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.     

紫外光固化环氧丙烯酸酯的贮存稳定性

为制备贮存稳定性优良的紫外光(UV)固化涂料,采用自制改性环氧丙烯酸酯树脂、活性稀释剂、光引发剂和阻聚剂制备了UV固化涂料体系并通过考察50°C下贮存7 d前后黏度的变化,研究了活性稀释剂、光引发剂和阻聚剂种类及用量对贮存稳定性的影响,并确定了最优体系:活性稀释剂w(己二醇二丙烯酸酯)=20%~30%,光引发剂w(Darocur 11733)=3.0%,阻聚剂w(对羟基苯甲醚)=0.04%。用红外光谱、凝胶渗透色谱等对贮存前后的体系进行了表征。测试了以最优体系为基础配制的UV涂料的涂膜性能。结果表明,加速贮存7 d后,涂料体系的重均分子量和数均分子量分别增加393 g/mol和403 g/mol,C═C双键含量仅损失4.9%,可见涂料具有较好的贮存稳定性,其漆膜性能与贮存前相比并无差异。     

UV固化低聚物及其涂料研究进展

综述了UV固化低聚物(主要是环氧丙烯酸酯和聚氨酯丙烯酸酯)的研究进展。环氧丙烯酸酯研究进展包括:降低黏度、改善柔韧性、光敏活性、耐热性、耐磨性和阻燃性能;聚氨酯丙烯酸酯的研究进展包括:紫外光固化的聚氨酯丙烯酸酯预聚物合成方法;聚氨酯丙烯酸酯/无机纳米复合材料;光固化无机/有机杂化材料;水性UV固化聚氨酯丙烯酸酯和UV固化超支化聚氨酯丙烯酸酯。较为详细地论述了氧阻聚的3种作用机理及解决方法(物理和化学2种方法),最后对光固化技术的5大发展趋势进行了展望。     

UV固化环氧丙烯酸酯涂料研究进展

综述了UV固化环氧丙烯酸酯的合成与改性,介绍了反应温度、原料配比、催化剂及阻聚剂的影响;改性主要是针对降低黏度,增加柔韧性,提高耐热、阻燃等性能。介绍了光引发剂及活性单体的研究进展,最后对光固化技术的发展趋势进行了展望。     

含氟活性稀释剂对环氧树脂流变性能的影响

为解决环氧树脂的高粘度给成型带来的困难,用NXS-11A型旋转粘度计研究了含氟活性稀释剂对环氧树脂体系的流变性能的影响。研究结果表明,含氟活性稀释剂/环氧树脂体系在常温(35℃)时为牛顿型流体;常温下,环氧树脂体系粘度随含氟活性稀释剂添加量的增加下降显著,当氟活性稀释剂添加6%时,其粘度约可下降50%;但温度较高时,粘度随含氟活性稀释剂添加量的增加下降缓慢。随着含氟活性稀释剂的增加,环氧树脂体系的流动活化能明显下降。     

UV固化聚氨酯丙烯酸酯涂料的研究进展

简要介绍了UV(紫外光)固化涂料的发展历程,阐述了PUA(聚氨酯丙烯酸酯)的合成机制及原料选择;重点综述了3种新型UV固化涂料[如WPUA(水性PUA)、双重固化型PUA和改性PUA等]的研究进展,提出了目前UV固化PUA涂料所存在的不足之处及解决办法。最后对UV固化PUA涂料的发展方向及应用前景进行了展望。     

光固化环氧丙烯酸酯体系的增韧研究

在癸二酸增韧环氧丙烯酸酯(GEA)的基础上,研究了通过加入聚氨酯丙烯酸酯(PUA),改善环氧丙烯酸酯紫外光固化材料的柔韧性,同时避免强度的较大损失。结果显示,对于癸二酸改性的环氧丙烯酸酯(癸二酸与环氧树脂的摩尔比为0.3),当GEA∶PUA∶稀释剂:光引发剂(质量比)为61.6∶15.4∶20∶3时,PUA共混改性的GEA光固化体系具有良好的综合性能,此时拉伸强度为8.84 MPa,断裂伸长率为109%,柔韧性为1 mm。     

UV固化聚氨酯丙烯酸酯耐黄变涂料的制备

以聚己二酸丁二醇乙二醇酯多元醇(PBEA)、异佛尔酮二异氰酸酯(IPDI)、丙烯酸羟乙酯(HEA)、复合活性稀释剂1,6-己二醇二丙烯酸酯(HDDA)/季戍四醇三丙烯酸酯(PETA)为原料,合成了紫外光(UV)固化聚氨酯丙烯酸酯耐黄变预聚体,研究了聚氨酯丙烯酸酯中IPDI和PBEA的物质的量比、活性稀释剂的选择和复配比...     

Properties of UV-curable polyurethane acrylates: Effect of reactive diluent

Several families of UV-cured polyurethane acrylates were synthesized, and the effects of reactive diluent type and content on their physical properties were investigated. Increasing reactive diluent content promoted the development of a second, high glass transition temperature phase in all the materials, thereby leading to increased strength and modulus. Changes in the extensibility of the samples upon addition of reactive diluent were inversely related to the effect of the diluent on the crosslink density. The effects of using different reactive diluents (di-, tri-, and tetraethylene glycol diacrylate and N-vinyl pyrrolidone) on the physical properties of the samples were attributed to differences in the softening point (T_g) of the homopolymer reactive diluents and the relative compatibility of the reactive diluents with the urethane acrylate segments.     

Fabrication of quaternary phosphonium-intercalated vermiculite for reinforcing UV-curable epoxy acrylate coatings

In this study, UV-curable epoxy acrylate film was reinforced with benzyl triphenyl phosphorus chloride-intercalated vermiculite (BTPC-VMT). BTPC-VMT was prepared by intercalating benzyl triphenyl phosphorus chloride (BTPC) into vermiculite (VMT) and was used as reinforcing filler. Then, X-ray diffraction and Scanning electronic microscope results of hybrid films indicated that BTPC-VMT was well dispersed in the matrix. The hybrid films displayed enhanced tensile strength, impact strength, and pencil hardness without sacrificing elongation at break. Moreover, the thermal property of hybrid films was generally improved. The resulting hybrid films are promising for a number of applications, e.g. for metal and wood for their surface protection.     

New UV-curable cyclotriphosphazenes as fire-retardant coating materials for wood

A series of (2-hydroxyethylmethacrylate)(n-propoxy)cyclotriphosphazenes (HPCP) has been prepared by the reaction of N₃P₃Cl₆ with n-propanol and 2-hydroxyethylmethacrylate (HEMA) sequentially in the appropriate solvents. These phosphazene compounds are characterized by a combination of Fourier transform infrared, ultraviolet, and nuclear magnetic resonance spectroscopies. It was found that the compounds were soluble in most of the organic solvents, exhibited an absorption between 207–216 nm, and were curable by UV irradiation. After curing, the surfaces of the HPCP-coated woodblocks were transparent and had a fire-retardant property, which has been ascribed to the intumescent behavior during the burning process. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 115–122, 1998     

Synthesis and properties of silsesquioxane-based hybrid urethane acrylate applied to UV-curable flame-retardant coatings

The silsesquioxane-based hybrid urethane acrylate (SHUA) was synthesized by modifying silsesquioxane-based hybrid polyol (SBOH) with the half adduct of isophorone diisocyanate and 2-hydroxyethyl acrylate, and characterized by Fourier transfer infrared (FTIR) and ¹H NMR spectroscopy. The SHUA was mixed with a phosphorus-containing trifunctional acrylate, TAEP, with different ratios to prepare a series of UV-curable organic–inorganic hybrid flame-retardant resins. Both the maximum photopolymerization rate and final unsaturation conversion in the UV-cured films determined by photo-DSC decreased along with SHUA content due to the decrease in functionality density and the increase in viscosity. The limiting oxygen index indicated the flame-retardant property reached to a high level of over 32 even with 40% SHUA addition, while the initial decomposition temperature and the char residue at 850 °C increased. The chemical structure change during the thermal degradation process was monitored by in situ FTIR analysis to demonstrate the condensed-phase flame-retardant mechanism. The dynamic mechanical thermal analysis results showed that the elastic storage modulus on the rubbery plateau region and glass transition temperature of the cured film increased by incorporating a small amount of SHUA, but decrease with over 10 wt.% addition of SHUA. Moreover, the addition of SHUA led to an increase in elongation at break and enhancement in abrasion resistance and hardness of film, even though no enhancement in tensile strength.     

Synthesis and properties of UV-curable waterborne unsaturated polyester for wood coating

UV-curable waterborne unsaturated polyesters for wood coatings were prepared. The effects of different polyols and acids on the properties of the UV-curable waterborne unsaturated polyesters were investigated. Several different unsaturated polyester prepolymers were prepared from three different polyols [ethylene glycol (EG), diethylene glycol (DEG), and propylene glycol (PG)] and three different acids [tetrahydrophthalic anhydride (THPAn), terephthalic acid (TPA), and trimellic anhydride (TMAn)]. UV-curable coating materials were formulated from the prepolymers and 2-hydroxy-2-methylphenyolpropane-1-one as a photoinitiator with distilled water as a diluent. Trimethylolpropane diallyl ether was used as an air inhibitor of cure. The dynamic mechanical studies showed the properties of those unsaturated polyesters were well correlated with their glass transition temperature behaviors. It was found that the unsaturated polyester prepared with 60/40 (mol %) TMAn/THPAn and the equimolar mixture of EG, DEG, and PG showed balanced coating properties such as good tensile properties and weatherability, as well as proper viscosity (ca. 2500 cps) when using distilled water as a diluent. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 695–708, 1998     

UV固化聚氨酯丙烯酸酯涂料的合成及性能研究

以异佛尔酮二异氰酸酯(IPDI)、新戊二醇(NPG)和季戊四醇三丙烯酸酯(PETA)等为主要原料,采用溶液聚合法合成了PUA(聚氨酯丙烯酸酯)低聚物;然后以此为基体树脂,通过探讨低聚物、活性稀释剂、光引发剂和助剂含量等对涂膜性能的影响,优选出制备UV(紫外光)固化PUA涂料的最佳工艺条件。研究结果表明:当w(PUA低聚物)=57%、w(活性稀释剂)=35%和w(光引发剂)=6%(均相对于涂料质量而言)时,该涂料具有相对较好的综合性能,其UV辐照50 s后即可固化,相应胶膜的硬度为3H、柔韧性为3 mm、附着力为1级且具有较高的耐热性。     

ABS塑胶紫外光固化涂料的配方设计

采用低黏度的3官能树脂搭配脂肪酸改性环氧纯丙树脂(6071)和三羟甲基丙烷三丙烯酸酯(TMPTA)树脂为主要成膜物,以1173、184为光引发剂,添加少量的2官能团硅改性丙烯酸酯以改善流平性能,研制出ABS塑胶紫外光固化涂料,讨论了预聚体结构、光引发剂及稀释剂等对UV光固化表面涂层性能的影响以及塑胶用UV涂料常见问题的解决措施.所制涂料综合性能良好,可应用于ABS塑胶底材的表面涂饰.     

聚氨酯丙烯酸酯UV固化涂料的制备及性能研究

以甲苯二异氰酸酯(TDI)、聚氧化丙烯三醇和甲基丙烯酸羟乙酯(HEMA)为主要单体,1,6-己二醇二丙烯酸酯(HDDA)为活性稀释剂,二月桂酸二丁基锡(DBTDL)为催化剂,合成了UV固化涂料制备用聚氨酯丙烯酸酯(PUA)低聚物。研究结果表明:当n(TDI)∶n(聚氧化丙烯三醇)∶n(HEMA)=3.08∶1∶3时,PUA低聚物的Mr(相对分子质量)比较理想;当固化时间为4 min、w(PUA低聚物)=87%、w(光引发剂Irgacure184)=5%、w(HDDA)=4%和w(其他助剂)=3%(均相对于总物料质量而言)时,UV固化涂料的综合性能相对最好,其胶膜硬度为2H、附着力为1级、耐酸碱性大于72 h和Tg(玻璃化转变温度)为38.9℃。     

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。     

A highly branched polythiourethane acrylate used for UV-curable high antireflection coatings

A series of highly branched polythiourethane acrylates (BPTUAs) were prepared through the double thiol-ene click reaction of thiol-endcapped difunctional thiourethane as an oligomer A₂ (Oligo-TU) with trimethylolpropane tri(thioglycolate ethylene glycol acrylate) (TMPTTA) as a trifunctional monomer B₃ in different ratios. The Oligo-TU was synthesized via the addition reactions of 2,4-toulene diisocyanate with 1,4-butanediol, and further with 4,4′-thiobisbenzenethiol. The TMPTTA was synthesized by the thiol-ene click reaction of trimethylolpropane tri(thioglycolate) (TMPTT) with an excess of ethylene glycol diacrylate. For comparison, a tetrafunctional thiourethane acrylate (TUA) was also synthesized. Finally, the obtained BPTUA and TUA were further modified with 2-mercaptobenzothiazole, 2-mercaptothiazoline and mercapto-5-methyl-thiadiazole, respectively, to form highly branched polyfunctional thiazole-based acrylates BPTUA-TAs and TUA-TAs. The molecular structures were confirmed by FT-IR and ¹H NMR analyses. The number average molecular weights and their polydispersity were determined by GPC spectroscopy. The UV irradiation using a medium pressure mercury lamp was applied to prepare the optical films in the presence of a photoinitiator. The refractive indices of UV-cured films were measured using a He-Ne laser at 632.8 nm. The results showed that both BPTUA and TUA films possess the similar refractive indices in the range of 1.592–1.604. However, the higher refractive indices in the range of 1.603–1.620 with BPTUA-TA films than 1.601–1.609 of TUA-TA films were obtained. All samples showed the high pencil hardness and impact resistance, as well good flexibility.     

新型紫外线固化环氧树脂/丙烯酸酯改性水性聚氨酯的合成与性能

合成了一种新型的具有高交联密度和优异涂膜性能的环氧树脂和丙烯酸酯同时改性的紫外线（UV）固化水性聚氨酯（UV-EP-AC-WPUD）。通过环氧基团与以异氰酸酯基团（-N=C=O）封端的聚氨酯预聚体之间的反应引入质量分数为4%的环氧树脂E-20。同时,通过聚氨酯链的-N=C=O与二元丙烯酸酯（PEDA）以及季戊四醇三丙烯酸酯（PETA）的羟基之间的反应引入碳碳双键（C=C）,C=C的含量达到4.65 meq·g-1。 质量分数为3%的光引发剂Irgacure 2959被用于引发涂膜中C=C的聚合,涂膜的凝胶含量在12 s UV辐射之后达到91%,意味着C=C的聚合和交联速度快,同时所得到的涂膜的交联度非常高,不溶于溶剂丙酮,测试表明环氧树脂和两种丙烯酸酯单体已经成功嵌入聚氨酯链中,涂膜具有优异的力学性能和化学性能。     

UV-curable waterborne polyurethane acrylate modified with octavinyl POSS for weatherable coating applications

UV-curable waterborne polyurethane acrylate (WPUA) modified with octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) was prepared via photopolymerization between OVPOSS and WPUA. Structural and morphological features of WPUA/OVPOSS coatings were assessed using Fourier transform infrared spectroscopy, transmission electron microscopy and X-ray diffraction. Thermal properties of the WPUA/OVPOSS hybride coatings have been improved over the pure waterborne polyurethane acrylate analyzed by thermal gravimetric analysis. Performance of the coatings was also evaluated using water absorption, hardness, contact angle, X-ray photoelectron spectroscopy (XPS). The data showed that the WPUA/OVPOSS coatings possessed better water resistance and thermal oxidative stability in comparison with pure WPUA.