Vinyl Stearate Research Articles

Copolymerisation of Vinyl Stearate with Other Fatty Vinyl Monomers

AbstractHomopolymerisation of vinyl stearate and its copolymerisation with five other fatty vinyl monomers have been carried out in benzene using benzoyl peroxide as the initiator. The comonomers included stearyl acrylate, stearyl methacrylate, allyl stearate, stearyl vinyl ether and divinyl sebacate. Stearyl acrylate and stearyl methacrylate furnished copolymers with inherent viscosities much higher than that of the vinyl stearate homopolymer while allyl stearate and stearyl vinyl ether gave copolymers with inherent viscosities much lower than that of the vinyl stearate homopolymer.

Chain transfer constants for vinyl monomers polymerized in methyl oleate and methyl stearate

AbstractChain transfer constants were obtained for styrene, methyl methacrylate, methyl acrylate and vinyl acetate, polymerized in methyl oleate and methyl stearate at 60°C. Transfer constants increased in the order: methyl methacrylate < styrene < methyl acrylate ≪ vinyl acetate in both solvents. Average values of the transfer parameters were: for methyl oleate, Qtr = 2.04 × 10−4, etr = 1.08; for methyl stearate, Qtr = 0.373 × 10−4, etr = 1.01. Indication that polar species predominate in the transition state is supported by the observed order of reactivity. The usual rate dependence appeared to be followed by all of the monomers except vinyl acetate, which was retarded, severely in methyl oleate. Transfer in methyl oleate was about 5.8 times greater than that found in methyl stearate for these four monomers. The internal allylic double bond of methyl oleate had about the same reactivity in transfer as had the terminal unsaturation in N‐allylstearamide at 90°C. Rough estimates were obtained of the monomer transfer constants for the long side‐chain homologs of these four monomers from the respective monomer transfer constants and the experimental transfer constants, corrected for transfer to the labile groups of the solvent. It was concluded that the rate of polymerization would determine in large measure the degree of polymerization for the reactive 18‐carbon homologs but that the molecular weight of poly(vinyl stearate) and (oleate) will be regulated primarily by transfer to monomer.

Emulsion polymerization of vinyl stearate

AbstractThe polymerization of vinyl stearate in aqueous emulsions with a non‐ionic emulsifying agent and potassium peroxydisulfate as initiator has been investigated by use of a dilatometric method to follow the reaction. In general, the reaction kinetics do not follow the pattern established for styrene. Variation of initiator concentration produced latices containing approximately equal numbers of latex particles, even though the rate of reaction was almost directly proportional to the peroxydisulfate concentration. For a given initiator and monomer concentration polymerization occurs very slowly when the monomer is completely solubilized but as the number of micelles is reduced and the number of emulsion droplets increased, the rate increases to an optimum value, whereafter it decreases. A mechanism is proposed by which the sparsely soluble vinyl stearate reacts and redistributes itself into latex particles of a different size range from the micelles and emulsion droplets originally present.

The Use of Unsaturated Hydrocarbons as Boundary Lubricants for Stainless Steels

Friction and wear experiments with 1-cetene and cetane on stainless steel demonstrated the effect of a carbon-carbon double bond in the boundary lubrication of stainless steel. Experiments with cold-rolled steel, nickel, and chromium indicated the chromium to be the constituent in the steel that is markedly affected. The use of the unsaturated 1-cetene resulted in a lowering of the friction coefficient and the wear over its saturated analog, cetane. It is postulated that the improvement in friction and wear observed using the olefin 1-cetene is due to chemical attachment to the chromium or chromium oxide present in the wearing surface of the stainless steel reducing the amount of intermetallic contact. Experiments using the pure polar olefin vinyl stearate as the lubricant resulted in even further improvement of the frictional properties of stainless steel rubbing surfaces than the olefin alone, and a mechanism is proposed. It is also shown that these same improvements in frictional properties can be obta...

Determination of the solubility of vinyl stearate in water by a monolayer technique

The surface activity of vinyl stearate has provided a method for determining its solubility in water to be 0,7±0,2×10−6 mole/litre. The methods described above could be used to determine the solubility in water of any sparingly soluble surface active compound, such as stearic acid or cetyl alcohol, which formed a stable monolayer at theA/W interface. Method A could be used for compounds with a solubility as low as 10−5 mole/litre where as for Method B solubilities as low as 10−7 mole/litre could be measured.

Proton magnetic resonance of poly(ethyl acrylate), poly(butyl acrylate), poly(ethyl vinyl ether), poly(vinyl propionate), poly(vinyl stearate), and vinyl stearate from 77°K

AbstractMolecular motion in one monomeric and five polymeric materials was investigated by means of broad line nuclear magnetic resonance (NMR) measurements, the widths and second moments of the resonant absorption lines being obtained at temperatures from 77 to 280–340°K. The materials investigated were: poly(ethyl vinyl ether), poly(ethyl acrylate), poly(vinyl propionate), poly(butyl acrylate), vinyl stearate, and poly(vinyl stearate).

Free Radical Cross-Linking of Synthetic Polymers on Cotton Textiles

A variety of saturated thermoplastic polymers have been cross-linked as interfiber coatings on cotton fabric, without the cotton cellulose. the polymer with catalytic amounts of benzoyl peroxide or 2,4-dichlorobenzoyl peroxide on fabric at 100-165° C caused fixation of the coatings within a few minutes. Polyvinyl esters, acetals and ethers, and linear aliphatic polyesters were used. Copolymers of vinyl chloride with vinyl esters and with alkyl acrylates were also found applicable. The efficiency of polymer insolubility was 60-80% and was independent of the fabric used. whether cotton, glass, paper. Orlon,2 nylon, Dacron,3 or acetate rayon, Grafting of polymer to substrate apparently did not occur. Multiple layers of cross-linked coatings were readily formed. Application of poly(vinyl stearate) at add-ons of 4-30% imparted considerable water repellency to cotton and moderately increased the flex abrasion re sistance, while leaving air permeability, breaking strength, and tearing strength essen tially unchanged, Most of the polymer was located in interfiber spaces within individual yarns. Protection of interfiber bonding in cellulose from disruption by water occurred when cross-linked vinyl chloride-alkyl acrylate coatings were used.

Crystallinity of poly(vinyl stearate)

Journal of Polymer Science Part B: Polymer LettersVolume 2, Issue 1 p. 31-33 Article Crystallinity of poly(vinyl stearate) D. A. Lutz, D. A. Lutz Eastern Regional Research Laboratory, Eastern Utilization Research and Development Division Agricultural Research Service, U.S. Department of Agriculture, Philadelphia, PennsylvaniaSearch for more papers by this authorL. P. Witnauer, L. P. Witnauer Eastern Regional Research Laboratory, Eastern Utilization Research and Development Division Agricultural Research Service, U.S. Department of Agriculture, Philadelphia, PennsylvaniaSearch for more papers by this author D. A. Lutz, D. A. Lutz Eastern Regional Research Laboratory, Eastern Utilization Research and Development Division Agricultural Research Service, U.S. Department of Agriculture, Philadelphia, PennsylvaniaSearch for more papers by this authorL. P. Witnauer, L. P. Witnauer Eastern Regional Research Laboratory, Eastern Utilization Research and Development Division Agricultural Research Service, U.S. Department of Agriculture, Philadelphia, PennsylvaniaSearch for more papers by this author First published: January 1964 https://doi.org/10.1002/pol.1964.110020108Citations: 36AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume2, Issue1January 1964Pages 31-33 RelatedInformation

Preparation and polymerization of vinyl 12‐hydroxystearate

AbstractVinyl 12‐hydroxystearate was prepared from 12‐hydroxystearic acid by vinyl interchange procedure with vinyl acetate. In the reaction, no products having a free hydroxyl group were obtained. The main addition product had the 1‐alkoxyethyl acetate structure. Vinyl 12‐hydroxystearate was obtained by the treatment of this addition product with acid washed activated alumina in ether solution. Vinyl 12‐hydroxystearate polymerized in an emulsion system at a pH of 7–8.5 with standard free radical initiation to give a colorless solid polymer (softening range was 71–75°C.). Vinyl 12‐hydroxystearate was copolymerized with vinyl acetate, vinyl stearate and vinyl chloride and the copolymers thus obtained have been characterized.

Some polymers and copolymers of vinyl ketostearates

AbstractVinyl esters of 4‐ketostearic acid, 9(10)‐ketostearic acid, and 12‐ketostearic acid have been homopolymerized and copolymerized with vinyl chloride. Reactivity ratios have been determined for the three vinyl ketostearates with vinyl acetate and vinylidine chloride. Also reactivity ratios for the 4‐ and 10‐ketostearates with vinyl chloride and those of the 9(10)‐ketostearates and 12‐ketostearate with acrylonitrile were determined. The mechanical properties of typical vinyl chloride‐vinyl ketostearate copolymers have been examined and compared with a similar vinyl chloride‐vinyl stearate copolymer and with a plasticized vinyl chloride‐vinyl acetate copolymer. The copolymers of vinyl chloride with vinyl 9(10)‐ketostearate and with vinyl 12‐ketostearate compare favorably with the compolymer of vinyl chloride and vinyl stearate in general properties.

Radiation crosslinking of vinyl chloride–vinyl stearate copolymer

AbstractThe crosslinking of internally plasticized polyvinyl chloride–stearate copolymer by irradiation with high‐energy electrons was studied. Based on gel yields and swelling as a measure of relative crosslinking, the effect of added tetra‐functional monomers, and of carbon black and silica fillers are discussed. Crosslinking by dicumyl peroxide a t 170°C. even in the presence of a stabilizer, causes concurrent decomposition (dehydrochlorination) which is avoided in the radiation‐crosslinking process. The heat stability of the copolymer is not impaired by radiation crosslinking under the proper conditions. Results of tensile measurements a t 25 and 150°C. are given for the radiation‐crosslinked copolymer with and without filler reinforcement.

Dielectric Behavior and Crystal Structure of Ethyl and Vinyl Stearate

Measurements of the real (ε′) and imaginary (ε″) components of the complex dielectric constant have been made on ethyl and vinyl stearate and on mixtures of ethyl stearate in n-heneicosane at temperatures from +60° to —80°C and over a frequency range from 100 to 50 000 cps. A relaxation dispersion region, which was similar in shape and position for all samples, occurred below 0°C for the frequency range considered here. The magnitudes of the dispersions were found to be greater the more quickly the samples were frozen, and very much reduced for samples crystallized from acetone. Annealing of the solid samples at temperatures as low as 20 centigrade degrees below the freezing points resulted in a gradual decrease in polarization. Cooling curve data was obtained in order to supplement the above work. The results suggest that the molecular rotations involved in the observed solid state dispersions are associated with metastable crystal structures and that, in particular, the decrease in polarization with time is due to a gradual transformation in parts of the sample from a vertical to a tilted crystal structure.

Crystalline Transitions and Mechanical Resonance Dispersion in Vinyl and Ethyl Stearate

Dynamic shear compliance measurements on vinyl and ethyl stearate yield results depending critically on the particular crystalline modification in which these materials exist at the time of measurement. When first crystallized from the melt the materials are in a metastable state and only a few very small resonance dispersions are found in the range 50 to 5000 cps. At later times many large resonances occur; the largest is in the vicinity of 300 cps for both vinyl and ethyl stearate. While vinyl stearate is in its metastable state (about 60 days) a reversible transition takes place at 24.85±15°C such that above this temperature there are no resonances from 50 to 600 cps, but below the transition point the large resonance near 300 cps always appears. A break in the slope of density-temperature curves for vinyl stearate occurs between 25 and 24°C indicating that a transition occurs in the vinyl stearate while in its β form (with the molecules tilted with respect to the planes formed by the terminal groups). X-ray powder diffraction photographs show no changes in the long spacing between planes so the transition must involve alterations in cross-sectional packing of the chains or a change from a monoclinic to triclinic unit cell rather than a variation in angle of tilt. While the details of the crystalline modification at 24–25°C are not as yet sufficiently clear to define a specific mechanism for the resonance phenomena, the results do prove conclusively that the dispersions are intimately connected with the crystalline state of the material. Eventually a kind of mechanical spectroscopy may be evolved yielding information on the actual crystalline state of solids in much the same way that electromagnetic spectra now aid in determinations of molecular structures.

Surface films of vinyl stearate, cetyl-vinyl ether, and their polymers

Monolayers of vinyl stearate and cetyl-vinyl ether, spread at an air/water interface on substrates of different acidity (0.005 N-5 N HCl), have been examined by the techniques of surface pressure, surface potential, and surface moment. The vinyl compounds were chosen as representative of monomers subject in the one case to free radical polymerization, and in the other to cationic polymerization. Parallel studies of the corresponding saturated compounds, ethyl stearate and cetyl-ethyl ether, permitted an analysis of the influence of the double bonds in the vinyl compounds. All four compounds gave condensed films at 25°C. As compared with the corresponding saturated compound vinyl stearate was found to have a substantially higher and cetyl vinyl ether a substantially lower, surface moment. In the case of cetyl vinyl ether the surface moment was very sensitive to the acidity of the substrate. These results show that the vinyl groups affect the properties of the monolayers in a way which can be related to the interaction of the adjacent polar groups with the double bonds. Polymers of the two monomer species were also prepared and examined as monolayers, the results being interpreted in terms of the structure and orientation of the monomer units.

Copolymers of vinyl alcohol and vinyl stearate

AbstractCopolymers of vinyl formate containing various amounts of vinyl stearate were prepared by mass polymerization at 30°C. in the presence of small amounts of isopropanol. A study of the molecular weights and the viscosity properties of these copolymers indicated that they have high degrees of polymerization and are little branched. A study of the x‐ray diffraction patterns of the copolymers of vinyl alcohol and vinyl stearate indicated that the alcohol and stearate segments crystallize in separate lattices. The tensile strength of vinyl alcohol copolymers decreased as the vinyl stearate content increased and as their water content increased. When the samples were dried or were oriented, their tensile strengths increased. Copolymers of vinyl alcohol containing as little as 1.5 mole‐% of vinyl stearate had greatly improved resistance to water and were insoluble in water at 98°C.

The kinetics of the heterogeneous hydrolysis of poly(vinyl formate) and of poly(vinyl formate‐co‐stearate)

AbstractThe rate of hydrolysis of formate and stearate segments from poly(vinyl formate) and from poly(vinyl formate‐co‐stearate) suspended in dilute aqueous hydrochloric acid was studied. Evidence was presented to show that the hydrolysis follows pseudo‐first‐order kinetics. The Arrhenius constants and the entropies and free energies of activation for the hydrolysis of formate and stearate groups from copolymers containing 0, 3, 5, and 10 mole‐% vinyl stearate were calculated from the partially reduced reaction rate constants at three temperatures. For the hydrolysis of formate segments, ΔS‡ is markedly affected by the stearate content, whereas the variation in ΔF‡ is small. Variations in vinyl formate content have smaller effects on the thermodynamic constants of the activated complex for the hydrolysis of the stearate segments. At approximately 95°C., some anomalous kinetic behavior was observed.

Polymerization of vinyl stearate by high energy electrons

AbstractVinyl stearate has been polymerized by 1000 kv. electrons with field intensities ranging from 1.0 × 103 to 20 × 103 rep per second; the polymers are considered to be branched. A discontinuity of reaction rate and molecular weight with respect to temperature was noted in the vicinity of monomer melting point, and it is suggested that in this temperature region, the diffusion constant for propagation is easily affected. A linear relationship between field intensity and polymerization rate, and a constancy in molecular weight with varying field intensities, at constant total dose, indicated that polymerization occurs in “volume elements.”

Reactivity ratios for vinyl stearate–vinyl acetate copolymers

Reactivity ratios for vinyl stearate–vinyl acetate copolymers

Correction - "Cost Estimate on Technical Grade Vinyl Stearate."

Correction - "Cost Estimate on Technical Grade Vinyl Stearate."

Polymerizable Derivatives of Long-Chain Fatty Acids - Vinyl Stearate and Copolymerization of Vinyl Chloride with Other Vinyl Esthers

Polymerizable Derivatives of Long-Chain Fatty Acids - Vinyl Stearate and Copolymerization of Vinyl Chloride with Other Vinyl Esthers