发绿光醇酸树脂涂料的制备及其性质研究

合成了稀土铽配合物Tb(OPri)(acac)2,通过配合物中稀土铽离子与醇酸树脂涂料中的羰基发生配住作用后将铽离子引入到涂料中,制得了在紫外灯照射下可发绿光的醇酸树脂涂料.用紫外吸收光谱、红外吸收光谱、荧光光谱、原子力显微镜等分析手段研究了该发光涂料.研究表明,该稀土离子配合物能够与涂料发生配位,所得的涂料具有较好的光致发光性质.     

马来酸酐改性氯化聚丙烯和醇酸树脂相容性的研究

研究了由70％的二甲苯、不同配比的醇酸树脂和马来酸酐改性氯化聚丙烯构成的三元体系复配互容情况。用红外表征了马来酸酐改性氯化聚丙烯与344#树脂的质量比为1／2时复配液的相容性;用光泽值表征溶剂挥发后。马来酸酐改性氯化聚丙烯与醇酸类树脂的质量比分别为2／1、l／l、1／2、1／10、0／10时二元共混涂膜的透明性。结果表明：随着改性氯化聚丙烯接枝率的提高。氯化聚丙烯和醇酸树脂的相容性明显增强。     

新型改性醇酸树脂涂料的制备及性能研究

采用脂肪酸一步法合成了端羟基醇酸树脂,并给出了甲苯二异氰酸酯(TDI)改性醇酸树脂的制备工艺。从树脂涂料的固含量、表面干燥时间、硬度等方面考察了n(—NCO)∶n(—OH)、二羟甲基丙酸(DMPA)和三乙胺的用量、初期及中期聚合温度的影响,并对其进行了红外表征。实验结果表明:n(—NCO)∶n(—OH)=1.8,w(DMPA)≈5%,三乙胺在改性反应前加入,用量为1.7g(每20g样品),初期聚合温度30℃、中期聚合温度80~85℃时,制得的涂料综合性能优异。     

Effects of oil type on the properties of short oil alkyd coating materials

Short-oil alkyd resins were prepared by using five different oil types: corn oil, rice bran oil, sunflower oil, soya bean oil and dehydrated castor oil (DCO). Among these, soya bean oil gave alkyd resin with the darkest color because oxidation occurred. Auto air-dried coating films were developed and it was shown that film prepared from rice bran oil-based alkyd exhibited the longest drying time due to the low number of double bonds compared to other and the extra natural antioxidant in rice bran oil. DCO alkyd-based film revealed the shortest drying time, the greatest hardness but the poorest alkali and sea-water resistance. This is caused by the differences in the type of fatty acid and double bonds, the high amount of double bonds being in DCO. In addition, an increase in the reaction temperature only had an influence on darkening the alkyd color and decreasing the drying time of coating films. In terms of technical properties and cost competitiveness, soya bean oil-based film is the best. Coating films derived from all oil-based alkyds, except DCO, look promising for use in surfboard manufacturing.     

Emulsification, drying and film formation of alkyd emulsions

A method was developed and optimised for the emulsification of a conventional short oil alkyd resin which was solid at room temperature. The method was based on the emulsion inversion point (EIP) method whereby hot water (90°C) was added to molten alkyd resin (90°C) containing the emulsifier. Under slow mixing and addition of water, a point was reached where the emulsion instantaneously phase inverted from a water in oil emulsion (W/O) to an oil in water emulsion (O/W). Using optimum conditions, emulsions with droplet of diameters less than 0.8 μm were obtained. The drying and film formation of long oil alkyd emulsions were investigated with emphasis on loss of dry upon storage. The main reason for loss of dry was adsorption of the cobalt (drier) on pigment surfaces as a precipitated hydroxide. Titanium dioxides with alumina surface treatment and organic pigments were most detrimental to drying. Acrylate- and phosphate-based dispersants also deactivated cobalt presumably due to complexation and precipitation of cobalt. Emulsions prepared with an emulsifiable cobalt drier containing 2,2′-bipyridyl (complexing agent for cobalt) showed the best resistance to loss of dry. Films formed from the emulsions showed that surfactant migrated to the film surface which when washed with water leaves holes or pits in film. The pits were arranged in a hexagonal pattern, characteristic of Bénard cells which form due to interfacial tension gradients generated in the film during evaporation of water.     

Preparation and characterization of Jatropha Curcas oil based alkyd resin suitable for surface coating

Jatropha Curcas oil was extracted from Jatropha seeds by solvent extraction method. Three different alkyd resins have been developed from Jatropha Curcas oil by varying the amount of phthalic and maleic anhydride. The prepared resins are cured by using methyl-ethyl ketone peroxide (MEKP) as initiator and Co-octoate as an accelerator at 120 °C. The characterizations of the resins for structure establishment is carried out using Fourier transform infrared (FTIR) and proton nuclear magnetic resonance (¹H NMR) spectroscopic techniques. The concomitant properties of the cured resins such as acid value, saponification value, viscosity, molecular weight, etc. are also evaluated by standard methods. The cured resins have been tested for chemical resistance, pencil hardness, adhesion, thermal stability and gloss and it can be concluded that the resins may find potential applications in surface coating purposes.     

Preparation and characterization of water reducible alkyd resin/colloidal silica nanocomposite coatings

In this study, water reducible alkyd resins containing different amounts of colloidal silica were synthesized for the first time. In order to achieve this, alkyd resin, which has an oil content of 35%, was prepared with tall oil fatty acid, isophthalic acid, trimellitic anhydride, and trimethylolpropane. The alkyd resin was neutralized with triethylamine, and was dissolved in an isobutyl alcohol-isopropyl alcohol-butyl glycol mixture to produce 75% (wt.) solution, which was called stock alkyd resin. The stock alkyd resin was diluted with water to 50% (wt.) concentration with water and colloidal silica mixture in order to prepare an alkyd solution containing 0%, 5%, 10%, 15% and 20% colloidal silica. Then the effect of the silica nanoparticle addition on the surface coating properties, thermal behaviors and surface morphologies of water reducible alkyd resins was investigated. As a result, the addition of colloidal silica has improved surface coating properties and thermal behaviors of nanocomposite water reducible alkyd resin.     

An investigation on synthesis of alkyd resin with sorbitol

Sorbitol, as an abundant, cheap and renewable resource, is considered as a potential raw material for the manufacture of alkyd resin. In this study, the kinetics on preparation of alkyd resin using phthalic anhydride, sorbitol and soya bean fatty acid as raw materials is investigated. Three kinds of sorbitol based alkyd resins (SAR) samples having fatty acid content (OL_f) of 42% (SAR1), 52% (SAR2) and 62% (SAR3) were prepared with phthalic anhydride, sorbitol aqueous solution and soya bean fatty acid using fatty acid method. Kinetic studies showed that the initial and latter stages of the reaction follow a second-order rate law. The second-order rate constants were found to be of the order of 10⁻⁵ g/mg KOH/min. Molecular weight and polydispersity index were determined by GPC and end-group analysis. The number average molecular weight of the alkyd resins ranged from 1435 to 1626 and the weight average molecular weight ranged from 3041 to 3648. A large polydispersity index was found in a range from 2.12 to 2.24. The varnish of alkyd resin SAR1 containing 50% 200# solvent gasoline and 1.25% cobalt naphthenate (drying agent) by weight dried faster than the others. The physical and chemical film properties of the sorbitol based alkyd resins were determined and compared with standard alkyd resins. The results showed that the performance of alkyd resin having fatty acid contents (OL_f) of 42% (SAR1) was almost the same as the standard alkyd resins. It could be a choice binder for alkyd resin paint and helpful to reduce production cost.     

叔胺催化环氧树脂/水性醇酸树脂固化行为及其性能研究

从合成的水性醇酸树脂(AR)和水性环氧树脂(ER)出发,合成了水性ER/AR树脂,用红外光谱仪、差示扫描量热仪研究了叔胺催化的固化行为;用动态力学谱仪、热重分析技术研究了材料的玻璃化转变温度(Tg)和热降解性能,测定了ER/AR玻璃钢复合材料的力学和电性能以及涂膜的性能。结果表明,N-N二甲基苄胺对该体系有很好的催化作用;材料的Tg随着AR含量的增加呈现降低的趋势,当ER/AR的质量比为5 ：5时,Tg为64.6 ℃,拉伸强度为141.67 MPa,冲击强度达到120.54 kJ/m2;ER/AR玻璃钢复合材料的介电常数在1.5 1.99之间, 损耗角正切在0.001~0.008之间;涂膜的硬度高于4H,冲击强度可达20 kg·cm。     

374—3醇酸树脂的制备及应用

用Ｔａ尔油和聚酯废料生产３７４－３树脂,用于制铁红醇酸底漆,漆膜性能优良,介绍了３７４－３树脂的生产配方、合成工艺及应用。     

Effects of formulation on set-to-touch time of waterborne alkyd resin by uniform design

In order to optimize the formulation of waterborne alkyd resin preparation, a 9-level-3-factor uniform design and regression analysis were firstly employed to evaluate the effects of the selected variables including fatty acid content (L), hydroxyl/carboxyl molar ratio (r) and molar ratio of polyatomic acids (f) on set-to-touch time of film. The results indicate that the data can be adequately fitted with a first-order polynomial model, and the main factors successively affecting set-to-touch time are fatty acid content (L) and molar ratio of polyatomic acid (f). The above model is proved valid within the designed scopes of the investigated formulation parameters by validation experiments. The optimized formulation parameters for waterborne alkyd resin synthesis is predicated as follows according to the model, i.e. L is 30%, r is 1.2, f is 2.2, the result set-to-touch time is 43 min, which significantly shorten the drying time.     

Stability and film properties of tung oil modified soybean alkyd emulsion

A series of tung oil modified soybean alkyd emulsions are prepared by an inversion emulsified technique. In these alkyd resins, the tung oil contents are about 0, 12.5, and 25.0 wt % (based on the total oil). Using IGEPAL CO‐630 as the surfactant, a very stable alkyd emulsion can be obtained. With the increase of the tung oil contents in alkyd emulsions, the initial droplet sizes of the emulsions increase dramatically. Aging under 50°C can eliminate the difference in droplet sizes; the final droplet sizes of the emulsions are about 50 nm. The alkyd resins also have good hydrolytic stability. The tung oil contents in the alkyd resins also strongly influences the film properties; suitable tung oil content improves the film gloss. An atomic force microscopy investigation shows that the film from the alkyd emulsion is more water sensitive; after a 50‐h deionized water immersion, the film surface appears to have a lot of dents. This indicates that the film surface may be very rich in surfactant species. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1698–1706, 2000     

丙烯酸改性松香基醇酸树脂的合成研究

采用丙烯酸预聚物,植物油、马来海松酸酐等通过单甘油酯法合成了丙烯酸改性松香基醇酸树脂,对产物结构进行了红外表征,通过涂膜性能以及酸值测试研究了丙烯酸树脂用量,植物油的种类和用量以及反应时间对产物性能的影响。结果表明,最佳反应条件为:采用豆油和亚麻油,慢速升温,丙烯酸树脂质量分数2%～8%。合成的改性醇酸树脂较传统的醇酸树脂表干、实干时间短,硬度高,耐冲击性、附着力和耐介质性好。     

低黏度室温固化环氧灌封胶的研制

在配方中采用了低黏度的室温固化剂和耐热性能良好的丁腈橡胶,降低了体系的黏度,改善了环氧树脂灌封胶的耐热性能。实验确定了灌封胶的配比,并考核了胶的理化性能、工艺性能、热反应性能、耐高温性能等。结果表明：本灌封胶固化反应缓和、短时间耐300％高温、柔韧性好、黏度低,适宜作为狭窄腔体的灌封胶。     

Offset printing inks based on rapeseed and sunflower oil. Part I: Synthesis and characterization of rapeseed oil-and sunflower oil-modified alkyd resins

Two sets of alkyd resins of variable oil lengths with the required properties for offset printing ink formulations, modified by sunflower and rapeseed oil, were synthetized according to the “monoglyceride” process. The influence of the acyl composition of the modifying vegetable oil and of the oil content on alkyds’ properties was determined by detailed chemical and rheological characterization. Molecular structure, size, and molecule size distribution appeared to be linked to these two factors. A comparative study with two usual linseed oil-modified alkyds led to determination of the more appropriate alkyds for applications in offset varnishes.     

Photoassisted oxypolymerization of alkyd resins: Kinetics and mechanisms

A new three-component system for photoassisted oxypolymerization of alkyd resins containing a drier, a photosensitizer and a radical generator was investigated. Polymerization profiles were recorded by real-time infrared spectroscopy for a thin film exposed for 1 h to simulated sunlight radiation. The kinetic results showed that the system follows complex kinetics. Multiple regression analysis was used to model the influence of the drier, the photosensitizer and the radical generator on the final conversion and total polymerization rate during photooxidation. The mechanisms involved were studied through laser spectroscopies. Laser flash photolysis was used to measure the rate constants of reaction between the radicals formed from the photodissociation of the radical generator and the model compounds of alkyd resins, leading to the rapid formation of hydroperoxides. The photosensitizer was expected to produce singlet state molecular oxygen that reacts on the alkyd resin, and time-resolved chemiluminescence technique was used to determine the quenching rate constant of singlet oxygen by model compounds. On the basis of these results, a mechanism for the photoassisted oxypolymerization of alkyd resins is proposed that account for the all the different reaction pathways.     

Influence of catalyst type on the curing process and network structure of alkyd coatings

Recent studies have shown that cobalt catalysts, used for curing of alkyd coatings, are potentially carcinogenic, and hence replacement by new environmental friendly catalysts is needed. The influence of different metal based catalysts on the oxidation process has been studied extensively in model systems, consisting of unsaturated oils. However, these results may not be representative for real coatings, since in these systems the oxygen diffusion is much lower than in model systems and therefore may have a large effect on the curing. In this paper, we will show how the curing of an alkyd coating depends on the type of catalyst (cobalt or manganese based). The curing process is studied using a high spatial resolution nuclear magnetic resonance (NMR) setup. The final network structure and cross-link density are found to be correlated with the catalyst used, i.e. a cobalt based catalyst and two manganese based catalysts. The difference in final network structure is investigated by NMR T₂ relaxation analysis and the glass transition temperature T_g measured using a differential scanning calorimeter (DSC). In case of the cobalt based catalyst a cross-linking front was observed and a high cross-link density was found, compared to the manganese based catalysts, in which case no sharp cross-linking front was observed. To interpret the observed NMR profiles in more detail, simulations based on a reaction-diffusion model were performed. From the results of these simulations estimates were obtained for the reaction constants and the diffusion of oxygen for the different catalysts.     

Jatropha curcas oil based alkyd/epoxy resin/expanded graphite (EG) reinforced bio-composite: Evaluation of the thermal,mechanical and flame retardancy properties

Bio-composites were prepared from blends of Jatropha curcas oil based alkyd and epoxy resin with different weight percentage of expanded graphite (EG). The effect of EG loading on the thermal, mechanical, flame retardancy and water absorption properties of the bio-composites were studied. Significant improvement in thermal and mechanical properties was observed with 5 wt% EG loading. The prepared bio-composites were characterized by fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, X-ray diffractometry and tensile strength measurement. Morphological study showed the homogeneous dispersion of the EG sheets in the resin matrix. Limiting oxygen index (LOI) of the bio-composites showed a noticeable improvement in flame retardancy in comparison to neat blend of alkyd and epoxy resin. In vitro degradation of the bio-composites showed low degradation in phosphate buffer solution (pH 7.4).     

低黏度环氧树脂性能研究

对自制低黏度环氧树脂的黏度特性、固化特性、浇铸体的力学性能、耐热性以及复合材料的电性能进行了测试与分析。结果表明,该低黏度环氧树脂在常温下具有很低的黏度(120 mPa.s)和较长的适用期;在中温(80℃)条件下即可凝胶,固化产物力学性能和电性能优异,耐热性良好。     

醇酸树脂水分散型乳液的研究进展及性能

水分散型醇酸树脂乳液不依赖石油资源,且绿色环保。但由于水分散型树脂延长了涂膜的干燥时间且耐水性下降。寻求具有良好水分散性、适宜干燥时间及力学性能的水性醇酸树脂,是目前亟需解决的问题。综述了水性醇酸树脂的国内外研究状况,展望了其发展方向。