High-performance waterborne UV-curable polyurethane dispersion based on thiol–acrylate/thiol–epoxy hybrid networks

Synthesis, characterization, and film performance of waterborne thiol–acrylate/thiol–epoxy hybrid coatings are highlighted in this article. A dimer acid-modified epoxy (DME) polyol, containing both hydroxyl and epoxy functional groups, was prepared by reacting epoxy resin (EEW = 190 g/equi) with dimer fatty acid at 2:1 molar ratio. Further, a base UV-curable polyurethane acrylate dispersion (UV-PUD), with a pendant epoxy functional group, was prepared by reacting polyol (DME), isophorone diisocyanate, and dimethylol propionic acid and end-capped with hydroxyethyl methacrylate with subsequent dispersion in water. Prepared intermediates were characterized for the parameters relevant to the study by physical, spectroscopic, and chemical methods. UV-curable thiol–acrylate/thiol–epoxy hybrid coatings were prepared by blending UV-PUD with trimethylolpropane tris(3-mercaptopropionate) (TMPMP) at four different thiol ratios (0, 0.3, 0.6, and 1.0) with respect to acrylate/epoxy groups. Cured films of the hybrid coating were identified by FTIR spectroscopy. The impact of thiol ratio on film performance was evaluated in terms of mechanical, chemical, thermal, and coating properties. The gel content measurements confirm that the addition of TMPMP increased the double bond conversion along with the epoxy group. Evaluation of cured samples shows the significant improvement in storage modulus, glass transition temperature, tensile strength, and hardness with increase in thiol ratio. The cured films possessed excellent water and acid resistance (<4%) even after 28 days of immersion. Moreover, the notable improvement was alkali resistance of cured films, i.e., as thiol ratio was increased from 0 to 1, weight loss in alkaline environment deceased from 49.5 to 4.5% after 28 days. Better properties of the thiol–acrylate/thiol–epoxy hybrid films will allow it as a potential application in low-volatile high-performance coatings.     

水性环氧涂料耐盐雾性影响因素的研究

研究了水性环氧涂料的乳液粒径与PVC(颜料体积浓度)对其耐盐雾性的影响。选择了粒径较小的乳液于适宜的PVC下配制水性环氧涂料,其耐盐雾性与溶剂型环氧涂料相当。通过对比,得出了水性环氧涂料的耐盐雾性不同于溶剂型环氧涂料的影响规律。     

聚氨酯丙烯酸酯/环氧丙烯酸酯分散体系的制备

用水性聚氨酯丙烯酸酯改性环氧丙烯酸酯,制备了聚氨酯丙烯酸酯/环氧丙烯酸酯分散体系。随着分散体中聚氨酯丙烯酸酯浓度的增加,体系稳定性增加,当其浓度达到30%时,可制得稳定的分散体系。这种分散体系可作为一种紫外光固化水性涂料,其涂膜的耐磨性、柔韧性都比环氧丙烯酸酯涂膜增强,而硬度变化不大。     

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.     

颜填料体积浓度对水性环氧导静电防腐蚀涂层性能的影响

考察了颜填料体积浓度（PVC）对水性环氧导静电防腐蚀涂料涂层导静电性能和防腐蚀性能的影响,运用X射线能谱（EDX）分析了导电填料的元素组成,采用电化学阻抗谱（EIS）、扫描电镜（SEM）等手段对不同颜填料体积浓度的涂层进行了性能测试及表征,根据不同颜填料体积浓度涂层的物理机械性能、盐水浸泡实验结果和电化学阻抗谱分析,确定该水性环氧导静电防腐蚀涂料的最佳颜填料体积浓度为35%。     

Boron containing UV-curable epoxy acrylate coatings

In the present work boron acrylate monomer was synthesized by esterification reaction. UV-curable boron containing epoxy acrylate coatings were prepared and applied on plexiglass substrates to obtain thermally and mechanically stable coatings. The physical and mechanical properties of UV-cured coatings were investigated such as gel content, solvent resistance, hardness, flexibility and tensile tests. The thermal behavior of coatings was also evaluated. It was observed that the tensile properties and thermal stabilities of boron modified epoxy coatings mainly depend on the boron content.     

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。     

Water‐borne melamine–formaldehyde‐cured epoxy–acrylate corrosion resistant coatings

Organic protective coatings are widely used in corrosion control. However, environmental standards establish that the volatile organic compounds either must be removed or controlled at the lowest possible levels. The carcinogenic environmental impact of volatile organic compounds has led to the substitution of solvent‐borne coatings by water‐borne coating systems. Among recently developed water‐borne coatings, epoxy‐ and acrylic‐based coatings have a special significance over other reported water‐borne systems. Keeping in mind, the importance of water‐borne coatings in the present work, we report the synthesis of water‐borne epoxy–acrylate (EpAc) and melamine–formaldehyde (MF) as well as formulation of their anticorrosive coatings. The structural elucidation of MF‐cured EpAc was carried out by FTIR, ¹H NMR, and ¹³C NMR spectroscopic techniques. The coatings of EpAc‐MF were applied on mild steel strips and were evaluated for physicochemical, physicomechanical characterization, and the anticorrosive performance under different environmental conditions. The present coating system EpAc coatings exhibited superior performance as compared to the reported water‐borne epoxy–acrylatecoatings. The presence of melamine–formaldehyde in the resin increases the scratch hardness, impact resistance, alkali resistance, and thermal stability of these coatings. EpAc‐MF‐1 was found to cure at ambient temperature and exhibit good physicomechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

水基型路面标线涂料的研制及其应用

采用合成的具有核壳结构的环丙乳液配制的水性路面标线涂料 ;讨论了乳化剂、环氧树脂、丙烯酸酯功能单体的用量对乳液性能的影响和对涂料的干结时间、耐水性能及施工泛黄的影响因素 ,并提出了相应的解决措施。     

MAn-HTPB改性环氧丙烯酸酯光敏涂料的研制

利用顺丁烯二酸酐（MAn）与端羟基聚丁二烯（HTPB）的酯化产物对自制环氧丙烯酸酯进行改性,制得具有一定柔韧性的改性环氧丙烯酸酯预聚体,进而制备出性能优良、易于施工的紫外光固化涂料。对环氧丙烯酸酯改性的催化剂用量、反应温度、反应时间进行了研究,得出了最佳的合成反应条件。并讨论了光敏剂的种类、用量及不同组分配比对涂膜固化性能的影响。     

水性环氧-丙烯酸酯复合涂料技术进展

介绍了环氧-丙烯酸酯复合乳液的2种制备方法:自由基接枝共聚和酯化法。综述了水性环氧-丙烯酸酯复合涂料的制备及应用技术进展。     

紫外光固化环氧丙烯酸酯的研究进展

环氧丙烯酸酯树脂是紫外光(UV)固化领域中用量最大的一类光固化树脂,具有粘接强度大、硬度高及耐化学药品性等优点,但也存在黏度较大、韧性较差等问题。为了提高环氧丙烯酸酯的综合性能,有必要对其进行改性。介绍了环氧丙烯酸酯的合成基本原理及主要合成条件对树脂的影响,综述了国内外近期对环氧丙烯酸酯改性的主要方法及研究进展,指出了目前环氧丙烯酸酯在涂料中应用存在的主要问题,为今后对环氧丙烯酸酯性能的进一步改进提供了参考。     

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.     

羟烷基酰胺体系低温固化超耐候粉末涂料用聚酯树脂的合成研究

为克服聚酯树脂的性能缺陷,进一步提升羟烷基酰胺体系超耐候粉末涂料的耐候性能,使用溶液聚合制备环氧基丙烯酸酯预聚物,通过研究丙烯酸预聚物环氧值、用量对改性聚酯性能的影响,考察酸解剂对聚酯性能的作用,采用酯化缩聚工艺设计并制备出适用于羟烷基酰胺（ Primid）体系低温固化超耐候粉末涂料的新型聚酯树脂。结果表明：合成的新型聚酯具有高反应活性, 160 ℃固化涂层可兼顾耐冲击性和流平效果,涂料同时具有优异的贮存稳定性和突出的超耐候性。     

Emulsion polymerization of an epoxy‐acrylate emulsion stabilized with polyacrylate. i. influence of salt,initiator, neutralizing amine,and stirring speed

The past decade has seen the development of high‐performance epoxy‐acrylate coatings. Some of these coatings are used exclusively as can coatings. To improve chemical resistance, emulsion polymerization in the presence of the dispersed epoxy resin can be conducted. Replicated factorial designs were designed to investigate some of the factors that contribute to the performance and stability of the epoxy‐acrylate coating. The factors investigated in this study were: the type and amount of neutralizing amine, the type of initiator, the presence or absence of salt, and the stirring speed of the impeller. The measured responses for the experimental design were particle size, particle size distribution, and conversion. It has been shown in this study that the type of amine used to neutralize the polyacrylic stabilizer significantly influenced the observed responses probably by acting as chain transfer agent during polymerization. The addition of salt significantly affected the observed responses by shielding the surface charges on the particle surface that impart stability to the latex through electrostatic repulsion. Stirring speed of the impeller and the type of initiator as factors in the range investigated do not influence the kinetics or the particle size and polydispersity to any great extent either on their own or in combination with other factors. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1347–1360, 1999     

UV光固化环氧丙烯酸酯耐磨涂料的研究

以E51和E44环氧树脂和丙烯酸为原料,制备了UV固化环氧丙烯酸酯耐磨涂料。不同光引发剂、稀释剂和助剂等对UV固化环氧丙烯酸酯涂料固化性能均有影响。研究结果表明,用安息香乙醚与二苯甲酮(质量比为2∶1)的混合体系作为光引发剂的引发效率最高,最佳涂料配方:环氧丙烯酸酯∶丙烯酸丁酯∶安息香乙醚∶二苯甲酮∶滑石粉为70∶20∶4∶2∶4(质量比)。     

环氧/叔胺/丙烯酸树脂三元配比对复合水性涂料性能影响的研究

在掌握环氧树脂与丙烯酸树脂酯化反应凝胶规律的基础上，在临界凝胶方程给出的环氧／叔胺／丙烯酸树脂三角图的非凝胶区域，利用酯化反应合成了不同三元配比的六种环氧丙烯酸树脂复合物，通过研究这六种复合物的相对分子质量、加水乳化和涂膜性能等变化规律，最终给出适合做防腐涂料的配方选择范围和涂料配方设计的指导原则。     

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。     

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     

水基光敏环氧丙烯酸酯的合成

以环氧豆油、双酚A环氧树脂、丙烯酸和马来酸酐合成了具有羧基的环氧丙烯酸酯齐聚物，经胺中和后，水性化，可得自乳化光敏树脂水分散体系。并且用LR表征了环氧树脂与丙烯酸的混合物。流变学研究显示其水稀释过程体系粘度变化有明显的异常现象。考察了在光引发剂作用下，树脂中组成最终对光固化涂层综合性能的影响。