Dehydrated Castor Oil Fatty Acids Research Articles

Development of a novel hyperbranched unsaturated polyester resin: Synthesis, characterization, and potential applications in car body putty

This work presents a comprehensive synthesis method for the development of a new hyperbranched unsaturated polyester resin (HUPR). The resin is synthesized by modifying dehydrated castor oil fatty acid (DCOFA) with methyl methacrylate (MMA) and styrene, dicyclopentadiene-maleate (DCPD-M), and trimethylol propane diallyl ether (TMPDE). The synthesis process involves the radical addition reaction of DCOFA with MMA and styrene, followed by the addition of DCPD-M and TMPDE to form a HUPR. The resulting resin exhibits enhanced properties, making it a promising candidate for car body putty in the polymer industry.

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

ABSTRACTHyperbranched 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, Tg 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.

Non-isocyanate polyurethane (NIPU) from tris-2-hydroxy ethyl isocyanurate modified fatty acid for coating applications

Abstract Conventional polyurethanes, in spite of their excellent properties and wide applications possess safety and handling issues related to isocyanate compounds while synthesis. The cyclic carbonate-amine reaction resulting into hydroxyurethane is said to be an isocyanate free polyurethane system and novel route of synthesis as well as good alternative to conventional polyurethanes. In the present work, non-isocyanate polyurethane was synthesized by modification of dehydrated castor oil fatty acid (DCOFA) with tris-2-hydroxy-ethyl isocyanurate (THEIC). The synthesis involved three steps viz esterification of DCOFA with THEIC, epoxidation of the ester formed (TEFA) and subsequent cyclocarbonation of THEIC–ester of fatty acid (CTEFA). The products obtained were confirmed by Fourier Transform Infrared Spectroscopy (FTIR) as well as 1H and 13C Nuclear Magnetic Spectroscopy (NMR). The CTEFA was cured with various amines such as dimethyl diphenyl sulphone (DDS), Isophorone Diamine (IPDA) and hexamethylene diamine (HMDA) to obtain NIPU coatings. The cured coatings were studied for chemical, mechanical, thermal and electrochemical properties. Also, the effect of amine curing agents on the performance of NIPU coatings was investigated. Experimental results showed that incorporation of THEIC into the system significantly improved coating properties.

Benzyl ester of dehydrated castor oil fatty acid as plasticizer for poly(vinyl chloride)

The poly(vinyl chloride) (PVC) industry plays an important role in today's total plastics industry. The major volume of PVC is used as soft and plasticized PVC. PVC applications consume approximately 80% of the total production of plasticizers. Most of the common plasticizers are aromatic esters of phthalic acid. In the majority of countries, phthalate plasticizers are banned due to their carcinogenic properties. The concern raised about toxicity led to a large demand for bio-based non-toxic plasticizers. Hence, there is an increasing interest in replacing the phthalate plasticizers with those produced from simple bio-based materials. Dehydrated castor oil fatty acid (DCOFA) is a renewable resource which can be esterified and used as an environment friendly plasticizer for PVC. Benzyl ester (BE) was prepared by reacting DCOFA with benzyl alcohol in the presence of catalyst at 170–180 °C. Esterification was further confirmed by acid value, hydroxyl number, 1H NMR and Fourier transform IR spectroscopy. The modified plasticizer was used in various proportions as a co-plasticizer in PVC for partial replacement of dioctyl phthalate (DOP). With an increase in the proportion of BE in PVC samples, a good plasticizing performance was observed. The incorporation of BE also resulted in a reduction in viscosity and viscosity pick-up and improved mechanical, exudation, thermal degradation and chemical resistance properties. The presence of BE showed a reduction in the whiteness index due to presence of conjugated double bonds in the structure. The results of DSC, XRD and Shore hardness studies showed no significant variation in properties compared with those of DOP-plasticized sheets and thus we can conclude that BE can be used as a co-plasticizer in PVC. © 2013 Society of Chemical Industry

Synthesis of polymeric dispersants from renewable DCO fatty acid and their multifunctional behavior in waterborne flat paint

Copolymers containing 50% dehydrated castor oil fatty acids (DCOFA) derived from renewable resources, were synthesized via free radical solvents less polymerization with maleic anhydride, styrene, and butyl acrylate. The copolymer was crosslinked further with polyethylene glycol 400 (PEG 400) to increase its molecular weight. The copolymers with and without crosslinking were then neutralized with sodium hydroxide to prepare polymeric dispersants DFCD1 and DFCD2 respectively in aqueous medium. It was observed via surface-tension measurement that both DFCD1 and DFCD2 transfer to the air–water interface before forming any aggregates, and the ease of forming the aggregates is in the order of DFCD1 > DFCD2. The efficacy of these dispersants was examined in the dispersion of the titanium dioxide pigment and conventional extenders like calcite, talc, and china clay using flow point and zeta potential measurements. The results reveal that DFCD2 improved the dispersing ability for the pigment and extenders studied. The performance of these polymeric dispersants was also studied and compared in waterborne flat paint as a rheology modifier and pigment-dispersing agent. The paint rheology profile and dE data indicate the superior performance of the paint containing dispersant DFCD2. When used in combination with conventional styrene-acrylic latex, DFCD1 and DFCD2 reduced the minimum film-forming temperature (MFFT) of the polymer latex.

Study of hexafunctional polyol in high solids air-drying alkyd: Improved film performance

A series of high solid alkyd polymers from soya oil fatty acid (SOFA) and dehydrated castor oil fatty acid (DCOFA) combinations with varying percentage of dipentaerythritol (DPE, a hexafunctional polyol) have been synthesized and characterized for their physicochemical, optical, thermal and mechanical properties. For the study purpose the polymers were prepared at 80% solids in mineral turpentine oil (MTO) keeping the oil length constant. The curing behavior of the alkyds was studied using FT-IR and DSC. Increasing DPE content in resin backbone was found to increase gloss and hardness. The gloss improvement was also supported well by atomic force microscopy (AFM) pictures. Results of 500 h of QUV exposure revealed higher gloss retention for DPE-based systems. When compared for the anticorrosive properties, the EIS spectrum reveals that alkyd film containing 100% DPE has the higher value of impedance.

Weathering characteristics of epoxy-ester paints

The diglycidyl ethers of bisphenol A (DGEBPA), bisphenol F (DGEBPF), bis 2,6-xylenol F (DGEBXF), bis 2,6-xylenol S (DGEBXS) and biS 2,6-xylenol (DGEBX) were converted to epoxy-esters by reacting them with dehydrated castor oil fatty acid (DCOFA). Simple TiO 2 paints were prepared using the epoxy resins as well as their epoxy-esters and compared for the weathering characteristics by subjecting them to accelerated and environmental weathering. The weathering characteristics of the epoxy-ester paints were found to be better than their corresponding epoxy paints cured with amine terminated dimer fatty acid based polyamide (FPA). The paint prepared with DGEBPA modified with DCOFA and cured with Co and Pb octoate gave the best weathering characteristics with appreciable improvement in chalk resistance, optimum yellowing and gloss retention.

Characteristic properties of cutting fluid additives derived from the reaction products of hydroxyl fatty acids with some acid anhydrides

AbstractSeveral adducts were prepared from the thermal reaction of hydroxyl fatty acids (ricinoleic acid oligomers, 12‐hydroxystearic acid oligomers, oleyl alcohol, dehydrated castor oil fatty acids, and dimer acid) with maleic anhydride and screened as water‐soluble cutting fluids. For example, aqueous solutions of triethanolamine salts with the products of ricinoleic acid oligomers, 12‐hydroxystearic acid dimer, and 12‐hydroxysteric acid hexamer showed good antirust properties for waterbased cutting fluids. Various half esters of hydroxyl fatty compounds with acid anhydrides were prepared. Aqueous solutions of triethanolamine salts of half esters of maleic anhydride and succinic anhydride and phthalic anhydride with hydroxyl fatty acids gave good antirust and antiwear properties for waterbased cutting fluids.

Reactive polyamides from cycloaliphatic C 21 dicarboxylic acid and their evaluation as epoxy curing agents

Reactive polyamides with amine values ranging from 310 to 389 were prepared by reacting C 21 cycloaliphatic dicarboxylic acid, prepared from acrylic acid and dehydrated castor oil fatty acids, with various polyamines, namely diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Some reactive polyamides of matching amine values were also prepared by using C 36 dimer acids and tetraethylenepentamine for comparison. The polyamides were then reacted with an epoxy resin (epoxy resin of equivalent weight 450) in different equivalent weight ratios. The cured product obtained by using an equivalent weight ratio of 1.00:1.00 of epoxy resin and reactive polyamide had better binding properties in comparison to other binders. The binders derived from C 21 dicarboxylic acid were better than those derived from C 36 dimer acids in both adhesion and hardness, and were superior in tensile strength.

Solvent extraction of Fe(III) by dehydrated castor oil fatty acids

The effect of temperature on the extraction of FE(III) by dehydrated castor oil fatty acids (DCOFA) has been studied in the temperature range 283–313 K at 1.0 M constant ionic strength (NaClO 4). The temperature dependence of the conditional constant of extraction is given in the form: ln K ext=31.95 − 12800(1/ T). Also, it was found that the average thermodynamic parameters, Δ H° ext, Δ G° ext, and Δ S° ext are 106.5 kJ/mole, 27.3 kJ/mole, and 0.3 kJ. mole −1.K −1, respectively. The extracted species in toluene solution were identified as FeR 3.HR and Fe(OH)R 2, where HR represents the fatty acid used.

Kinetics of reaction of C21 cycloaliphatic dicarboxylic acid and ethylenediamine

AbstractKinetic studies were carried out on the reaction between ethylenediamine and C21 cycloaliphatic dicarboxylic acid, prepared from dehydrated castor oil fatty acids and acrylic acid, in melt phase. The reaction was performed at six different temperatures ranging from 210 to 260°C and followed by determining the acid value of the product. The polyamidation reaction was found to follow an overall third order kinetics with an activation energy of 15.5 kcal/g mol.

Kinetics of oligomerization of methyl ester of dehydrated castor oil fatty acid over molybdenum oxide on silica–alumina catalyst in comparison with the thermal oligomerization process

AbstractA process is described for the oligomerization of methyl ester of dehydrated castor oil fatty acid over molybdenum oxide on silica–alumina catalyst. The process is compared with thermal oligomerization. The nature of the reaction in both the processes are shown to be the same from the structural elucidation of the product despite the variation in product composition. The percentage of dimer in the product in both the processes is observed to attain an equilibrium value at around 270°C. The catalytic process is shown to follow a second‐order kinetics with respect to the monomer, whereas the thermal reaction follows a first‐order kinetics. The kinetic scheme derived for the catalytic process is shown to be consistent with the steps of the general mechanism proposed for oligomerization reactions over transition metal catalysts [V. G. Kumar, S. Venkatachalam, and K.V.C. Rao, J. Poly. Sci. Polym. Chem. Ed., 22, 3850 (1984)].

Reduction of unsaturated fatty acids and fatty alcohols with diimide from hydroxylamine‐ethyl acetate

AbstractHydroxylamine has been recently found to react with ethyl acetate to generate diimide in situ. This reaction was used to reduce 10‐undecenoic, oleic, linoleic, stearolic, concentrates of ricinoleic, cyclopentene and cyclopropene fatty acids (FA), dehydrated castor oil FA, 10‐undecen‐1‐ol, oleyl alcohol and castor fatty alcohols. Unsaturated FA and their corresponding alcohols reacted in a similar manner. Terminally unsaturated, cyclopropene and cyclopentene FA were more reactive than oleic acid, which, in turn, was more reactive than hydroxymonoenoic acids. Conjugated dienoic FA reduced faster than nonconjugated dienoic acids. Partial hydrogenation using this reagent is particularly advantageous in determining geometry and the position of double bonds in the polyunsaturated FA, as it can be carried out in the absence of oxygen or oxidizing agents unlike hydrazine reductions.

Isocyanate‐modified dehydrated castor oil

AbstractEsters of dehydrated castor oil fatty acids with polyhydric alcohols like ethylene glycol, propylene glycol, glycerol, pentaerythritol and sorbitol have been prepared. The esters, having hydroxyl value ranging from 78.5 to 167, were reacted with toluene diisocyanate. The scratch hardness and other film properties of the resulting urethanes have been studied. Urethanes obtained from various mixtures of the above esters also have been studied. The best results have been obtained when a mixture of ethylene glycol ester and plenaerythritol ester of dehydrated castor oil fatty acids in the ratio of 4:1 are reacted with one equivalent of toluene diisocyanate. One equivalent of glycerol ester (hydroxyl value 78.5), ethylene glycol ester (hydroxyl value 167), or propylene glycol ester (hydroxyl value 159.4) of DCO fatty acids when reacted with 1.25 equivalent of toluene diisocyanate also gave satisfactory products.

Polymerization of dehydrated castor acids using an acid earth catalyst

AbstractThe atmospheric pressure polymerization of a commercial dehydrated castor oil fatty acid mixture, by using as catalyst the acid clay Filtrol 13, has been studied under different conditions of temperature, catalyst concentration, reaction time, and concentration of conjugated linoleic acid in the starting material. At 180C or above, extremely rapid polymerization of the conjugated fatty acids occurred (50% complete in about 4 min at 66% concentration). This was accompanied bytrans isomerization and some hydrogen transfer to form oleic (oriso‐oleic) acids. The ratio of dimer/polymer in the product was approximately 2 to 2.5 and was only slightly affected by variation in the reaction conditions.

The geometric isomers of conjugated octadecadienoates from dehydrated methyl ricinoleate

AbstractThe dehydration of methyl ricinoleate by heatingin vacuo in the presence of KHSO4 resulted in the formation of the following conjugated octadecadienoates expressed as a percentage of the final product:cis, trans (trans, cis), 14.3;cis, cis, 11.2;trans, trans, 7.3. The isomers contained the double bonds predominantly in the 9,11 position but the possible presence of traces of 8,10 and other conjugated isomers is not excluded. Using urea 舠inclusion舡 fractionation and low temp crystallization from acetone methyl,cis‐9,cis‐11‐octadecadienoate was isolated.The methyl esters of commercially dehydrated castor oil fatty acids on the other hand, contained the following percentages of conjugated octadecadienoate isomers:cis, trans (trans, cis), 20.3;cis, cis, 8.0;trans, trans, 5.4. From these mixtures conc ofcis, trans (trans, cis)‐ andtrans, trans‐octadecadienoates were prepared by fractional distillation and low temp crystallization. It was found that the conjugated octadecadienoates consisted of mixtures of positional isomers with double bonds mainly in the 8,10 and 9,11 positions with lesser amounts in the 7,9 and 10,12 positions.