Wilma J. Schneider

Polyester amides from linseed oil for protective coatings

The sodium alkoxide-catalyzed reaction of linseed oil or linseed methyl esters with diethanolamine produces almost exclusively linseed diethanolamides. Reaction conditions, e.g., temperature, amount of excess diethanolamine and mode of adding reactants, are reported. The best conditions for producing diethanolamide directly from linseed oil (1 mole) required adding oil to the sodium alkoxide in diethanolamine (6 moles) and heating at 110–115C for 35 min. The linseed diethanolamide isolated in 93–95% yield was an amber oil. Progress of the reaction, followed by thin-layer chromatography, showed only trace amounts of byproducts.Polyester amides were prepared by heating linseed diethanolamide in refluxing xylene with dibasic acids or anhydrides, e.g., azelaic, maleic, fumaric, phthalic, terephthalic, itaconic, brassylic and dimer acids. Molecular weight, viscosity and film properties (air-dried and baked) of the polyester amides were determined.

Polyesteramides from linseed oil for protective coatings low acid-value polymers

Linseed and soybean diethanolamides, from the sodium alkoxide-catalyzed reaction of the corresponding oil with diethanolamine, were used as diols to prepare a series of polyesteramides. The diols and dibasic acids or anhydrides were heated in refluxing xylene until the theoretical amount of water was collected in a trap. Low acid-value linseed polymers were prepared with 10, 20, and 30 mole percent excess diol over the dibasic acid, and the effect of the excess diol on molecular weight, viscosity, and film properties of the polymers was examined. Polyesteramides which contained 10 mole percent excess fatty diethanolamide were made with 11 dibasic acids or anhydrides. The polymers were brown-orange oils with Gardner viscosities of Z7 to >>Z10.Number-average molecular weights ranged from 2,200 to 5,200. Data on drying characteristics, hardness, and chemical resistance of films were obtained. The better polymers air-dried rapidly to give hard, glossy films (Sward rocker 20–60). Films baked at 190C for 10 min were softer than the corresponding air-dried films. Xylene resistance of soybean and linseed polymer films was generally excellent, and alkali resistance was moderate. Soybean films showed the better alkali resistance.

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.

Polyesteramides from linseed and soybean oils for protective coatings: Diisocyanate-modified polymers

New polymeric coating materials have been prepared by a triethylenediamine-catalyzed reaction of hydroxyl-terminated polyesteramides (HTPA) from soybean or linseed oils with diisocyanates. Eight dibasic acids or anhydrides were reacted with excess N,N-bis(2-hydroxyethyl) fatty amide to yield HTPA; those containing 10 mole per cent excess gave isocyanate-modified polymers with best overall film properties. Reactivity of four diisocyanates with a linseed-HTPA was measured by disappearance of the isocyanate band in the infrared. Depending on chemical composition, structure and curing conditions, films prepared from these polymers have a wide range of drying characteristics, hardness and chemical resistance. Drying times of linseed HTPA-urethane polymer films varied from 0.3 to 48 hr, hardness values (Sward) were from 4 to 70, alkali resistance ranged from 2 to 126 min and the hydrochloric acid and xylene resistances were good to excellent. Impact resistance exceeded 160 in.-lb for all films except two. The soybean-derived polymer films likewise exhibited a wide range of properties; they chiefly differed from linseed-derived films in having greater flexibility and improved alkali resistance.

Composition of methyl esters from heat-bodied linseed oils

Two heat-bodied linseed oils, with Gardner viscosities of 37 and 55 min, were saponified, converted to their methyl esters, and separated into 2 fractions with urea and methanol. Gas-liquid chromatography showed the adduct fraction, which comprised 38–41% of the total methyl esters, to contain: palmitic, stearic, oleic, “linoleic,” and trace amounts of “linolenic” acid. The nonadducting fraction (59–62%) of the total methyl esters was separated by molecular distillation at 140C/7 μ into a distillate and residue. The distillate amounted to 18–25% of the total methyl esters and had an iodine value (I.V.) of 142–145; its absorption at 232 mμ indicates 2.5–3.0% conjugated diene. Hydrogenation of this distillate gave a liquid product with an iodine number of 4 and a pour point of −50C. Gas chromatograms of the distillate and its hydrogenated derivative indicated at least 5–7 components. Comparison of these peaks with known fatty acid methyl esters indicates that the components of these fractions were either cyclic or branched esters. The nonadducting residue fraction was composed mainly of polymeric acids.

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.

Reactions of unsaturated fatty alcohols. V. Preparation and properties of some copolymers of unsaturated fatty vinyl ethers with lower alkyl vinyl ethers

SummarySoybean vinyl ethers derived from soybean alcohols were copolymerized with lower alkyl vinyl ethers,e.g., ethyl, butyl, isobutyl, 2-chloroethyl, 2-methoxyethyl, and 2-ethylhexyl, in methylene chloride at −30°C., using boron trifluoride etherate catalyst. Molecular weights ranging from 2,000 to 4,000 were obtained on these copolymers by cryoscopic measurements in cyclohexane. An analytical method, using infrared spectroscopy, was employed to determine the composition of the copolymers.The properties of each alkyl-soybean vinyl ether copolymer were studied at three molar compositions,e.g., 3∶1, 1∶1, and 1∶3. The products were water-white to amber viscous liquids and were soluble in aromatic, chlorinated, and gasoline type of solvents.Copolymers films were prepared under conditions that were shown to produce extensive degradation of some homopolymer films in order to magnify small differences in properties. These films were hard, wrinkle-free, and resistant to most common solvents, also were 20 to 500 times more resistant to 5% aqueous alkali than soybean vinyl ether polymer prepared under the same conditions.Copolymer films were baked on silver chloride plates and examined in the infrared. Oxidative degradation of the C−O−C ether linkage was observed in all copolymer films; however the 2-chloroethyl-soybean copolymer series was least susceptible to this degradation.

Reactions of unsaturated fatty alcohols. III. Viscosity and molecular weight studies on some vinyl ether polymers

SummaryMolecular weights of the polymers of the vinyl ethers of stearyl, soybean, and linseed fatty alcohols were measured cryoscopically in cyclohexane at three different concentrations. Corrected number-average molecular weights were obtained by extrapolation to zero cocentration. For each family of polymers a series of preparations varying in degree of polymerization were studied with number-average molecular weights ranging from 1,500 to 15,000 or higher.Reduced viscosity measurements at 25°C. were made on benzene solutions of each polymer preparation at three different concentrations. Intrinsic viscosities were obtained by extrapolating to zero concentration. Intrinsic viscosities for the polymers range from 0.05 to 0.20.Logarithmic plots of molecular weightvs. intrinsic viscosity gave linear relationships for stearyl, soybean, and linseed polymers. Values forK′ anda in the equation of Mark and Houwink were obtained from these plots.

Reactions of unsaturated fatty alcohols. XIV. Preparation and properties of styrenated fatty vinyl ether polymers

New polymeric products have been prepared from conjugated linseed vinyl ether polymers and styrene. Up to 64% by weight of styrene can be incorporated by heating the preformed fatty vinyl ether polymer and monomeric styrene in an aromatic solvent. Primary factors influencing the course of the reaction were molecular weight and peroxide content of the starting vinyl ether polymer, reaction temperature, and type of solvent used. Formation of heterogeneous reaction products and gelation were encountered unless styrene was consumed in the reaction or removed.Films of these styrenated vinyl ether polymers show improved properties over the homopolymers previously studied. Baked films exhibit better gloss, color, and hardness; are more throughly cured; and show good flexibility and adhesion. Their resistance to 5% aqueous alkali is outstanding. The films also exhibit air-drying properties.Fatty vinyl ether polymers and copolymers have shown only limited compatibility with commericial resins. However, styrenated polymers are compatible with long oil alkyd, urea, epoxy, hydrogenated rosin, and polyurethane resins.

Reactions of unsaturated fatty alcohols. XV. Styrentation of fatty vinyl ether polymers in terpene solvents

Styrenation of fatty vinyl ether polymers in dipentene at 145–165C gives products containing from 20 to 67% styrene by weight but little or no unreacted monomeric styrene remained. After 27 mounths no gelation occurred in these products. Apparently dipentene serves as an effective chain transfer agent during styrenation, keeps the growing polymer chains short, and reduces crosslinking reactions. The amount and type of unsaturation needed in the fatty side chains of the polymer to produce homogeneous products were studied. Ultraviolet and infrared analyses were useful in determining the function of unsaturation in these reactions.Tests on baked films from these products showed that as the amount of styrene was increased, both hardness and alkali resistance were significantly increased. Films prepared from products containing 34 and 67% styrene had Sward hardness values of 10 and 60, and alkali resistance of 33 days and over 65 days, respectively. Films from products prepared in aromatic solventsversus dipentene at the same styrene level showed no difference in hardness, but the alkali resistance of the “dipentene film” was greater.