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     

高性能改性丙烯酸酯乳液的制备

研究了有机硅单体与丙烯酸类单体的乳液聚合反应,制备出高性能的改性丙烯酸酯乳液。主要研究了乳化剂、引发剂、有机硅加入方式及用量对乳液性能的影响,用有机硅改性丙烯酸酯乳液制成的涂料具有优越的耐水性,其耐洗刷性达4万次。     

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.     

高性能含氟丙烯酸涂料的研制

将液态含氟丙烯酸单体与丙烯酸酯类单体采用常压溶液聚合工艺，合成了支链含氟的丙烯酸树脂。配成白色磁漆后，机械性能、耐介质性能及耐候性与其他含氟树脂所制磁漆相当。     

The structure and properties of acrylic‐polyurethane hybrid emulsions and comparison with physical blends

Aqueous acrylic‐polyurethane hybrid emulsions were prepared by semibatch emulsion polymerization of a mixture of acrylic monomers (butyl acrylate, methyl methacrylate, and acrylic acid) in the presence of polyurethane dispersion. Equivalent physical blends were prepared by mixing acrylic emulsion and polyurethane dispersion. The weight ratio between acrylic and polyurethane components varied to obtain different emulsion properties, microphase structure, and mechanical film properties of hybrid emulsions and physical blends. Particle size and molecular mass measurements, scanning electron microscopy, glass transition temperature, and rheological measurements performed characterization of the latex system. The mechanical properties were investigated by measuring tensile strength and Koenig hardness of dried films. The experimental results indicate better acrylic‐polyurethane compatibility in hybrid emulsions than in physical blends, resulting in improved chemical and mechanical properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 67–80, 2000     

Effects of the chemical structure on the heat resistance of thermoplastic expandable microspheres

The effects of various additional non‐nitrile‐containing monomers on the heat resistance of thermoplastic expandable microspheres containing acrylonitrile and methacrylonitrile were investigated to determine the correlation between the chemical structure and expandable properties. Thermoplastic expandable microspheres were synthesized by suspension polymerization, with acrylonitrile and methacrylonitrile as the main ingredients and seven kinds of methacrylic acid derivatives, methacrylic acid, and acrylic acid as non‐nitrile‐containing monomers. The expandable properties, that is, the maximum expansion temperature, the expansion start temperature, and the maximum dimension change, were measured with thermomechanical analysis. For the development of heat‐resistant microspheres, polymer structures with smaller functional free volumes, higher glass‐transition temperatures, and higher cohesive energy densities, such as methyl acrylic acid, were applied as non‐nitrile‐containing monomers. Molecular structures such as ? COOH groups with strong electrostatic interactions and hydrogen‐bonding forces were found to be suitable for high heat resistance. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1306–1312, 2005     

ABS塑料用涂料的研制

通过选择合理的原料单体配比制备具一定玻璃化温度的热塑性丙烯酸树脂，作为ABS塑料用涂料的基料，具有较好的物理性能以及优良的耐醇性。     

Preparation and properties of urethane/acrylate composite by emulsion polymerization technique

Aqueous polyurethane–acrylic hybrid emulsions were prepared by semibatch emulsion polymerization of a mixture of acrylic monomers (styrene, butyl acrylate and acrylic acid) in the presence of polyurethane dispersion. Equivalent physical blends were prepared by mixing acrylic emulsion and polyurethane dispersion. The weight ratio between acrylic and polyurethane components was varied to obtain enhanced performance properties and microphase structure of hybrid latexes. The synthesized emulsion hybrids and physical blends were characterized by fourier transform infrared spectroscopy, thermogravimetric analysis. The experimental results indicate better acrylic–polyurethane compatibility in hybrid emulsions than in physical blends, resulting in improved chemical and mechanical properties. The blend ratio 50:50% (w/w) exhibited synergistic effects between the two polymers and revealed remarkable improvement in various coating properties over other blend ratios and the individual resin components.     

有机氟改性环氧丙烯酸阴极电泳涂料的研究

选择合适的丙烯酸类单体、有机氟单体与环氧树脂接枝共聚合成了用于阴极电泳涂料的阳离子型含氟环氧丙烯酸树脂.探讨了氟单体的用量、接枝反应温度、胺化温度、胺化时间等对树脂反应的影响,并对所得阴极电泳涂料的性能进行了测试.结果表明:在合适的电泳工艺参数下,所得漆膜与不含氟的环氧丙烯酸漆膜相比,其耐盐水性、耐老化性、冲击强度都有所提高.     

Synthesis of acrylate modified vinyl chloride and vinyl isobutyl ether copolymers and their properties

With acrylic acid, butyl acrylate and methyl methacrylate as the monomers, acrylate modified vinyl chloride and vinyl isobutyl ether copolymers were prepared by solution polymerization. Firstly, vinyl chloride and vinyl isobutyl ether copolymers were grafted with acrylic monomers to obtain a product containing acrylate grafted vinyl chloride and vinyl isobutyl ether copolymers and polyacrylate, which was then neutralized by triethylamine and dispersed into water to get a self-emulsified emulsion. The acrylate modified vinyl chloride and vinyl isobutyl ether copolymers were characterized by Fourier transform infrared spectroscopy. The mean molecular weight of grafted polymer was determined by gel permeation chromatography, and the particle sizes and their distributions of the dispersions were measured by laser light scattering. The influences of initiator concentration, acrylate content, acrylic acid content and neutralization degree upon the properties of the modified copolymers were discussed. The results show that the emulsion will be with good storage stability, and the modified polymer will be with high water resistance, impact resistance and excellent adhesion when initiator concentration is 1.5%, acrylate content is 50%, acrylic acid content ranges from 9% to 11%, and neutralization degree is between 80% and 100%.     

Perfluoropolyether polymers by UV curing: design,synthesis and characterization

Perfluoropolyether (PFPE) structures can be functionalized with acrylic groups using appropriate hydrogenated acrylic monomers: the macromers obtained are highly reactive under UV irradiation, and fluorinated polymers can be obtained. In the first part of this work is described the synthesis of new PFPE (meth)acrylic oligomers by extending OH‐terminated fluorinated chains with urethane groups and reactive acrylic functions. The photopolymerization reaction of each product is then reported followed by the characterisation of the main thermal, mechanical and surface properties of UV‐cured coatings. The polymers have good thermal resistance and fair mechanical and chemical resistance. More interestingly they show very low refractive index and low surface tension. For these latter properties the products can be advantageously used in highly demanding applications such as photonic devices and nano‐patterning. Copyright © 2011 Society of Chemical Industry     

Acrylic-fluoropolymer mixtures and their use in coatings

Fluoropolymer coatings, particularly those based on polyvinylidene fluoride (PVDF) resins, have a 35 year history of outstanding performance in outdoor applications. However, the chemical inertness of PVDF presents challenges to the paint formulator in that it prevents adhesion to substrates and makes it difficult to disperse pigments. To overcome these difficulties, an acrylic modifier resin is usually added to the PVDF resin. The acrylic modifier is traditionally physically blended with the PVDF resin to improve coating adhesion and enhance pigment dispersion. The physical blending results in a PVDF/acrylic mixture on a macro-molecular scale. ATOFINA Chemicals, Inc. has developed a novel approach to mix the fluoropolymer and acrylic on micro-molecular scale. Because of this intimate mixing, and the wide latitude of the acrylic and fluoropolymer monomers that can be utilized, a wide range of unique properties can be achieved in solvent-base dispersion coatings, and water-borne coatings. The unique properties of the solvent-base and water-borne coatings are discussed in this paper.     

高性能改性丙烯酸酯乳液及其涂料的研制

研究了有机硅单体与丙烯酸类单体的乳液聚合反应，制备出高性能的改性丙烯酸酯乳液。主要讨论了乳化剂、引发剂、有机硅加入方式及用量对乳液性能的影响。用有机硅改性丙烯酸酯乳液制成的涂料具有优越的耐水性，其耐洗刷性达60000次。     

Reaktive polyacrylate für den oberflächenschutz

Acrylic polymers find increasing application as binders for protective coatings. The monomeric acrylic compounds easily copolymerize with each other and with many other monomers, thus permitting the synthesis of polymeric substances with very different properties. By introduction of suitable functional groups into the copolymers the synthesis of reactive polymers is possible. These products are well soluble and easily processable and can be crosslinked by the application of heat to give products of excellent chemical and mechanical resistance. The reactive groups may be introduced either by use of reactive monomers or by reaction with a suitable prepolymer. Especially acrylic polymers with hydroxyl-, amide-, N-methylolamide-, epoxy-, and active CH-groups in the molecule have received considerable attention for protective coatings. The most important types of these polymers and their crosslinking reactions are discussed with special consideration of polymers with methylolamide functions. Finally examples of important fields of application for reactive acrylic coatings are given.     

有机硅改性-丙烯酸酯共聚乳液的制备与性能研究

文章研究了有机硅单体与丙烯酸类单体的乳液聚合反应,制备出高性能的改性丙烯酸酯乳液。主要讨论了乳化剂、引发剂、有机硅加入方式及用量对乳液性能的影响。用有机硅改性丙烯酸酯乳液制成的涂料具有优越的耐水性,其耐洗刷性可达6万次。     

Emulsion Semi-Batch Terpolymerization Process Using Hybrid Emulsifiers for Synthesizing New Emulsion Pressure Sensitive Adhesives (EPSAs)

In order to obtain a suitable formulation of designing direct synthesis of acrylic latexes to be used as emulsion pressure sensitive adhesives (EPSA), having high shear resistance together with high peel strength and tack, free radical emulsion polymerization of hard monomers, such as styrene (St), vinyl acetate monomer (VAM), methyl methacrylate (MMA) and butyl methacrylate (BMA), and soft monomers, butyl acrylate (BA) and 2-ethylhexyl acrylate (2-EHA) along with multifunctional monomers, namely acrylic acid (AA), were carried out. The effect of the type of hard and soft acrylic monomers, the type and level of emulsifiers, and the initiator concentration on the emulsion polymer stability and final properties of the EPSA were investigated. The results obtained showed an optimized composition. This composition led to a significant increase in shear strength and peel strength to 909 kPa and 0.45 N/mm, respectively, while the synthesized PSA was still too tacky, 5.5 cm, according to adhesion performance testing. For making this successful balance of the conflicting adhesion properties of PSA, a series of anionic and nonionic emulsifiers were investigated. It was interestingly found out that the hybrid emulsifiers (anionic coupling with nonionic) with the optimized compositions could enhance the stability of the emulsion system and improve the properties of PSA compared with the mono-emulsifier. We also tried to adjust the initiator concentration with the level of the optimized hybrid emulsifier, polyoxyethylene alkyl phenyl ether (K30), dioctyl sulfosuccinate (DOSS), and sodium vinyl sulfonate (SVS) with the ratio 2:1:1, resulting in a highly preferred proportion of the 0.5 part of the initiator versus 1.25 parts of the hybrid emulsifier in terms of the total weight of the monomers.     

Waterborne polyurethane/acrylate: Comparison of hybrid and blend systems

Polyurethane/acrylate hybrid composites in a broad range of composition (10, 30, 50, 70 and 90 wt.% of acrylic content), were obtained by emulsion polymerization of acrylic monomers (methyl methacrylate/n-butyl acrylate/acrylic acid mixture) in the presence of preformed polyurethane chains with polymerizable terminal vinyl groups. Blends with the same acrylic content were also prepared by mixing polyurethane and acrylic dispersions. Samples were characterized by SEC, DLS, FTIR, UV, TEM, AFM, SAXS/WAXS and gel fraction content. Mechanical properties, Buccholz and pencil hardness, surface roughness and water contact angle of films were also determined. The effect of the acrylic content on morphology and film properties was also evaluated. Hybrids are crosslinked systems showing changes in the particle and film morphologies with increasing acrylic content. The properties of hybrid films show a non-linear behavior with the increase of the acrylic component, while physical blends exhibit a gradual behavior from PU to AC. FTIR results indicate better acrylic-polyurethane compatibility in hybrid systems than in physical blends. Hybrid composites with up to 70 wt.% of acrylic component are homogeneous by SAXS. On the other hand, AFM results show that blends are phase segregated systems at all composition levels.     

Cure mechanism and properties of acrylosilane coatings

Acrylosilane resin, a copolymer of trialkoxysilylalkyi methacrylate and other acrylic monomers, was developed for use as a vehicle resin for weather and chemical resistant coatings. This report discusses the crosslinking mechanism, hydrolysis and condensation reactions with two types of hardening catalysts: organotin and organic acid. This report also demonstrates the advantages of its coating properties in weather resistance, acid resistance, stain resistance, and adhesion to anodized aluminum. The coating properties are a function of its crosslinking mechanism.     

Study of performance properties of itaconic acid based acrylic-modified polyester for industrial baking finishes

Itaconic acid based unsaturated polyesters have been synthesized followed by their co-polymerization with commonly used acrylic monomers. Series of such acrylic-modified polyesters have been prepared and examined their physical and performance characteristics. Apart from determining various physico-chemical characteristics, these resins were also characterized for their molecular weight distribution and grafting of acrylic on polyester using gel permeation chromatography (GPC) and FT-IR techniques respectively. The performance of cured film and the effect on cross-linking density of the synthesized acrylic-modified polyesters were investigated through dynamic mechanical analyzer (DMA) using melamine formaldehyde resin as a cross-linker at elevated temperature. The resultant polymeric film showed excellent hardness, flexibility, impact resistance, adhesion, and cupping with improved weathering resistance over non-acrylated polyester.     

改性水性硝化纤维素乳液研究

采用醇酸树脂转相乳化法和丙烯酸酯类单体互穿聚合物网络聚合法制备改性硝化纤维素乳液。研究了醇酸树脂、丙烯酸酯类单体乳化剂用量等因素对乳液性能的影响。结果表明，丙烯酸酯类单体改性互穿聚合物网络聚合法制得的乳液效果好.