Preparation of Sebacic Acid via Alkali Fusion of Castor Oil and its Several Derivatives

Castor oil and its three derivatives including methyl ricinoleate, sodium ricinoleate and ricinoleic acid were used as the raw material for alkali fusion to prepare sebacic acid. The reaction parameters including catalyst, ratio of oleochemicals/NaOH, reaction time and reaction temperature were optimized. It was found that Pb₃O₄ (1%) showed the best catalytic performance, and 553 K was considered as the most suitable reaction temperature. The oleochemicals/NaOH ratios of 15:14, 15:14, 15:12 and 15:14 were determined as the optimal ratio for alkali fusion of castor oil, methyl ricinoleate, sodium ricinoleate and ricinoleic acid, respectively. In addition, the optimal reaction time of alkali fusion of castor oil was 5 hours, and that of its derivatives was 3 hours. The maximum yield in sebacic acid of 68.8%, 77.7%, 80.1%, 78.6% can be obtained by using castor oil, methyl ricinoleate, sodium ricinoleate and ricinoleic acid as the raw material, respectively. High purity of sebacic acid was confirmed by GC and melting point analysis. ICP-OES results illustrated that the content of Pb in sebcic acid was less than 1 mg kg⁻¹. Separating glycerol from castor oil was beneficial for alkali fusion, by which, the yield of sebacic acid was increased of approximately 10%, and the reaction time was reduced from 5 to 3 hours. This study provided guiding significance for the future industrial production of sebacic acid.     

Synthesis,physicochemical and thermal properties of urethane-modified polyesteramide films using mahua and castor oil as sustainable resources

In this work, a number of urethane-modified polyesteramide (UmPEA) films were developed from mahua and castor oils, which are renewable resources. Mahua oil and diethanolamine were reacted to form mahua fattyamide, which was then reacted with itaconic acid to prepare polyesteramide. In order to make the UmPEA films, different proportions of polyesteramide and castor oil as polyols were reacted with isophoronediisocyanate. The UmPEA films showed excellent chemical resistance against water, acid, alkali, salt, and organic solvents and were found insoluble in common organic solvents. The thermal stability of the UmPEA films was investigated through TGA and DSC analyses, and their T_g values are between 69.1°C and 56.1°C for UmPEA films, which indicated that a higher content of CO enhances the T_g, and it was also found that the films were highly stable up to 230°C. The E_a values [224 kJ mol⁻¹ (T_p1) and 226 kJ mol⁻¹ (T_p2)] indicate that the castor oil enhances the thermal stability of the films due to better cross-linking density occurring through the high hydroxyl groups of CO as the polyol which also showed better flame retardancy in the synthesized UmPEA films. Our findings demonstrate that the newly developed UmPEA films can be potent coating materials.     

Assessment of Variation in Castor Genetic Resources for Oil Characteristics

Castor (Ricinus communis L.) oil is used in production of wide range of industrial products because of the presence of nearly 85% of ricinoleic acid in it. Any increase in the ricinoleic acid level would be great benefit to industry. None of the existing castor cultivars possess ≥90% ricinoleic acid because donors with this level of ricinoleic acid are not available to develop high ricinoleic type cultivars. In order to search for high ricinoleic acid genotypes, the present investigation was under taken. Fatty acid and oil content were assayed in 392 castor genotypes comprising 335 Indian and 57 non-Indian collections. Great variation was observed among the collections for oil content and fatty acid composition. Oil content ranged from 38.5 to 53.5% while ricinoleic acid was between 71.15 and 93.68%. Diversity analysis was done using K-means clustering which clustered the entire collection into 30 diverse groups by minimizing the dissimilarity within each cluster while maximizing the dissimilarity between clusters. Finally, 15 accessions having high oil (52–54%), high ricinoleic acid (91.12–93.68%) and high monounsaturates (92.8–94.95%) levels were identified. These would be of great value as donors to develop high oil, high ricinoleic type castor cultivars.     

Simultaneous interpenetrating polymer networks based on bromoacrylated castor oil polyurethane

In the first part of this study, simultaneous addition of bromine and acrylate to the double bonds of castor oil was achieved. In the second part of the study, bromoacrylated castor oil (BACO) was reacted with toluenediisocyanate (TDI), to form a prepolyurethane (BACOP). The prepolyurethanes were reacted with styrene (STY), 2‐hydroxyethyl methacrylate (HEMA), methyl methacrylate (MMA), and 3‐(acryloxy)‐2‐hydroxy propyl methacrylate (AHPMA) free radically, using the acrylate functional group to prepare the simultaneous interpenetrating polymer networks (SINs). 2,2′‐Azobis (isobutyronitrile) (AIBN) was used as the initiator and diethylene glycol dimethacrylate (DEGDMA) was used as the crosslinker. BACO and BACOP were characterized by IR, ¹H‐NMR, and ¹³C‐NMR techniques. Synthesized polymers were characterized by their resistance to chemical reagents, thermogravimetric analysis, and dynamic mechanical thermal analyzer (DMTA). All the polymers decomposed with 6–10% weight loss in a temperature range of 25–240°C. MMA‐type SIN showed the highest T_g (126°C), while STY‐type SINs showed the highest storage modulus (8.6 × 10⁹ Pa) at room temperature, with respect to other synthesized SINs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2947–2955, 2006     

New resinous ricinoleic polyol for urethane reactions

A new resinous polyol has been described based on a fusion reaction of Epon Resin 829 with Bisphenol A and further esterification with ricinoleic acid. This was based on a modified short oil alkyd cook reaction with unsaturated fatty acids following previously employed techniques. The method was modified by reaction with ricinoleic acid, a 12-hydroxy oleic acid, the main fatty acid component of castor oil. The resinous polyol derived from this technology is designated Ester 597. Ester 597 was further reacted with a series of urethane prepolymers based on castor oil. A two-component formula based on this study was used to prepare a two-can epoxy-urethane coating system that may have coatings potential as a marine coating and as a maintenance coating for industrial use.     

DC-Trennung von Ricinusölfettsäure-Estoliden

TLC Separation of Estolides of Castor Oil Fatty Acids Estolides of castor oil fatty acids (polyricinoleic acids) with varying degrees of condensation were synthesized by heating the castor oil fatty acids at 120° C–240° C under vacuum and CO₂ circulation. These products were analyzed by chemical constants and fractionated by TLC on silicagel 60 precoated plates into ricinoleic acid and di-, tri- as well as tetra-ricinoleic acids. Furthermore, the estolides were separated by two-dimensional TLC into two series of estolides, i.e. estolides containing only ricinoleic acid and those which contain fatty acids other than ricinoleic acid at the chain terminal. Hydrogenated castor oil fatty acids (technical 12-hydroxystearic acid) also form estolides which can be fractionated in a similar manner. Thus, TLC provides information on the oligomeric and polymeric character of the estolides of castor oil fatty acids and permits separation even of the decamers.     

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     

Identification of TAG and DAG and their FA Constituents in Lesquerella (Physaria fendleri) Oil by HPLC and MS

Castor oil has many industrial uses because of its high content (90 %) of the hydroxy fatty acid, ricinoleic acid (OH¹²18:1⁹). Lesquerella oil containing lesquerolic acid (Ls, OH¹⁴20:1¹¹) is potentially useful in industry. Ten molecular species of diacylglycerols and 74 molecular species of triacylglycerols in lesquerella (Physaria fendleri) oil were identified by electrospray ionization mass spectrometry as lithium adducts of acylglycerols in the HPLC fractions of lesquerella oil. Among them were: LsLsO, LsLsLn, LsLsL, LsLn–OH20:2, LsO–OH20:2 and LsL–OH20:2. The structures of the four new hydroxy fatty acid constituents of acylglycerols were proposed by the MS of the lithium adducts of fatty acids as (comparing to those in castor oil): OH¹²18:2^9,14 (OH¹²18:2^9,13 in castor oil), OH¹²18:3^9,14,16 (OH18:3 not detected in castor oil), diOH^12,1318:2^9,14 (diOH^11,1218:2^9,13 in castor oil) and diOH^13,1420:1¹¹ (diOH20:1 not detected in castor oil, diOH^11,1218:1⁹ in castor oil). Trihydroxy fatty acids were not detected in lesquerella oil. The differences in the structures of these C18 hydroxy fatty acids between lesquerella and castor oils indicated that the polyhydroxy fatty acids were biosynthesized and were not the result of autoxidation products.     

Synthesis of Thumba,Castor and Sal Fatty Ethanolamide-Based Anionic Surfactants

The study involved the preparation and evaluation of anionic surfactants from non-edible oil based thumba (containing unsaturated-rich fatty acids, 80.9 %), castor (containing ricinoleic acid, a hydroxy fatty acid 89.3 %) and sal (containing saturated-rich fatty acids, 56.5 %). The oils extracted from these seeds (using Soxhlet) were reacted with monoethanolamine and diethanolamine to get corresponding fatty mono- and diethanolamides. The ethanolamides were sulfated using chlorosulfonic acid and the sulfated sodium salts were evaluated for surfactant properties namely surface tension, critical micelle concentration (CMC), emulsifying property, wetting, foaming power and calcium tolerance. The properties were compared with sodium dodecyl sulfate (SDS) a well known anionic surfactant. Among the different sulfated sodium salts of ethanolamides, thumba showed superior surfactant properties compared to castor and sal. Sulfated sodium salt of thumba monoethanolamide showed better properties (CMC, 0.035 mmol/L, surface tension 30.2 mN/m and calcium tolerance >1,000 ml, 0.5 % calcium acetate solution) compared to sulfated sodium salts of thumba diethanolamides, followed by sulfated sodium salts of castor monoethanolamide (CMC 0.037 mmol/L, surface tension 35.3 mN/m and calcium tolerance >1,000 ml, 0.5 % calcium acetate solution). Sal being saturated rich was not properly soluble in water and showed poor surfactant properties compared to the other two. Also the sulfated sodium salts of thumba and castor ethanolamides exhibited superior properties compared to SDS.     

Studium der lebenden radikalischen Polymerisation mit der Differential Scanning Calorimetry (DSC)

The living radical polymerization of styrene, some styrene-analogous vinyl monomers as well as methyl methacrylate (MMA) and butyl methacrylate (BuMA) was investigated with a differential scanning calorimeter. The ability to polymerize was estimated by dynamic measurements, showing that p-methylstyrene, p-chlorostyrene, 3,4-dimethoxystyrene and 4-vinylpyridine polymerize in the presence of 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) while MMA and BuMA do not. Isothermal measurements revealed an activation energy of E_A = 81 kJ mol^–1 for thermal bulk polymerization of styrene and values of E_A = 78–94 kJ mol^–1 were measured with different iniferter systems. These polymerizations have induction times which depend on the reaction temperature and the initial concentration of the iniferter systems. An influence of the kind of nitroxyl radical on the induction times was not observed.     

蓖麻油基热稳定剂制备及其在聚氯乙烯制品中的作用行为研究

将蓖麻油酸与马来酸酐、六氢苯酐分别制备了2种蓖麻油基二元酸,并合成出相应的新型蓖麻油基钙/锌(Ca/Zn)盐。通过刚果红法、电导率法和热重分析等方法研究了蓖麻油基Ca/Zn盐与传统的石油基异辛酸Ca/Zn盐分别在聚氯乙烯制品中的热稳定性能。结果表明,改性蓖麻油基二元酸锌不易“锌烧”,锌离子含量为2 %时,静态热稳定时间分别为9.8、9.2 min,异辛酸钙/蓖麻油基二元酸锌盐之间协同效应较为显著,且热稳定效果随Ca/Zn离子含量比的变化而变化。     

Accelerated weathering behavior of castor oil bio-based thermosets

Bio-based thermosets based on vegetable oils are promissory materials due to their good performance, renewability and biodegradability. In this work, accelerated weathering tests were performed over bio-based thermosets obtained from castor oil to evaluate the long-term performance under environmental conditions. The thermosets were obtained through homopolymerization or copolymerization with styrene of maleated castor oil methacrylate. The changes in chemical and physical properties were monitored by Fourier-transform infrared spectroscopy (FTIR), color measurements, scanning electron microscopy (SEM) and proton nuclear magnetic resonance (¹HNMR). Both materials showed evidences of chemical changes, such as formation of double bonds and hydroxyl groups, as well as the decomposition of carbonyl ester groups. The observed physical changes were discoloration as well as the formation of cracks and blistering. However, the degradation phenomena were less severe in the copolymer due to the high stability of styrene moieties.     

A simple and rapid polarimetric method for quantitative determination of castor oil

A simple and rapid polarimetric method is developed for quantitation of adulteration of castor oil in edible oils such as cottonseed, coconut, mustard, olive, palm, peanut, rice bran, safflower, soybean, and sunflower. The method is based on the optical activity of ricinoleic acid (12-hydroxy octadecenoic acid), a major constituent of castor oil. There is a good correlation between optical rotation and castor oil content in admixtures above 5%. Highly colored and viscous oils interfere in the measurement of optical activity. The method is highly specific and cost-effective. No solvents and chemicals are required for the analysis because no sample processing is involved in the present method.     

Interpenetrating polymer networks from castor oil-based polyurethanes and polystyrene,XXV

Interpenetrating polymer networks (IPNs) of castor oil-based polyurethanes and polystyrene were prepared by simultaneous polymerization. The liquid prepolyurethanes were formed by reacting the hydroxyl functionality of castor oil with isophorone diisocyanate using different stoichiometric NCO/OH ratios. These prepolyurethanes were mixed with styrene monomer and subsequently polymerized by free radical polymerization initiated by benzoyl peroxide in the presence of the crosslinker 1,4-divinyl benzene. The interpenetrating polymer networks. PU/PS IPNs, were obtained as tough and transparent films by the transfer moulding technique. These IPNs were characterized by the static mechanical properties (tensile strength, Young's modulus and % elongation), thermal properties and morphology. The dielectric relaxation properties (σ, E′, E″ and tanδ) of the IPNs at different temperatures were studied.     

Kinetics of the catalytic esterification of castor oil with lauric acid using <Emphasis Type="Italic">n</Emphasis>-butyl benzene as a water entrainer

The esterification of castor oil with lauric acid was investigated using tetra n-butyl titanate (TBT), SnCl₂·2H₂O (stannous chloride), CoCl₂·6H₂O (cobalt chloride), and (CH₃COO)₂Zn·2H₂O (zinc acetate dihydrate) as catalysts. Effects of catalyst concentration and reaction temperature on the progress of the reaction were investigated. TBT was the best catalyst for the esterification of castor oil with lauric acid at temperatures lower than 200°C. The reaction was first order with respect to each reactant. The activation energy for the esterification reaction of castor oil with lauric acid using TBT was 26.69 kcal/mol. The rate constants obtained for the esterification of castor oil with decanoic, lauric, palmitic, and stearic acids were nearly the same (15.80, 15.44, 15.06, and 14.67 mL mol⁻¹ min⁻¹), as were the rate constants obtained for the reaction of castor oil and hydrogenated castor oil.     

Effect of tris(bathophenanthroline)iron(III) on the polymerization of styrene

The polymerization of styrene at 60°C initiated by 2,2′-azobisisobutyronitrile (AIBN) was studied in N,N-dimethylformamide (DMF) in the presence of tris-(bathophenanthroline)iron(III) complex, [Fe(bathophen)₃]³⁺. The complex was prepared in situ by mixing hexakis(N,N-dimethylformamide)iron(III) perchlorate with bathophen-anthroline (systematic IUPAC nomenclature: 4,7-diphenyl-1,10-phenanthroline) in the molar ratio of 1 : 3. The equilibrium constant for was 3.12×10³ L³ mol⁻³. The transfer constant for bathophenanthroline was found to be 0.38 ± 0.01 for the styrene/DMF system at 60°C. Mean velocity constant at 60°C for interaction of polystyryl radical with [Fe(bathophen)₃]³⁺ was 3.73× 10⁴ L mol⁻¹ s⁻¹. © 1996 John Wiley & Sons, Inc.     

纳米PANI-DBSA/EA/PU互穿网络导电膜的制备及其性能

用原位乳液聚合法在环氧丙烯酸树脂(EA)中合成了十二烷基苯磺酸掺杂的纳米聚苯胺(PNAI-DBSA),纳米PNAI-DBSA/EA混合物与蓖麻油聚氨酯(PU)预聚体、交联剂(苯乙烯、丙烯腈)等混合后,在引发剂过氧化苯甲酰(BPO)的作用下形成了纳米PANI-DBSA/EA/PU互穿网络导电复合膜。通过测定电导率和拉伸强度,研究了PANI-DBSA含量、交联剂及偶联剂的种类和用量以及BPO用量对复合膜导电和力学性能的影响。结果表明:在PANI-DBSA含量为12.5%、苯乙烯含量为60%、KH-550用量为3%、BPO用量为0.4%时,复合膜的电导率达2×10 ^-5 S/m,拉伸强度为15.8 MPa。     

Synthesis of poly(epichlorohydrin‐g‐methyl methacrylate) and poly(epichlorohydrin‐g‐styrene) graft copolymers by a combination of cationic and photopolymerization methods

Poly(epichlorohydrin‐g‐styrene) and poly (epichlorohydrin‐g‐methyl methacrylate) graft copolymers were synthesized by a combination of cationic and photoinitiated free‐radical polymerization. For this purpose, first, epichlorohydrin was polymerized with tetrafluoroboric acid (HBF₄) via a cationic ring‐opening mechanism, and, then, polyepichlorohydrin (PECH) was reacted ethyl‐hydroxymethyl dithio sodium carbamate to obtain a macrophotoinitiator. PECH, possessing photolabile thiuram disulfide groups, was used in the photoinduced polymerization of styrene or methyl methacrylate to yield the graft copolymers. The graft copolymers were characterized by ¹H‐NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Features of the enzymatic hydrolysis of castor oil

Ricinoleic acid, which is used in medicine and veterinary science and is the initial material in the organic synthesis of various valuable products, is obtained via the hydrolysis of castor oil. The enzymatic hydrolysis of castor oil, which allows us to conduct the process under mild conditions (in the temperature range of 35–45°C and without high pressures) is a promising method for obtaining ricinoleic acid. This work demonstrates the feasibility of the enzymatic hydrolysis of castor oil with lipase from Candida rugosa in oil-water systems without an emulsifier. We propose a method for hydrolysis without emulsifiers, simplifying the process of isolating the target product (a mixture of free fatty acids in which ricinoleic acid predominates) and thus the relevant technology. The catalyst that we use ensures the environmental friendliness of the process. Our selection of the experimental conditions for hydrolysis resulted in a 47% yield of fatty acids.     

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

Hydroxylamine 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.