紫外光固化松香基聚酯丙烯酸酯的合成研究

通过两步法合成了涂料用紫外光固化(UV)松香基聚酯丙烯酸酯(APAPEA)预聚物。对产物结构进行了红外表征,并采用DSC分析研究了其光固化行为。考察了酸醇物质的量比、合成工艺、反应温度及催化剂用量对APAPEA收率的影响。结果表明,适宜的合成条件为:醇酸物质的量比1.1∶1,慢速升温,反应温度120℃,催化剂用量0.8%~1.2%。合成的APAPEA涂膜固化速度67 s,硬度3H,柔韧性2 mm,附着力1级,耐冲击性50 cm,较市售聚酯丙烯酸酯(PEA400)固化速度快,涂膜硬度高,柔韧性及附着力相当,可作为UV固化涂料用低聚物。     

Ultraviolet‐curing behavior and mechanical properties of a polyester acrylate resin

Ultraviolet (UV) curing technology has been widely used in many applications because it has several distinct advantages compared to solvent‐based processes or thermal‐curing technology. The effects of photoinitiator types and their contents as well as reactive diluent types and their contents on the UV‐curing behavior and mechanical properties of a UV‐curable polyester acrylate resin were investigated in this study. Three photoinitiators, Irgacure 184, Darocur 1173, and benzophenone, were used in this study. Hexanediol diacrylate, tripropylene glycol diacrylate, and trimethylol propane triacrylate were used as reactive diluents to modify the properties of the acrylate resin. The change of chemical structure during UV curing was monitored by FTIR. A universal testing machine was used to measure the tensile properties of various UV‐cured acrylate films of different compositions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3921–3928, 2004     

New polyester acrylate resins from palm oil for wood coating application

The aim of this study is to investigate the potential use of palm oil and to prepare new UV (ultraviolet) radiation‐curable acrylated polyester prepolymers, which could be used in the wood coating industry. Thus, palm oil‐based acrylated polyester resins PEPP‐1 (from refined, bleached, and deodorized palm oil) and PEPP‐2 (from crude palm oil) were synthesized at the Advanced Oleochemical Technology Centre (AOTC) laboratory of Palm Oil Research Institute of Malaysia (PORIM). The performances of these resins with respect to their curing rate and physical‐mechanical properties of cured products under UV radiation were studied. It can be concluded that newly synthesized UV radiation‐curable polyester acrylated prepolymers (palm oil based), namely PEPP‐1 and PEPP‐2, can be used as radiation curable coating materials for wood coating applications. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2156–2163, 2001     

Ultraviolet curing of epoxy coating on wood surface

Different formulations were developed with EB-600 (Ebcryl-600), an epoxy acrylate oligomer in the presence of N-vinylpyrrolidone and trimethylol propane triacrylate. Thin films were prepared with these formulated solutions under ultraviolet (UV) radiation. These solutions were coated on a low-grade wood substrate (simul) and cured under UV light. Both UV-cured thin films and surface coatings were characterized, and the best formulations for coating wood surface were evaluated. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1997–2004, 1997     

Photopolymerization behavior and properties of highly branched polyester acrylate containing thioether linkage used for UV curing coatings

The highly branched polyester acrylate containing thioether linkage (HBAT) was synthesized using an “oligomeric A₂ + B₃” approach. The dithiol, 1,6-hexamethylene bis(3-mercaptopropionate) (HMBM), was prepared through the esterification between 1,6-hexanediol and 3-mercaptopropionic acid, and then underwent an amine-catalyzed thiol-Michael addition to the acrylic double bond of 1,6-hexamethylene diacrylate to obtain an oligomeric dithiol (oligomeric A₂), then further with trimethylolpropane triacrylate as a B₃ monomer. The molecular structure was characterized with FT-IR and ¹H NMR spectroscopy. A broader molecular weight distribution from 1.74 to 2.75 was obtained for different oligomeric dithiol chains by GPC measurements. The photopolymerization kinetics study by photo-DSC analysis showed that the HBAT greatly reduced the oxygen inhibition in radical photopolymerization of acrylates in air. The maximum polymerization rate decreased along with the addition of HBAT into the UV curable resin (EB605) containing bisphenol A epoxy diacrylate and tripropylene glycol diacrylate due to the reduced double bond density and increased viscosity, whereas the final unsaturation conversion in cured film increased because of the longer spacer chain in HBAT compared to that in EB605 and the reduced crosslinking density by HBAT addition. The dynamic mechanical thermal analysis results showed that both the elastic modulus in the rubbery plateau and glass transition temperature of cured film decreased along with the incorporation of HBAT into EB605. The water swelling test and thermogravimetric analysis indicated that the thioether linkage in HBAT can greatly improve the water absorption resistance and oxidative stability of cured film.     

Effect of CaCO3 on the performance of Partex surface modification by ultraviolet radiation curing method

Several UV‐curable formulations containing epoxydiacrylate (EB‐600) oligomer with a tri‐functional monomer, trimethylol propane triacrylate (TMPTA), and photoinitiator Irgcure‐369 were developed to improve the surface of Partex. Filler or extender CaCO₃ was incorporated into the solution. Thin polymer films were prepared on glass plate with these formulated solutions and finally applied on polished Partex surface, and both were cured under UV‐radiation. The properties of UV‐cured thin films were studied as a function of CaCO₃ concentration. Pendulum hardness and gel content were found to decrease on glass plate with the increase of CaCO₃ concentration. Pendulum hardness, scratch hardness, and abrasion resistance of the cured Partex were found to be higher with the increase of CaCO₃ content up to 4%. Thus, the formulation containing 4% CaCO₃ showed the best performance over all formulations containing CaCO₃. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1858–1867, 2001     

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固化超支化聚酯的合成及性能研究

以马来海松酸(MPA),环氧氯丙烷(ECH)合成了超支化聚酯(HBPE),通过丙烯酸羟乙酯(HEA)对HBPE改性合成了涂料可用UV固化超支化聚酯。采用GPC,FT-IR,DSC等对产物结构进行了表征,研究了原料配比、加料方式和反应温度等对产物的影响,并考察了其光固化行为,测试了固化膜的性能。结果表明,HBPE合成最佳条件:n(MPA)∶n(ECH)=1∶1,反应温度90℃,HBPE与HEA最佳物质的量比为1∶2。该UV固化超支化聚酯固化膜附着力1级,抗冲击力40 kg/cm,铅笔硬度4H,耐甲乙酮100,可作为UV固化涂料中的主体树脂。     

萜烯基聚酯丙烯酸酯的合成及性能研究

以萜烯马来酸酐(TMA)、DCPD、顺酐(MA)、乙二醇(EG)、丙二醇(PG)、丙烯酸(AA)为主要原料,通过三步法合成了聚酯丙烯酸酯。通过红外光谱分析仪、动态机械分析仪和TG研究了不同原料配比、缩聚反应时间、阻聚剂用量对涂膜性能的影响。结果表明,该光固化涂膜具有良好的力学性能、耐化学性能和耐热性,且固化速度快,可单独作为UV固化的预聚物使用。     

Performance of polyester and modified polyester coil coatings exposed in different environments with high UV radiation

Coil coating is a continuous strip coating technology, which enjoyed rapid growth. It provides a cost-effective method of applying a coating to a metal substrate with a low solvent emission, and nowadays paints of different nature are applied this way on a range of metal substrates, for a large variety of products and uses.

Coil coatings can be more or less degraded by high UV radiation. However, differences in distribution of light intensity as a function of wavelength between exposure environments, can lead to significant differences in the degradation results, depending on coating nature. In this work, the behaviour of polyester and silicone polyester coatings exposed in three different high UV environments (natural atmosphere and two accelerated UV tests), was studied. Coatings of two different colours (blue and brown) were considered for each paint system. Colour change, gloss and chalking measurements and, visual inspections of coating defects were carried out. In order to explain their corresponding performance, chemical changes on coil coated exposed surfaces were studied by to Fourier transform infrared spectroscopy equipped with a photoacustic detector (PAS/FTIR).     

A method for polymethymetacrylate coating via self-curable unsaturated polyester primer on metal and glass surfaces

A method was developed for protective coating of steel and glass surfaces with poly(methylmethacrylate) (PMMA). In this method, first, a primer coating was formed on the flat surfaces using self-curable polyester, poly(2-hydoxypropyl maleate) (Polymer-1). The polyester was applied onto polished surfaces and heated at 180 °C for 15–120 min to obtain transparent and crosslinked primer layer without using additional crosslinker.     

Radiation curing of hyperbranched polyester resins

A research area that has obtained increasing interest during the last decade concerns improvement of macromolecular properties by changes in the macromolecular architecture. One group of these materials is dendritic polymers, which are highly branched structures exhibiting very different properties compared with linear polymers. One potential application for these polymers is as radiation curable thermoset resins. This article describes a study where the use of an aliphatic hyperbranched polyester as a base for new radiation curable thermoset resins. The hyperbranched polyesters have been characterized with respect to cure rate and final mechanical properties compared with conventional resins. It is shown that hyperbranched polyesters can be used as versatile scaffolds for various radiation curable resin structures. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 612–618, 2000     

Liquefaction of wood,synthesis and characterization of liquefied wood polyester derivatives

Liquefaction of Central‐European softwoods meal was performed using a mixture of diethylene glycol and glycerol and a minor addition of p‐toluenesulfonic acid as a catalyst. The liquefied wood was used as a replacement of a certain amount of the polyhydroxy alcohol in the polyester synthesis, enabled by the large number of hydroxyl groups that were available in the liquefied wood. Three different polyesters were synthesized by using adipic acid and phthalic acid anhydride as reagents. The products were characterized using FTIR, GPC/SEC, and viscosity measurements. The polyesters have hydroxyl values that were reduced due to esterification, from 1043 mg KOH/g of the liquefied wood to 400–800 mg KOH/g. Polyhydroxyl alcohols (22–23%) in the polyester formulations were replaced by wood derivatives. Such saturated polyesters are suitable for further use in polyurethane foam production. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fluorinated hyperbranched polyester acrylate used as an additive for UV curing coatings

The fluorinated hyperbranched polyester acrylate (FHPA) was synthesized by modifying the hyperbranched polyester Boltorn H20 with fluorinated isocyanate, and characterized with ¹H NMR and FTIR spectroscopic analysis. The water and oil wettability of the UV cured film with FHPA as an additive was investigated by measuring the contact angle. The results showed that an extremely low concentration of FHPA, even below 0.1 wt%, resulted in efficient decrement of the surface tension of UV cured film to 10–15 mN/m, and thus makes the film highly hydrophobic and oleophobic. The film with FHPA addition was stable in acidic and neutral solutions, and still had good water repellency after immersion in a pH 1 solution for several days. The X-ray photoelectron spectroscopic analysis confirmed that the film surface was enriched with fluorinated species. Moreover, the molecule with the highest average number of perfluoroalkyl groups had the highest tendency to aggregate at the surface of the UV cured film.     

紫外光固化涂料的发展及应用

紫外光固化涂料是一种环保型涂料。在此详细阐述了紫外光固化涂料的特点、固化原理、涂料组成及应用,此外,介绍了我国此我固化涂料的发展概况２。     

Role of sand on curing of partex surface by UV radiation

A partex surface was modified by a UV‐curing system with epoxy acrylate (EB‐600). A set of formulations was prepared with oligomer and the trifunctional monomer trimethylol propane triacrylate in different combinations of percentages (1–5%) of sand to study the role of sand in various physical properties of UV‐cured thin films, as well as partex surfaces. Increased pendulum hardness (PH), gloss, adhesion, and abrasion values were obtained by the addition of sand into the partex surfaces. The best results were obtained with the formulation containing 3% sand. An enhanced PH and a decreased percentage of gel content of the UV‐cured film was observed with an increase of the sand concentration. A simulated weathering test was performed with partex surfaces cured by a formulation containing 3% sand in the base coat. The losses of the physical properties were found to be lower over the surface treated with the formulation containing sand. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2385–2392, 2002     

不饱和聚酯/复合引发体系非等温固化动力学研究

采用非等温DSC法研究了不饱和聚酯/复合引发体系在不同升温速率下的固化行为,通过T-Φ外推法确定了该体系的凝胶温度、固化温度和后固化温度分别为102.7℃,124.0℃和196.5℃。通过Kissinger和Crane方程对DSC数据进行处理,获得了固化反应的表观活化能E=116.88 kJ/mol,碰撞因子A=7.35×1014,反应级数n=0.945,并由此得到了该体系的固化动力学方程。     

UV固化萜烯聚酯丙烯酸酯的合成研究

以松节油-马来酸酐(TMA)、一缩乙二醇(DEG)、邻苯二甲酸酐(PA)、丙烯酸(AA)为主要原料合成了涂料用紫外光固化(UV)萜烯聚酯丙烯酸酯(TPEA)预聚物。通过分子质量、酯化率及涂膜性能测试以及GPC,TG分析以考察了原料物质的量比、合成工艺、反应温度等对TPEA树脂合成及涂膜性能的影响。结果表明,适宜的工艺条件为:TPEA酯化反应温度125℃,n(TMA)∶n(DEG)∶n(PA)∶n(AA)=1∶2.2∶0.5∶2,采用两步法,制备出的TPEA树脂综合性能较好。     

UV固化水性环氧树脂的合成研究

对紫外光固化水性环氧树脂的合成工艺进行了研究,讨论了反应温度、反应时间、催化剂种类和用量,阻聚剂、羧基含量及固含量、中和剂等对水性环氧丙烯酸酯的合成和性能的影响。结果表明,合成环氧丙烯酸酯的最佳反应温度110℃,环氧丙烯酸酯与马来酸酐的最佳反应反应温度为80℃。反应时间均为5 h,三乙胺作催化剂,用量为反应物总质量的0.5%,对羟基苯甲醚作阻聚剂。实验表明,提出的紫外光固化水性环氧树脂的合成工艺可行,合成树脂具有水性特征,性能指标可以满足应用要求。     

紫外光固化系统对光纤光缆涂层固化效果的影响

从紫外光固化系统方面讨论了影响紫外光固化涂层固化效果的因素,分析了紫外光发射光谱、紫外光强度、紫外光剂量、红外辐射热效应和反射面及其能量分布对光纤光缆涂层固化效果的影响。