H. M. Teeter

Polyamides from polymeric fat acids

SummaryThe preparation and properties of various polyamides, copolyamides, and modified polyamides, of polymeric fat acids have been described. These polymers are of interest because of their unusual properties and because of the unsaturation and relatively high molecular weight of the polybasic acids involved. Despite the presence of tribasic acids in polymeric fat acids, ungelled polymers having molecular weights of 3,000 to 5,000 are obtainable. A brief discussion has been given concerning the application of theoretical principles of polymerization to the preparation of these polymers. Possible industrial uses for the polyamides are indicated.

Ozonization of soybean oil. The preparation and some properties of aldehyde oils

A polyaldehydie product called aldehyde oil was prepared by the ozonization of soybean oil, followed by reductive decomposition of the ozonolysis products. Reductive decomposition by chemical means gave 85–90% yields of carbonyl in the aldehyde oil. Catalytic reduction gave 75–80% yields. Partially-hydrogenated soybean oil gave more efficient results than did unhydrogenated oil. The polyfunctional aldehyde oil was found to undergo condensation reactions with phenolic compounds, urea, amines, and polyols to give cross-linked polymers.

Reactions of unsaturated fatty alcohols. I. Preparation and properties of some vinyl ethers

SummaryA number of vinyl ethers of C18 fatty alcohols have been prepared by reaction of the alcohol with acetylene at atmospheric pressure in the presence of a basic catalyst. Infrared spectroscopic data on long-chain fatty alcohols, their vinyl ethers, and related chemical derivatives have been obtained. Methods of analysis of long-chain vinyl ethers for vinyl group have been developed, namely, iodometric, hydroxylamine, and infrared methods.Preliminary experiments on the polymerization of long-chain vinyl ethers with ionic catalysts were carried out.

Polymerization of drying oils. VI. Catalytic polymerization of fatty acids and esters with boron trifluoride and hydrogen fluoride

SummaryAt relatively low temperatures boron trifluoride and hydrogen fluoride gave high yields of polymers from soybean fatty acids and methyl esters.The use of 2% boron trifluoride as catalyst at 150° to 200° resulted in the polymerization of 50–60% of the methyl esters within one hour. The viscous polymeric fraction usually had a dark color, a high acid number, and a low ratio of dimer to higher polymer.The boron trifluoride-ether complexes were equally effective catalysts and more convenient to handle. Use of the aliphatic ether complexes resulted in products having lighter colors.It was necessary to use large amounts of hydrogen fluoride to produce comparable yields at less than 100°, but 70% yields of polymers having light colors and low acid numbers were obtained.

Reactions of conjugated fatty acids. V. Preparation and properties of diels-alder adducts and their esters fromtrans,trans-conjugated fatty acids derived from soybean oil

SummarySoybean fatty acids were conjugated with alkali, and the contained, conjugated dienoic acids were isomerized with iodine to thetrans,trans configuration. Adducts were prepared from thesetrans,trans-conjugated acids by condensation with maleic anhydride and acrylic acid. The adducts were isolated, purified, and converted to esters by using a variety of alcohols, including methyl, ethyl,n-propyl,n-butyl, and allyl alcohols. Esters made from saturated alcohols were converted into the corresponding epoxy derivatives.All of the esters (except allyl) and all of the epoxy esters were compatible with an equal weight of polyvinyl chloride and appeared to be primary plasticizers for this plastic. The epoxy esters were effective in inhibiting heat deterioration of polyvinyl chloride.

Reactions of unsaturated fatty alcohols. II. Polymerization of vinyl ethers and film properties of polymers

SummaryVinyl ethers of stearyl, soybean, and linseed fatty alcohols have been prepared and polymerized in solution in hydrocarbon or chlorinated solvents at temperatures down to −30°C. with several Lewis-acidtype catalysts. Stearyl polyvinyl ether was a white, waxy solid melting at 44°–50°C. while soybean and linseed polyvinyl ethers were colorless, viscous liquids. Molecular weights of these polymers range from 1,500 to 15,000 and higher, depending on the conditions of polymerization.Films of soybean and linseed polyvinyl ethers containing driers were cast from toluene solution. Hard films were obtained with cobalt drier by baking at 150°C. while softer films were obtained under these conditions when lead driers were used.Soybean films containing cobalt drier and baked on Pyrex glass dissolved completely in 5% aqueous alkali. A fatty acid coresponding to the fatty alcohol side chain was isolated from this solution along with a material that appeared to be partially oxidized polyvinyl alcohol. Baked films of soybean polyvinyl ether with lead drier did not dissolve in alkali. Some improvement of alkali resistance was obtained with cobalt films by adding aromatic amines as antioxidants. Soybean polymer films containing cobalt and baked on soft glass or metal surfaces were resistant to 5% aqueous alkali for at least three days.Soybean polyvinyl ether was emulsified with an equal weight of water, using ammonium salts of fatty acids as emulsifiers. Films were prepared from this emulsion that appeared to be continuous.

A convenient laboratory method for preparingtrans, trans-9, 11-octadecadienoic acid

A convenient laboratory method to preparetrans,trans- 9,11-octadecadienoic acid (TTA) via a polyester intermediate is described. Ricinelaidic acid was heated at 235C under vacuum for 3-4 hr to form a polyester having a mol wt of 1,500-1,600. Pyrolysis of this polyester and simultane-ous distillation of the products gave crude dehy-drated acids. TTA was crystallized from a 95% ethanol solution of these acids, in a yield of 35%. Of the variables affecting pyrolysis, the mol wt of polyester had the greatest effect on yield of TTA.

Unsaturated aldehyde oils by the partial ozonization of soybean oil

Aldehyde oils containing an average of one or two aldehyde groups per glyceride molecule were prepared by partial ozonization of soybean oil. Ozonization was carried out in ethyl acetate-methanol solvent, and reduction of the ozonolysis products was done catalytically with palladium on charcoal in the presence of pyridine. Under these conditions, maximum conversion of unsaturated to carbonyl functionality was achieved without saturation of the unozonized double bonds. The products were oils having three different types of functionality: aldehydic, olefinic, and glyceride ester.

Reactions of unsaturated fatty alcohols. VII. Polymerization of vinyl ethers catalyzed by stannic and ferric chlorides

SummaryVariables affecting the use of stannic chloride as a catalyst for initiating polymerization of conjugated and nonconjugated soybean vinyl ether were studied. Molecular weight of the polymers increased with an increase in catalyst and a decrease in initiation temperature, and it decreased when the amount of moisture in the solvent, the amount of free fatty alcohol in the monomer, or the ratio of solvent to monomer was increased. Aromatic and aliphatic hydrocarbon solvents were superior to halogenated solvents for conducting polymerizations. Similar results were obtained with nonconjugated monomers except that viscosities of the polymers were considerably lower than those of polymers of the same molecular weight obtained from conjugated monomer.To obtain polymers suitable for film-forming studies (4,000–6,000 molecular weight) polymerization is initiated preferably at 25°C. with 3 ml. of anhydrous toluene used per gram of monomer and 4.8 mmoles of stannic chloride per mole of monomer. Monomer purity should be at least 98%.Ferric chloride hexahydrate initiated polymerization at 25°, but polymerization was incomplete, and the polymers had relatively low molecular weights.

Reactions of conjugated fatty acids. VI. Selenium catalysis, a method for preparing diels-alder adducts from cis,trans-octadecadienoic acid

SummaryAdducts of dienophiles and alkali-conjugated safflower fatty acids containing conjugated linoleic acid in thecis,trans form were prepared by heating the reactants in the presence of selenium as a catalyst. The products appeared to be identical to those prepared fromtrans,trans conjugated linoleic acid so that isomerization ofcis-trans totrans,trans acids is eliminated as a separate step. Although yields of pure product were lower than desired because of difficulties in removing selenium, yields of crude adducts ranged from 64–82%. The adducts obtained could be epoxidized with hydrogen peroxide and an ion-exchange resin as catalyst in 80–93% yield or with peracetic acid in 89–98% yield.