯乳液的合成及表征

以甲苯二异氰酸酯(TD I)、聚醚二元醇(N220)、1,4-丁二醇(BDO)和二羟甲基丙酸(DMPA)为原料,采用丙酮法合成了水性聚氨酯(WPU)分散体。在此基础上,采用三羟甲基丙烷(TMP)对其进行了交联改性并通过环氧树脂和丙烯酸酯对其进行共聚改性,制得了以丙烯酸酯为核,聚氨酯为壳的核壳交联型水性聚氨酯分散体。通过乳液粒度、黏度和涂膜的耐水性和硬度、接触角等分析以及透射电镜观测研究了二羟甲基丙酸(DM-PA)、TMP、环氧树脂以及MMA用量对水性聚氨酯涂膜耐水性等性能的影响,确定了最佳物料配比。结果表明,当DMPA、E-20、TMP和MMA在聚氨酯水性分散体中的质量分数分别为7.5%、6%、1%和20%时,合成的水性聚氨酯乳液平均粒径80 nm,黏度适中,胶膜的物理力学性能较好,耐水性提高。     

Synthesis of an acrylate elastomer with UV stabilization and its application in polyoxymethylene

In this study, an acrylate elastomer with light‐stable functional groups was synthesized by methyl methacrylate (MMA), butyl acrylate (BA), and a polymerizable UV stabilizer 2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxylproroxy) benzophenone (BPMA) via emulsion polymerization, and the product was poly[methyl methacrylate‐co‐butyl acrylate‐co‐2‐hydroxy‐4‐(3‐methacryloxy‐2‐hydroxylproroxy) benzophenone] [poly(MMA‐co‐BA‐co‐BPMA)]. The composition and characteristics of poly (MMA‐co‐BA‐co‐BPMA) were determined by using Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H‐NMR), and ultraviolet–visible absorption spectroscopy (UV–vis). Further, the obtained poly(MMA‐co‐BA‐co‐BPMA) was blended with polyoxymethylene (POM) to modify its photostabilization, as well as the mechanical properties of POM composite were tested before and after UV irradiation. The result showed that poly(MMA‐co‐BA‐co‐BPMA) can be dispersed well in the POM matrix, which could play a role of improving compatibility with and toughening for POM, and its light‐stable functional groups could increase the UV resistance of POM composite. Mechanical properties of modified POM were kept well with higher impact strength and elongation at break than pure POM after UV irradiation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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。     

Design and synthesis of polymeric dispersant for water-borne paint by atom transfer radical polymerization

A series of chains of triblock amphiphilic copolymers were synthesized by atom transfer radical polymerization (ATRP) techniques and post modified to polymeric dispersant for waterborne paint. Poly(butyl acrylate (BA))-b-poly(hydroxy ethyl methacrylate (HEMA))-b-poly(methyl methacrylate (MMA)) triblock copolymers having predetermined molecular weights were synthesized by ATRP using CuBr, 2-bromoisobutyrate, and pentamethyldiethylenetriamine as a catalytic system in dioxane at 80 °C. The copolymers were further reacted with cyclic chlorophosphate and triethyl amine to form dispersible modified poly(BA-HEMA-MMA). The synthesized copolymers were structurally evaluated by Fourier transform infrared, ¹H NMR, ³¹P NMR, gel permeation chromatography (GPC), energy dispersive X-ray spectroscopy, and their hydroxyl equivalent, respectively. The surface activity of modified copolymers as dispersing additives was investigated by the surface tension analysis and wetting ability test. The ability of additives to function as wetting and dispersing agents was evaluated by analyzing their mechanical, optical, chemical, and rheological properties of water-based paints at different pigment volume concentrations. The effects of the chain length of copolymers on dispersibility and optical properties were studied. The optical properties of paints suggested that the dispersibility of modified poly (BA)-b-poly (HEMA)-b-poly (MMA) (MPBHM) increased with an increase in the molecular weight of the copolymer.     

A Strategy for Preparation of Anionic Polyurethane/Acrylate Emulsions

In this article we proposed a new strategy for preparation of polyurethane/acrylate (PUA) hybrid emulsions. In the preparation of the polyurethane dispersion, methyl methacrylate (MMA) was used as the reactive solvent to reduce the viscosity of the reaction mixture, and 2-(Dimethylamino)ethyl methacrylate (DMEMA) as the reactive neutralizer. We then let MMA and DMEMA undergo further polymerization to form PUA hybrid emulsions. The morphology of the PUA hybrid emulsions was characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The structures of the waterborne polyurethanes (WPU) and PUA hybrid emulsions were characterized by Fourier transform infrared spectrometer (FTIR) and contact angle measurements.     

丙烯酸酯改性磺酸型水性聚氨酯乳液的合成及性能研究

以甲苯二异氰酸酯(TDI-80)、聚酯二元醇为主要原料,1,4-丁二醇(BDO)为小分子扩链剂,丙烯酸羟乙酯(HEA)为封端剂,乙二胺基己磺酸钠(N60)为亲水扩链剂,成功制备了封端型水性聚氨酯乳液(WPU)。再以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)对上述乳液进行接枝共聚,成功制备出丙烯酸酯-水性聚氨酯复合乳液(WPUA)。通过红外(FTIR)、透射电镜(TEM)、热重分析(TGA)、耐水性和力学性能测试等分析手段研究了WPUA乳液及其涂膜的结构与性能。结果表明,WPUA乳液具有良好的室温贮存稳定性及成膜性能,与WPU乳液相比,WPUA乳液粒径有所增大,且粒子呈核壳结构。其胶膜的耐热性、耐水性和力学性能较WPU胶膜均有所提高。     

Copolymers of methyl methacrylate and acrylate comonomers: Synthesis and characterization

Methyl methacrylate (MMA) has been copolymerized with n-butyl acrylate (n-BA), ethyl acrylate (EA), and 2-ethylhexyl acrylate (2-EHA) in solution at 70°C using benzoyl peroxide as free radical initiator. The copolymer composition was estimated by the ¹H-NMR spectroscopic technique. The copolymers were further characterized by IR, XRD, TGA, DTA, DSC, GPC, and solubility. The adhesive characteristics of the copolymers to cellulosic substrate are also reported. © 1995 John Wiley & Sons, Inc.     

Morphologies and dynamic mechanical properties of core‐shell emulsifier‐free latexes and their copolymers for P(BA/MMA)/P(MMA/BA) and P(BA/MMA)/PSt systems in the presence of AHPS

Different poly(methyl methacrylate/n‐butyl acrylate)/poly(n‐butyl acrylate/methyl methacrylate) [P(BA/MMA)/P(MMA/BA)] and poly(n‐butyl acrylate/methyl methacrylate)/polystyrene [P(BA/MMA)/PSt] core‐shell structured latexes were prepared by emulsifier‐free emulsion polymerization in the presence of hydrophilic monomer 3‐allyloxy‐2‐hydroxyl‐propanesulfonic salt (AHPS). The particle morphologies of the final latexes and dynamic mechanical properties of the copolymers from final latexes were investigated in detail. With the addition of AHPS, a latex of stable and high‐solid content (60 wt %) was prepared. The diameters of the latex particles are ～0.26 μm for the P(BA/MMA)/P(MMA/BA) system and 0.22–0.24 μm for the P(BA/MMA)/PSt system. All copolymers from the final latexes are two‐phase structure polymers, shown as two glass transition temperatures (T_gs) on dynamic mechanical analysis spectra. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3078–3084, 2002     

Synthesis and thermal self-crosslinking reaction of copolymers from 2,3-epoxypropyl methacrylate and p-substituted phenyl methacrylates

Copolymers of 2,3-expoxypropyl (glycidyl) methacrylate (GMA) with various phenyl methacrylates such as 4-nitrophenyl methacrylate (NPMA), 4-chlorophenyl methacrylate (CPMA), or phenyl methacrylate (PMA), and other monomers such as methyl methacrylate (MMA), ethyl acrylate (EA), or styrene (ST) were synthesized by radical copolymerization, and then thermal self-crosslinking reactions of the obtained copolymers were carried out using various catalysts such as quarternary ammonium salts, tert-amines, or the crown ether/potassium salt systems at 100–150°C. Although the copolymer of GMA–NPMA–MMA does not produce any gel products without catalyst upon heating at 110°C for 5 h, this copolymer gives gel products in 82% yield using 10 mol% of tetrabutylammonium bromide as a catalyst under the same conditions. The rate of gel production of the copolymer of NPMA is faster than those of copolymers of CPMA and PMA. The rate of the gel production of the copolymer of GMA–NPMA–EA is also faster than those of copolymers of MMA and ST. Furthermore, it was found that the rate of gel production of the copolymer was strongly affected by the kind of catalyst, the catalyst concentration, and the reaction temperature.     

丙烯酸酯核壳纳米粒子的合成及其改性环氧树脂

以丙烯酸丁酯(BA)为软单体、甲基丙烯酸甲酯(MMA)为硬单体和甲基丙烯酸缩水甘油脂(GMA)为官能单体,采用乳液聚合法合成出具有活性结构的BA/MMA/GMA核壳纳米粒子,并以此作为环氧树脂(EP)的增韧改性剂。研究结果表明:当w(核壳粒子)=10%、m(BA):m(MMA):m(GMA)=80:20:10时,与纯EP体系相比,改性EP体系的断裂伸长率提高了42.5%,剥高强度提高了近3倍,25℃和150℃时的剪切强度分别提高了48.6%和31.2%,坡璃化转变温度变化不大;红外光谱(FT-IR)证实,该核壳纳米粒子具有典型的特征吸收峰;透射电镜(TEM)观察结果表明,合成粒子具有纳米级核壳结构。     

BA‐MMA‐POMA copolymer latexes prepared by using HMPS polymerizable emulsifier

BA‐MMA‐POMA copolymer latex was successfully prepared by soap‐free emulsion polymerization of 2‐(perfluoro‐(1,1‐bisisopropyl)‐2‐propenyl)oxyethyl methacrylate(POMA) with butyl acrylate(BA), methyl methacrylate (MMA) initiated by K₂S₂O₈ in the water. POMA was synthesized from the intermediate perfluoro nonene and 2‐hydroxyethyl methacrylate as the staring reactants. The structure of BA‐MMA‐POMA copolymer latex was investigated by Fourier transform infrared (FTIR). The characteristics of the film such as hydrophobicity and glass transition temperature were characterized with the contact angle and differential scanning calorimetry respectively. The influences of the amount of the fluorinated monomer and the initiator on the soap‐free emulsion polymerization and performance of the latex were studied. In addition, comparison with the latex prepared by the conventional emulsifier SDBS is investigated. Results show that the hydrophobicity and glass transition temperature (T_g) of the latex are increased when the fluorinated monomer is introduced to copolymerize with other monomers. The hydrophobicity can be improved further with heating. Compared with the latices prepared by using SDBS emulsifier, the latices prepared by using HMPS emulsifier have larger particle size, higher surface tension. However, the difference of their T_g is extremely minute. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fluorocarbon‐containing hydrophobically modified poly(acrylic acid) gels as drug release system

Hydrophobically modified acrylic acid (AA) hydrogels containing fluorocarbon hydrophobic group and hydrocarbon‐modified gels using 2‐(N‐ethylperfluorooctanesulfoamido) ethyl methacrylate (FMA), and lauryl acrylate (LA) respectively, 2‐(N‐ethylperfluorooctanesulfoamido) ethyl methacrylate (FMA), were synthesized. Acetaminophen, with analgesic and antipyretic property, acted as the model drug. Swelling, rheological, and mechanical properties of the gels were investigated. Fluorocarbon‐modified gels show the stronger hydrophobicity than do the hydrocarbon‐modified gels, which affected the gel's drug‐releasing behavior. The drug release behavior depends on pH of the solution medium, the type of hydrophobic modification and the amount of hydrophobes. Hydrophobically modified PAA gels have higher storage modulus E′ than the unmodified PAA gels. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of oil sorbers based on docosanyl acrylate and methacrylates copolymers

Docosanyl acrylate (DCA) monomer was copolymerized with different monomer feed ratios of cinnamoyloxy ethyl methacrylate (CEMA) or methyl methacrylate (MMA) monomer to produce different compositions for DCA/CEMA or DCA/MMA copolymer with low conversions.¹H NMR spectroscopy was used to confirm the copolymer structure. DCA was crosslinked with different mol % of CEMA or MMA using dibenzoyl peroxide as initiator and various weight percentages of either 1,1,1‐trimethylolpropane triacrylates or 1,1,1‐trimethylolpropane trimethacrylates crosslinkers. The effects of monomer feed composition, crosslinker concentration, and the hydrophobicity of the copolymer units on swelling properties of the crosslinked polymers were studied through the oil absorbency tests. The network parameters, such as polymer solvent interaction (χ), effective crosslink density (υ_e), equilibrium modulus of elasticity (G_T), and average molecular weight between crosslinks (M_c), were determined and correlated with the structure of the synthesized copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface modification of MWNTs with BA‐MMA‐GMA terpolymer by single‐step grafting technique

In this article, a facile strategy was developed to prepare BA‐MMA‐GMA/MWNTs (multiwalled carbon nanotubes) hybrid nanoparticles as nanofillers in rubber by single‐step grafting technique. First, a new macromolecular surface modifier butyl acrylate (BA)‐α‐methyl methacrylate(MMA)‐glycidyl methacrylate (GMA) terpolymer was synthesized via radical copolymerization. Afterward, this terpolymer modifier was covalently grafted onto the surface of crude MWNTs by single‐step grafting technique. The structure, surface properties, and thermal stability of modified MWNTs were systematically investigated by FTIR, TGA, and TEM. FTIR results showed that BA‐MMA‐GMA terpolymer was successfully grafted onto the surface of MWNTs. TGA indicated that the optimum mass fraction of macromolecular modifier coated on the surface of MWNTs was 9 wt %. TEM images revealed that an organic coating layer was formed and the modified MWNTs showed good dispersibility in acetone. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of core–shell nanosilica/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) latex

A core–shell nanosilica (nano‐SiO₂)/fluorinated acrylic copolymer latex, where nano‐SiO₂ served as the core and a copolymer of butyl acrylate, methyl methacrylate, and 2,2,2‐trifluoroethyl methacrylate (TFEMA) served as the shell, was synthesized in this study by seed emulsion polymerization. The compatibility between the core and shell was enhanced by the introduction of vinyl trimethoxysilane on the surface of nano‐SiO₂. The morphology and particle size of the nano‐SiO₂/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) [P(MMA–BA–TFEMA)] core–shell latex were characterized by transmission electron microscopy. The properties and surface energy of films formed by the nano‐SiO₂/P(MMA–BA–TFEMA) latex were analyzed by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, and static contact angle measurement. The analyzed results indicate that the nano‐SiO₂/P(MMA–BA–TFEMA) latex presented uniform spherical core–shell particles about 45 nm in diameter. Favorable characteristics in the latex film and the lowest surface energy were obtained with 30 wt % TFEMA; this was due to the optimal migration of fluorine to the surface during film formation. The mechanical properties of the films were significantly improved by 1.0–1.5 wt % modified nano‐SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

半本体法合成醇溶性聚丙烯酸酯及在快干型涂料中的应用研究

以丙烯酸丁酯、甲基丙烯酸甲酯、苯乙烯、丙烯酸羟乙酯为单体,以过氧化二苯甲酰为引发剂,工业酒精为溶剂,采用半本体法合成醇溶性的丙烯酸酯聚合物。研究了引发剂种类、引发剂浓度、功能单体用量、软硬单体配比、加料方式对聚合物性能和相应涂料防腐性能的影响。结果表明:选用过氧化二苯甲酰为引发剂,且用量为2%、苯乙烯用量为5%、极性单体用量为10%、m(丙烯酸丁酯):m(甲基丙烯酸甲酯)=1:1时,以半本体法合成的聚合物配制的涂膜在25℃,相对湿度为90%的条件下,表干时间小于10 min,实干小于40 min,综合防腐性能好。     

Aqueous polyacrylate/poly(silicone‐co‐acrylate) emulsion coated fertilizers for slow nutrient‐release application

Waterborne polyacrylate/poly(silicone‐co‐acrylate) emulsions were synthesized to develop coated fertilizers. The effects of the n‐butyl acrylate (BA)/methyl methacrylate (MMA) ratio, vinyltriethoxysilane, and synthesis method on the water resistance, glass‐transition temperature, mechanical properties, and nutrient‐release profiles were investigated. The results show that miniemulsion polymerization with a BA/MMA ratio of 55:45 was the most suitable for slow nutrient‐release applications. Under these conditions, the preliminary solubility rate of the nutrient was about 3%, and the 30‐day cumulative nutrient release was 15% at 25°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40369.     

蓖麻油和丙烯酸酯双重改性水性聚氨酯复合乳液的研制

以1,4-丁二醇(BDO)、二羟甲基丙酸(DMPA)和乙二胺(EDA)为扩链剂,蓖麻油(C.O.)为内交联剂,以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)改性聚氨酯(PU)制得水性聚氨酯-丙烯酸酯复合乳液(PUA).研究了C.O.、DMPA和BA对乳液及涂膜性能的影响.