Synthesis and application of a novel epoxy grafted thermosetting acrylic resin

A novel manufacturing process for high performance metallic can coating was carried out based on an epoxy‐grafted acrylic resin. Firstly, the epoxy resin was reacted with acrylic amide forming a ring opened product epoxy‐amide resin, and then the product obtained copolymerized with all other monomers, such as acrylic acid (AA), butyl acrylate (BA), hydroxypropyl acrylate (HPA), 2‐ethylhexyl acrylate (2‐EHA), methyl methacrylate (MMA), styrene (St), using free radical solvent polymerization in the presence of BPO. The resins prepared present the transparent appearance, and the target resin coating based on these resins exhibits excellent boiling resistance and chemicals resistance and can be applied as the protective coating for metallic can. The effects on the coating properties, such as amount of acrylic acid, 2‐EHA wt % between 2‐EHA and BA, amount of amino resin, amount of catalyst, and so forth, were investigated. In addition, the influences of polymerization time on the conversion ratio of monomers were also studied. Results show that under the optimal conditions, the target resin coating provides excellent physical and mechanical properties. The various properties tests for this coating have been performed in accordance with the standards of ASTM. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of Nanoparticles on Film Properties of Waterborne Acrylic Emulsions

Waterborne acrylic emulsion was obtained by using methyl methacrylate, ethyl and butyl acrylate monomers. Emulsions containing nanoparticles were prepared by blending the stable dispersions containing SiO₂ or MMT nanoparticles. The films were prepared from emulsions and coating tests were applied. The physical properties of prepared emulsions are better than the commercial emulsions. The addition of the nanoparticles especially SiO₂ have positive effect on the resistance to environmental conditions of emulsions. Waterborne acrylic emulsions containing nanoparticles prepared in this study can be used in the manufacturing of the semi-lustrous emulsion type nano paint with low cost, high performance and environmentally friendly.     

Performance properties of acrylic and acrylic polyol–polyurethane based hybrid system via addition of nano‐caco3 and nanoclay

Thermosetting acrylic (TSA) resin was prepared by solution polymerisation of acrylic acid and methyl methacrylate (MMA). Hybrid polymer consisting of acrylic polyol–polyurethane was prepared by addition of hydroxy ethyl acrylate and hexamethylene diisocyanate (HMDI). Incorporation of Functionalised nanocalcium carbonate and bentonite nanoclay were accomplished by in situ method during the synthesis of both the polymers. Loading of nano‐CaCO₃ and nanoclay was varied from 0 to 4 wt.% to investigate variation in mechanical, optical and high performance properties. The superiority of nanoclay in enhancing the mechanical and performance properties like the salt spray and humidity resistance in comparison to that of nano‐CaCO₃ was clearly established. It was also observed that, addition of nanomaterials in hybrid resins system shows superior results compared to neat acrylic system and in situ additions of these nanomaterials improve the dispersion and stability in the matrix.     

Synthesis of water‐reducible acrylic–alkyd resins based on modified palm oil

Water‐reducible acrylic–alkyd resins were synthesized from the reaction between monoglycerides prepared from modified palm oil and carboxy‐functional acrylic copolymer followed by neutralization of carboxyl groups with diethanolamine. Modified palm oil was produced by interesterification of palm oil with tung oil at a weight ratio of 1 : 1, using sodium hydroxide as a catalyst, whereas carboxy‐functional acrylic copolymer was prepared by radical copolymerization of n‐butyl methacrylate and maleic anhydride. The amount of acrylic copolymer used was from 15 to 40% by weight, and it was found that homogeneous resins was obtained when the copolymer content was 20–35 wt %. All of the prepared water‐reducible acrylic–alkyd resins were yellowish viscous liquids. Their films were dried by baking at 190°C and their properties were determined. These films showed excellent water and acid resistance and good alkali resistance. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1170–1175, 2005     

氟改性双组分水性丙烯酸聚氨酯涂料性能研究

以甲基丙烯酸十二氟庚酯（DFMA）、丙烯酸（AA）、甲基丙烯酸羟乙酯（HEMA）、甲基丙烯酸甲酯（MMA）和丙烯酸丁酯（BA）为原料,采用溶液聚合法合成了一系列氟含量不同的水性羟基丙烯酸树脂。将含氟水性羟基丙烯酸树脂、亲水性异氰酸酯固化剂和助剂混合制备氟改性双组分水性丙烯酸聚氨酯（2K—WPU）涂料。利用傅里叶变换红外光谱（FT-IR）对其结构进行了表征,并对涂料的接触角、吸水率和清漆性能分别进行了测试。结果表明,该水性树脂粒径在28．2～68．1nm之间,粒径分布均匀。当水性羟基丙烯酸树脂组成中DFMA质量分数从0增加至20％时,所制备氟改性2K-WPu涂料的水接触角从70．3。增大到97．6。,吸水率从11．4％降低至6．31％,涂膜的耐水性显著提高。清漆性能测试表明,所制氟改性2K．WPu的各项性能优异。     

Comparison of Approaches to Prepare Polysiloxane-Functionalized Acrylic Latexes

Three methods were used to prepare polysiloxane-functionalized acrylic latexes via emulsion polymerization. Ethyl acrylate and 2-ethylhexyl acrylate were used in all three methods as the acrylic phase. In the first method, an acrylic core was prepared with addition of a coupling agent, 3-(trimethoxysilyl) propyl methacrylate, after which a cyclic siloxane monomer (octamethylcyclotetrasiloxane) was reacted with the coupling agent. In the second method, a silane-terminated polysiloxane (H-PDMS) was reacted with ethylene glycol dimethacrylate, and then copolymerized with ethyl acrylate and 2-ethylhexyl acrylate in a batch emulsion polymerization. In the third method, cyclic siloxane monomer was added during emulsion polymerization of ethyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl methacrylate. Particle size distribution and particle morphology were evaluated using dynamic light scattering (DLS) and transmission electron microscopy (TEM), respectively. A core-shell morphology was observed in TEM for the first preparation method as proposed. After film formation, surface tension, morphology and dynamic mechanical properties were investigated. Stratification was also examined by Fourier-transform infrared spectroscopy (FT-IR) and energy dispersive X-ray (EDX). Microphase separation was observed by atomic force microscopy (AFM) after polysiloxane modification. Energy dispersive X-ray data indicated that only the second preparation method had a higher silicon content at the film-air interface than film-substrate interface. In all methods, the storage modulus and surface energy of latex films decreased after polysiloxane modification.     

n‐Butyl acrylate based latex interpenetrating polymer networks used as processing modifiers and impact modifiers of poly(vinyl chloride)

A latex interpenetrating polymer network (LIPN), consisting of poly(n‐butyl acrylate), poly(n‐butyl acrylate‐co‐ethylhexyl acrylate), and poly(methyl methacrylate‐co‐ethyl acrylate) and labeled PBEM, with 1,4‐butanediol diacrylate as a crosslinking agent was synthesized by three‐stage emulsion polymerization. The initial poly(n‐butyl acrylate) latex was agglomerated by a polymer latex containing an acrylic acid residue and then was encapsulated by poly(n‐butyl acrylate‐co‐ethylhexyl acrylate) and poly(methyl methacrylate‐co‐ethyl acrylate). A polyblend of poly(vinyl chloride) (PVC) and PBEM was prepared through the blending of PVC and PBEM. The morphology and properties of the polyblend were studied. The experimental results showed that the processability and impact resistance of PVC could be enhanced considerably by the blending of 6–10 phr PBEM. This three‐stage LIPN PBEM is a promising modifier for manufacturing rigid PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1168–1173, 2004     

Novel synthesis of carboxy-functional soybean acrylic-alkyd resins for water-reducible coatings

A new process was developed for synthesis of alkyd resins in which a conventional monoglyceride is reacted with a carboxy-functional acrylic copolymer. The novel products are called acrylicalkyd resins. The carboxy-functional acrylic copolymers were synthesized by solution-free radical polymerization. Gelation during alkyd resin synthesis was avoided by: (1) limiting the molecular weight of the acrylic copolymers to M_n 3500–5000 and (2) limiting the number average functionality about 6.5–10 carboxyl groups per molecule. Further, the carboxyl groups were derived from a mixture of acrylic and methacrylic acids (1/1.2 mol ratio) in the expectation that this would help control the process. Three series of acrylic copolymers were prepared from various combinations of acrylic monomers and reacted with a monoglyceride prepared from soybean oil and trimethylol propane. The composition of the acrylic resin was adjusted to minimize phase separation [observed visually and by scanning probe microscopy (SPM)] within cast films. The most satisfactory results were obtained with copolymers of 62–71 wt% of methyl methacrylate, 5–21 wt% of lauryl methacrylate, 7.2 wt% of acrylic acid, and 10.3 wt% of methacrylic acid. In preliminary tests, waterborne coatings made from acrylic-alkyd resins based on these acrylics had excellent stability, with acid numbers changing less than 10% after nine months of storage. Coatings Research Institute Ypsilanti MI 48197 Department of Physics, Ypsilanti, MI 48197.     

Preparation,characterisation and properties of waterborne fluorinated polyurethane acrylate/SiO2 hybrid

Abstract

Waterborne fluorinated polyurethan acrylate dispersion was prepared from the polyether polyol, isophorone diisocyanate, dimethylpropionic acid, hexafluorobutyl acrylate and trimethylolpropane triacrylate as monomers. Then, the prepolymer containing alkoxysilane Si(OR)₃ was synthesised from dispersion and coupling agent methacryloxypropyl trimethoxy silane. The Si(OR)₃ group was hydrolysed and reacted with different content tetraethoxysilane hydrolysis solutions in via hybridisation and gelatinous. A series of waterborne fluorinated polyurethane acrylate/SiO₂ hybrids were prepared by sol–gel technique. The physical properties of dispersion such as storage stability, viscosity, particle size and surface tension were measured. The results indicated that all the prepared dispersions showed acceptable storage stability. The mechanical properties such as tensile strength, elongation at break and hardness and chemical resistance such as water absorption and acid resistance of the films were investigated. The hybrid materials were characterised using Fourier transform infrared, SEM and X-ray diffraction. The obtained hybrid materials have great potential application such as coatings, adhesion, leather finishing, adhesives, sealants, plastic coatings and wood finishes.     

Methacrylate/acrylate terminated derivatives of diglycidyl hexahydrophthalate: Synthesis,structural, and thermal characterization

Mono‐ or di(meth)acrylate‐terminated derivatives of diglycidyl hexahydrophthalate (ER) were prepared by reacting 1 : 1 or 1 : 2M ratio of ER and methacrylic acid or acrylic acid. These vinyl ester (VE) resins were characterized by determining epoxy equivalent weight, acid number, and molecular weight by gel permeation chromatography. Structural characterization was done by FTIR and ¹H NMR spectroscopy. In the ¹H NMR spectra of acrylate‐terminated VE resins, three proton resonance signals were observed in the region 5.8–6.4 ppm due to vinyl group while in methacrylate‐terminated VE resins only two proton resonance signals due to vinylidene protons were observed at 5.6–6.1 ppm. The Brookfield viscosity (room temperature (25 ± 2)°C) of these resins diluted with varying amounts of MMA was determined at 20 rpm. Curing behavior was monitored by determination of gel time and differential scanning calorimetry. An exothermic transition was observed in the DSC scans in the temperature range of (81–150)°C. Isothermal curing of MMA‐diluted VE resins containing AIBN as an initiator was done at 60°C for 2 h in N₂ atmosphere, and then heating for another 2 h in static air atmosphere. Thermal stability of isothermally cured resins in N₂ atmosphere was evaluated by thermogravimetric analysis. All cured resins decomposed above 310°C in single step. Thermal stability of the cured resins having acrylate end caps was marginally higher than the resins having methacrylate end groups. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis,characterization, and thermal behavior study of methyl methacrylate polymers containing 4‐carbazole substitutes

A new polymerizable monomer, [4‐(9‐ethyl)carbazolyl]methyl methacrylate ( 2 ), was synthesized by reacting of methacrylic acid and 4‐hydroxymethyl‐9‐ethyl carbazole ( 1 ) by esterification procedure in the presence of N,N′‐dicyclohexylcarbodiimide. The resulting monomer was then polymerized free‐radically to form the poly(methyl methacrylate) containing 4‐(9‐ethyl)carbazolyl pend ent groups. Also, copolymerization of monomer 2 with various acrylic monomers such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, and n‐butyl acrylate by azobisisobutyronitrile as a free radical polymerization initiator gave the related copolymers in high yields. The structure of all the resulted compounds was characterized and confirmed by FTIR and ¹H NMR spectroscopic techniques. The average molecular weight of the obtained polymers was determined by gel permeation chromatography using tetrahydrofurane as the solvent. The thermal gravimetric analysis and differential scanning calorimeter instruments were used for studying of thermal properties of polymers. It was found that, with the incorporation of bulky 4‐(9‐ethyl)carbazolyl substitutes in side chains of methyl methacrylate polymers, thermal stability and glass transition temperature of polymers are increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4989–4995, 2006     

Optimization and comparison of polysiloxane acrylic hybrid latex synthesis methods

Two methods were used to prepare polysiloxane-functionalized acrylic latexes via emulsion polymerization. Ethyl acrylate and 2-ethylhexyl acrylate were used in both methods as acrylic phase. In the first method, an acrylic core was prepared with addition of a coupling agent, 3-(trimethoxysilyl) propyl methacrylate, after which cyclic siloxane monomer (octamethylcyclotetrasiloxane) was reacted with the coupling agent. In the second method, a silane-terminated polysiloxane (H-PDMS) was reacted with ethylene glycol dimethacrylate, and then copolymerized with ethyl acrylate and 2-ethylhexyl acrylate in a batch emulsion polymerization. Particle size distribution and particle morphology were evaluated by using dynamic light scattering (DLS) and transmission electron microscopy (TEM), respectively. Core-shell morphology was observed in TEM for the first preparation method as proposed. After film formation, surface tension, morphology and dynamic mechanical properties were investigated. Stratification of polysiloxane was examined by Fourier-transform infrared spectroscopy (FT-IR) and energy dispersive X-ray (EDX). Energy dispersive X-ray data indicated that only the second preparation method had higher silicon content at film-air interface than film-substrate interface. In both methods, storage modulus and surface energy of latex films decreased after grafting polysiloxane.     

水性羟基丙烯酸分散体亚光树脂的制备及其性能研究

以叔碳酸缩水甘油酯（ E10P）和钛酸丁酯为溶剂,采用本体聚合法分两步滴加甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸羟乙酯、苯乙烯、丙烯酸和引发剂的混合溶液,再将上述制备的树脂用碱中和,加水分散,即可得到水性亚光羟基丙烯酸分散体。将制备的树脂与水性多异氰酸酯固化剂固化成膜,测试其性能。结果表明：自制水性羟基丙烯酸分散体物理性能均较好,具有较好的耐水、耐溶剂性能。清漆光泽（ 60°）在 50~60之间,具有优异的亚光性能。     

Thermal stability and dynamic mechanical behavior of acrylic resin and acrylic melamine coatings

Acrylic polyols of different hydroxyl numbers consisting of hydroxy ethyl methacrylate, methyl methacrylate, butyl acrylate, and styrene were prepared by free‐radical solution as well as suspension polymerization techniques in the presence of benzoyl peroxide initiator. These polyols were crosslinked with butoxy methyl melamine at a ratio of 85 : 15 in the presence of acid catalyst. The thermal stability of polyols and their corresponding crosslinked films was studied by thermogravimetric (TG) technique. The Broido and Coats–Redfern methods were used to calculate the activation energy of thermal decomposition from standard TG curves. Dynamic mechanical thermal analysis was used to study the dynamic mechanical properties and determination of glass‐transition temperature of acrylic/melamine crosslinked films. The results indicate that the thermal stability of polyols and crosslinked films strongly depends on the hydroxyl number of the acrylic polyols. It was found that acrylic polyols synthesized by suspension polymerization methods upon crosslinking yield more thermally stable and flexible films than polyols prepared by solution polymerization methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 27–34, 2004     

Preparation and properties of polyurethane coatings based on acrylic polyols and trimer of isophorone diisocyanate

This paper presents a study on the effect of NCO/OH ratio and an increase in hydroxyl content of acrylic polyols on the properties of polyurethane (PU) coatings. Coating properties studied are gloss, scratch resistance, flexibility and adhesion, mechanical properties include tensile strength, modulus, percent elongation and Shore hardness, while physicochemical properties include chemical resistance and solvent absorption of coated PU samples. A series of acrylic polyols (copolymers) based on butyl acrylate (BA), methyl methacrylate (MMA), styrene and 2-hydroxy ethylacrylate (HEA) were prepared by selecting different percentage of hydroxyl content. Trimer of isophorone diisocyanate (IPDI) was also synthesized in the laboratory. This trimer has trifunctionality. Isocyanurate ring of trimer increases thermal properties of PU. Polyurethanes from these acrylic polyols (containing different percent hydroxyl) and trimer of IPDI were prepared with two different NCO/OH ratios viz, 1.1:1 and 1.2:1. Polyurethanes were coated on substrates for measuring coating properties. Mechanical properties were measured on cast films of the PUs. The experimental results revealed that all polyurethane coatings based on acrylic polyols and IPDI trimer showed good gloss, scratch resistance and excellent adhesion. Thermal stability of these PU samples was found to be better. Physicochemical properties reflected that these PU have excellent chemical and solvent resistance.     

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     

Polymerization of methacryl and triethoxysilane functionalized stearate ester: Titanium dioxide composite films and their photocatalytic degradations

Stearoyl chloride was reacted with 3‐(acryloyloxy)‐2‐hydroxypropyl methacrylate (AHM). Then the resulting product (SAHM) was reacted with 3‐amino propyl ethoxysilane (APTES) by Michael addition on the acrylate. The product (SAHMA) is a specialized coupling agent containing an oleophilic 18 carbon alkyl chain, a radically polymerizable methacrylate and an alkoxysilane group capable of coupling to inorganic surfaces, analyzed by FT‐IR, NMR, and UV techniques. Photopolymerization and free radical homo and copolymerization of SAHMA with styrene were examined. SAHMA was coupled to powdered titanium dioxide (P25‐Degussa) and polymerized. TiO₂ filled materials were analyzed by SEM, UV and TGA techniques. Glass transiton temperatures (T_g) of the polymers were determined by differential scanning calorimeter (DSC). Interfacial compatibility between SAHMA and TiO₂ was demonstrated by FT‐IR spectroscopy. The photocatalytic degradation of the TiO₂‐SAHMA polymer films was also investigated under medium pressure mercury lamp illumination in air. SAHMA based film containing 2 wt % TiO₂ showed the highest degradation and the highest loss in weight. The weight of the polymer was reduced by 25% of its initial value after irradiation for 40 h. To examine the surface morphology of the irradiated polymer films, SEM analysis was carried out and cavities were detected around TiO₂ particles. The photocatalytic and thermomechanical properties of SAHMA and styrene (STY) based copolymers were also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Narrow‐disperse or monodisperse crosslinked and functional core–shell polymer particles prepared by two‐stage precipitation polymerization

Narrow‐disperse and monodisperse cross‐linked core–shell polymer particles containing different functional groups, such as esters, hydroxyls, chloromethyls, carboxylic acids, amides, cyanos, and glycidyls, in the shell layers in the micrometer size range were prepared by a two‐stage precipitation polymerization in the absence of any stabilizer. Commercial divinylbenzene (DVB), containing 80% DVB, was precipitation polymerized in acetonitrile without any stabilizer as the first‐stage polymerization and was used as the core. Several functional monomers, including methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2‐hydroxyethyl methacrylate, glycidyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, t‐butyl acrylate, i‐octyl acrylate, acrylic acid, acrylamide, acrylonitrile, styrene, and p‐chloromethyl styrene, were incorporated into the shells during the second‐stage polymerization. The resulting core–shell polymer particles were characterized with scanning electron microscopy and Fourier transform infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1776–1784, 2006     

Preparation and characterization of acrylic resin/protein composite crosslinked films

A series of ambient self-crosslinkable acrylic resin/protein composite emulsions (PA–Ps) were prepared by copolymerizing the functional monomer acetyl acetylethyl methacrylate (AAEM) with methyl acrylate, butyl acrylate and acrylic acid, and then protein crosslinking agents such as gelatin and casein were also added. The PA–P films were characterized by Fourier transform IR spectroscopy, contact angles, differential scanning calorimeter, thermogravimetric analysis, antisolvent testing and physicomechanical testing. Influences of AAEM and protein dosages on properties of composite films were examined in detail. The results indicate that influences of AAEM and protein on PA–P films are diverse on solvent resistance, physicomechanical properties and thermal properties. With enhancement of AAEM and protein dosages, hardness, solvent resistance to tetrahydrofuran and glass transition temperature (T _g) of PA–P films are markedly enhanced, but the decomposing temperatures (T _d) are decreased. Tensile strengths are evidently reinforced while elongations at break are lessened. Suitable AAEM and protein dosages could render PA–P films with good water resistance.     

A novel UV‐curable epoxy acrylate resin containing arylene ether sulfone linkages: Preparation,characterization, and properties

UV‐curing processes are used in industrial applications because of their advantages such as high‐speed applications and solvent‐free formulations at ambient temperature. UV‐curable epoxy acrylate resins containing arylene ether sulfone linkages (EAAES) were synthesized through the condensation of bis(4‐chlorophenyl)sulphone and bisphenol‐A, followed by end‐caping of epichlorohydrin and subsequently acrylic acid. UV‐cured coatings were formulated with epoxy acrylates, reactive diluents such as pentaerythritol tri‐acrylate and pentaerythritol dia‐crylate and photoinitiator. Fourier transfer infrared, ¹H NMR, and thermal gravimetrical analysis were employed to investigate the structures and thermal properties of the EAs films. The introduction of EAAES into epoxy acrylate substantially improves its thermal properties and thermo‐oxidative stability at high temperatures. In addition, the acrylate containing arylene ether sulfone linkages can also improve pencil hardness and chemical and solvent resistance of the epoxy acrylate. The obtained UV‐curable epoxy acrylate containing arylene ether sulfone linkages is promising as oligomer for UV‐curable coatings, inks, and adhesives in some high‐tech regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41067.