Plasticizing properties of esters of monohydric alcohols and tall oil fatty acids

Tall oil fatty acid esters prepared as intermediates in an epoxy ester plasticizer program were similarly evaluated as low-temp plasticizers in polyvinyl chloride resins. Performance characteristics as primary and secondary plasticizers in polyvinyl sheeting and extruded tapes were determined on esters from methyl to heptadecyl tallate. Results indicate that these materials impart low-temp properties which would make them of value as low-cost plasticizers in extruded and molded products where light and heat stability are not primary factors.     

Ethylene and dimethyl acetals from hydroformylated linseed,soybean, and safflower methyl esters as plasticizers for polyvinyl chloride

Dimethyl and ethylene acetals of polyformylated unsaturated fatty esters were prepared, characterized, and evaluated as polyvinyl chloride plasticizers. Dimethyl acetals were prepared with trimethyl orthoformate as a water scavenger in the acid catalyzed acetalation reaction. With ethylene acetals, water was removed azeotropically. Although the acetals prepared were mixtures, molecular distillation gave diacetal esters of 80–90% purity and triacetal esters of 80–95% purity. The samples were characterized by gas liquid chromatography and by IR and NMR spectra. Compared to di-2-ethylhexyl phthalate as a plasticizer for polyvinyl chloride, the triacetal esters (both dimethyl and ethylene acetals) gave less migration and at least equivalent volatility characteristics; the triacetals also gave equivalent compatibility and strength, but somewhat less desirable low temperature and heat stability properties. The diacetal esters also had good compatibility, equivalent strength, somewhat better low temperature, but less desirable migration and volatility properties. Presented at the AOCS Meeting, Chicago, Illinois, September 1973. ARS, USDA.     

Safflower oil adducts as plasticizers

Eleven esters and epoxides of adducts of conjugated linoleic acid with maleic and acrylic acids, and eight esters and epoxides of adducts of vegetable oils with acrylic and maleic esters were evaluated as plasticizers for polyvinyl chloride (PVC), acrylonitrile rubber, and polyvinylidene chloride, and in PVC plastisols. The dimethyl ester of the acrylic adduct of linoleic acid and its epoxide were the most promising as plasticizers for PVC and in PVC plastisols as their performance compared favorably with that of controls. In polyvinylidene chloride however these adducts had a slight adverse effect on color stability. The vegetable oil adduct esters and epoxides were incompatible with PVC but had extremely good compatibility with acrylonitrile rubber. In general, they performed like the petroleum type of plasticizers but were less volatile and less easily extractable. Paper VII in a series entitle “Reactions of Conjugated Fatty Acids”. Presented at Fall Meeting, American Oil Chemists' Society, New York, N.Y., October 17–19, 1960. The evaluation studies were conducted at Battelle Memorial Institute, Columbus, O., under contract with the U.S. Department of Agriculture and authorized by the Research and Marketing Act. The contract was supervised by the Northern Regional Research Laboratory. This is a laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, U.S. Department of Agriculture.     

Epoxidation of alkyl esters of 12,13-epoxyoleic acids and evaluation of the diepoxides as plasticizers for poly(vinyl chloride)

Methyl, propyl, butyl, isobutyl, hexyl, cyclohexyl, octyl and 2-ethylhexyl esters of 9,10:12,13-diepoxystearic acid were prepared by peracetic acid oxidation of the corresponding esters of 12,13-epoxyoleic acid. Using a 60 mole per cent excess of peracid at 30 C in chloroform as solvent, epoxidation was complete in 5 hr. A small aqueous phase was observed in the reaction mixture which decreases the amount of peracid available for reaction. This is due to the water and H₂O₂ present in the commercial peracetic acid used. Thin-layer and gas chromatographic analysis showed that the diepoxides formed as isomers. These did not react quantitatively with HBr by the Durbetaki method. Isomers of methyl and propyl diepoxy esters were separated by crystallization. The methyl (pure and mixed isomers), isobutyl, 2-ethylhexyl and octyl (all mixed isomers) diepoxy esters were evaluated as plasticizers of poly (vinyl chloride). Delta values showed that these esters have good compatibility. Results are compared with commercial epoxidized soybean oil control. These diepoxy esters show better low temperature properties and have higher migration and volatility values than the control. They are more efficient plasticizers than the control. The liquid isomer of the methyl ester, as well as the 2-ethylhexyl ester, should be useful as primary plasticizers and in combination with other plasticizers as plasticizer stabilizers. E. Utiliz. Res. Dev. Div., ARS, USDA.     

Catalytic hydroformylation of unsaturated fatty derivatives with cobalt carbonyl

Two cobalt-carbonyl oxo processes were developed to prepare useful products in high yield from fatty derivatives. In one process, hydroformylation in the presence of MeOH at 120 C gives dimethyl acetal esters from either methyl oleate or oleic acid. In the other, a two-step process, hydroformylation (120 C) followed by hydrogenation (180 C) gives better yields of hydroxymethyl esters from both mono- and polyunsaturated fatty substrates. Recycling the cobalt catalyst was demonstrated for the second process. The acetal and acetoxymethyl derivatives of the oxo products have utility as polyvinyl chloride plasticizers.     

Di(2‐propylheptyl) phthalate: A new plasticizer choice for PVC compounders

Science and practice have proven that phthalic acid esters are among the most functional plasticizers for polyvinyl chloride (PVC). The performance properties of phthalic acid esters can be modified for an advantageous cost/benefit position by varying the alcohol moiety of the ester molecule in the practical range of C4–C13 and by specifying the linearity of the alcohol main chain. The C8, C9, and C10 alcohols produce esters of most value as PVC plasticizers. Most plasticizer alcohols are produced by the oxonation process from primary olefins, of which ethylene, propylene, and butene are the major refinery products available on a world scale at costs acceptable to the application. This article introduces a C10 phthalate produced from butene rather than by the current route from propylene. J. VINYL. ADDIT. TECHNOL. 11:155–159, 2005. © 2005 Society of Plastics Engineers     

Tall oil fatty acid-formaldehyde derivatives and their application as vinyl plasticizers

Acid-catalyzed condensations of tall oil fatty acid and related materials with formaldehyde, in the absence of a carboxylic acid solvent, led to acidic products, lower in unsaturation, but partially polymeric due to formation of interester linkages. Hydrolysis of these linkages furnished products lower in mol wt but higher in free hydroxyl content. Some modified esters of these materials were evaluated as primary plasticizers for polyvinyl chloride by comparison with dioctyl phthalate and, when applicable, to Monsanto S409. In general, those plasticizer candidates in which free hydroxyl contents were lowered by acetylation exhibited a good overall balance of physical and permanence properties but possessed poor heat stability and borderline compatibility. A preliminary study on the acid-catalyzed reaction of ethyl tallate with anhydrous formaldehyde gave promise that an improved alternate route to fatty acid-formaldehyde esters could be developed.     

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

Summary Soybean 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. Presented at fall meeting. American Oil Chemists' Society, September 23–26, 1956, Chicago, Ill.     

Euphorbia andVernonia seed oil products as plasticizer-Stabilizers for polyvinyl chloride

Seed oils ofEuphorbia lagascae Spreng. andVernonia anthelmintica (L.) Willd. were prepared, refined and epoxidized; trivernolin was prepared fromV. anthelmintica and also epoxidized. These products were each comparatively evaluated as plasticizer-stabilizers for polyvinyl chloride against commercial controls. EpoxidizedEuphorbia andVernonia oils and epoxidized trivernolin have potential value as primary plasticizers with the added advantage of increased heat and light stability; they could also be used in combination with other plasticizers utilizing the latter properties. Crude and refinedEuphorbia andVernonia oils are not considered suitable primary plasticizers because of poor compatibility and permanence; at low levels they probably could be used as stabilizers. E. Utiliz. Res. Dev. Div., ARS, USDA.     

Some esters of mono-, di-, and tricarboxystearic acid as plasticizers: Preparation and evaluation

Methyl mono-, di-, and tricarboxystearates were prepared by either a two-step hydroformylation-oxidation reaction or direct hydrocarboxylation of unsaturated vegetable oil methyl esters. Procedures were developed for preparing alkyl dicarbomethoxy-, dicarboethoxy-, and dicarbobutoxystearates. These triesters, along with some di- and tetraesters from mono- and tricarboxystearic acids, were evaluated as primary plasticizers for polyvinyl chloride (PVC). Except for butyl carbobutoxystearate, the esters were compatible at the 32% level and had properties equal or superior to those of dioctyl phthalate. Methyl and butyl diesters of carboxystearic acid had undesirable migration and volatility properties. The migration and volatility properties of some tri- and tetraalkyl esters were equal to or better than the controls. Of the various esters tested, methyl dicarbomethoxystearate containing 13–49% methyl tricarbomethoxystearate was an efficient plasticizer for PVC at the 32% level.     

Preparation of some mixed diesters of aliphatic diols and their evaluation as plasticizers

Mixed diesters of three diols-ethylene glycol, diethylene glycol, and 2-butene-1,4-diol—were prepared wherein one of the ester moieties was benzoate. The laurates were shown to be excellent plasticizers for polyvinyl chloride (PVC) resin. Diesters containing two aroyl groups, or benzoyl and a short branched-chain alkanoyl group were also shown to be compatible plasticizers for PVC resin. Longer chain acids, including oleic and erucic, gave incompatible plasticizers. Benzoyloxyethoxyethyl laurate plasticized PVC had low temperature properties, volatility, and thermal stability superior to PVC plasticized with di-2-ethylhexyl phthalate.     

Recent developments in plasticized flame retardant polyvinyl chloride (PVC)

Triaryl and alkylaryl phosphates are plasticizers/flame retardants for polyvinyl chloride. The former are more effective flame retardants and the latter are better plasticizers. The latter also gives less smoke. A new phosphate ester blend with good plasticizer properties and low smoke is reported. A brominated triaryl phosphate ester is shown to be a highly effective flame retardant giving plasticized polyvinyl chloride compositions with oxygen index values up to 36. These compositions are suitable for high temperature wire and cable products.     

Synthesis and Functional Evaluation of Soy Fatty Acid Methyl Ester Ketals as Bioplasticizers

A facile synthesis of the soy fatty acid methyl ester ketal has been accomplished using acetone in the presence of catalytic anhydrous ferric chloride starting from commercially available soy biodiesel (soy fatty acid methyl ester) after evaluating various synthetic procedures. The soy ketal product was fully characterized by nuclear magnetic resonance, infra-red and chromatography. The physical and analytical properties of soy ketal as determined by thermogravimetric analysis, viscosity acid and saponification values are acceptable for plasticizer applications. Soy ketal was compounded with polyvinyl chloride for evaluation of plasticizer properties such as efficiency, gelation, viscosity, volatility, thickening/aging behavior and stability. The thickening and aging behaviors of the soy ketal bioplasticizer are better than those of petroleum-based plasticizers such as diisononyl phthalate and diisononyl-cyclohexane dicarboxylate, but they need improvement in the areas of thermal stability and water extractability.     

Thermal stability of phthalic esters

Phthalic esters, as typical plasticizers for vinyl plastics, were thermally decomposed by a flow reactor system and their decomposition products were analyzed in detail. The thermal decomposition products were olefin, alcohol, hydrogen phthalate, benzoates with alkyl groups corresponding to these of the original phthalate esters and phthalic anhydride. We found from the main thermal decomposotion products-olefin, alcohol and hydrogen phthalate-that phthalic esters were thermally decomposed throughcis-elimination in the same way as in the general case for esters. In the presence of polyvinyl chloride (PVC), hydrochlorinated products were identified in the decomposition products. A good relationship was found between the amount of chloroalkanes produced and the reaction temperature. Thecis-elimination reaction of phthalic esters was found to be promoted by PVC.     

Epoxidized esters of fatty acids as internal and external plasticizers for polyvinyl acetate

Summary Fatty acid esters modified with epoxy or acetoxy groups were found to be compatible with polyvinyl acetate. These esters are good plasticizers for polyvinyl acetate compositions and may be used for plasticizing polyvinyl acetate in latex form. The use of a good swelling agent, such as toluene, was found desirable for permitting plasticization of these emulsions. The epoxidized oils may also assist in reducing container corrosion and in stabilizing the emulsions by reacting with the acetic acid formed by the hydrolysis of residual vinyl acetate. Emulsions of copolymers of vinyl acetate and vinyl epoxystearate were prepared, yielding clear, hard films which were internally plasticized. The epoxy group in these interpolymers is a potential source for cross-linking vinyl acetate polymer films. The epoxy group of the co-polymers (internal-phase stabilization) and the epoxidized oils (external-phase stabilization) were found to be virtually equivalent for removal of acetic acid from polyvinyl acetate emulsions. Presented at the Fall Meeting, American Oil Chemists' Society, Philadelphia, Pa., October 11, 1955. A laboratory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Plasticizer structure/performance relationships

Plasticizers for poly(vinyl chloride) may be organized into eight chemical families and by seven key performance criteria. Cost-effective general-purpose phthalates provide a base line for comparing all other plasticizers. The wide range of performance characteristics associated with various phthalate isomers substantiates the large proportion of phthalate esters that are utilized as plasticizers. This article summarizes plasticizer structural/performance relationships using quantitative comparisons of cost, plasticizing efficiency, plastisol solvation characteristics, dryblending, volatility, and low temperature performance properties in PVC. Some generalizations are also made concerning structural effects of the alcohol isomers used in the syntheses of the various types of plasticizer esters.     

Copolyesters as non‐toxic plasticizers

Plasticized polymer materials have taken an enormous role in our everyday life. Most of the common plasticizers are aromatics, esters of phthalic acid. Since they are not chemically bonded to the polymer matrix, they can be released from material while being used. The concerns raised about toxicity led to a large demand for producing biodegradable and non‐toxic plasticizers. We investigated aliphatic copolyesters synthesized via ring opening polymerization of lactones as plasticizers for poly(vinyl chloride). The material properties of the formulations, such as glass transition temperature and mechanical performance, were studied. Copyright © 2011 Society of Chemical Industry     

邻苯二甲酸酯类增塑剂合成与应用研究进展

综述了近年来邻苯二甲酸酯类聚氯乙烯(PVC)增塑剂合成与应用研究的进展,并对我国增塑剂向绿色、环保方向发展提出了建议。     

Leaching of plasticized PVC: Effect of irradiation

Highly irradiated (2–26 MGy) polyvinyl chloride (PVC) was leached in an alkaline solution to investigate the impact of high doses on the leaching process and on the nature of the leaching products. The results show that leaching is controlled by diffusion phenomena as described by Fick's second law. The apparent diffusion coefficient (D_a) of plasticized PVC leaching products can be calculated for each sample. Irradiation at high dose causes D_a to diminish; this can be attributed to crosslinking and grafting reactions occurring during irradiation. The material microstructure thus becomes less permeable during radiolysis, which slows down the migration of species. Organic products of leaching are plasticizers contained in plasticized PVC or their degradation products. The main organic leaching products are phthalic ions formed by the hydrolysis of phthalic esters in alkaline leaching solution. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New benzoate plasticizers for polyvinyl chloride: Introduction and performance example

Two new unique benzoate ester plasticizers that will offer the vinyl formulator improved performance have been developed. One is an excellent solvator that will yield lower plastisol viscosities than existing plasticizers. The other will provide an excellent alternate with low volatility. The new products provide expanded performance utility over existing benzoates and phthalates on a global basis. Basic plastisol performance data and an example of use in a specific application, vinyl leathercloth, are presented. The data demonstrates that these blends are compatible, effective high solvating plasticizers and are performance alternates for plastisols and other polyvinyl chloride applications.