Drying and semidrying oil macromonomers. III. Styrenation of sunflower and linseed oils

Styrenation of drying and semidrying oils, namely sunflower and linseed oils, via the macromer technique was studied. For this purpose, the macromonomers of the oils were prepared by transesterification of methyl methacrylate (MMA) with the corresponding partial glycerides (PG). Subsequent styrenation was achieved by free radical copolymerization of the macromonomers with styrene using benzoyl peroxide as the initiator. The viscosity and the film properties of the products were studied and compared. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2373–2376, 2003     

Styrenation of triglyceride oils by macromonomer technique

A novel macromer technique is described for the styrenation of triglyceride oils. Triglyceride oil-based macromers were prepared via successive transesterification and condensation reactions. The macromers were styrenated at 100°C using benzoyl peroxide as an initiator. The styrenation led to improved film properties with semidrying oils. Homopolymerization of the macromonomers failed due to the stearic hindrance of the bulky oil moieties. The results obtained were also evaluated by considering the degree of unsaturation. Chemical Engineering Dept., 80628 Maslak — ISTANBUL Tel.: +90 212 285 6835 or 6836 Fax.: +90 212 285 2925.     

Production of oil-based binder by RAFT polymerization technique

In this study, air-blown linseed oil was styrenated by reversible addition–fragmentation chain transfer polymerization (RAFT). For this purpose, hydroperoxide groups were formed in the structure of linseed oil by blowing air through it. The oxidized oil was used as a macroinitiator in the styrenation process by RAFT technique using phenacyl morpholine dithiocarbamate (PMDC) as a RAFT agent. The obtained samples were characterized by GPC and FT-IR measurements. The effects of various parameters, such as the amount of PMDC, the number of peroxide groups, and the reaction time were investigated on polydispersity and molecular weight. For comparison, a copolymer sample was also prepared in the absence of PMDC. The film properties of all the samples were determined according to the related standards and compared. The sample obtained by the RAFT technique exhibited better film properties and a relatively narrow polydispersity, showing that the RAFT technique provides good control over the polymerization system in this study.     

Styrenation of air-blown linseed oil by nitroxide-mediated radical polymerization

Styrenation of air-blown linseed oil by a nitroxide-mediated radical polymerization (NMRP) technique is described. In this technique, air-blown linseed oil bearing hydroperoxide groups was used as a macroinitiator in NMRP of styrene in the presence of 2,2′,6,6′-tetramethylpiperidinyl-1-oxy (TEMPO). The effects of various parameters, such as the amount of TEMPO and hydroperoxide groups, were investigated in terms of molecular weight and polydispersity. For comparison, a copolymer sample of air-blown linseed oil with styrene was also prepared in the absence of TEMPO. The film properties of all samples were determined according to the related standards and were compared with respect to surface protection. Samples prepared by the NMRP technique exhibited relatively narrow polydispersity and better film properties compared to those of the samples obtained by the conventional method.     

Synthesis of oil based hyperbranched resins and their modification with melamine-formaldehyde resin

In this research hyperbranched resins containing fatty acid residues were synthesized. Dipentaerythritol which has six hydroxyl groups was used as the core molecule, and it was transesterified with (i) castor oil, and (ii) a mixture of castor oil and linseed oil at 240 °C. The resulting molecule had hydroxyl containing ricinoleic acid residue coming from castor oil. It was then esterified with dimethylol propionic acid at 140 °C in the presence of para-toluene sulfonic acid used as catalyst. The hyperbranched resin thus produced was then mixed with melamine-formaldehyde resin to improve its properties. The resins were characterized by FTIR spectroscopy, and the thermal properties were determined by DSC. The resins were thermally stable up to 316 °C. The viscosity of the resin that was synthesized by using only castor oil was 3.0 Pa s, while the one synthesized by using 50% linseed oil had a viscosity of 1.0 Pa s. When reacted with dimethylol propionic acid the viscosity of the former resin increased to 7.0 Pa s, and that of the second to 3.7 Pa s. The hyperbranched resins showed excellent adhesion, gloss, flexibility, and formability. The mixed resin (i.e. hyperbranched and melamine-formaldehyde) had higher hardness values but lower gloss, adhesion, and bending resistance. Both types of resins also had good impact and abrasion resistances.     

Preparation and properties of urethane alkyd based on a castor oil/jatropha oil mixture

Castor oil is the only major natural vegetable oil that contains a hydroxyl group and so it is widely used in many chemical industries, especially in the production of polyurethanes. In this work, castor oil was interesterified with jatropha oil and the product was subsequently reacted with toluene diisocyanate to obtain urethane alkyd. The prepared urethane alkyd was characterized and its properties were determined and compared with those of the conventional (glycerol/jatropha oil) and commercial urethane alkyds. The castor oil/jatropha oil-based urethane alkyd had a lower molecular weight and viscosity, a slightly lower hardness and greatly longer drying time than the conventional and commercial urethane alkyds, but otherwise the film properties were broadly similar, including being very flexible, with an excellent adhesion and high impact resistance. In addition, they also exhibited excellent resistance to water and acid.     

The decomposition of secondary esters of castor oil with fatty acids

In this study, thermal splitting of secondary fatty acid esters of castor oil was investigated to determine the reaction kinetics under various conditions. Zinc oxide,p toluenesulfonic acid and sulfuric acid were used as catalysts. Reactions were carried out at 260, 270, and 280°C. Experimental data fitted the first-order rate equation for the catalyzed and noncatalyzed reactions. In addition to the kinetic investigation, the splitting (pyrolysis) mixture was evaluated in the preparation of a synthetic drying oil. For this purpose, the mixed fatty acids of linseed, sunflower andEcballium elaterium seed oils were used in the esterification stage of the process. Pyrolysis mixtures were converted to drying oils by combining the liberated acids with equivalent amounts of glycerol. The oils thus obtained show good drying oil properties.     

Polyurethane Dispersions Based on Interesterification Product of Fish and Linseed Oil

Alkyd and styrenated alkyd resins based on fish oil and their interesterifications with linseed oil were synthesized. The various properties of fish oil, such as its iodine value, acid value, saponification value and moisture content were determined. The interesterification product of fish oil and linseed oil can be used to partially replace the commercially available linseed oil alkyd resin. Alkyd resin and styrenated alkyd resin were modified with 2,2 dimethylolpropionic acid to introduce acid functionality and then sequentially reacted with isophorone diisocyanate, neutralized with amine, chain extended with ethylenediamine and dispersed in water to form a polyurethane dispersion. The newly synthesized resins and polyurethane dispersions were studied for coating properties such as scratch hardness, adhesion, flexibility, impact, solvent and chemical resistance. The polyurethane dispersions exhibited superior coating properties to those of their respective alkyds and styrenated alkyds.     

Rigid urethane foams from hydroxymethylated linseed oil and polyol esters

Rigid urethane foams were prepared from hydroxymethylated linseed oil and its esters of glycerol, trimethylolpropane and pentaerythritol. These polyols were made by selective hydroformylation with a rhodium-triphenylphosphine catalyst followed by catalytic hydrogenation with Raney nickel. Although the hydroxymethylated linseed monoglyceride by itself yielded a satisfactory foam, better foams were made from all hydroxymethylated linseed derivatives when blended with a low-molecular weight commercial polyol. Linseed-derived foams were compared with foams from equivalent formulations of hydroxymethylated monoolein and castor oil. Hydroxymethylated products yielded polyurethane foams meeting the requirements of commercial products with respect to density, compressive strength and dimensional stability. National Flaxseed Processors Association Fellow. N. Market. Nutr. Res. Div., ARS, USDA.     

蓖麻油聚氨酯-丙烯酸酯复合乳液的合成

采用甲基丙烯酸甲酯（MMA）与蓖麻油水性聚氨酯乳液共聚反应制备聚氨酯丙烯酸酯（PUA）复合乳液,研究了蓖麻油水性聚氨酯性能、MMA添加量、引发剂种类和聚合温度对PUA复合乳液及涂膜性能的影响,并应用傅里叶红外光谱（FTIR）测定反应产物的结构.研究发现,用外观半透明或微透明的PU-M分散液制备的PUA乳液及涂膜性能优良.油溶性引发剂（AIBN）比水溶性引发剂（K₂S₂O₈）更适合本体系的乳液聚合.随着MMA含量增大,PUA复合乳液胶粒粒径增大,黏度减小,涂膜光泽度下降,机械性能变好,耐水性增加.合适的MMA含量为体系总固含量的20%～30%.提出了PUA复合乳液胶粒形成及粒径长大机理.     

Development of karanja oil based offset printing ink in comparison with linseed oil

The conventional offset lithographic printing ink is mainly based on linseed oil. But in recent years, due to stiff competition from synthetic substitutes mainly from petroleum products, the crop production shrinks down to an unsustainable level, which increases the price of linseed oil. Though soyabean oil has replaced a major portion of linseed oil, it is also necessary to develop alternate cost effective vegetable oils for printing ink industry. The present study aims to evaluate the performance of karanja oil (Pongamia glabra) as an alternative of linseed oil in the formulation of offset printing ink because karanja oil is easily available in rural India. Physical properties of raw karanja oil are measured and compared with that of alkali refined linseed oil. Rosin modified phenolic resin based varnishes were made with linseed oil as well as with karanja oil and their properties are compared. Sheetfed offset inks of process colour yellow and cyan is chosen to evaluate the effect of karanja oil in ink properties. In conclusion, karanja oil can be accepted as an alternate vegetable oil source with its noticeable effect on print and post print properties with slower drying time on paper. However, the colour and odour of the oil will restrict its usage on offset inks.     

Self-lubricating epoxy composite coating with linseed oil microcapsule self-healing functionality

Cured epoxy resins have poor abrasion resistance, which shortens the service life of the material. This work aims to improve the tribological properties of epoxy resins by coupling self-lubrication and auto-healing. In this study, linseed oil microcapsules with an average particle size of 38.57 μm and good thermal stability were successfully prepared by in situ polymerization. The effects of microcapsule content on the tribological, mechanical, and self-healing properties of the composite coatings were studied. It was demonstrated that the composite coating has outstanding self-lubricating properties. The coefficient of friction reduced from 0.634 (pure epoxy resin) to 0.0459 (epoxy resin with 10 wt.% linseed oil microcapsules). Wear rate reduced from 7.16 × 10⁻⁴ mm³/(N m) to 1.74 × 10⁻⁵ mm³/(N m). The self-lubricating mechanism of the coating was investigated by SEM and EDS, which indicated that the formation of uniform and continuous lubricating film on the surface of the friction pairs was the key to improving the wear resistance of the material. In addition, the linseed oil released after the microcapsules rupture can repair the abrasion marks by reacting with oxygen during the friction process. The dual-functional effect of linseed oil microcapsules prolongs the life of epoxy resin coating and expands its application range.     

Enzymatic interesterification of blends of castor oil and some oils rich in saturated fatty acids

Interesterification of castor oil blended with some oils rich in saturated fatty acids was done with the help of 1,3-specific lipase from Mucor miehei in order to alter its viscosity characteristics and adhesion properties by the introduction of saturated fatty acid molecules. The interesterification was done by an oil blend ratio of 50 : 50. 10% enzyme were used. Temperature was kept at 60 °C under 2—5 mm Hg pressure with constant stirring, and the reactions were carried out for 6 h. The products were filtered to remove the enzyme and then analyzed for slip point, specific gravity, and kinematic viscosity. The slip point of the interesterified products was found to be much lower than the parent blend and was in the range of 15—25 °C. Specific gravity and iodine value of the products were in comparison with the theoretical ones. A very large depression in kinematic viscosity was found with every interesterified product from original castor oil and also from the blends at three different temperatures.     

Polyester amides from linseed oil for protective coatings

The sodium alkoxide-catalyzed reaction of linseed oil or linseed methyl esters with diethanolamine produces almost exclusively linseed diethanolamides. Reaction conditions, e.g., temperature, amount of excess diethanolamine and mode of adding reactants, are reported. The best conditions for producing diethanolamide directly from linseed oil (1 mole) required adding oil to the sodium alkoxide in diethanolamine (6 moles) and heating at 110–115C for 35 min. The linseed diethanolamide isolated in 93–95% yield was an amber oil. Progress of the reaction, followed by thin-layer chromatography, showed only trace amounts of byproducts. Polyester amides were prepared by heating linseed diethanolamide in refluxing xylene with dibasic acids or anhydrides, e.g., azelaic, maleic, fumaric, phthalic, terephthalic, itaconic, brassylic and dimer acids. Molecular weight, viscosity and film properties (air-dried and baked) of the polyester amides were determined. Presented at the AOCS Meeting, Chicago, October 1964. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Emulsifiers derived from linseed oil and their potential use in coatings

In the development of a stable linseed oil emulsion paint, a series of emulsifiers were prepared from linseed, oil and its fatty acids and alcohols: (a) linseed monoglycerides, (b) mono-and dilinseed fatty sorbitan esters and a mixed ester obtained by the transesterification of linseed oil with sorbitol, (c) polyoxyethylene ether adducts formed by reacting, ethylene oxide with these sorbitan esters, and (d) linseed polyoxyethylene ether made by ethoxylation of linseed alcohols. Another series of surfactants was prepared by esterifying a polyoxyethylene ether of sorbitol with various amounts of linseed fatty acids. Conditions of preparation and pertinent physical, and chemical properties of the emulsifiers are given. Some of these emulsifiers demonstrated filmforming properties. Combinations were formulated into linseed oil emulsion paints with and without zinc oxide. Paints containing zinc oxide have been relatively stable in viscosity for about 2 yr.     

Soybean and castor oil based monomers: Synthesis and copolymerization with styrene

In this study, castor oil was alcoholyzed with both aliphatic alcohols, such as glycerol and pentaerythritol, and an aromatic alcohol, bisphenol A propoxylate. The resulting alcoholysis products were then malinated and cured in the presence of styrene. Soybean oil pentaerythritol glyceride maleates were also prepared for a direct comparison of the properties of the castor oil and soybean oil based resins. Castor oil was directly malinated as well to see the effect of the alcoholysis step on the properties of the castor oil based resins. The monomers synthesized were characterized by ¹H‐NMR spectroscopy, and the styrenated resin liquid properties, such as viscosity and surface energy values, were determined. The conversion of polymerization was determined using time resolved FTIR analysis for the styrenated soybean oil pentaerythritol glyceride maleates, castor oil maleates, and castor oil pentaerythritol glyceride maleates. The effect of monomer identity and styrene content on the conversion of polymerization was explored. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2433–2447, 2006     

Synthesis and characterization of hyperbranched and air drying fatty acid based resins

In this research four hyperbranched resins having fatty acid residues were synthesized. Dipentaerythritol, which was used as the core molecule of the resins, was twice esterified with dimethylol propionic acid. This resin was then esterified with the castor oil fatty acids. The hydroxyl group present in the ricinoleic acid which constitutes almost 87% of the castor oil fatty acids was then reacted with linseed oil fatty acids and benzoic acid. The linseed fatty acids were incorporated into the structure to esterify 0, 15, and 70% of the ricinoleic acid on mole basis. These resins were named as HBR-1, 2, and 3. A fourth resin (e.g. HBR-4) was synthesized by the incorporation of ‘15% linseed fatty acids + 55% benzoic acid’. The chemical characterization of the resins was achieved by FTIR spectroscopy and the thermal properties were determined by DSC. The physical and the mechanical properties of the resins were determined. The hardness value of the resins was measured as 24, 27, 25, and 68 Persoz for HBR-1, 2, 3, and 4, respectively. The viscosity of the resins was measured as 17.3, 9.7, 5.8, and 17.5 Pa·s at a shear rate of 200 s⁻¹. The increase in the amount of the linseed fatty acids increased the hardness, and decreased the viscosity of the resins. All resins showed excellent adhesion, gloss, and flexibility.     

The preparation and properties of some urethane foams from castor oil and elaidinized castor oil

Summary The preparation and properties of two series of castor oil urethane foams, one from castor oil and the other from elaidinized castor oil, were investigated. The first series of foams was made from prepolymers containing 60% of castor oil prepared at increasing temperature levels to vary the degree of crosslinking in the final foams. These foams had lower tensile strengths than observed for a previously prepared foam of 60% castor oil and did not show significant differences in water resistance as crosslinking varied. They were increased nearly 100% in compressive strength with increased crosslinking and had very good shrinkage characteristics as values of only 1 to 2% were obtained. A second series of foams was prepared from 50, 60, 70, and 80% of elaidinized castor oil to compare with foams from a similar series from castor oil. This series of foams of 50 to 80% elaidinized castor oil contents was similar in density (1.7 to 6.7 lbs./cu. ft.), had improved shrinkage characteristics (11, 1, 3, and 4%, respectively), showed increased compressive and tensile strengths (up to 12.1 p.s.i. at 50% compression modulus and 34.7 p.s.i. ultimate tensile for the 60% foam formulation), and had better water-resistance properties (411 to 155%vs. 515 to 170% water absorption) than the analogous foams from castor oil. In general, humid aging only slightly affected the values obtained for the foams and was significant in only a few instances,e.g., decreased tensile in the elaidinized castor oil series. Thus increasing crosslinks in the foam apparently did not improve water resistance but did improve shrinkage characteristics in addition to some increased strength properties, as would be anticipated. Foams from elaidinized castor oil, while similar in density and foaming characteristics to analogous foams from castor oil, exhibited less shrinkage and improved water-resistance. Presented at the 50th Annual Meeting of the American Oil Chemists' Society, New Orleans, La., April 20–22, 1959. Ono of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

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.     

Changes in triacylglycerol molecular species and thermal properties of blended and interesterified mixtures of coconut oil or palm oil with rice bran oil or sesame oil

Blended oils were prepared by mixing appropriate amounts of coconut oil (CNO) or palm oil (PO) with rice bran oil (RBO) or sesame oil (SESO) to get approximately equal proportions of saturated/monounsaturated/polyunsaturated fatty acids in the oil. These blended oils were subjected to interesterification reactions using lipase to randomize the fatty acid distribution on the glycerol molecule. The fatty acid compositions of the modified oils were evaluated by gas chromatography while changes in triacylglycerol molecular species were followed by HPLC. The triacylglycerol molecular species of the blended oils reflected those present in the parent oil. Interesterification of the blended oils resulted in the exchange of fatty acids within and between the triacylglycerol molecules, resulting in alterations in the existing triacylglycerol molecules. Emergence of new triacylglycerol molecular species following interesterification was also observed. The thermal profiles of the native, blended and interesterified oils were determined by differential scanning calorimetry. Thermal behaviour, melting and crystallization properties of the modified oils showed significant changes reflecting the changes in the triacylglycerol molecules present in the oil. Therefore, interesterification of oils introduces significant changes in the physical properties of oils, even though the overall fatty acid composition of blended and interesterified oils remains the same.