Analysis of Bodied Drying and Semidrying Oils

Cowan, J. C.; Falkenburg, L. B.; Teeter, H. M.

doi:10.1021/i560126a005

Cited by 18 publications

(8 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The reeovered monomer was similarly treated with di-t-butyl peroxide, and the monomer from this second stage was again similarly treated. The results on these three stages of polymerization are summarized in Table I. A composite of the residual dimers from the three stages was distilled in an alembic molecular still to give a distilled dimer fraction (7,8). Figure 1 shows the results of the.…”

mentioning

confidence: 99%

Dimer acid structures. The dehydro‐dimer from methyl oleate and Di‐t‐butyl peroxide

Paschke

Peterson

Harrison

et al. 1964

J Americ Oil Chem Soc

View full text Add to dashboard Cite

The dehydro-dimer of methyl oleate was prepared and its structure determined as a model of a non-ring dimer for reference in studying the structure of other fatty dimer acids.The dehydro-dimer of methyl oleate is formed by the action of all-t-butyl peroxide on methyl oleate. The reaction is stoiehiometric; one mole of DTBP producing one mole of dehydrodimer and two moles of t-BuOH, when excess methyl oleate is used. The dimer was shown to contain two double bonds, and to be formed by carbon-tocarbon linkages predominantly and equally at the 8, 9, 10 and 11 carbons of the oleate monomer segments.l~nsaturation was determined by quantitative hydrogenation and far I?V absorption. The points of linkage were established by diagnosis of the positions of the involved tertiary carbons of the hydrogenated dimer 1) by chemical oxidation, and 2) by mass spectrometry. Positions of the double bonds were determined by quantitative ozonization, reduetive cleavage followed by gas chromatography of the aldehydes and aldehyde esters. Precise molecular weight of the hydrogenated dimer was determined from the parent mass peak at the expected m/e of 594, confirming the non-ring structure. The unhydrogenated dimer showed a parent m/e peak at the expected ~alue of 590.The bridging at the 8 and 10 positions is explained as being due to coupling of radicals with limiting resonance structures resulting from loss of a hydrogen atom from the methylene at position 8. The bridging at the 9 and 11 positions is explained as due to coupling of limiting resonance structures resulting from loss of a hydrogen atom from the methylene at position 11.Mass spectrometric data indicate~ that the dimerization is a coupling of the expected free radical forms, rather than attack by an oleate free radical on the double bond of an intact oleate molecule, with subsequent loss of hydrogen to form the second double bond in the dimer.Coupling at the 2-position (a to COOCHa) occurs in not more than 5-10% of the molecules. A small amount of cyclic dimer may be present.

show abstract

mentioning

confidence: 99%

Dimer acid structures. The dehydro‐dimer from methyl oleate and Di‐t‐butyl peroxide

Paschke

Peterson

Harrison

et al. 1964

J Americ Oil Chem Soc

View full text Add to dashboard Cite

show abstract

“…Polymerized cottonseed oil. An examination of the polymeric material in the acidic products has been made, using the method of Cowan, Falkenburg & Teeter (1944). The methyl ester of the acid was distilled in an alembic-type still under reduced pressure and the distillate collected in small fractions.…”

Section: Experimental and Resultsmentioning

confidence: 99%

Heat transformation products of cottonseed oil

Chalmers

1954

Biochemical Journal

View full text Add to dashboard Cite

1. Preformed mycelial felts of A. niger treated with cyanide at four concentrations between 0-006 and 0-040M, utilized more sugar, synthesized more mycelial substance and formed a greater total of acids (citric, oxalic and gluconic) in a given period than did controls. The most effective concentration used was 0020M.2. In presence of 0-010 or 0-020M cyanide the yields of all products were not only actually greater than with the controls but were also greater when expressed as percentages on the weight of sugar consumed.3. The breakdown of citric acid by A. niger is impeded by cyanide.4. Possible modes of action of the cyanide are discussed.

show abstract

“…Polyesters prepared with polymeric fat acids from linseed oil contain a higher percentage of tribasic fat acids than do the polyesters prepared with polymeric fat acids from soybean oil. This difference arises from the composition of the polymeric fat acids (7). The millable polyesters derived from linseed oil contained 64%.…”

Section: Discussion Of Resultsmentioning

confidence: 99%

Polymerization of drying oils

Cowan¹,

Ault²,

Teeter³

1946

Ind. Eng. Chem.

View full text Add to dashboard Cite

Polyesters of polymeric fatty acids with ethylene glycol may be compounded and cured with sulfur and other conventional reagents to yield a vulcanízate having improved properties as compared with factice. When special effort is made to complete the polyesterification reaction, further improvement in the vulcanízate is achieved. Soybean, linseed, and tall oils are possible raw material sources for this rubber substitute.Evaluation tests indicate that it can be calendered onto cloth, that it has good resistance to oxygen and ozone, and that it has sufficient tackiness for use as an adhesive.THE high price and shortage of natural rubber during certain periods in the last forty years have led to a large number of investigations to find substitutes for the product of the Hevea tree. One phase of investigation has been the attempt to modify vegetable oils by polymerization, sulfurization, and oxidation.A large number of experimental variables, such as catalyst, sulturizing agents, and compounding agents, were studied in an endeavor to improve the basic discovery that vegetable oils will give rubbery products, and a review of the literature was given (15). These studies showed that products possessing high tensile strength but low elasticity could be achieved. All attempts to achieve high elasticity with good tensile characteristics failed. Many research developments in the chemistry of polymeric materials served to emphasize that one requisite of elastomers is that they be composed of long linear chains. The authors believed that if the functionality of a vegetable oil or oil derivative was correctly controlled, a product would be obtained superior in tensile strength and elasticity to any previously known rubberlike materials made from vegetable oils. An investigation of a number of oil derivatives led to a vulcanized polyester of polymeric fatty acids and ethylene glycol. If the polyesterification were carried to a sufficient degree, no special procedures were required to give a vulcanized product. It was necessary to increase the viscosity of polyesters of relatively low molecular weight by heating in air and to give the compounded polyester a precure.The vulcanized product had sufficient strength and elasticity so that its production and use on a large scale was investigated by industrial concerns. THEORETICAL Carothers (5) discussed the possibility that one structural requisite of rubberlike molecules may be long linear chains, and Bradley (2) published some excellent papers and gave other references on the relation of functionality to the polymerization of oils.Our discussion on these two subjects will be limited to the possible production of rubberlike materials from vegetable oils. 1 Northern Regional Polymer. Some of the information contained in this paper was submitted for publication to the director of the Northern Regional Research Laboratory in June, 1942. Publication was stopped by issuance of a secrecy order by the Patent Office, dated July 9, 1942, on a patent application of Cowan and Ault entitled "Pro...

show abstract

Analysis of Bodied Drying and Semidrying Oils

Cited by 18 publications

References 9 publications

Dimer acid structures. The dehydro‐dimer from methyl oleate and Di‐t‐butyl peroxide

Dimer acid structures. The dehydro‐dimer from methyl oleate and Di‐t‐butyl peroxide

Heat transformation products of cottonseed oil

Polymerization of drying oils

Contact Info

Product

Resources

About