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.     

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.     

不同松香改性树脂对农药可分散油悬浮剂物理稳定性的影响

研究了添加松香及其改性氢化松香甘油酯、氢化松香季戊四醇酯、松香改性对特辛基苯酚树脂对以油酸甲酯为介质的12.5%氰霜唑·吡唑醚菌酯可分散油悬浮剂物理稳定性及流变特性的影响。傅里叶变换红外光谱表征结果表明,与松香酸相比,氢化松香甘油酯、氢化松香季戊四醇酯和松香改性对特辛基苯酚树脂的羧基吸收峰消失且出现酯基的特征吸收峰。实验中,随加成烷基醇碳链的延长,软化点升高。且随着树脂的质量分数增加,制剂的粘度提高,物理稳定性也相应提高(析油率降低)。流变结果表明,添加松香改性树脂的可分散油悬浮剂体系呈正触变性,且树脂种类对体系的屈服值影响较大,具体表现为:松香改性对特辛基苯酚>氢化松香季戊四醇酯>氢化松香甘油酯>松香,制剂的物理稳定性也呈现相同的趋势。因此,松香改性树脂具有作为可分散油悬浮剂物理稳定剂的应用潜力。     

Polyurethane Dispersions Based on Sardine Fish Oil,Soybean Oil,and Their Interesterification Products

Alkyd resins were synthesized from different ratios of sardine fish oil and soybean oil. Three alkyd resin samples were styrenated. The styrenated alkyd resins and alkyd resins were subsequently converted into the polyurethane dispersions. The physicochemical properties, such as iodine value, saponification value, and specific gravity were determined. Infrared spectroscopy and nuclear magnetic resonance techniques were used for structural elucidation of newly synthesized resins. The coating properties, such as adhesion, flexibility, scratch hardness, pencil hardness, impact, solvent, and chemical resistance were evaluated. Thermogravimetric analysis was used to investigate the thermal stability of alkyd resin and polyurethane dispersions. Cost effective volatile organic components (VOC) compliant coatings for various applications can be synthesized successfully by partly replacing soybean oil with commercially available, inexpensive sardine fish oil.     

13C-Isotope ratio mass spectrometry as a potential tool for the forensic analysis of white architectural paint: a preliminary study

Paints have a dual role in society, to protect materials from environmental agents such as ultraviolet light, moisture and oxygen, and to make painted materials look more attractive. Variability in paint samples is often due to binder and pigment type within the sample. The most common resin used in decorative paints is drying oil alkyd resin, which incorporates soybean oil and vinyl acrylic based latexes. Traditional analytical methods used by forensic scientists may be able to say whether two paint samples are indistinguishable but cannot conclusively say that they both originate from the same source. To find out if isotopic composition can provide an added dimension of information, 28 different white architectural paints were analysed for (13)C abundance using isotope ratio mass spectrometry. In addition, variations in application, drying time and thickness were also investigated to assess the discriminatory power of (13)C data from white paints with an unknown history. Preliminary results indicate that this method could aid screening of paint samples.     

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。     

Characterisation of fresh and aged terpenic resins by micro-FTIR and GC-MS analyses of varnishes in XVI-XVII centuries paintings

Resinous materials, generally added to drying oils, were often employed as final protective films in paintings, both in tempera and oil techniques. Most of the resins used in fine arts come from exudates of plants. Natural resins are mainly composed by terpenoids. Among these resins, dammar, rosin, mastic, elemi gum, Venice turpentine were frequently employed in easel paintings. The aim of this work is the identification of natural resins in samples collected from works of art. In this paper we propose to use micro-FTIR spectrometry as a preliminary and non destructive technique to detect the presence of resinous materials in microsamples collected from paintings, followed by GC-MS analyses to obtain a precise identification of the resin. To reach this aim commercial resins, employed as standard, were analysed previously by micro-FTIR spectrometry and then analysed by GC-MS chromatography, searching characteristic chemical compounds used as "markers" of resins. The results obtained on standards allowed us to successfully analyse samples collected from two works of art: the "Portrait of a Young Gentleman", by Lorenzo Lotto (XVI century), and the "Madonna with the Infant Jesus and Saints": by Carlo Maratta (XVII secolo).     

Synthesis of novel hyperbranched polymers featuring oxazoline linear units and their application in fast‐drying solvent‐borne coating formulations

Novel acid‐terminated hyperbranched polymers (HBPs) containing adipic acid and oxazoline monomers derived from oleic and linoleic acid have been synthesized via a bulk polymerization procedure. Branching was achieved as a consequence of an acid‐catalyzed opening of the oxazoline ring to produce a trifunctional monomer in situ which delivered branching levels of >45% as determined by ¹H and ¹³C NMR spectroscopy. The HBPs were soluble in common solvents, such as CHCl₃, acetone, tetrahydrofuran, dimethylformamide, and dimethyl sulfoxide and were further functionalized by addition of citronellol to afford white‐spirit soluble materials that could be used in coating formulations. During end group modification, a reduction in branching levels of the HBPs (down to 12–24%) was observed, predominantly on account of oxazoline ring reformation and trans‐esterification processes under the reaction conditions used. In comparison to commercial alkyd resin paint coatings, formulations of the citronellol‐functionalized hyperbranched materials blended with a commercial alkyd resin exhibited dramatic decreases of the blend viscosity when the HBP content was increased. The curing characteristics of the HBP/alkyd blend formulations were studied by dynamic mechanical analysis which revealed that the new coatings cured more quickly and produced tougher materials than otherwise identical coatings prepared from only the commercial alkyd resins. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3964–3974     

Epoxy resins from rosin acids: synthesis and characterization

A series of multifunctional cycloaliphatic glycidyl ester and ether epoxy resins were synthesized by reaction of condensed rosin acid‐formaldehyde resins with epichlorohydrin. The chemical structure of the produced resins was determined by IR and ¹H‐NMR analysis. The molecular weight of the produced resins was determined by gel permeation chromatography (GPC). A series of poly‐ (amide‐imide) hardeners were prepared from condensation of Diels–Alder adducts of rosin acid‐maleic anhydride and acrylic acid with triethylene tetramine and pentaethylene hexamine. These amines were also condensed with Diels–Alder adducts of rosin ketones. The curing exotherms of the produced epoxy resins with poly(amide‐imide) hardeners were investigated. The data of mechanical properties, solvent and chemical resistance indicate the superior adhesion of the cured epoxy resins. Copyright © 2004 John Wiley & Sons, Ltd.     

Cross‐linked waterborne alkyd hybrid resin coatings modified by fluorinated acrylate‐siloxane with high waterproof and anticorrosive performance

Waterborne alkyd resin coatings are ideal for use as corrosion protection coatings because of its high cost‐effective and environmental advantages. However, their uses are restricted to general applications due to their poor acid, water, and alkali resistance. In this work, waterborne alkyd hybrid resins modified with fluorinated acrylate‐siloxane were synthesized via a surfactant‐free miniemulsion polymerization process using maleic anhydride and silicon modified alkyd resin, dodecafluoroheptyl methacrylate, methyl methacrylate, and butyl acrylate as monomers. And then, crosslinking alkyd resin films were prepared at room temperature using trimethylolpropane‐tris‐(β‐N‐azir‐idinyl) propionate (XR‐100) as the crosslinking agent. The acquired films had lower water absorption and higher water contact angles and had better mechanical/thermal properties, as well as good waterproof property. Most importantly, the electrochemical corrosion studies revealed that the cross‐linked coating exhibited superior corrosion resistance performance with an inhibition efficiency of 99.95% and a corrosion rate of 6.95 × 10^?3 mm per year.     

Water-Based Oil Spill Dispersants Based on Rosin Formaldehyde Resins

Water-soluble surfactants based on rosin acids were synthesized from condensed rosin acid-formaldehyde. This was completed by esterification of series of rosin acid formaldehyde resins with poly(ethylene glycol) having different molecular weights to produce series of rosin esters. The structure of the produced resins was determined by infrared and ¹HNMR analysis. The molecular weight of the produced surfactants was determined by gel permeation chromatography (GPC) technique. The surface properties of the prepared surfactants were determined by measuring the surface tension at different temperatures. The surface tension, critical micelle concentration (CMC), and surface activities were determined at different temperatures. Surface parameters such as surface excess concentration (Γmax), the area per molecule at interface (A_min), and the effectiveness of surface tension reduction (πCMC) were determined from the adsorption isotherms of the prepared surfactants. Some thermodynamic data for the adsorption process were calculated and are discussed. The dispersion efficiency of the prepared surfactants as petroleum oil spill dispersants was determined and correlated with the surface activity, concentrations of the prepared surfactants and type of petroleum crude oil.     

Characterisation of cured alkyd paint binders using swollen state 13C-NMR

Swollen state ¹³C-NMR can be used to characterise commonly encountered air-dried alkyd paint binders. Deuterochloroform is the solvent of choice and a conventional Fourier transform spectrometer can be used. The polyol and aromatic acid present in the binder can be readily identified and some useful information on the drying oil fatty acids can be obtained. The study of partially cured materials leads to information concerning curing mechanisms. Modifiers present in the alkyds such as silicones, polyurethanes and styrenic materials can readily be identified. The presence of titanium dioxide pigment in the cured binder does not greatly alter the quality of the spectra obtained thus allowing full characterisation of the resin used.     

Investigation of fungal deterioration of synthetic paint binders using vibrational spectroscopic techniques

The deterioration of synthetic polymers caused by biological process is usually evaluated by visual inspection and measuring physical effects. In contrast to this approach, we have applied vibrational spectroscopies to study the biodegradation of the synthetic resins. 29 synthetic resins used as paint binding media, including acrylic, alkyd and poly(vinyl acetate) polymers, were examined for potential susceptibility to fungal degradation using the standard method ASTM G21-96(2002). In addition, the degraded resins were analysed by Raman spectroscopy, FT-IR and FT-IR photoacoustic spectroscopy. Almost all the acrylic resins studied proved to be resistant to microbial attack, while all alkyd resins and some poly(vinyl acetates) turned out to be biodegradable. Within a few days of inoculation Aspergillus niger was the most copious fungus on the biodegraded resins. A comparison of the IR and Raman spectra of control and biodegraded resins did not show any differences, but photoacoustic spectroscopy revealed additional bands for the fungal-degraded resins, consistent with the presence of fungal-derived substances. The additional bands in the photoacoustic spectra were due to the presence of Aspergillus niger and melanin, a fungal pigment. Since IR photoacoustic spectroscopy can be also a suitable technique for the chemical characterisation of binding media, the same spectroscopic analysis can be employed to both characterise the material and obtain evidence for fungal colonization. Microbial growth on Sobral 1241ML (alkyd resin) after 28 d (growth rating 4) compared with the non-inoculated resin.     

松脂的催化歧化反应产物的气相色谱-质谱分析

采用气相色谱-质谱技术对松脂的催化歧化新工艺的反应产物进行分析,共分离出45个峰,鉴定出其中的38个化合物,并发现松脂歧化产物中歧化松节油的主要成分为对伞花烃,含量为16.26%;歧化松香的主要成分为脱氢枞酸和氢化树脂酸,其含量分别为41.58%和21.43%。在此基础上对松脂歧化反应过程进行了初步探讨,认为松脂原料中的酸性物质发生分子间氢转移反应,萜烯烃的存在促进了脱氢反应的进行;在树脂酸提供的酸性环境下松脂原料中中性油的主要成分双环单萜烯发生开环异构形成单环单萜烯,单环单萜烯再进行催化脱氢转化为对伞花烃。分析结果表明,直接以松脂为原料进行催化歧化反应可同时获得特级歧化松香和高含量的对伞花烃。     

Adhesives and coatings based on phenolic/epoxy resins

Low molecular weight epoxy resin based on bis (4‐hydroxy phenyl) 1,1 cyclohexane was prepared and modified with various types of the prepared phenolic resins. Phenol–, cresol–, resorcinol–and salicylic acid–formaldehyde resins were used. The optimum conditions of formulation and curing process were studied to obtain modified wood adhesives characterized by high tensile shear strength values. This study indicated that the more suitable conditions are 1:2 weight ratio of phenol–or cresol–formaldehyde to epoxy resin in the presence of phthalic anhydride (20 wt%) of the resin content as a curing agent at 150°C for 80 min. Resorcinol–or salicylic acid–formaldehyde/epoxy resins formulated at 1:2 weight ratio were cured in the presence of paraformaldehyde (20 wt%) at 150°C for 60 min. The effect of the structure of phenolic resins on the tensile shear strength values of formulated resin samples, when mixed with the epoxy resins and cured under the previously mentioned optimum conditions for different times, was investigated. Metallic and glass coatings from the previous resins were also prepared and evaluated as varnishes or paints. Copyright © 1999 John Wiley & Sons, Ltd.     

Alkyd-based-thermosetting resin

In this work, the rate of cure of different oxidative drying oil modified alkyd resins are investigated by DSC measurements. We determine, from the Kissinger equation, the apparent activation energy of the curing process. We show that this activation energy depends on the curing duration and that these variations lead to the determination of a time constant, characteristic of the material.     

Novel flame retardant paint based on Co(II) and Ni(II) metal complexes as new additives for surface coating applications

The study is focused on the synthesis of a new Co(II) and Ni(II) metal complexes, which is synthesized by the reaction of the isatin 4‐aminoantipyrine Schiff base ligand with selected divalent Co(II) and Ni(II) ions and their possible applications as flame retardant additives in paint formulations for surface coating application. The prepared metal complexes were characterized using a combination of Fourier transform infrared, elemental analysis, proton nuclear magnetic resonance, ¹³C‐NMR spectra, and mass spectroscopy. The prepared Schiff base ligand metal complexes were physically added to alkyd paint formulation to give coating formulations at a laboratory scale and then applied onto plywood and steel panels using a brush. The ignitability and oxygen index values obtained indicated that the paint which contained the prepared Co(II) and Ni(II) metal complexes as additives exhibited very good flame retardant. The physical and mechanical characteristics of the coatings were studied in order to estimate any disadvantages due to the incorporation of the additives. It was discovered that the added substances did not impact the hardness, flexibility, and adhesion of the prepared coating films. The gloss of the paint formulation film was improved due to the incorporation of the aromatic ring into the formulation and the level of the oil percent.     

Determination of resin acid composition in rosin samples using cyclodextrin‐modified capillary electrophoresis

Rosins are used in a wide variety of industries in varnishes, adhesives, drug coatings, etc. In this project a novel capillary electrophoresis method was developed to investigate the resin acid composition of rosins. The acids were separated and the concentrations of individual acids present in gum rosin samples determined in order to investigate any links between the presence and concentration of these acids and the tendency of rosins to crystallize. The capillary electrophoresis method successfully separated nine resin acids in various rosin samples where previously they could not all be separated. Calibration curves were created to determine acid concentration. Abietic, dehydroabietic, neoabietic, pimaric, isopimaric, levopimaric, sandaracopimaric, palustric, and 7‐oxo‐dehydroabietic acids were separated using a 20 mM tris buffer at pH 9 containing 15% methanol 5 mM (2‐hydroxypropyl)‐γ‐cyclodextrin 10 mM sulfobutylether‐β‐cyclodextrin. Their concentrations in a crystallizing and a noncrystallizing rosin sample were determined.     

Phosphorus Modified Cardanol: A Greener Route to Reduce VolaTile Organic Compounds and Impart Flame Retardant Properties to Alkyd Resin Coatings

Novel phosphorylated cardanol molecules based on phosphonate (PO₃CR) and phosphate (PO₄CR) functions were synthetized. Those molecules have two main actions which are described in this article: the reduction in volatile organic compounds (VOC) and the development of flame retardant (FR) properties conferred on alkyd resins used as coatings for wood specimen. Phosphorylated cardanol compounds have been successfully grafted by covalent bonds to alkyd resins thanks to an auto-oxidative reaction. The impact of the introduction of PO₃CR and PO₄CR on the film properties such as drying time and flexibility has been studied and the thermal and flame retardant properties through differential scanning calorimeter, thermogravimetric analysis and pyrolysis-combustion flow calorimeter. These studies underscored an increase in the thermal stability and FR properties of the alkyd resins. In the cone calorimeter test, the lowest pHRR was obtained with 3 wt% P of phosphate-cardanol and exhibited a value of 170 KW.m⁻², which represented a decrease of almost 46% compared to the PO_xCR-free alkyd resins. Moreover, a difference in the mode of action between phosphonate and phosphate compounds has been highlighted. The most effective coating which combined excellent FR properties and good coating properties has been obtained with 2 wt% P of phosphate-cardanol. Indeed, the film properties were closed to the PO_xCR-free alkyd resin and the pHRR decreased by 41% compared to the reference alkyd resin.     

含三乙烯二胺强弱碱功能基阴离子交换树脂的制备及其吸附性能

含三乙烯二胺强弱碱功能基阴离子交换树脂的制备及其吸附性能;三乙烯二胺; 强弱碱基阴离子交换树脂; 滴定曲线; 苯甲酸; 吸附性能