UV curable glycidyl carbamate based resins

The synthesis and characterization of UV curable resins based on glycidyl carbamate chemistry have been explored. Glycidyl carbamate (GC) functional resins have been used to obtain crosslinked coatings with a wide range of properties using several crosslinking techniques such as epoxy-amine, self-crosslinking, and sol-gel. GC resin technology was further expanded to UV curable coatings by reacting polyfunctional GC resins with acrylic acid to yield acrylated glycidyl carbamate (AGC) resins. Alcohol-modified UV curable GC resins were also prepared to obtain lower viscosity. Commonly used reactive diluents were used to prepare a UV curable GC coating formulations. The coatings were cured in air using a Fusion LC6B Benchtop Conveyer with an F300 UV lamp. The degree of conversion of acrylic double bonds during UV curing was determined using real time FTIR and showed that the resins had fast cure rates and high extents of conversion of acrylate groups. Coating properties such as hardness, impact strength, methyl ethyl ketone double rubs, flexibility, and adhesion were studied. Dynamic mechanical analysis was used to determine crosslink density of the coatings. Differential scanning calorimetry and thermogravimetric analysis were used to study the thermal properties of the coatings. The type of polyisocyanates and the extent of modification in GC resins influenced the degree of conversion, crosslink density, and coating performance.     

Preparation and properties of UV‐curable fluorinated polyurethane acrylates

A series of UV‐curable polyurethane acrylates (PUA0, FPUA3, FPUA6, FPUA 9 FPUA12, FPUA15, where the numbers indicate the wt % of perfluoroalkyl acrylate), were prepared from a reactive oligomer [4,4 ?‐dicyclohexymethanediisocyanate(H12MDI)/ poly(tetramethylene glycol)(PTMG)/2‐hydroxyethyl methacrylate (HEMA): 2/1/2 molar ratio, prepolymer:40 wt %] and diluents [methyl methacrylate (MMA, 20 wt %)/ isobornyl acrylate (IBOA, 40–25 wt %)/heptadecafluorodecyl methacrylate (PFA, 0–15 wt), total diluents: 60 wt %]. This study examined the effect of PFA/IBOA weight ratio on the properties of the UV‐curable polyurethane acrylates for antifouling coating materials. The as‐prepared UV‐curable coating material containing a 15 wt % PFA content in diluents (MMA/IBOA/PFA) form a heterogeneous mixture, indicating that a PFA content of approximately 15 wt % was beyond the limit of the dilution capacity of diluents for the oligomer. In the wavelength range of 400–800 nm, the UV‐cured PUA0 film sample was quite transparent (transmittance%: near 100%). On the other hand, the transmittance% of the FPUA film sample decreased markedly with increasing PFA content. XPS showed that the film‐air surface of the UV‐cured polyurethane acrylate film had a higher fluorine content than the film‐glass dish interface. As the PFA content increased from 0 to 12 wt %, the surface tension of the UV‐cured urethane acrylates decreased from 26.8 to 15.6 mN/m, whereas the water/methylene iodide contact angles of the film–air surface increased from 90.1/63.6° to 120.9/87.1°. These results suggest that the UV‐curable polyurethane acrylates containing a PFA content up to 12 wt % have strong potential as fouling‐release coating materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40603.     

Novel reactive diluents for UV/moisture dual‐curable coatings

The novel silicone‐modified polyacrylate reactive diluents for UV/moisture dual‐curable coatings were synthesized from N,N‐bis[3‐(trimethoxysilyl)propyl]amine and multifunctional acrylates such as ethoxylated trimethylolpropane triacrylate and polyethyleneglycol diacrylate through Michael addition reaction. Their structures were characterized by NMR and FTIR and their average molecular weights were determined by vapor pressure osmometry. With FTIR, it was found that the obtained diluents could be cured both by UV radiation and moisture mode. The ²⁹Si‐NMR showed that dimer was the main condensation product at the initial stage of moisture curing. The rheological behavior of the diluents investigated by rotary viscometer indicated they were very close to Newtonian fluid, and the viscosity of coatings decreased evenly with increasing concentration of reactive diluents in the coatings. In particular, they were found to be highly efficient in diluency and reactivity for UV polymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1500–1504, 2005     

UV固化超支化聚氨酯丙烯酸树脂的研究进展

超支化聚氨酯是一种新型的功能性树脂,UV固化超支化聚氨酯丙烯酸树脂作为一种新型的涂料成膜物质,具有固化速度快、涂膜性能好、环境污染小等优点,对制备环境友好、性能优异的产品以及用其改性普通的UV光固化树脂具有实际意义,展现出良好的发展前景。本文就国内外有关UV固化超支化聚氨酯丙烯酸树脂的制备方法、固化动力学和固化流变行为等方面的研究工作进行了综述,并介绍了UV固化超支化聚氨酯丙烯酸树脂在改善涂膜力学性能和阻尼性能等方面的应用研究现状,提出完善UV固化超支化聚氨酯丙烯酸树脂的基础研究和在此基础上的相关产品的开发将是今后研究的主要发展方向。     

Synthesis of UV-curable acrylate polymer containing sulfonic groups for anti-fog coatings

A series of UV curable hydrophilic acrylate polymers containing sulfonic acid group was prepared via free radical copolymerization using 2-acrylamido-2-methyl propane sulfonic acid (AMPS) as hydrophilic monomer, which were used as prepolymers for anti-fog coatings. The expected structures were confirmed by FT-IR, ¹H NMR and gel permeation chromatography (GPC). These UV-curable acrylate polymers were then mixed with reactive diluents and photoinitiator to form coating formulas. Various substrates were coated with these formulas and cured under UV exposure to obtain transparent coatings with good adhesion and hardness. The anti-fog properties of UV-cured coating were measured by contact angle test and anti-fog test. The results showed that the AMPS content in prepolymer had a great influence on the anti-fog properties of UV-cured coating. The formula was optimized and the corresponding UV-curing anti-fog coating was manufactured. The test results indicated that the coatings showed good mechanical properties, great optical transparency and excellent anti-fog performance.     

Effects of reactive diluents on mechanical and physical properties of a UV curable acrylated urethane prepolymer

In this study, the dependence of the mechanical properties of a UV curable acrylated urethane on reactive diluent types and their amounts was investigated. The acrylated urethane prepolymer was synthesized from isophorone diisocyanate (IPDI), an aliphatic diisocyanate, and polypropylene glycol monomethacrylate (PPGMMA) by stepwise addition reaction. UV sensitive mixtures containing N-vinylpyrrolidinone (NVP), thiodiethylene glycol diacrylate (TDGDA) and isobornyl acrylate (IBoA) as reactive diluents were irradiated by UV light. An increase in reactive diluent content, either TDGDA or IBoA, caused an increase in tensile strength and a decrease in elongation values. In contrast, above a certain concentration a decrease in tensil strength was observed when NVP was used as reactive diluent. The water absorption capacities of the UV curable acrylated urethane films were observed to depend on type and amount of reactive diluent that was used. Thermooxidative properties of the films were also improved by incorporation of reactive diluents into formulations.     

水性紫外光木器涂料的研制

以水性UV丙烯酸酯树脂、水性UV脂肪族聚氨酯丙烯酸酯树脂为基料制备成水性紫外光木器涂料,经检测,水性UV涂装性能上大大得到改善,气味比普通UV涂料低、硬度比水性木器涂料高、表面效果与施工方法得到有效的改善,解决了水性木器、UV光固化涂料在喷涂技术领域遇到的技术瓶颈。     

全球辐射固化材料近期市场分析（一）

辐射固化技术于20世纪60～70年代,在欧美市场上初步确立了自身的产业地位,成为全球经济体系中的一个组成部分.各种专业分工不同的企业（原材料生产供应商、化学配方产品生产供应商、装置设备制造供应商和下游客户）,共同构建了UV/EB固化产业的价值链.近年来,世界三大主要地区（北美、欧洲和亚洲）辐射固化市场以近两位数的速度在增长,尽管全球经济形势持续低迷.2012年,全球辐射固化市场配方产品的消耗量据统计大约为457000t.亚洲市场消耗量已超过欧美市场而居全球首位.辐射固化配方产品在世界三大主要地区市场中应用的重点领域虽然各不相同,然而工业涂料在全球的市场份额中仍然比例最大.本文还列出了辐射固化原材料在不同市场中的消费量与价格.     

Effect of titania and zinc oxide particles on acrylic polyurethane coating performance

The outer environment, especially UV portion of solar radiation and water (in the form of moisture or rain) has an adverse effect on the surface appearance of heat-treated wood. Exposure to UV triggers the chain scission reactions which change the intrinsic properties of heat-treated wood and discoloration of wood surface. Repeated temperature and humidity variations cause swelling and shrinking of wood surface, which consequently create cracks and fissures exposing wood's sub superficial layers to atmospheric agents. Therefore, wood industries move towards the development of coatings in order to protect the heat-treated wood while retaining wood's natural look. Water based acrylic polyurethane coatings are highly efficient, non toxic and durable coatings with upgraded film properties. In this study, an attempt is made to improve the performance of these coatings by incorporating natural antioxidant (bark extract) and inorganic UV absorbers (nano and micro titania and nano zinc oxide) into the coatings. The main objectives of this study are to investigate the wetting and penetration characteristic of these new coatings on the wood surface and to study coating thickness variation with weathering time. The Sessile-drop method and fluorescence microscope are used for this investigation. The wettability of different coatings applied to heat-treated jack pine early wood and late wood is compared. The results show that there is a significant difference between the contact angle of early wood and late wood for acrylic polyurethane coating containing titania micro particles. The contact angle between water and coated wood surface reveals that the degree of orientation of the coating materials increases as the weathering time increases. The penetration characteristics of all the four coatings are found to be very poor. In addition, the relationship between the coating thickness and the UV exposure time is studied for four water based acrylic polyurethane coatings with different additives. It is found that the coating thickness decreases with increasing weathering time and a tissue deformation beneath the coating surface takes place during weathering.     

Design and synthesis of bio-based UV curable PU acrylate resin from itaconic acid for coating applications

UV curable PUA resin was successfully synthesized from polyol based on sustainable resource originated from itaconic acid (IA), isophorone diisocyanate (IPDI) and 2-hydroxyethyl methacrylate (HEMA). A polyol was synthesized by condensation reaction of IA with 16-hexanediol in the presence of p-Toluenesulfonic acid (pTSA). The synthesized PUA resin was characterized for its structural elucidation by using Fourier Transform Infrared Spectrophotometer (FTIR), ¹H and ¹³C NMR spectroscopy. The synthesized UV curable PUA resin was incorporated in varying concentrations in conventional PUA coating system. The effects of varying concentration of synthesized UV curable PUA resin on rheology, crystallinity, thermal and coating properties were evaluated. The rheological behavior of the resins were evaluated at variable stress and result showed decrease in viscosity of resin as concentration of synthesized UV curable PUA resin increases in conventional PUA resin. The cured coatings have been evaluated for glass transition temperature (T_g) and thermal behavior by differential scanning calorimeter and thermogravimetric analysis respectively. The degree of crystallinity of the coatings was determined from X-ray diffraction patterns using the PFM program. It was found that increase in the mass proportion of IA based PUA in coatings, the coating becomes more rigid and crystalline. The synthesized UV curable PUA coatings showed interesting mechanical, chemical, solvent and thermal properties as compared to the conventional PUA. Further, cured coatings were also evaluated for gel content and water absorption.     

Study of cationic UV curing and UV laser ablation behavior of coatings sensitized by novel sensitizers

To improve the laser ablation performance of cycloaliphatic epoxide cationic UV curable coatings, two novel reactive sensitizers were synthesized and characterized and their effect on coating properties examined. The sensitizers were synthesized based on the reaction between naphthalene or anthracene derivatives and monomers or oligomers used in the coating system. HPLC and GC-MS confirmed the formation of the desired products. Three coating systems based on cycloaliphatic epoxide with either oxetane or polycaprolactone polyol were formulated with the reactive sensitizers. The sensitized coatings had higher conversion during UV curing in the oxetane containing formulation and did not deter the curing in the polyol containing formulation. Better UV laser ablation performance was observed in all sensitized coatings compared to the controls. Coatings with the anthracene based sensitizer even had better laser ablation performance than a commercial polyimide. The sensitized coatings had higher hardness, T_g and crosslink density while the adhesion and solvent resistance were not affected. An optimal amount of sensitizer was found for each coating formulation in terms of UV curing behavior. The relationship between coating T_g and laser ablation behavior was investigated and it was found that the higher the T_g and crosslink density, the poorer the laser ablation performance.     

Novel approach to convert non-self drying palm stearin alkyds into environmental friendly UV curable resins

UV curable coating is a form of green technology that reduces or eliminates completely the emission of volatile organic compounds (VOC) and is in line with the current global call in preserving nature. The objective of this project is to produce UV curable resins from non-self drying palm stearin alkyds by the incorporation of maleic anhydride (MAH) which could introduce more unsaturation into the main chains of alkyds. Four alkyds with different level of unsaturation were prepared and the successful incorporation of MAH was confirmed by FTIR and ¹H NMR analyses. Methyl methacrylate (MMA) was used as the reactive diluents, and benzophenone as the UV-photoinitiator. The UV-cured coatings were tested using standard methods adopted from ASTM, and results showed that coatings of maleated alkyds exhibited good film properties. This novel approach has succeeded in converting a non-self drying palm stearin alkyd into UV-curable resins.     

乳液型紫外光固化聚氨酯丙烯酸酯的涂膜性能及其影响因素

合成了一系列乳液型紫外光(UV)固化聚氨酯丙烯酸酯,针对其涂膜性能进行研究,考察了辐射时间、膜厚、光引发剂用量、分子结构等因素对涂膜性能的影响;通过对各种影响因素的研究,得到了具有优良的涂膜性能和装饰性的乳液型UV固化聚氨酯丙烯酸酯,附着力在0~1级,正反耐冲击性都在50 cm以上,铅笔硬度可以达到3H以上。     

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.     

EIS study on failure process of two polyurethane composite coatings

The performance of acrylic polyurethane composite coating and aliphatic urethane composite coating in 3.5% NaCl solution under ultra-violet radiation was studied with methods of EIS, SEM and FTIR. For aliphatic polyurethane coating, the coating resistance decreased and the coating capacitance and porosity increased more quickly than acrylic polyurethane coating. The acrylic polyurethane composite coatings showed better performance than aliphatic polyurethane composite coatings. IR spectra showed that under UV irradiation conditions, the failure mechanism of the two polyurethane coatings was the transformation of sec-amide to primary amides. The fractured bonds in acrylic polyurethane were mainly C–O bonds, while in aliphatic polyurethane they were mainly C–N bonds. The lower protection property of aliphatic polyurethane coating may be mainly attributed to the C–N bonds which are more liable to be broken.     

Properties of UV-curable polyurethane acrylates for primary optical fiber coating

Studies have been made on the effects of the chemical structure of reactive urethane acrylate prepolymers and diluents (reactive monomers) and overall composition of the prepolymer/diluent on the properties of the UV-curable polyurethane acrylates for primary optical fiber coating. We prepared several urethane acrylate prepolymers from two different isocyanates, 4,4′-dicyclohexylmethane diisocyanate (HMDI) or isophorone diisocyanate (IPDI), and two different polyols, polybutadiene diol (PBD) or polypropylene oxide diol (PPG), and 2-hydroxyethyl acrylate (HEA) with dibutyl tin dilaurate as a photoinitiator. UV-curable coating materials were formulated from the prepolymers and 2,2-dimethyl 2-phenyl acetophenone as a photoinitiator with one of four different diluents such as 1-vinyl 2-pyrrolidone (VP), lauryl methacrylate (LMA), acrylic acid 2-ethyl hexyl ester (AEHE), and acrylic acid n-butyl ester (ABE). It was found that AEHE is the desirable diluent in the formulation of the primary fiber-coating material. The desirable composition of PBD, when mixed PBD/PPG diols are used, should be about 50 wt % for optimum formulation. Most of the urethane acrylate prepolymers prepared in this study could be applied in the formulation of primary optical fiber coating and exhibited good properties of buffer functions, including low glass transition temperature, low modulus even at low temperature, say, below ?40°C, high refractive index, and low viscosity. © 1992 John Wiley & Sons, Inc.     

Preparation,characterization of UV‐Curable Waterborne Polyurethane‐Acrylate and the application in metal iron surface protection

Hydroxyethyl methyl acrylate (HEMA) capped waterborne polyurethane‐acrylate (WPUA) oligomer was firstly prepared from isophorone diisocyanate (IPDI), polyether polyol (NJ‐220), dimethylolbutanoic acid (DMBA), HEMA via in‐situ and anionic self‐emulsifying method. Ultraviolet (UV) curable WPUA coating was obtained from HEMA‐capped oligomer, butyl acrylate (BA) and multifunctional acrylates (TPGDA) as reactive diluents, and Darocur 1173 as photoinitiator. The physical properties of WPUA oligomers, such as particle size, apparent viscosity, and surface tension were investigated. Some mechanical properties of UV‐WPUA films, such as contact angles, thermal properties, and solvent (water, HCl, NaOH, NaCl, and ethanol) resistance of UV‐WPUA coating films were measured. The surface morphologies were measured by scanning electron microscope and atomic force microscope. The surface free energy of the UV‐cured film was calculated from contact angle measurements using the Lewis acid–base three liquids method. The specific UV‐WPUA coating was selected to protect the iron materials that observed the effect of the protection. The results indicate that the prepared UV‐WPUA coating has excellent protective behavior to metal iron materials and may offer some contributions to protect iron cultural relics. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3142–3152, 2013     

Preparation and evaluation of epoxy methacrylate UV‐curable coatings containing phthalazinone

Epoxy methacrylate resin (EMA) UV‐curable coatings exhibit high reactivity, low viscosity and excellent chemical resistance in environmentally friendly coatings. A novel EMA containing phthalazinone moieties for high temperature resistant UV‐curable coatings was synthesized. The formulations were cured with hexanediol diacrylate (HDDA) and trimethylol propane triacrylate (TMPTA) as reactive diluents promoted by a photoinitiator, and then interpenetrating polymer networks were generated. The mechanical, chemical and thermal properties of the clear coatings were characterized using Chinese National Standard methods (GB). EMA was used with UV radiation curing in combination with 6.7 wt% of HDDA and 13.4 wt% of TMPTA, and the properties of the cured films were as follows: pencil hardness of 5 H, 30% NaOH resistance for 30 days, 15% HCl resistance for 10 days, 3% NaCl resistance for 30 days and 5% weight loss temperature of 300.5 °C. EMA UV‐curable coatings containing phthalazinone exhibit excellent chemical and thermal stability, and could be potential candidates for UV‐curable zero volatile organic compound coatings applied in the fields of salt spray corrosion, strong radiation and high‐temperature resistance. Copyright © 2009 Society of Chemical Industry     

Preparation and properties of UV‐curable fluorinated polyurethane acrylates containing crosslinkable vinyl methacrylate for antifouling coatings

To obtain highly effective antifouling coatings, a series of UV‐curable polyurethane acrylates containing diluents [heptadecafluorodecyl methacrylate (PFA, 6 wt %)/isobornyl acrylate (IBOA, 34 wt %)/methyl methacrylate (MMA, 20‐5 wt %)/vinyl methacrylate (VMA, 0–15 wt %)] were prepared. This study examined the effect of bulky MMA (20‐5 wt %)/crosslinkable VMA (0–15 wt %) weight ratio on the properties of the UV‐curable polyurethane acrylates. The fluorine concentration in UV‐cured film surface increased with increasing VMA content up to 9 wt % and then decreased. The T_gα, transparency, elasticity, and mechanical properties of the UV‐cured film samples increased with increasing VMA content. The water/methylene iodide contact angles and surface tension of samples increased from 107/79 to 121/91° and decreased from 17.8 to 12.7 mN/m with increasing VMA content up to 9 wt % and then decreased/increased, respectively. From these results, it was found that the optimum VMA content was 9 wt % to obtain a high‐performance antifouling coating. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42168.     

Novel binder system for ultraviolet‐curable coatings based on tobacco seed (Nicotiana rustica) oil derivatives as a renewable resource

Several coatings have been developed to reduce volatile organic component emissions, such as water‐borne coatings, high‐solid coatings, powder coatings, and radiation‐curable coatings. Ultraviolet‐curable coatings are one such boon to paint industries, not only reducing volatile organic components but also increasing productivity. Most polymers industrially produced nowadays are based on petroleum, which is a limited resource. Developing new procedures for making polymers based on natural renewable resources is a resounding theme for this decade and the future also. In response to both these needs, we have investigated the use of tobacco seed (Nicotiana rustica) oil in the synthesis of radiation‐curable coatings. In this work, the alcoholysis of oil in various ratios with polyhydroxyl compounds was performed to prepare novel polyols, and these different polyols were reacted further with excess polyisocyanate to produce isocyanate‐terminated prepolymers. The prepolymer were further reacted with hydroxyethyl methacrylate to produce urethane acrylate oligomers. The radiation‐curable coating compositions were than prepared by the mixing of these oligomers with different reactive diluents, photoinitiators, and activators. These coating compositions were studied for their various physical and film characteristics, and certain coating compositions from tobacco seed oil were found to show very excellent overall coating properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008