Preparation of UV-curable PEG-modified urethane acrylate emulsions and their coating properties. II. Effect of chain length of polyoxyethylene

To prepare self-emulsifiable urethane acrylate, poly(ethylene glycol)-modified urethane acrylates (PMUA), containing polyoxyethylene chains as a terminal group were synthesized by the reaction of a residual isocyanate group with poly(ethylene glycol) (PEG). Five types of PMUA were synthesized using five types of PEG having different molecular weight. As the chain length of polyoxyethylene of PMUA increased, the thermal stability of their emulsions improved and the tensile strength of their UV-cured films were also increased. For PMUA600 prepared using PEG600, the thermal stability of the emulsion and tensile strength of UV-cured film were relatively low. However, the emulsions of PMUAs which were synthesized using PEG2000, PEG4000, and PEG6000 were stable with increasing temperature and the tensile strength of their cured films was greater than that of PMUA 600. When PMUA600 was mixed with PMUA2000, PMUA4000, and PMUA6000, the thermal stability of the emulsions of mechanical properties of their UV-cured films were improved greatly. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2657–2664, 1997     

Preparation of UV-curable emulsions using PEG-modified urethane acrylates: The effect of nonionic and anionic groups

To prepare self-emulsificable urethane acrylate resin, PEG-modified urethane acrylates (PMUA), containing polyoxyethylene chains as a terminal hydrophilic group and urethane acrylate anionomers (UAA) incorporated dimethylolpropionic acid (DMPA) as a pendant hydrophilic one were synthesized. For PMUA emulsions, the reaction molar ratio of PEG to 2-hydroxyethyl methacrylate (2-HEMA) significantly influenced the viscosity and droplet size of the emulsion and tensile strength of cured films. These emulsions were stable to pH change and the addition of electrolyte, but coagulated around 60°C. In the case of UAA, emulsions, however, were very stable to elevated temperatures and coagulated in adding even a little bit of electrolyte. For soap-free emulsions of the mixture of PMUA and UAA, emulsion stabilities of these mixtures against temperature, pH change, the addition of electrolyte, and the rate of shear and freeze–thaw increased synergetically. Additionally, the tensile strength of cured films was also improved. © 1996 John Wiley & Sons, Inc.     

紫外光固化敷形涂布胶的制备与性能

用环氧丙烯酸树脂30-50份（质量,下同）,丙烯酸酯类单体40～65份,光引发剂2～5份,偶联剂及助剂0.1～3份,研制出可紫外光固化的敷形涂布胶,并测试了性能。结果表明,该胶具有较好的附着力,优异的耐湿热性和较快的表干速度,可满足印刷线路板的涂敷要求。     

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。     

氨基甲酸酯基丙烯酸酯的合成及其光固化性能

利用碳酸亚乙酯与1,6-己二胺、异佛尔酮二胺反应，制备出两种含氨基甲酸酯基的二元醇，基于氨基甲酸酯二元醇与1,6-己二醇二丙烯酸酯（HDDA）、新戊二醇二丙烯酸酯（NPGDA）及三羟甲基丙烷三丙烯酸酯（TMPTA）本体条件下的Oxa-Michael加成反应及酯交换反应，合成出6种含氨基甲酸酯基的丙烯酸酯混合物。利用FTIR及高分辨质谱分析了产物结构，用FTIR考察了所合成氨基甲酸酯基丙烯酸酯光固化过程的动力学,测定了光固化膜的性能。结果表明，在含占总质量分数3% 的2-羟基-2-甲基-1-苯基-1-丙酮（1173）光引发剂的引发下，氨基甲酸酯基丙烯酸酯能在30s内固化形成表面平整、柔韧性（0.5~2.5mm）良好、透明或半透明的膜；固化膜的凝胶率及铅笔硬度分别为92%~96%、4~5H，对玻璃的附着力为0~1级。     

Preparation and properties of phase‐change heat‐storage UV curable polyurethane acrylate coating

Phase‐change heat‐storage UV curable polyurethane acrylate (PUA) coating was prepared by applying microencapsulated phase change materials (microPCMs) to PUA coating. MicroPCMs containing paraffin core with melamine‐formaldehyde shell were synthesized by in situ polymerization. The effect of stirring speed, emulsification time, emulsifier amount, and core/shell mass ratio on particle size, morphology, and phase change properties of the microPCMs was studied by using laser particle size analyzer, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopic analysis, scanning electron microscopy, and differential scanning calorimetry. The results showed that the diameter of the microcapsules decreased with the increase of stirring speed, emulsification time, and emulsifier amount. When the mass ratio of emulsifier to paraffin is 6%, microcapsules fabricated with a core/shell ratio of 75/25 have a compact surface and a mean particle size of 30 μm. The sample made under the above conditions has a higher efficiency of microencapsulation than other samples and was applied to PUA coating. The dispersion of microPCMs in coating and heat‐storage properties of the coating were investigated. The results illustrated that the phase‐change heat‐storage UV curable PUA coating can store energy and insulate heat. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41266.     

光敏性含磷丙烯酸酯的合成和性能研究

将三氯氧磷分别与乙二醇及一缩乙二醇反应合成了2种双磷酸酯酰氯,将其再进一步与丙烯酸羟乙酯反应,制备了2种四官能度的UV固化含磷丙烯酸酯,通过1H-NMR和FT-IR对最终产物结构进行了表征。研究了中间反应物配比对产物收率的影响,2种含磷丙烯酸酯对UV固化体系中C==C双键转化率的影响,固化膜的热稳定性和UV固化体系的物理力学性能。结果表明:双磷酸酯酰氯与丙烯酸羟乙酯物质的量比为1:3.94～3.97时,产物收率98.9%。2种含磷丙烯酸酯25℃下黏度较低(280mPa.s),固化膜800℃残炭率较高(5.5%),附着力1级,硬度5H,剪切强度12.7MPa,是优良的紫外光固化促进剂。     

紫外光固化环氧丙烯酸酯涂料的表征

研制了一种用于艺术玻璃彩绘的新型涂料——紫外线固化环氧丙烯酸酯涂料，主要通过涂膜硬度的测定、红外光谱(FTIR)和差示扫描量热分析法(DSC)研究了涂膜固化程度与辐射时间之间的关系，并用紫外光谱和红外光谱研究了引发剂及其引发涂膜固化的机理。     

一种UV固化抗静电型硬化薄膜的制备

以六官能度聚氨酯丙烯酸酯预聚物和乙氧基化三羟甲基丙烷三丙烯酸酯单体为主体,甲基异丁基酮、丁酮和丙二醇甲醚为混合溶剂,1-羟基环己基苯基甲酮为光引发剂,纳米SiO_2分散液和导电高分子分散液CIL313为添加剂,有机硅聚醚为流平剂,制备了高硬度、耐摩擦抗静电型硬化薄膜,讨论了光引发剂用量、UV固化条件、纳米SiO_2分散液用量、流平剂、抗静电剂用量等对硬化薄膜外观与性能的影响。结果表明,当光引发剂用量8质量份,固化条件:200 mW/cm~2、300 mJ/cm~2,纳米SiO_2分散液用量30质量份,流平剂用量0.4质量份,抗静电剂用量10质量份时制备的硬化薄膜综合性能优异,其铅笔硬度3H5/5,耐摩擦性116次/200 g,表面电阻10~(10)Ω,全光透过率90.4%,雾度0.9%。     

Surface modification of a UV curable acrylate coating: In situ introduction of hydrophobic properties

Two polyfunctional silanes polymethyl-hydrosiloxane (I) and octakis(dimethylsiloxy)-T8-silsequioxane (II) are proposed as new co-initiators for radical acrylate photopolymerization reactions. In the presence of a type II photoinitiator such as benzophenone, isopropylthioxanthone or camphorquinone, these compounds are found reactive. The influence of oxygen is also examined. Incorporating only 1% (w/w) of I into an epoxy acrylate matrix allows the formation, under air, of a coating exhibiting a hydrophobic surface. In free radical promoted cationic polymerization, the addition of I to a BP/Φ₂I⁺ system significantly enhances, under air, both the polymerization rate and the final conversion. The autoxidation reaction of I in the presence of BP under air generates a hydrophobic polymer surface. The reaction mechanisms are discussed on the basis of laser flash photolysis experiments.     

光固化低黏度环氧丙烯酸酯的合成与性能研究

合成了可紫外光固化的低黏度环氧丙烯酸酯树脂,通过红外光谱、核磁共振氢谱、碳谱对树脂结构进行了表征;采用综合热分析仪(DSC-TG)对树脂固化膜的耐热性能进行了分析。结果表明,在树脂中添加活性单体时,随单体官能度的增加,固化膜的耐热性能增加,但双官能团单体的用量对固化膜的耐热性能没有明显影响。固化膜具有较好的耐热性,初始分解温度为330.7℃,玻璃化转变温度为76.9℃。所得树脂黏度仅为3~4Pa.s(60℃),为市售产品的1/3,附着力1级,硬度4 H,耐水性能优异,无需添加单体使用。     

Preparation and properties of poly(urethane acrylate) films for ultraviolet‐curable coatings

Four different UV‐curable poly(urethane acrylate)s were prepared through the reaction of two diisocyanates [i.e., toluene‐2,4‐diisocyanate (TDI) and isophorone diisocyanate (IPDI)] and two polyols [i.e., polycaprolactone triol (PCLT) and polycaprolactone diol (PCLD)], and they were characterized with Fourier transform infrared spectroscopy. The mechanical properties, thermal properties, and water sorption of the cured poly(urethane acrylate)s were also investigated with respect to the chemical structures of the polyols and diisocyanates. In comparison with linear PCLD–TDI and PCLD–IPDI, crosslinked PCLT–TDI and PCLT–IPDI with trifunctional PCLT showed relatively high thermal decomposition temperatures. The hardness and modulus of the UV‐cured poly(urethane acrylate) films, which were measured by a nanoindentation technique, were in the following increasing order: PCLD–IPDI ～ PCLD–TDI < PCLT–IPDI ～ PCLT–TDI. The pencil hardness was 3H for PCLT–IPDI and PCLT–TDI and HB for PCLD–IPDI and PCLD–TDI. Two urethane acrylates prepared from the trifunctional polyol showed better acid and alkali resistances than those made from the bifunctional polyol. These mechanical properties and chemical resistances may have been strongly dependent on the chain flexibility of the molecules and crosslinking density. Regardless of the functionality in the polyol, the change in the yellowness index showed a lower value in the poly(urethane acrylate) coating containing the aliphatic diisocyanate IPDI in comparison with the corresponding poly(urethane acrylate) with the aromatic diisocyanate TDI. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A novel dendritic acrylate oligomer: Synthesis and UV curable properties

An dendritic acrylate oligomer with eight double bonds (DAO) was synthesized by Michael addition reaction of ethylene diamine (EDA) and trimethylolpropane triacrylate (TMPTA) under mild conditions, and was easily separated from the reaction system with methanol. The structure of DAO was characterized by IR, ¹H‐NMR, and elemental analysis. DAO is UV curable oligomer with low viscosity and high curing speed. Its viscosity was 10.85% of that of the linear acrylic oligomers with similar molecule weight (EBECRYL Resin 285). With Darocure 1173 as the photoinitiator, the curing speed of DAO was respectively 7.5 and 10.3 times higher than that of EBECRYL Resin 605 and EBECRYL Resin 285. Furthermore, the effect of the photoinitiator and active diluent on curing speed of DAO UV curing system was studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1018–1022, 2004     

Effects of UV curable urethane acrylate resins treatments on the physical properties of medium‐ and small‐diameter softwoods

This study analyzed the effects of ultraviolet curable urethane acrylate resin (UV resin) treatments on surface homogeneity, dimensional stability, and change in colors of medium‐ and small‐ diameter softwoods produced in Taiwan. The UV resins were formulated with urethane acrylate oligomer/methyl methacrylate (MMA) monomer by the weight ratio of 50/50, 60/40, 70/30, 80/20, and 90/10, and 3% of photoinitiator (benzil dimethyl ketal) by the total weight of UV resins was added, respectively. Four kinds of softwoods, including Taiwanina, China fir, Taiwan incense cedar and Japanese fir with a diameter of 10–15 cm were obtained from Hui‐Sun Forest Station, Taiwan. Results show that the oligomer derived from 2‐hydroxyethyl methacrylate (2‐HEMA) and polymeric toluene diisocyanate (PTDI) by the molar ratio of NCO/OH = 1.0 could be readily synthesized and the prepared UV resin were also easily applied to the woods at room temperature and normal pressure. The surface hardness and moisture excluding efficiency (MEE) of woods were markedly enhanced and correlated with the increased in oligomer content of the UV resins as well as the homogeneity of softwood surfaces were also improved. According to the antiswelling efficiency (ASE), the increased in dimensional stability of woods were achieved; especially for the lower specific gravity China fir had the greatest improved efficiency of 60.68% at oligomer/MMA ratio of 80/20. In addition, a massive, colorful, and warm feeling in sense of sight on UV resin‐treated wood, which would appeal to most people, was also obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

非离子水性环氧树脂乳化剂及其乳液的制备与性能研究

以EP(环氧树脂)、PEG(聚乙二醇)、邻苯二甲酸酐为原料,合成了一种非离子反应型水性EP乳化剂,并通过相反转法制备了稳定的水性EP乳液,对酯化反应条件进行了优化,并探讨了PEG分子量、乳化剂用量、相反转条件对乳液性能的影响。研究结果表明:在温度110℃、时间2.5 h下能较好控制酯化过程,红外光谱和GPC分析结果表明得到了预期结构的乳化剂;选择基于PEG-6000合成的乳化剂,在乳化剂用量为15.0%、相反转条件为60℃、转速2 500 rpm时获得的水性EP乳液具备良好的稳定性。     

Preparation and properties of UV-curable polydimethylsiloxane urethane acrylate

A new type of a UV-curable polyurethane acrylate resin based on hydroxyterminated polydimethylsiloxane (PDMS) soft segments with molecular weight 1800 and 2,4-toluene diisocyanate (TDI)/2-hydroxyethyl methacrylate (HEMA) hard segments were synthesized. The reactivity of 2,4-TDI with the hydroxy groups of silanol and HEMA was discussed by means of IR measurements. The characteristic absorption peaks of the —NCO groups of 2,4-TDI in the para- and ortho-position should decline with increasing the reaction time. The measurements of fundamental physical properties of this type of UV-curable materials had been widely studied in addition to the effects of using various reactive diluents and some pigments. This kind of resin with good optical, electrical insulating, and adhesive properties on various matrices, could be improved in chemical properties and reduced in viscosity while promoting the coating processability by mixing with various reactive diluents. The excellent adhesive properties on glass plates can be attributed to the similar structure between the PDMS soft segments and glass which makes the application in the coating industry possible.     

Preparation and characterization of dual curable adhesives containing epoxy and acrylate functionalities

Bisphenol A type methacrylate, glycidyl methacrylate, acrylic acid and a trifunctional monomer were cured using both ultraviolet (UV) and thermal methods. The UV and thermal curing behavior of these components was evaluated using photo-differential scanning calorimetry (Photo-DSC) and Fourier Transform infrared spectroscopy (FT-IR) analyses, as well as gel fraction and pendulum hardness measurements. The reaction rate was fast, and an increasing amount of CC double bond character was observed by FT-IR, demonstrating an effective reaction in the presence of both UV irradiation and heat. The gel fraction analysis also confirmed the formation of crosslinks in the structure after the curing process. The pendulum hardness test revealed the nature of the curing process at different UV doses after UV and thermal curing. The adhesion strength was also evaluated as a function of epoxy group concentration, demonstrating that adhesion increased with increasing epoxy group content. The thermal degradation characteristics were monitored by thermal gravimetric analysis (TGA). The bonding between the epoxy and carboxyl groups resulted in a delayed degradation of the cured adhesive.     

填料对紫外光固化环氧丙烯酸酯体系阻光效应的影响

在UV(紫外光)固化EA(环氧丙烯酸酯)体系中分别加入SiO2(二氧化硅)、滑石粉、CaCO3(碳酸钙)或TiO2(钛白粉)填料,配制不同的填充EA体系。采用UV-vis(紫外-可见分光光度)法、FT-IR(红外光谱)法和凝胶含量等评价了不同填充EA体系的UV固化特性,并探讨了填料类型、粒径和含量对不同填料阻光效应的影响。试验结果表明:四种填料的阻光效应为TiO2>CaCO3>滑石粉>SiO2;当填料粒径为1~10μm时,粒径5μm填料的阻光效应相对最小;填料含量越多,阻光效应越大,但10%SiO2填充EA体系的凝胶含量仍高达96%。     

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.     

低温固化环氧阴极电泳涂料的制备

采用乙二醇单丁醚和甲乙酮肟对甲苯二异氰酸酯(TDI)进行全封闭,并将其加入到二乙醇胺改性的环氧树脂乳液中进行混合搅拌,制备了一种低温固化环氧阴极电泳涂料。研究了封闭反应温度、TDI用量和接枝反应温度对漆膜性能的影响,确定了适宜的工艺条件:甲乙酮肟封闭反应温度为40°C,接枝反应温度80°C,TDI质量分数为15%左右。在此条件下制备的漆膜可以在150°C/30min的条件下固化,所得漆膜厚度20μm,光泽70°,附着力1级,柔韧性1mm,铅笔硬度3H,冲击强度>50kg.cm,耐水性>800h,达到设计要求。