Vernolic acid esters as plasticizers for polyvinyl chloride

The methyl, propyl, butyl, isobutyl, hexyl, cyclohexyl, octyl, and 2-ethylhexyl esters of vernolic (epoxyoleic) acid, a naturally-occurring epoxy acid, were prepared and evaluated as plasticizers of polyvinyl chloride. All the esters showed good compatibility. The data indicated that they are excellent low temperature plasticizers having T_f temperatures below −50C. They also have the added advantage of greatly increasing the heat stability of the polyvinyl chloride and improving the light stability. The results are compared with DOP and other epoxy-containing plasticizers now being used commercially. These esters should not only be useful as primary plasticizers but also in combination with other plasticizers as plasticizer-stabilizers. Presented at the AOCS Meeting. Cineinnati, October 1965 E. Utiliz. Res. Dev. Div., ARS, USDA.     

Derivatives of jojoba oil as plasticizers for vinyl polymers and Buna-N rubber

Summary Ten maleinated jojoba oil derivatives were screened as plasticizers in a standard polyvinyl resin formulation and as softeners for Buna-N rubber. Three of these, the methyl and butyl esters and hydrogenated methyl esters of maleinated jojoba acids, were comparable to the reference standard, DOP, as primary plasticizers for the vinyl resin. Three others were satisfactory only as secondary plasticizers. Six of the derivatives were comparable to the reference softener, dibutyl sebacate, as softeners in a Buna-N formulation and yielded rubbers meeting the low temperature flexibility requirements (−40°C.) of the automotive industry. Two of the six, those made with the butyl and hydrogenated butyl esters of maleinated jojoba acids, met the still more stringent low-temperature requirements of the aircraft industry (−55°C.). In general, hydrogenation of a derivative adversely affected its compatibility in either the vinyl copolymer or the Buna-N formulations. Presented at the 51st annual meeting, American Oil Chemists’ Society, Dallas, Tex., April 4–6, 1960. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

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.     

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.     

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     

Citrate esters as plasticizers for poly(lactic acid)

Citrate esters were used as plasticizers with poly(lactic acid) (PLA). Films were extruded using a single-screw extruder with plasticizer contents of 10, 20, and 30% by weight. All of the citrate esters investigated were found to be effective in reducing the glass transition temperature and improving the elongation at break. It was observed that the plasticizing efficiency was higher for the intermediate-molecular-weight plasticizers. Hydrolytic and enzymatic degradation tests were conducted on these films. It was found that the lower-molecular-weight citrates increased the enzymatic degradation rate of PLA and the higher-molecular-weight citrates decreased the degradation rate as compared with that of unplasticized PLA. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1507–1513, 1997     

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.     

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.     

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.     

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.     

The Preparation and Plasticizing Characteristics of the N,N-bis(2-Alkoxyethyl) Amides of Long Chain Fatty Acids

A number of N-acyl derivatives of bis(2-alkoxyethyl) amines have been prepared, characterized and screened as plasticizers for poly (vinyl chloride-vinyl acetate) copolymer. Included were the N,N-bis (2-alkoxyethyl) amides of saturated (normal and branched), unsaturated, epoxy, dimer, terpenic and naphthenic acids as well as mixed acids from animal fats, rapeseed, Limnanthes douglasii seed, parsley seed and selectively hydrogenated cottonseed oils. With the exception of the linoleic acid derivative, all these amides, including the stearamide derivative, were compatible. Some exhibited low-temp properties comparable to the adipate plasticizers without the adverse volatility characteristics of the adipates. With the exception of the epoxystearamide derivative the N,N-bis(2-alkoxyethyl)amides were inferior to dioctyl phthalate in thermal stability. The N,N-bis(2-ethoxyethyl)stearamide is of special significance in that it seems to be the only carboxylic derivative of stearic acid known to be effective as a primary plasticizer.     

Acetoxyglycerol acetal derivatives of mono- and polyformyloctadecanoate esters: Plasticizers for poly(vinyl chloride)

Methyl and butyl(acetoxyglycerol acetal) esters were prepared from 9(10)-formyloctadecanoate or its dimethyl acetal. Mixtures of acetoxy mono- and diglycerol acetals, plus acetoxy mono-, di-, and triglycerol acetals, were prepared respectively from hydroformylated safflower and linseed methyl esters. The glycerol acetals were characterized with respect to physical, thermal, chromatographic, and spectroscopic properties. Acetoxy-mixed glycerol acetals from safflower and linseed methyl esters were good primary plasticizers for poly(vinyl chloride) (PVC), whereas acetoxyglycerol acetals of hydroformylated methyl and butyl oleate were good secondary PVC plasticizers. As primary plasticizers, the poly(acetoxyglycerol acetal) esters showed less migration, better heat stability, and higher tensile strength than the generally used PVC plasticizer di(2-ethylhexyl) phthalate.     

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.     

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.     

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.     

The preparation and plasticizing characteristics of pipendides of long chain fatty acids and n-fatty acyl derivatives of other cyclic imines

Forty-six N-acyl derivatives of cyclic imines have been prepared, characterized, and screened as primary plasticizers for poly (vinyl chloridevinyl acetate) copolymer. Among these were the piperidides of decanoic, palmitic, stearic, oleic, erucic, ricinoleic, epoxystearic, epoxyoleic, diepoxystearic, sebacic, pinic, cottonseed, hydrogenated cottonseed, rapeseed,Limnanthes douglasii, animal, 2-ethylhexanoic, naphthenic, and dimer acids, as well as the N-oleoyl derivatives of a number of substituted piperidines and other cyclic imines including pyrrolidine, piperazine, hexamethylenimme, tetrahydroquinolme, 3-azabicyclo [3.2.2] nonane, dipyridylamine, and carbazole. In general these amides of the 5-,6-, and 7-membered cyclic imines exhibited exceptionally high plasticizing efficiencies. The compatibilities observed were the best to date for fatty acid derivatives on the basis of both individual and ternary fatty acid composition-compatibility data. Several of these amides exhibited low-temp characteristics in the adipate plasticizer range without the adverse volatility characteristics of the adipates. There are indications that some of them have appreciable antifungal activity. It has been concluded that cyclic imines will, in general, produce fatty acid derivatives of better than average compatibility as vinyl plasticizers.     

Effects of Plasticizers and Stabilizers on Thermal Stability of Polyvinyl Fluoride

The study was focused on the choosing of plasticizers and stabilizers for improving thermal stability of polyvinyl fluoride (PVF) during the thermoplastic processing. Five kinds of organic esters as plasticizers for PVF were evaluated. The results showed that dimethyl phthalate (DMP) had better compatibility with PVF and phase separation didn't occur up to a relatively high concentration level, and DMP significantly decreased the melting temperature of PVF and showed the good plasticized effect. The optimum DMP content, considering homogeneous compound, good melt fluidity, and dynamic thermal stabilization, can be determined from the melt flow index and torque measurements. Five kinds of additives as stabilizers for PVF/DMP system were evaluated by the color change during static ageing. It was found that pentaerythritol had remarkably positive effects on both thermal and color stability of PVF.     

合成柠檬酸酯类增塑剂催化剂及柠檬酸酯类增塑剂的应用

介绍柠檬酸酯类增塑剂的最新发展概况,重点阐述合成柠檬酸酯类增塑剂催化剂的研究进展及柠檬酸酯类增塑剂的应用。合成柠檬酸酯的催化剂有磺酸、固体超强酸、杂多酸、离子液体和无机盐,柠檬酸酯类增塑剂应用于食品包装、儿童玩具和医疗器具。展望柠檬酸酯类增塑剂的发展前景。     

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.     

增塑剂的研究与发展

对增塑剂的研究与发展做了全面的概述,重点介绍了邻苯二甲酸酯类（PAEs）作为橡塑制品增塑剂的应用与危害,指出了环保型增塑剂的发展趋势,以及我国增塑剂目前所面临的环保压力和发展状况。