Reaction of Maleic Anhydride with Unsaturated Fatty Acids in the Presence of Organic Peroxides

Nagakura, Minoru; Yoshitomi, Kazuhiko

doi:10.5650/jos1956.21.83

Cited by 4 publications

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“…The increased viscosity is most likely due to an increase in hydrogen bonding as MA is grafted into the TG structure. It is not due to opening of the anhydride ring and copolymerization through reaction of the carboxylic groups as was suggested previously, since esterification of the maleated SO with 1-octanol yielded a product with an acid value of 0.1 and a viscosity of only 200 cP (10).…”

Section: Resultssupporting

confidence: 58%

Free radical meleation of soybean oil via a single‐step process

Tran

Seybold

Graiver

et al. 2005

J Americ Oil Chem Soc

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In this study a new value-added product was developed from soybean oil for use as a chemical feedstock. The investigation and optimization of this work resulted in a fast and simple process to maleate soybean oil. An anhydride functionality was introduced into soybean oil through a free radical-initiated maleation. Two initiators were evaluated, 2,5-bis(tertbutylperoxy)-2,5-dimethylhexane peroxide and di-tert-butyl peroxide. The effects of reaction time, initiator concentration, maleic anhydride concentration, and reaction temperature were investigated. The maleated soybean oil was characterized using acid value, iodine value, and FTIR spectroscopy. The acid value was directly related to the initial concentration of maleic anhydride, whereas the concentration and type of initiator had little effect on the acid value. The peroxide-initiated functionalization of soybean oil with maleic anhydride in a closed vessel at elevated pressure and temperature was found to proceed by a Diels-Alder mechanism.Paper no. J10942 in JAOCS 82, 189-194 (March 2005). KEY WORDS:Free radical initiation, maleation, maleic anhydride, process, soybean oil.As the demand for petroleum exceeds production, alternative feedstocks must be found. Agriculturally based chemicals are one of the most attractive alternatives because they are environmentally friendly chemical feedstocks and offer a sustainable source of development. In previous work, we have reported on the rationale, design, and engineering of biobased materials (1,2). One potential agricultural feedstock is soybean oil (SO), which is a mixture of TG containing long-chain FA. Typically, SO contains 4.3-4.6 double bonds per mole depending on the origin of the seed. The presence of unsaturation allows for chemical modifications through specific reactions with these double bonds and the introduction of reactive carbonyl functional groups. There is a great deal of literature on the functionalization of vegetable oils using maleic anhydride (MA) to enhance their reactivity. Morrel and Samuels (3) studied the reaction between MA and conjugated oil systems using oils from china wood and oiticica containing FA with conjugated double bonds. The reaction was found to follow a typical Diels-Alder addition. Root (4) investigated the functionalization of SO with MA and described the use of benzoyl peroxide in the maleation reaction.He concluded that the use of benzoyl peroxide as a catalyst was advantageous, as it allowed the reaction to proceed at a lower reaction temperature of 110°C as compared with 160-190°C when benzoyl peroxide was not used. Root hypothesized that the presence of a peroxide leads to electron delocalization, resulting in conjugation of the double bonds within the unsaturated FA in the SO to form a conjugated system, as shown in Figure 1. However, the mechanism of MA addition to SO and the products of this reaction are still ill defined and are the subject of a great deal of debate in the literature. Clocker (5) postulated a cyclobutane structure for oleic acid adducts. Bickf...

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Section: Resultssupporting

confidence: 58%

Free radical meleation of soybean oil via a single‐step process

Tran

Seybold

Graiver

et al. 2005

J Americ Oil Chem Soc

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“…Reactions of maleic anhydride with linoleic and oleic acid in the presence of organic peroxide were investigated by Nagakura and Yoshitomi 11. Di‐ tert ‐butyl peroxide and dicumyl peroxide were the best initiators of the maleinization reaction at 130°C.…”

Section: Resultsmentioning

confidence: 99%

Polymerization of maleic anhydride–modified plant oils with polyols

Eren

Küsefoǧlu

Wool

2003

J of Applied Polymer Sci

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ABSTRACT:In this study soybean oil triglycerides were reacted with maleic anhydride in an ene reaction to introduce more than two maleate residues per triglycerides. The maleinized soybean oil (SOMA) was then polymerized with diols to the half-ester stage only. Two different types of alcohols was used in this work: (1) short-chain polyhydroxy linear or cyclic alcohols having 2, 3, 4, or 6 hydroxyl groups; and (2) long-chain dihydroxy alcohols. The aim was to determine the effect of functionality and chain length by choosing alcohols with increasing number of hydroxyl groups and different chain lengths. The reaction of alcohols with anhydride functionalized soybean oil to give a polymeric halfester is a reaction that proceeds without the formation of byproducts and is different from complete polyesterification of maleinized oils, which are well known. To improve the reaction yields, different catalysts and different reaction conditions were examined. The structural analysis of the products was done with 1 H-NMR and IR spectroscopy. All of the new polymers obtained were resilient and soft rubbers at room temperature. Castor oil polymer mixed with 60% CaCO 3 and 12% cork powder gave a resilient and nontacky linoleum composition.

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“…Although the reaction of maleic anhydride with soy oil to yield MSO has been reported in the literature,16, 17 a recently developed single‐step, free‐radical‐initiated procedure that proceeds smoothly and gives high product yields was used 18. Briefly, the reactions were carried out by the charging of maleic anhydride, soybean oil (or methyl soyate), and L101 into a 2‐L Parr reactor equipped with a motorized stirrer, thermocouple, and heating element.…”

Section: Methodsmentioning

confidence: 99%

Biocomposites synthesized from chemically modified soy oil and biofibers

Tran

Graiver

Narayan

2006

J of Applied Polymer Sci

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ABSTRACT:Composites with good mechanical properties were prepared from chemically modified soy oils and biofibers without additional petroleum-based polymers. These composites were prepared from maleic anhydride and epoxide functionalized soybean oils that were cured in the presence of various biofibers (e.g., kenaf, kayocell, protein grits, and solka-floc) by a flexible amine catalyst. Rigid thermosets characterized by a high-crosslink-density network and a high gel fraction were obtained. Fourier transform infrared was used to follow the cure reaction via the disappearance of the characteristic anhydride adsorptions. Composites with high tensile strength and low elongation were obtained when kenaf fibers were treated with (2-aminoethyl)-3-aminopropyl-trimethoxysilane and then added to the epoxidized/maleated soy matrix and cured with hexamethylenediamine. These biobased composites could provide inexpensive epoxy resin alternatives for a wide variety of industrial applications.

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Reaction of Maleic Anhydride with Unsaturated Fatty Acids in the Presence of Organic Peroxides

Cited by 4 publications

References 0 publications

Free radical meleation of soybean oil via a single‐step process

Free radical meleation of soybean oil via a single‐step process

Polymerization of maleic anhydride–modified plant oils with polyols

Biocomposites synthesized from chemically modified soy oil and biofibers

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