涤纶／松香改性醇酸树脂及其在涂料中的应用

选用豆油酸,松得,涤纶废丝等原料合成了改性醇酸树脂,用其制成的涂料具有优良异的光泽和丰满度。该树旨与中油度醇酸树脂配合,制得的醇酸磁漆具有光泽优,硬度等,硬度高,附着力强,柔韧性好等特点。讨论了影响生醇酸树脂合成的因素。探讨了其增光作用。     

双组分聚氨酯涂料用改性醇酸树脂的研究

采用不同改性的短油度醇酸树脂作甲组分,异氰酸酯预聚物作乙组分,配制双组分聚氨酯涂料,探讨甲组分对双组分聚氨酯涂料性能的影响。结果表明,椰子油改性短油度醇酸树脂,颜色水白、耐黄变性能和丰满度好,可以作为高档的亮光清面漆、耐黄变的面漆用树脂;蓖麻油改性短油度醇酸树脂,颜色较深、丰满度较好、干燥速度慢及柔韧性好,可以作为普通的亮光面漆用树脂;豆油改性短油度醇酸树脂,干燥速度较快,应用于底漆和哑光面漆;合成脂肪酸改性短油度醇酸树脂,颜色水白、流平好、干燥速度慢、丰满度高及硬度高,可以作为高档的亮光面漆用树脂。     

Studies on the preparation of Parinari polyandra benth seed oil alkyd resins

Parinari polyandra Benth seed oil was utilized in the preparation of four sets of alkyd resin (35%, 50%, 60%, and 75% oil formulations) using a two‐stage alcoholysis‐polyesterification method. The rate of polyesterification was depended on the amount of oil used during synthesis. The properties of the alkyds (drying times, film characteristics, water and acid resistances, and solubility) were evaluated using relevant standards. Inclusion of cobalt naphthenate drier in the alkyds and their exposure to outdoor temperature improved the drying properties. White gloss paints formulated from the alkyds, considering a pigment‐volume concentration of 20.67% in the gloss paint formulation compare well with commercial standard. FTIR and ¹H‐NMR analysis confirm the alkyd (glycerol‐phthalate) structure. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

水溶性苯乙烯改性醇酸树脂的合成工艺研究

采用脂肪酸法合成基础醇酸树脂,然后用苯乙烯和丙烯酸接枝共聚,制得了水溶性苯乙烯改性醇酸树脂.通过探讨油度、K值、苯乙烯、丙烯酸用量等因素对改性后树脂成膜性能的影响,确定了水溶性苯乙烯改性醇酸树脂的最佳工艺和配方;同时比较了水溶性常规未改性醇酸清漆、溶剂型苯乙烯改性醇酸清漆与水溶性苯乙烯改性醇酸清漆的性能优劣.结果表明:水溶性苯乙烯改性醇酸树脂较未改性醇酸树脂干性、硬度有了较大提高,与溶剂型苯乙烯改性醇酸树脂相当;当选取油度60％、K值1.05、苯乙烯质量分数35％、丙烯酸质量分数6.5％时,水溶性苯乙烯改性醇酸树脂白干表干达到0.5 h,实干20 h,硬度HB,水溶性优异,漆膜耐水、耐碱性获得很大提高,同时兼具了性能要求和环保要求.     

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     

自干型改性水溶性醇酸树脂的研制

用妥尔油酸、间苯二甲酸、顺丁烯二酸酐、三羟甲基丙烷等原材料制得水性醇酸树脂,将苯乙烯、丙烯酸(酯)单体与醇酸树脂通过接枝共聚制得改性醇酸树脂,改性后的醇酸树脂具有较好的干性、硬度和耐水性。     

Effect of branching in hyperbranched alkyd on the performance of alkyd polyurethane coating

Hyperbranched alkyd was synthesized by single‐step approach using trimethylolpropane, mono pentaerythritol as core material, and 2,2‐bis(methylol)propionic acid (DMPA), a combination of dehydrated castor oil fatty acid and coconut oil fatty acid as chain extender. A series of hyperbranched alkyds were prepared at different degree of branching in the alkyd structures by changing the amount of DMPA in the alkyd resin formulation. The resins were characterized by Fourier transform infrared and ¹H‐nuclear magnetic resonance (NMR) spectroscopic technique. These hyperbranched alkyds were converted into polyurethane coating after reaction with hexamethylene diisocyanate trimer at a definite ratio in the presence of dibutyltin dilaurate as a catalyst. The effect of branching and polymeric chain entanglement on the glass transition temperature, T_g of the alkyd polyurethane coating (APUC) was studied by differential scanning calorimetry technique. The performance of such APUC in terms of gloss, gloss retention under accelerated QUV radiation, natural outdoor exposed condition, mechanical, and corrosion resistance properties were enhanced with the increase of polymeric chain entanglement, i.e., compactness or higher order of branching in the alkyd resin structure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45835.     

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.     

丙烯酸改性醇酸树脂的合成、应用及发展趋势

利用新疆本地丰富的葵花油和石化资源,通过单甘油酯法研制出一种干燥迅速,保光保色和耐候性好且成本适中的丙烯酸改性醇酸树脂。并对丙烯酸改性醇酸树脂的应用领域及发展趋势进行了阐述。     

Fully renewable limonene‐derived polycarbonate as a high‐performance alkyd resin

Limonene‐derived polycarbonate‐based alkyd resins (ARs) have been prepared by copolymerization of limonene dioxide with CO₂, catalysed by a β‐diiminate zinc–bis(trimethylsilyl)amido complex, and subsequent chemical modification with soybean oil fatty acids using triphenylethylphosphonium bromide as the catalyst. This quantitative partial modification was realized via epoxy–carboxylic acid chemistry, affording ARs with higher oil lengths, lower polydispersities and higher glass transition temperatures (T_g) in comparison to a conventional polyester AR based on phthalic acid, multifunctional polyol pentaerythritol and soybean fatty acid. The novel limonene polycarbonate AR and the conventional polyester AR were evaluated as coatings and both the physical drying (without the presence of the oxidative drying accelerator Borchi® Oxy Coat) and chemical curing (with Borchi® Oxy Coat) processes of these coatings were monitored by measuring the König hardness and complex modulus development with time. A better performance was obtained for the alkyd paint containing polycarbonates modified with fatty acids (FA‐PCs), which showed a faster chemical drying, a higher König hardness and a higher T_g in coating evaluation, demonstrating that the fully renewable FA‐PCs are promising resins for alkyd paint applications. © 2019 Society of Chemical Industry     

Novel waterborne hyperbranched acrylated-maleinized alkyd resins

Different waterborne hyperbranched acrylated-maleinized alkyd resins (HBRAAM) were synthesized by modifying a hyperbranched alkyd resin (HBRA) with three different butylmethacrylate–maleic anhydride copolymers (BMA–MA) in the presence of p-toluenesulfonic acid (PTSA). The HBRAAM resins were characterized by using infrared analysis, iodine value, hydroxyl value, vapor pressure osmometry (VPO), dynamic light scattering (DLS), acid value, rheological analysis, differential scanning calorimetry, adhesion, flexibility, drying time, gloss, hardness and chemical resistance to solvents. The iodine value and hydroxyl value decreased with the amount of BMA–MA copolymer employed in the synthesis. Infrared analysis, VPO, and hydroxyl values allowed us to conclude that the reaction between HBRA resins and BMA–MA copolymers occurred. The viscosity of the HBRAAM resins was between 50.5 and 468 Pa s. All HBRAAM resins presented good properties of adhesion, flexibility, drying time, gloss, hardness and chemical resistance.     

利用工业级对苯二甲酸合成醇酸树脂漆

使用工业级对苯二甲酸(CTA)代替现在大量使用的苯酐等二元酸,成功地合成了CTA醇酸树脂。所得树脂漆料各项性能均达到使用苯酐合成的同类产品的国家标准。有些性能如光泽、干率、硬度等甚至优于用苯酐生产的同类产品。在漆厂现有反应设备和工艺条件无需做大的改变条件下,使用CTA合成CTA醇酸树脂,可降低原料成本15%～20%。     

端羟基聚丁二烯改性醇酸树脂的合成与性能研究

利用梓油和桐油以及带端羟基的聚丁二烯(下文简称丁羟)合成了具有快干特征的醇酸树脂。利用该树脂配制的涂料不仅干性好,且涂层光泽高、鲜映性好,保色保光性优异,可用于农业机械、工程机械等涂装。     

紫胶改性水性醇酸树脂的合成工艺研究

从改进树脂综合性能着手,研究了水性醇酸树脂的合成工艺。确定了以熔融法和分步加料来制备醇酸树脂。以紫胶部分替代三羟甲基丙烷,顺丁烯二酸酐/偏苯三酸酐部分替代苯酐,所得水性醇酸树脂的干燥性能、硬度和柔韧性等性能得以提高。紫胶用量以5%为宜。     

水性苯丙共聚物改性醇酸树脂的制备及性能

以油酸、季戊四醇、邻苯二甲酸酐、苯甲酸为原料，采用丙二醇甲醚醋酸酯（PMA）为溶剂合成了基体醇酸树脂；用过氧化苯甲酰、过氧化苯甲酸叔丁酯双引发剂、分步引发烯类单体共聚，制备了一种苯丙烯树脂，并对醇酸树脂改性制得了水性醇酸树脂。考察了不同油度对水性醇酸树脂结构与性能的影响。通过FTIR、TGA、DLS分别对树脂的结构、稳定性和乳液性能进行了表征。测定了树脂的漆膜性能，包括耐水性、表干时间、硬度、电化学性能。结果表明，n（油酸）∶n（季戊四醇）∶n(邻苯二甲酸酐)∶n（苯甲酸）=1∶1∶1∶0.3，油度为47%时，聚合物乳液粒径为74.4 nm，PDI为0.262，胶膜的吸水率为14.5%，接触角为70.87?，有较好的耐水性。改性醇酸树脂的表干时间缩短为0.5 h，实干时间缩短为24 h，硬度达HB。     

Factors influencing the stability and film properties of acrylic/alkyd water-reducible hybrid systems using a response surface technique

Acrylic-grafted-alkyd resins were prepared by free radical chemistry. Long, medium, and short oil alkyds were prepared using soybean oil, glycerol, phthalic anhydride (PA), and tetrahydrophthalic anhydride (THPA) and used as the alkyd phase. Acrylic co-monomer formulas containing methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), and vinyl trimethoxysilane (VTMS) were polymerized in the presence of the different alkyds using 2,2′-azobisisobutyronitrile (AIBN) as the initiator to obtain the final grafted structures. Design of experiments was used to understand how different variables in the synthesis of the acrylated-alkyds affect the film performance. A Box–Behnkin design was used, varying the oil length of the alkyd phase, the degree of unsaturation in the polyester backbone, and acrylic to alkyd ratio. Acrylic–alkyd hybrid resins were reduced with an amine/water mixture. The hydrolytic stability of hybrid alkyd dispersed in water was evaluated. Cured films were prepared and basic coatings properties were also evaluated. It was found that the oil length of the alkyd is the most dominant factor for final coatings properties of the resins. The hydrolytic stability was dependent on the acrylic to alkyd ratio. The oil length of the alkyd backbone had a minimal effect on stability of the resin and film performance.     

Improving Jatropha curcas Linnaeus oil alkyd drying properties

The Jatropha curcas Linnaeus (JCL) oil was extracted, refined and modified through epoxidation, hydroxylation and dehydration steps in order to increase the degree of unsaturation in the oil alkyl chain. The modified oil was subsequently used for alkyd resin preparation (50% oil formulation) using a two-stage alcoholysis-polyesterification method. Drying performances of white gloss paints formulated from the desaturated oil alkyd, considering a pigment-volume concentration of 20.67% gave improved results. Blending of the improved 50% JCL oil alkyd with acrylic further enhanced the drying properties and compare well with commercial standards. White gloss paint formulated from the improved JCL alkyd–acrylic blends (1:3) dried hard within 2 h at an outdoor temperature of 37 °C ± 2.     

豆油脚脂肪酸制备松香改性醇酸树脂的配方研究

利用豆油脚脂肪酸-松香-甘油-苯酐，采用脂肪酸法制备松香改性醇酸树脂。通过实验得到较佳工艺条件，确定经济合理的配方和各种原料用量，制备出符合标准的醇酸树脂产品，为加工成各色醇酸调合磁漆和脂肪酸调合磁漆奠定基础。此方法有效利用了废弃的大豆下脚料以代替市场紧缺的天然桐油和亚麻油，为豆油脚在涂料工业上的开发和利用开辟了新途径。     

利用大豆油脚制备松香改性醇酸树脂

以大豆油脚为原料,研制的松香改性醇酸树脂,性能可靠、质量稳定。可代替市场紧缺的天然桐油和亚麻油,加工成各色醇酸调和瓷漆和脂酸调和瓷漆。介绍了原料配方、生产指标、产品性能及应用的经济效益。     

Waterborne hybrid alkyd–acrylic dispersion: Optimization of the composition using mixture experimental designs

VOC-free waterborne hybrid alkyd–acrylic (50/50 wt/wt) dispersions were synthesized by melt condensation reactions between acrylic pre-polymers bearing carboxylic groups and medium-oil alkyd resins, followed by a self-emulsification through the neutralization of the carboxylic groups by an aqueous ammonia solution. A mixture experimental design was used to investigate how formulation components of the hybrid alkyd–acrylic resin affect the properties of the hybrid dispersion in terms of the viscosity of the dispersion, particle size, hydrolytic stability, and coating performance, namely gloss and film hardness. It was found that the content of ionizable monomers is the dominant factor controlling the particle size. This latter was shown to meaningfully affect the gloss of the coating after drying. The viscosity of the dispersion was mainly governed by the content of the soybean oil fatty acid which also controlled the hardness of the coating film after drying. An optimal composition that fits the requirement of paint formulation in terms of particle size, viscosity, hardness, and gloss was defined on the basis of the results of the mixture experimental design.