Preparation of rapid (chain-stopped) alkyds by incorporation of gum rosin and investigation of coating properties

In this study, the synthesis, characterization, and properties of a short oil length chain–stopped(rapid) alkyd resin is investigated. Gum rosin modified alkyd resin (RA-GR) was prepared using soybean oil, phthalic anhydride, glycerin and gum rosin acid. An alkyd modified with benzoic acid (RA-BA) was also prepared for comparison. FTIR analyses and GPC measurements of the alkyds were used for characterization. Other properties such as the viscosity, acid value, and solid content of the final resins were determined. Separately, the synthesized resins were used in paint formulations without any changes in other parameters such as filler, airdrying agents, solvents, etc. Paints were applied to metal and glass surfaces and the effect of gum rosin was investigated by looking at touch and hard drying times, adhesion to metals and gloss changes. Compared to the benzoic acid modified resin (RA-BA), gum rosin modified resin (RA-GR) exhibited remarkable positive effects on the paint with a better adhesion to the metals, and short drying times without any loses in the glosses.     

Properties of Aqueous Polyurethane Dispersion Modified by Epoxide Resin and Their Use as Adhesive

The aqueous polyurethane hybrid dispersion modified by the epoxy resin were synthesized using 1,4-butanediol ( BDO ) and dimethylolpropionic(DMPA) as chain extenders. A kind of automobile interior decoration adhesive was made by the modified hybrid dispersions. Effects of the content and the kinds of epoxide resin on the properties of dispersions and dispersion-cast films such as appearance, pot life, viscosity, particle size, molecular mass, hardness, swelling in water, contact angle, strength of stress, elongation at break, and other mechanical properties were studied. At the same time the effect of the E20 content on the peel strength of the adhesive for several automobile interior decoration substrates such as rubber/wood, poly(vinyl chloride)/wood; leather/wood, sponge/wood was investigated. The experimental results show that when the epoxy resin E20 content was 8%, the modified polyurethane hybrid dispersions possess better properties and the adhesive made by the modified dispersions posses better adhesion for automobile interior decoration substrates. The stress-strain curve of the modified aqueous polyurethane hybrid dispersions films shows the modified aqueous cast films possess better rigidity and toughness.     

Fatty Acid Composition of Tobacco Seed Oil and Synthesis of Alkyd Resin

The fatty acid composition of tobacco seed oil revealed that the oil is rich in unsaturated fatty acids, having linoleic acid （71.63%）, oleic acid （13.46%） and palmitic acid （8.72%） as the most abundant unsaturated and saturated fatty acids respectively. So the tobacco oil was characterized as semi-drying type on the basis of fatty acid composition. The synthesis of alkyd resin was carried out by alcoholysis or monoglyceride process using an alkali refined tobacco seed oil, pentaerythritol, cis-1,2,3,6-tetrahydrophthalic anhydride along with lithium hydroxide as catalyst. The alkyd resin so prepared was found to be bright and of low color with high gloss. The drying and hardness properties and adhesion of the tobacco seed oil derived alkyd resin were also found a bit superior to those of other alkyd resins of the same oil length. In addition, the water and acid resistance of the said alkyd was also found comparable to the other alkyds.     

Rubber Seed Oil-Based UV-Curable Polyurethane Acrylate Resins for Digital Light Processing (DLP) 3D Printing

Novel UV-curable polyurethane acrylate (PUA) resins were developed from rubber seed oil (RSO). Firstly, hydroxylated rubber seed oil (HRSO) was prepared via an alcoholysis reaction of RSO with glycerol, and then HRSO was reacted with isophorone diisocyanate (IPDI) and hydroxyethyl acrylate (HEA) to produce the RSO-based PUA (RSO-PUA) oligomer. FT-IR and ¹H NMR spectra collectively revealed that the obtained RSO-PUA was successfully synthesized, and the calculated C=C functionality of oligomer was 2.27 per fatty acid. Subsequently, a series of UV-curable resins were prepared and their ultimate properties, as well as UV-curing kinetics, were investigated. Notably, the UV-cured materials with 40% trimethylolpropane triacrylate (TMPTA) displayed a tensile strength of 11.7 MPa, an adhesion of 2 grade, a pencil hardness of 3H, a flexibility of 2 mm, and a glass transition temperature up to 109.4 °C. Finally, the optimal resin was used for digital light processing (DLP) 3D printing. The critical exposure energy of RSO-PUA (15.20 mJ/cm²) was lower than a commercial resin. In general, this work offered a simple method to prepare woody plant oil-based high-performance PUA resins that could be applied in the 3D printing industry.     

Characterization of Plukenetia volubilis L. fatty acid-based alkyd resins

Fatty acid-based alkyd resins prepared with different amounts of glycerol and pentaerythritol were characterized. Sacha inchi oil and linseed oil (comparative purposes) were used as fatty acids’ sources. FT-IR and ¹H NMR spectroscopy were done for alkyd structural verification. Alkyd resins were evaluated through physico-chemical (colour, density, viscosity) and thermal characterization. Film coating performance (drying, hardness, chemical resistance) was also studied. The oxidative crosslinking time tendency was corroborated by the quartz crystal microbalance (QCM) technique. Alkyd resins obtained with fatty acids from sacha inchi and linseed oils had similar properties. Results indicated that lighter resins can be obtained from sacha inchi oil, whereas pentaerythritol increases viscosity and thermal stability, and retards drying time of fatty-acid based alkyd resins.     

Effect of structure on properties of polyols and polyurethanes based on different vegetable oils

We synthesized six polyurethane networks from 4,4′‐diphenylmethane diisocyanate and polyols based on midoleic sunflower, canola, soybean, sunflower, corn, and linseed oils. The differences in network structures reflected differences in the composition of fatty acids and number of functional groups in vegetable oils and resulting polyols. The number average molecular weights of polyols were between 1120 and 1300 and the functionality varied from 3.0 for the midoleic sunflower polyol to 5.2 for the linseed polyol. The functionality of the other four polyols was around 3.5. Canola, corn, soybean, and sunflower oils gave polyurethane resins of similar crosslinking density and similar glass transitions and mechanical properties despite somewhat different distribution of fatty acids. Linseed oil–based polyurethane had higher crosslinking density and higher mechanical properties, whereas midoleic sunflower oil gave softer polyurethanes characterized by lower T_g and lower strength but higher elongation at break. It appears that the differences in properties of polyurethane networks resulted primarily from different crosslinking densities and less from the position of reactive sites in the fatty acids. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 809–819, 2004     

Thermoset Alkyd-Acrylic Hybrid Emulsions for Coatings

Alkyd acrylic hybrid emulsions can offer cost/performance advantages over common 1K coatings such as polyurethane dispersions (PUDs), acrylic emulsions and blends. Hybrid emulsions with different ratios of alkyd resin to acrylic monomers were synthesized. Emulsion with resin-to monomer ratio of 1:1 (wt/wt) with total solids as high as 50% had a shelf stability of more than 8 months. Morphology of hybrid emulsions was studied by scanning electron microscopy. Hybrid emulsions were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Films obtained from the hybrid emulsions were found to be homogeneous and exhibited excellent thermal and coating properties.     

水性丙烯酸酯聚氨酯涂料的研究

合成了含羟基的丙烯酸酯树脂,并与甲苯二异氰酸酯反应制备预聚体Ⅰ,Ⅰ与扩链剂二羟甲基丙酸反应得到含羧基的预聚体Ⅱ,最后用1,4-丁二醇交联,制得水性丙烯酸酯聚氨酯涂料,讨论了合成过程中影响乳液稳定性和涂膜性能的因素。测试结果表明：涂膜的强度、光泽、硬度等性能均优于传统的同类树脂。     

醇酸树脂热炼过程中分子量分布的研究

<正> 涂料工业中醇酸树脂基料分子量分布的研究,通常采用萃取分级法和沉淀分级法,近年来发展了高速凝胶色谱法。我们曾报道了高效GPC法测定醇酸树脂的分子量分布的方法。本文就醇酸树脂热炼过程产物作了物性表征和研究。 实验所测试样系取自5吨反应釜热炼生产中酯化过程各阶段和反应终点的产物。各品种醇酸树脂的配方见表1。     

固体酸催化醇酸树脂的分子量分布及其与性能关系的研究

本文用HPGPC法等研究了固体酸催化醇酸树脂合成中MWD及其与性能的关系。结果表明,固体酸催化醇酸树脂化过程的MWD等物性变化规律与未加催化剂的相似,logM_w和logd与p、M_w与分散度d及logη_G与M_w之间均呈线性关系。然而在达到同样M_w和MWD时,催化新工艺所需时间大大缩短,所需温度也有较大下降,而所得树脂粘度较低,贮存稳定性更好,其成膜干性更好,漆膜硬度也较高。     

Properties of acrylic–polyurethane hybrid emulsions synthesized by the semibatch emulsion copolymerization of acrylates using different polyurethane particles

Aqueous acrylic–polyurethane hybrid emulsions were prepared by the semibatch emulsion copolymerization of methyl methacrylate and butyl acrylate in the presence of eight polyurethane dispersions. The polyurethane dispersions were synthesized with isophorone diisocyanate, 1000 and 2000 molecular weight polyester polyols, 1000 molecular weight polyether polyol, butanediol, and dimethylol propionic acid. Acrylic monomers were added in the monomer emulsion feed. We studied the effect of the use of different polyurethane seed particles and the effect of different weight ratios of methyl methacrylate to butyl acrylate on the emulsion properties, microphase structure, and mechanical properties of hybrid films. The average particle size and distribution were determined by photon correlation spectroscopy. The rheological properties of polyurethane dispersions and hybrid emulsions were tested under destructive conditions by an examination of flow curves and under nondestructive conditions of oscillatory shear in a range of linear viscoelastic responses. Differential scanning calorimetry was performed to characterize the thermal‐response properties of polymeric films. The relative average molecular weights were determined by gel permeation chromatography. The interactions between the acrylic and polyurethane components in hybrid particles and particle structure were studied with infrared spectroscopy and nuclear magnetic resonance spectroscopy. Mechanical properties such as the Koenig hardness, tensile strength, elongation at break, and Young's modulus were measured. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4050–4069, 2005     

单组分聚氨酯清漆的制备与性能研究

不同的聚碳酸酯二元醇、聚四亚甲基醚二醇(PTMG)与二苯甲烷二异氰酸酯(MDI)、小分子二元醇反应,制得聚醚、聚碳酸酯型聚氨酯清漆。通过红外光谱分析结合其机械力学性能、耐水性等的测试结果,探讨聚碳酸酯型聚氨酯清漆的结构对形态和性能的影响。结果表明：随着硬段含量的增加,树脂涂膜的微相分离程度增加,机械性能提高;组分摩尔比例相同时,软段分子量的降低有利于提高树脂的软硬段相容性,增加树脂涂膜的物理机械性能;组分摩尔比例相同时聚酯型聚氨酯树脂的微相分离程度低于聚醚型聚氨酯树脂;MDI基溶剂型聚氨酯树脂的物理机械性能较好。     

Structure–property study of waterborne,polyurethane acrylate dispersions based on hyperbranched aliphatic polyester for UV-curable coatings

A series of waterborne, hyperbranched polyurethane acrylates for aqueous dispersions (WHPUDs) based on hydroxy-functionalized hyperbranched aliphatic polyester Boltorn H20 were synthesized and characterized by Fourier transform infrared spectroscopy (FTIR). The aqueous dispersions were electrostatically stabilized with carboxyl groups incorporated into their structures, which were neutralized by triethylamine (TEA). The effects of chemical structures of end groups on various properties of WHPUDs, such as particle size, interfacial tension, and rheological behavior were investigated. The average particle sizes of aqueous dispersions, 43–237 nm, were determined by laser light scattering. Owing to the enlargement of the stabilization site, the particle size decreased as the content of carboxyl group, degree of neutralization, and dielectric constant of the dispersion medium increased. Moreover, the surface tension of aqueous dispersions of WHPUDs decreased as the TEA/COOH mole ratio and degree of neutralization increased. The investigations of the rheological behavior of the WHPUDs suggested that all the dispersions belong to pseudoplastic fluids, and each of them has viscosity much lower compared with the commercial water-based resin EB 2002.     

A Comparison of the Syntheses of High Molar Mass Epoxy Resins on the Basis of two Groups of Modified Vegetable Oils

Application of epoxidized and hydroxylated natural oils as a new group of environmentally friendly and renewable raw materials for the synthesis of high molar mass epoxy resins is described. Selected vegetable oils were first oxidized and next reacted with mono and diethylene glycols. Obtained epoxidized soybean, rapeseed, linseed and sunflower oils were used together with Bisphenol A in the fusion process. Analogously, hydroxylated soybean and rapeseed oils were reacted with commercial grade Bisphenol A-based low molar mass epoxy resin. The fusion process was carried out in the presence of selected catalysts (i.e., lithium chloride, 2-methylimidazole, triphenylphosphine and triethanolamine) giving high molar mass epoxies. The relationship between type of modified oil used in the synthesis and reaction conditions and properties of synthesized resins (e.g., value and distribution of average molar mass, contents of epoxy groups and colour) is discussed.     

Curing of alkyds based on semi-drying oils with melamine resin

An alkyd/melamine resin mixtures are mainly used in industrial baking enamels. The aim of this work was to study the curing behaviour of alkyds based on dehydrated castor oil and soybean oil with melamine resin by differential scanning calorimetry (DSC). The kinetic parameters obtained by the transformation of dynamic DSC results into isothermal data through Ozawa kinetic model are in good agreement with those determined by the isothermal DSC experiments. The apparent degree of curing, determined by DSC measurements and sol/gel method, has a pronounced effect on the hardness of the resultant coating film.     

醇酸树脂的NMR分析

NMR用于涂料分析近年来已取得一些很有意义的结果本文探索NMR技术对长油醇酸树脂的定性定量分析。     

Preparation,Characterization, and Property Analysis of Environmentally Friendly Waterborne Polyurethane-Acrylate

Waterborne polyurethane (WPU) prepolymer was first prepared based on isophorone diisocyanate (IPDI), polyether polyol (NJ-210), dimethylol propionic acid (DMPA), and hydroxyethyl methyl acrylate (HEMA) via an in situ method. A series of waterborne polyurethane-acrylate (WPUA) dispersions were obtained with different proportions of acrylate (butyl acryolate and ethyl acrylate) and initiating agent by in situ dispersion technique. The structures and thermal properties of prepared WPU and WPUA were analyzed and characterized with FT-IR, UV-vis spectroscopy, and DSC. Performance of the emulsion and film was studied by means of apparent viscosity, particle size and polydispersity, surface tension, and mechanical properties. The results indicated that the particle sizes of the WPUA dispersions were larger than those of the pure WPU and the solvent resistance and mechanical properties of WPUA films were improved over those of the WPU film. The film had the greatest hardness and the least water absorption when the BA:EA mass ratio was 50:50. The obtained WPUAs have great potential application such as coatings, leather finishing, adhesives, sealants, plastic coatings, and wood finishes.     

光/潮气双重固化聚氨酯涂层的制备及性能研究

以甲苯-2,4-二异氰酸酯(TDI)和二乙醇胺(DEOA)为原料一步法合成了超支化聚氨酯,对其改性制备了光固化超支化聚氨酯丙烯酸酯(HPUA)和一系列双重固化(UV/潮气)超支化聚氨酯丙烯酸酯(DHPUA),使用傅立叶红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)和碳谱(13C-NMR)以及凝胶色谱(GPC)对其分子结构进行了表征.并以其为预聚物制备光固化涂层,通过对双重固化涂层的表面形貌、热性能和物理性能的研究,结果表明,超支化双重固化涂层经过潮气固化后,涂层表面的粗糙度随着树脂中硅氧烷端基的含量的增加先下降后上升;超支化双重固化涂层的物理性能和热稳定性都随着树脂中硅氧烷端基的含量的增加而提升.     

Synthesis,Characterization and Physicomechanical Properties of Novel Water-based Biodegradable Polyurethane Dispersion

Novel water-based biodegradable polyurethane dispersions with an aim to develop environmentally friendly materials, including medicine, various industries, have been prepared in this study. Biodegradable ionic polyurethanes (IPU) were synthesized based on polyols from renewable resources, such as castor oil (CO), in the presence of a polyester polyol and polyethylene glycol (PEG) with hydrophilic property and 1,6-hexamethylene diisocyanate. 1,4-Butanediol and dibutyltin dilaurate, were used as a chain extender and catalyst, respectively. The comprehensive investigations of the structure and properties of five types of synthesized polyurethanes demonstrated biodegradability relationship of these polyurethanes with their structure and composition. In this research effects of different types and content of polyols on biodegradability and physico mechanical properties of prepared PUDs were investigated. The structure, properties and physico mechanical and application behavior of mentioned materials were characterized by ¹H NMR, FTIR spectroscopy, thermogravimetric analysis (TG/DTG) and dynamic mechanical thermal analysis (DMTA). The adhesion properties were measured by pull off test as well. Particle size was measured by dynamic light scattering (DLS) methods. The biodegradability of prepared polyurethane dispersions was confirmed by water uptake, hydrolytic and enzymatic degradation in phosphate buffer saline (PBS) with lipase enzyme in PBS. Results showed that by the incorporation of natural components into the polymer chain, adjusting of hydrophilic and hydrolytic liability properties of soft segments and especial relevant designs, useful polyurethane can be synthesized with desirable property of biodegradability and dispersion stability. Except for one sample, other samples were decomposed totally in enzymatic media.     

Development of environmental friendly castor oil‐based waterborne polyurethane dispersions with polyaniline

This study describes the fabrication and characterization of castor oil‐based waterborne polyurethane/polyaniline (COWPU/PAni) conducting polymer blend films. The COWPU synthesized from isophorone diisocyanate was reacted with castor oil to form prepolymers, which were chain extended by reacting it with N‐methyldiethanolamine. Quaternization and self‐emulsification including deionized water followed in COWPU dispersions. Also, COWPU/PAni hybrid dispersions were synthesized with 2, 4, and 6 wt% of PAni–dodecyl benzene sulfonic acid to make different conductive composites. The outcome of COWPU/PAni was characterized by Fourier transform infrared spectrometer, differential scanning calorimeter, thermogravimetric analysis, dynamic mechanical and thermal analyzer, and scanning electron microscopy analysis. According to Fourier transform infrared spectrometer analysis, hydrogen bonding appears between –NH of PAni and C?O of COWPU. Meanwhile, incorporating PAni can improve the thermal stability of COWPU. The resulting COWPU/PAni conducting blend films can be used as antistatic and anticorrosive coating materials. Copyright © 2016 John Wiley & Sons, Ltd.