Euphorbia and Vernonia seed oil products as plasticizer‐Stabilizers for polyvinyl chloride

120

The kinetics for the epoxidation of methyl esters of palm olein (MEPOL) by peroxyformic acid and peroxyacetic acid generated in situ were studied. The rate-determining step was found to be the formation of peroxy acid. Epoxidized MEPOL (EpMEPOL), with almost complete conversion of the unsaturated carbon and negligible ringopening, can be synthesized by the in situ technique described.The kinetics of the oxirane cleavage of EpMEPOL by acetic acid were studied at various temperatures. The reaction was found to be first-order with respect to the epoxy concentration and second-order to the acetic acid concentration. The activation energy and the entropy of activation for the epoxidation of MEPOL were comparable to those for the oxirane cleavage of EpMEPOL by acetic acid, suggesting that the two reactions are competitive. The success of the epoxidation of MEPOL with only negligible oxirane cleavage is attributed to the heterogeneous nature of the system employed in the in situ technique.

“…Epoxidized soybean oil accounted for about 70% of the total epoxidized esters production (1,2). These epoxy esters have captured about 7% of the total plasticizer market.…”

mentioning

confidence: 99%

Kinetic studies of epoxidation and oxirane cleavage of palm olein methyl esters

Gan

Goh

Ooi

1992

120

“…Referred to collectively as epoxidized esters, three basic groups of epoxidized products are made from vegetable oils: (a) epoxidized triglyceride oils, (b) mixed epoxy fatty esters (e.g., linseedates, tallates) and (e) specific epoxy fatty esters (e.g., oleates, stearates). Their importance as plasticizers and additives in flexible polyvinyl chloride (PVC) resins stems from excellent heat and light stability imparted to the finished products by the oxirane groups (1). Since 1963, production of all such epoxidized esters has ranged from 60 to 150 million lb annually, averaging 7% of the 1 to 2 billion lb of annual plasticizer production ( Fig.…”

Section: Trends In Production Of Epoxidized Estersmentioning

confidence: 99%

“…It is conceivable that Vernonia oil could function as a diluent, pour point depressant or viscosity improver in admixture with other epoxy oils in some applications. Separation of vernolic acid from VO in the form of trivernolin (18) to function well as plasticizer-stabilizers in PVC resins (1,11). Alternatively, the DESt's may be obtained directly from EVO in 90% purity by simple transesterification.…”

Section: Potential Of Vo and Evomentioning

confidence: 99%

See 1 more Smart Citation

Chemical epoxidation of a natural unsaturated epoxy seed oil fromVernonia galamensis and a look at epoxy oil markets

Carlson

Chang

1985

160Since 1963, production of all epoxy esters has ranged from 60 to 150 million lb annually, a steady 7% of ~che 1 to 2 billion lb of annual plasticizer production. Growth rates in production averaged 4.3% for all plasticizers, 3.8% for all epoxy esters and 5.0% for epoxidized soybean oil (ESBO). ESBO accounted for 70-76% of total epoxy ester production (1963)(1964)(1965)(1966)(1967)(1968)(1969)(1970)(1971)(1972)(1973)(1974)(1975)(1976)(1977)(1978)(1979)(1980)(1981)(1982). The natural liquid epoxy oil from Vernonia galamensis seed, with oxirane value (4.1%) and viscosity (100 cps) similar to some commercial epoxy fatty esters but with molecular weight similar to epoxidized vegetable oils, combines some of the properties of both commercial types. Chemical epoxidation of Vernonia oil raises the oxirane content to 8.2, intermediate between ESBO and epoxidized linseed oil (ELSO), while consuming less of the costly epoxidizing reagents. Epoxidation proceeds in stepwise fashion through partially epoxidized products, which are converted to final product. Since the major fatty components of Vernonia oil are ds-12,13-epoxy-9-octadecenoic (75%) and linoleic (13%) acids, further epoxidation produces fatty acids that are specifically epoxidized at the 9,10-and 12,13-positions, and the major product has 6 epoxy units per triglyceride molecule. The resulting mixture of products has compositional and physical properties distinctly different from commercial samples of ESBO and ELSO.

“…Use of vernonia oil for coatings (4) and in the preparation of a variety of polymeric materials, from hard resins to elastomers (5)(6)(7), is feasible. The oil or its derivatives also function well as plasticizer-stabilizers in PVC resins (8)(9)(10)(11)(12). Chemical epoxidation of the oil yields a product that is primarily a hexaepoxy triglyceride {ca.…”

mentioning

confidence: 99%

Pilot plant extraction of oil fromVernonia galamensis seed

Ayorinde

Carlson

Pavlik³

et al. 1990

Vernonia galamensis seed containing 40-42% oil and 30-34% epoxy acid, (c/s-12,13-epoxy-c/s-9-octadecenoic) was processed to oil and meal. Seed conditioning, pressing and solvent extraction research were conducted in pilot facilities at the French Oil Mill Machinery Co. (Piqua, OH). The robust lipase system was successfully inactivated by treating 200 lb. batches of V. galamensis seed in a cooker/conditioner at 195-200~ and >10% moisture. Conditioned seed was mechanically pressed and the press discharge cone setting was varied during operation from 1/32" to 3/32" to demonstrate the feasibility of both full pressing and prepressing. Prepressing successfully reduced oil level in the press cake to ca. 20%. Press cake was extracted with hexane in a 1.5-ft 3 batchtype, four-stage percolation unit with a 6" square extrac~ tion cross section. Solvent extraction reduced oil level in the defatted meal to 1-2%. The defatted meal was desolventized and toasted. Excessive foaming of the vernonia oil extract made complete solvent stripping in the oil stripping unit difficult.KEY WORDS: Epoxy oil, lipase inactivation, mechanical pressing, pilot plant, seed oil, solvent extraction, Vernonia galamensis, vernolie acid.