Preparation and characterization of sol–gel derived UV-curable organo-silica–titania hybrid coatings

In this work, UV-curable organic–inorganic hybrid coatings based on cycloaliphatic epoxyacrylate were prepared by sol–gel technique. Acid catalyzed solutions of tetraethylorthosilane (TEOS) containing Ti:acac complex were used as an inorganic precursors. UV-curable, transparent hybrid coating materials were applied on plexiglass substrates and their coating performance was investigated by the analyses of various tests such as hardness, gloss, cross-cut adhesion tests, stress–strain test and optical transmission. The mechanical measurements showed that, the tensile properties of coatings underwent an abrupt change from a brittle to a tough material when the inorganic part was incorporated into the cycloaliphatic epoxy acrylate based organic network. UV–vis transmission spectroscopy results indicated that the hybrid materials with high titanium content have good transparences. The thermal behaviour of the coatings was also evaluated. It is observed that the thermal stability of the hybrids is enhanced with incorporation of sol–gel precursor.     

Synthesis and characterization of flame retarding UV‐curable organic–inorganic hybrid coatings

UV‐curable, organic–inorganic hybrid materials were synthesized via sol–gel reactions for tetraethylorthosilicate, and methacryloxypropyl trimethoxysilane in the presence of the acrylated phenylphosphine oxide resin (APPO) and a bisphenol‐A‐based epoxy acrylate resin. The sol–gel precursor content in the hybrid coatings was varied from 0 to 30 wt %. The adhesion, flexibility, and hardness of the coatings were characterized. The influences of the amounts of inorganic component incorporated into the coatings were studied. Results from the mechanical measurements show that the properties of hybrid coatings improve with the increase in sol–gel precursor content. In addition, thermal properties of the hybrids were studied by thermogravimetric analysis in air atmosphere. The char yield of pure organic coating was 32% and that of 30 wt % silicate containing hybrid coating was 30% at 500°C in air atmosphere. This result demonstrates the pronounced effect of APPO on the flame retardance of coatings. Gas chromatography/mass spectrometry analyses showed that the initial weight loss obtained in thermogravimetric analysis is due to the degradation products of the photoinitator and the reactive diluent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1906–1914, 2006     

光固化光纤彩色涂料的研制

采用环氧丙烯酸酯和脂肪族聚氨酯丙烯酸酯共混的方法研制了一种新型光固化光纤彩色涂料。研究了基料树脂、活性稀释剂、光引发剂、颜料、助剂等对涂料综合性能的影响。结果表明，环氧丙烯酸树脂与脂肪族聚氨酯丙烯酸酯配比为40：20，单、双、多官能团稀释单体配比为3：20：10，复合光引发剂用量10％，有机颜料用量1．5％，所配制的光固化光纤涂料性能优良。     

Ultraviolet‐curing behavior of an epoxy acrylate resin system

Ultraviolet (UV)‐curing behavior of an epoxy acrylate resin system comprising an epoxy acrylate oligomer, a reactive diluent, and a photoinitiator was investigated by Fourier transform infrared (FTIR) spectroscopy. The conversion changes of the resin system containing 20 phr of 1,6‐hexanediol diacrylate as a reactive diluent and 2‐hydroxy‐2‐methyl‐1‐phenyl‐propan‐1‐one as a photoinitiator were measured under different UV‐curing conditions. The fractional conversion was calculated from the area of the absorption peak for the vinyl group vibration occurring at 810 cm^?1. The effects of photoinitiator concentration, total UV dosage, one‐step or stepwise UV irradiation, UV intensity, atmosphere, and temperature on the curing behavior of the resin system were investigated. The conversion of the resin system increased rapidly at the initial stage of the UV‐curing process but increased very slowly after that. The final conversion of the resin system was mainly affected by total UV dosage. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1180–1185, 2005     

环氧厚浆涂料的制备

以环氧树脂、聚酰胺、改性胺、活性稀释剂等为原料，制备了环氧厚浆涂料。讨论了原料配比、催化剂用量等因素对配方性能的影响。结果表明，环氧树脂为85g，混合固化剂为98g，活性稀释剂为14g，催化剂为2g，涂料助剂1g时配方的性能最优。     

Transparent UV curable antistatic hybrid coatings on polycarbonate prepared by the sol–gel method

UV curable, hard, and transparent organic–inorganic hybrid coatings with covalent links between the inorganic and the organic networks were prepared by the sol–gel method. These hybrid coating materials were synthesised using a commercially available, acrylate end-capped polyurethane oligomeric resin, hexanedioldiacrylate (HDDA) as a reactive solvent, 3-(trimethoxysilyl)propoxymethacrylate (MPTMS) as a coupling agent between the organic and inorganic phase, and a metal alkoxide, tetraethylorthosilicate (TEOS). The materials were applied onto polycarbonate sheets and UV cured, followed by a thermal treatment to give a transparent coating with a good adhesion and abrasion resistance. The high transmission and the thermogravimetric behaviour indicate the presence of a nanoscale hybrid composition. In a taber abrasion test, uncoated polycarbonate sheets exhibit a 48% decrease in light transmittance at 633 nm after 300 wear cycles, whereas the hybrid coating system containing 10 wt% silica shows only 10% decrease in light transmittance. For obtaining antistatic coatings, an intrinsically conductive polymer (ICP) was added to the optimised coating formulation. It is shown that the surface resistivity of the organic–inorganic hybrid coating can be reduced from 10¹⁶ to 10⁶ Ω for a high concentration of ICP in the coating formulation.     

光固化涂料用低粘度环氧丙烯酸酯的研究

采用双羟基化合物与环氧树脂进行反应,制取低粘度改性环氧树脂,然后用丙烯酸酯化,制得光固化涂料用低粘度环氧丙烯酸酯。研究了催化剂类型和用量对环氧树脂改性反应,以及不同结构、不同链长双羟基化合物和双羟基化合物与环氧树脂当量比对环氧丙烯酸酯粘度及其配制的光固化涂料的性能影响。确定了环氧树脂改性反应和丙烯酸酯化反应的最佳条件。     

Design and UV-curable behaviour of boron based reactive diluent for epoxy acrylate oligomer used for flame retardant wood coating

Difunctional boron-containing reactive flame retardant for UV-curable epoxy acrylate oligomer was synthesized from phenyl boronic acid and glycidyl methacrylate. The synthesized reactive diluent was utilized to formulate ultraviolet (UV)-curable wood coatings. The weight fractions of reactive diluent in coatings formulation was varied from 5 to 25 wt % with constant photoinitiator concentration. The molecular structure of reactive flame retardant was confirmed by Fourier-transform infrared, Nuclear magnetic resonance (NMR) and ¹¹B NMR spectral analysis. Further, the efficacy of flame retardant behaviour of coatings was evaluated using limiting oxygen index and UL-94 vertical burning test. Thermal stability of cured coatings films were estimated from thermogravimetric and differential scanning calorimetry analysis. The effects of varying concentration of reactive diluent on the viscosity of coatings formulation along with optical, mechanical and chemical resistance properties of coatings were also evaluated. The coatings gel content, water absorption behaviour, contact angle analysis and stain resistance were also studied.     

Synthesis and characterization of UV-curable dual hybrid oligomers based on epoxy acrylate containing pendant alkoxysilane groups

This work involves the synthesis of novel hybrid oligomers based on a UV-curable epoxy acrylate resin (EA). The EA resin was modified with various amount of 3-isocyanatopropyl trimethoxysilane (IPTMS) coupling agent. The modification percentage of the hybrid oligomer was varied from 0 to 50 wt.%. UV-curable, hard and transparent organic–inorganic hybrid coatings were prepared on Plexiglas substrates and their characterization was performed by the analyses of various properties such as hardness, gloss, tape adhesion test and stress–strain test. Results from the mechanical measurements show that the properties of hybrid coatings improve with the increase in modification ratio. The thermal behavior of coatings was also evaluated. It is observed that the thermal stability of epoxy acrylate coatings is enhanced with incorporation of siloxane. Gas chromatography/mass spectrometry analyses showed that the initial weight loss obtained in thermogravimetric analysis is due to the degradation products of the photoinitator and the acrylic acid moiety of acrylic monomers.     

水性涂料的最新研究进展

回顾了水性涂料的发展历史,介绍了现代水性涂料工业的发展现状,以及有关限制涂料中挥发性有机化合物(VOC)排放法规.着重讨论了,几类水性涂料(如水性聚氨酯涂料、水性丙烯酸酯涂料、水性环氧树脂涂料及水性紫外光固化涂料)的研究进展,并指出了水性涂料的研究方向.     

Effect of structure on coating performance properties of novel alkylenedioxydiphenol based epoxy resins

Although epoxy resins exhibit a wide range of useful properties for protective coatings on metal substrates, an increasing trend in the coatings industry toward more formable coatings places a severe burden on the traditional bisphenol. A based epoxy resins. Presented in this work are the results of experiments with a new series of epoxy resins based on alkylenedioxy diphenols demonstrating the relationship between coating performance properties (formability, chemical resistance, and adhesion) and structural parameters such as resin backbone flexibility, degree of phenol/formaldehyde crosslinkmg, and concentration of OH groups in the backbone of epoxy resins. Optimizing the three structural parameters for the new resins results in substantial improvements in coating performance properties over the traditional bisphenol A based resins.     

Epoxy acrylate UV/PU dual‐cured wood coatings

For improving the finishing performances of complicated three‐dimensional coated wood products (e.g., furniture) with some shadow zones in the absence of ultraviolet (UV) light, resulting in incomplete curing of UV coatings, the aim of this study was to investigate the characteristics and effects of curing process on the properties of epoxy acrylate UV/PU dual‐cured resin for wood coatings when compared with traditional UV and polyurethane (PU) coatings. The epoxy acrylate oligomer was synthesized for providing a double bond of acryloyl group and a secondary hydroxyl group. The UV/PU dual‐cured coating was formulated with epoxy acrylate resin/tripropylene glycol diacrylate (TPGDA) monomer by the weight ratio of 80/20, 3% dosage of benzil dimethyl ketal as a photoinitiator, and the NCO/OH mole ratio of 1.0. The aromatic polymeric diphenylmethane diisocyanate was used as a hardener. The films of the dual‐cured coating, obtained from UV‐cured or room temperature‐cured process, showed an excellent tensile strength, elongation at break, impact resistance, and lightfastness when compared with traditional UV and PU coatings; especially, the adhesion of UV/PU dual‐cured coating by UV‐cured process was better than that of traditional UV coating. It can therefore be concluded that the epoxy acrylate oligomer‐based dual‐cured coating could readily be used for complicated wood products finishing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

钛纳米聚合物涂料在NaCl溶液中的电化学阻抗谱

采用电化学阻抗谱方法对钛纳米聚合物涂料的防腐性能进行了研究,并通过与环氧树脂清漆、环氧玻璃鳞片涂料的对比,说明钛纳米聚合物涂料的防腐性能显著优于上述两种涂料的防腐性能。     

新型环保型防水涂料的改性研究进展

综述了三种防水涂料的改性方法。重点介绍了丙烯酸酯类乳液防水涂料,水性聚氨酯和聚脲的反应机理及改性后材料的性能变化,用环氧树脂和有机硅等对其改性后,提高了防水涂料的拉伸强度,断裂伸长率和附着力,降低了吸水率。探讨了聚脲防水涂料的发展方向。     

新型环氧硅酸酯防腐涂料的研制

将环氧树脂和硅酸酯预聚物通过催化缩合反应,制得环氧硅酸酯涂料,兼有有机和无机涂料的优点,具有高硬度、高耐磨、高附着力、优异的抗渗性、抗溶剂溶胀、抗介质氧化等性能。本文介绍了环氧硅酸酯树脂的合成以及环氧硅酸酯新型防腐涂料的制备。     

高温防腐涂料与热障防腐涂层技术的研究进展

综述了国内外耐高温防腐有机、无机和有机-无机复合涂料和热障防腐涂层技术的研究与应用的新进展,介绍了有机硅树脂、有机氟树脂、无机硅酸盐基涂料、无机磷酸盐基涂料、陶瓷涂层和搪瓷涂层的发展现状和前景.     

建筑涂料现状及展望

介绍了氟树脂,丙烯酸酯,环氧树脂,聚氨酯树脂的外墙,内墙及地面涂料的特点及组成,概述了建筑涂料市场的现状并作出展望。     

Ternary evaluation of UV-curable seed oil inorganic/organic hybrid coatings using experimental design

Inorganic/organic hybrid coatings were prepared using epoxidized linseed oil with combinations of the two sol–gel precursors (titanium(IV) isopropoxide, tetraethyl orthosilicate), and a telechelic silicate based on a modified oligomeric caprolactone. The coatings were UV-cured with sulfonium initiators which concomitantly cured the epoxy functional organic phase and the sol–gel inorganic phase to form a co-continuous inorganic/organic system. A ternary experimental design was employed to elucidate the influence of inorganic modifier on the mechanical properties of the inorganic/organic hybrid coatings. Small angle X-ray scattering (SAXS) was used to evaluate radius of gyration of the metal-oxo-cluster. Various coating properties, such as hardness, impact resistance, adhesion, solvent resistance, and surface energy were investigated as a function of sol–gel precursors. Inorganic/organic hybrid coatings containing both tetraethyl orthosilicate and the modified caprolactone resulted in improved hardness and solvent resistance with no loss of impact strength. The inclusion of titanium(IV) isopropoxide in to the systems resulted in a systematic reduction in the coatings properties. This was attributed to inhibition of the organic crosslinking process as a consequence of absorption of ultraviolet light by the titanium-oxo-clusters.     

水性自泳涂料及涂装技术进展

介绍厂丙烯酸酯类、聚偏二氯乙烯（PVDC）和环氧树脂类的自泳涂料制备技术及漆膜性能，探讨了自动沉积槽液的配制和涂装工艺。对PVDC类自沉积涂料，不用含铬化合物反应型浸渍，漆膜耐盐雾可达600h以上。自泳涂装是继阴极电泳后在金属表面涂装的一种新型技术。     

紫外光固化环氧丙烯酸酯涂料的制备及耐蚀性能研究

以E-51环氧树脂和丙烯酸为原料合成出光敏性环氧丙烯酸酯低聚物,制备了不同组成的紫外光固化涂料.合成产物的红外光谱分析结果表明,光敏性碳碳双键基团被引入到环氧树脂结构中;固化后涂层的红外表征结果表明,碳碳双键C=C的特征吸收峰消失,涂层固化较完全.在无水乙醇、5%NaOH和5%H2SO4溶液中的浸泡实验以及在3.5%NaCl溶液中的电化学阻抗谱测量结果表明,涂层具有较好的耐蚀性,其耐蚀性随着涂料中环氧丙烯酸酯含量的增加,呈先提高后下降的趋势.当环氧丙烯酸酯含量为40%,二缩三丙二醇双丙烯酸酯含量为50%时,所得涂层的耐蚀性最佳.