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    • 专利摘要:
    PLASTIFIER COMPOSITION, PLASTIFIED HALOGENED POLYMER COMPOSITION AND PVC ARTICLE Plasticizer compositions comprising epoxidized fatty acid mono-esters and epoxy-esters are provided. The plasticizer compositions are free of compatibilizer and may contain metal perchlorates and/or phenolic antioxidants and/or conventional plasticizers. The compositions are useful for reduced extraction and lower volatility of halogenated polymers containing the compositions. Plasticizer compositions give reduced extraction of at least 15%. A process for making the plasticizer compositions is also provided. Further provided is a reduced plasticizer extraction method from halogenated polymers such as polyvinyl chloride. Plasticizer compositions can be added to PVC resins in effective amounts ranging from 1 to 200 phr.
    公开号:BR112014008711B1
    申请号:R112014008711-3
    申请日:2012-10-11
    公开日:2021-05-04
    发明作者:Peter Frenkel；Steven McKeown
    申请人:Galata Chemicals Llc；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [0001] The present invention relates to plasticizer compositions prepared from renewable raw materials that are suitable for plasticizing halogen-containing polymers, such as polyvinyl chloride (PVC) and PVC-based copolymers, terpolymers and grafted polymers . FUNDAMENTALS OF THE INVENTION
    [0002] Plasticizers are commonly incorporated into polyvinyl chloride (PVC) to transform rigid PVC resin into flexible PVC articles. Phthalic acid esters (phthalates) are used as primary plasticizers in about 10-60 parts per 100 parts (phr) of PVC. Vegetable oil epoxidized, such as soy oil epoxidized (ESBO) and linseed oil epoxidized (ELSO), are used as secondary plasticizers. Other examples of secondary plasticizers are fatty acid monoester epoxidized, such as methyl soate epoxidized and 2-ethylhexyl talate epoxidized. Furthermore, octyl talate epoxidized and butyl epoxy stearate are commercially used as secondary plasticizers for PVC [a) PVC Handbook by Charles, Wilkes, Charles Daniels, James Summers, Hanser GardnerPublishers; 2005, p.180; and b) Theory and Practice of Vinyl Compounding by Vic Struber; Argus Chemical Corporation; 1968; Library of Congress Catalog No. 68-19157, p.4]. Struber refers to the epoxidized 2-ethylhexyl talate which is commercially available from Galata Chemicals LLC as Drapex® 4.4. Struber also describes octyl oleate epoxidized, which Galata Chemicals LLC offers as Drapex 3.2. ESBO and ELSO have limited compatibility with PVC due to its high molecular weight, while epoxidized monoesters are known for their unacceptably high extraction out of the PVC matrix.
    [0003] Several patents and patent applications relate to plasticizers derived from fatty acids containing epoxy functional groups, as referred to hereinafter.
    [0004] Patent no. US 2,895,966 describes plasticizer stabilizers for synthetic resins and plastic compositions, comprising said plasticizer stabilizers.
    [0005] Patent no. US 3,049,504 relates to plasticizer stabilizers for synthetic resins.
    [0006] Patent Application No. US 2002/0013396 discloses compositions and methods for plasticizing polyvinyl chloride polymers where the plasticizers contain fatty acids derived from vegetable oils and the fatty acids are substantially fully esterified with an alcohol (monool or polyol) , fatty acids having unsaturated bonds that are substantially fully epoxidized, and wherein the fatty acids are added substantially randomly to one or more hydroxyl sites on the alcohol. Plasticizers can be added in amounts between about 10 to 230 phr of PVC resin.
    [0007] WO2009/102592 describes unimpeded polyols used to react with a sorbate epoxidate to make epoxidized diester sorbate in the presence of a catalyst. The unimpeded polyol can be 1,3-propanediol or any polyol having four or more carbon atoms with no two adjacent carbon atoms having hydroxyl functionality. A combination of catalysts is used to promote the unhindered transesterification reaction of the soiate epoxidate with the polyol to produce a high percentage of the sorbate diester epoxidate with retained epoxy functionality. The main catalyst is a metal hydroxide, and the secondary catalyst is a titanate. Bioderived soiate diester epoxidized plasticizers useful for thermoplastic and thermoset output.
    [0008] Patent Application No. US 2010/0010126 describes the use of the interesterification reaction between vegetable or animal oils as monoacid esters (preferably with 1 to 12 carbons) and monoalcohol esters (preferably with 1 to 12 carbons). The use of ethyl acetate is preferable as it is a product that can be obtained from ethanol (renewable) and has a boiling point (77 degrees. C.), which facilitates separation by vacuum distillation at the end of the reaction and its reuse. By varying the molar ratio between glycerol triester (oil or fat) and monoalcohol ester, different proportions of glycerol esters with 1 or 2 bonded fatty acids and 1 or 2 short-chain bonded acids are obtained, together with the formation of glycerol ester. fatty acid and mono alcohol ester. After distilling off the excess residual ethyl acetate, products with a viscosity of 21 to 33 cPs at 25 degrees are obtained. C., in the case of the reaction with soybean oil.
    [0009] Patent Application Publication No. US2010/0010127 relates to bioplasticizers or primary oleochemical plasticizers and the improved process for obtaining the same. It mainly refers to oil-chemical plasticizer epoxidizers produced from vegetable oils, as a substitute for traditional petrochemical plasticizers.
    [0010] Patent No. US 7,071,343 describes epoxidized glyceride acetates made by a process comprising the reaction of a fatty acid ester of epoxy and triacetin.
    [0011] WO2011/143028 refers to PVC resin-based compositions that include biochemical plasticizers as the primary plasticizers. Compositions include PVC resin, a compatibilizer, one or more biochemical plasticizers and, optionally, a thermoplastic elastomer impact modifier. Biochemical plasticizers are present in substantial amounts in the compositions and, in some embodiments, are the only plasticizers present in the compositions.
    [0012] Notwithstanding the above literature, there is a continuing need for improved biobased plasticizers having reduced extraction properties and lower volatility for halogen containing polymers such as polyvinyl chloride (PVC) and its copolymers. SUMMARY OF THE INVENTION
    [0013] In one aspect, the invention is directed to plasticizer compositions for reduced plasticizer extraction from plasticized halogenated polymers comprising (i) a fatty acid mono-ester epoxidate and (ii) an epoxy-ester. In certain embodiments, the plasticizer compositions of the invention are substantially free of compatibilizers. In yet some embodiments, the plasticizer compositions of the invention additionally comprise a metal perchlorate and/or antioxidant.
    [0014] In a second aspect, the invention is directed to a process for the preparation of plasticizer compositions for reduced plasticizer extraction from plasticized halogenated polymers comprising the steps of: providing a fatty acid monoester epoxidate; and mixing said fatty acid monoester epoxidate with an epoxy ester for a predetermined amount of time at room temperature to achieve a homogeneous liquid mixture.
    [0015] In a third aspect, the invention provides a process for making a plasticized halogenated polymer composition comprising the steps of (i) providing a fatty acid mono-ester epoxidate, (ii) mixing said fatty acid mono-ester epoxidate. fatty acid with an epoxy-ester for a predetermined amount of time at room temperature to achieve a homogeneous liquid mixture, and (iii) adding said homogeneous liquid mixture to a halogenated polymer.
    [0016] In a fourth aspect, the invention is directed to a plasticized polyvinyl chloride composition for reduced plasticizer extraction prepared by a process comprising the steps of (i) providing a fatty acid monoester epoxidate, (ii) mixing said fatty acid monoester epoxidate with an epoxy ester for a predetermined amount of time at room temperature to achieve a homogeneous liquid mixture, and (iii) adding said homogeneous liquid mixture to the polyvinyl chloride, in an amount of 1 at 200 parts per 100 parts of polyvinyl chloride at a temperature in the range of 10-300°C.
    [0017] In a fifth aspect, the invention provides a plasticizer composition, comprising (i) a fatty acid mono-ester epoxidate and (ii) an epoxy-ester, wherein the fatty acid mono-ester epoxidate comprises fatty acid derived from pine oil or soybean oil; and wherein the fatty acid derived from pine oil or soybean oil is substantially fully esterified with monohydric alcohol having at least three carbon atoms.
    [0018] In a sixth aspect, the invention is directed to a plasticizer composition comprising at least one fatty acid mono-ester epoxidate and at least one conventional co-plasticizer ester.
    [0019] In a seventh aspect, the invention is directed to a plasticizer composition comprising: an epoxidized fatty acid mono-ester, an epoxy-ester and a metal and/or antioxidant perchlorate. DETAILED DESCRIPTION OF THE INVENTION
    [0020] The present invention relates to plasticizer compositions, which may be suitable for reduced extraction of plasticized halogenated polymers. In some embodiments, the plasticizer compositions of the invention comprise epoxidized acid monoesters and epoxy esters. In one embodiment, the plasticizer compositions comprise a mixture containing the epoxidized fatty acid mono-esters and epoxy-esters. In a further embodiment, the epoxidized fatty acid mono-esters and epoxy-esters are substantially free of mono and/or diglycerides.
    [0021] In some embodiments, the fatty acid monoester epoxidates comprise fatty acids derived from natural oils and animal fats. Exemplary natural oils are vegetable oils and plant oils, which may also contain fatty acid triglyceride esters. Are suitable natural oils; soybean oil, palm oil, olive oil, pine oil, castor oil, cottonseed oil, linseed oil, safflower oil, sunflower oil, canola oil, canola oil, rapeseed oil, jatropha oil, algae oil, corn oil, tung oil and mixtures of any two or more thereof. Preferred natural oils include soybean oil, linseed oil and pine oil.
    [0022] Appropriate animal fats include mutton, pork, beef, poultry fat, to name a few. Of these, tallow, drip, tallow, lard, bacon, bacon, butter, poultry fat, schmaltz, whale oil and the like are preferred.
    [0023] In one embodiment, fatty acids derived from natural oils and animal fats are substantially fully esterified with mono alcohols. Exemplary monohydric alcohols suitable for substantially complete esterification include methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, cyclohexanol, octanol, noctanol, iso-octanol, 2-ethylhexanol, nonanol, neodecanol, decanol, undecanol, dodecanol, tetradecanol, cetyl alcohol, stearyl alcohol, docosanol, prop-2-en-1-ol epoxidized and the like and mixtures of at least the same.
    [0024] Still in some embodiments, monohydric alcohols have at least three carbon atoms. At least six, eight, ten, twelve and eighteen carbon atoms are preferred. Of those at least eight carbon atoms are more preferred.
    In further embodiments, the fatty acids included in the epoxidized fatty acid monoesters of the invention contain unsaturation. Suitable examples of fatty acids containing unsaturation include oleic acid, linoleic acid, linolenic acid, ricinoleic acid, dehydrated ricinoleic acid and the like and mixtures of two or more thereof.
    [0026] In other embodiments, the fatty acids containing unsaturation are substantially fully epoxidized to provide the epoxidized fatty acid monoesters of the invention. Suitable examples of fatty acid monoester epoxidized include 2-ethylhexyl talate epoxidized, 2-ethihexyl soiate epoxidized, octyl talate epoxidized, octyl soiate epoxidized, octyl oleate epoxidized, epoxidized methyl soiate and any two mixtures. or more of them. A preferred example is 2-ethihexyl talate epoxidized or 2-ethylhexyl soiate epoxidized.
    [0027] Examples of suitable epoxy-esters are vegetable oil epoxidized and natural oil epoxidized. Preferred vegetable oil epoxidizers are soybean oil epoxidized, linseed oil epoxidized, and mixtures of any two or more thereof. Most preferred is epoxidized soybean oil.
    [0028] Suitable examples of epoxy-esters also include propylene dioleate epoxidized, ethylene glycol dioleate epoxidized, propylene glycol disoiate epoxidized and mixtures of any two or more thereof.
    [0029] In further embodiments, the epoxy-esters are substantially fully esterified with polyhydric alcohols. Representative polyhydric alcohols include glycols, glycerols, glycerol monoacetate, pentaerythritol and the like, and mixtures of at least two thereof. Preferred substantially fully esterified glycols are substantially free of mono and/or diglycerides.
    [0030] In some of these embodiments, the plasticizer compositions of the invention may be substantially free of compatibilizers. Exemplary compatibilizers include, but are not limited to, chlorinated polyolefins, vinylacetate copolymers, ethylene methyl acrylate copolymers, ethylene butyl acrylate copolymers, ethylene/acetate/carbon monoxide terpolymers, ethylene/acrylate/carbon monoxide terpolymers, fluoride of polyvinylidene, nitrile butadiene rubber, polybutadiene epoxidized, natural rubber epoxidized, poly(tetramethylene oxide), glutarimide copolymers, thermoplastic polyurethane and chlorinated polyurethane. Examples of chlorinated polyolefins are, for example, a) a chlorinated polyethylene homopolymer, b) a chlorinated copolymer which contains copolymerized units of i) ethylene and ii) a copolymerizable monomer, or c) a combination thereof. Representative chlorinated olefin polymers include a) chlorinated ethylene homopolymers and b) chlorinated ethylene copolymers and at least one ethylenically unsaturated monomer selected from the group consisting of C3-C10 alpha mono-olefins; C1-C12 alkyl esters of C3-C20 monocarboxylic acids; unsaturated C3-C20 mono or dicarboxylic acids; anhydrides of unsaturated C4 - C8 dicarboxylic acids; and vinyl esters of saturated C2 - C18 carboxylic acids. Chlorinated graft copolymers are also included. Specific examples of polymers include, for example, chlorinated polyethylene (CPE); chlorinated ethylene vinyl acetate copolymers; chlorinated ethylene acrylic acid copolymers; chlorinated ethylene methacrylic acid copolymers; chlorinated ethylene methyl acrylate copolymers; chlorinated ethylene methyl methacrylate copolymers; chlorinated ethylene n-butyl methacrylate copolymers; chlorinated ethylene glycidyl methacrylate copolymers; chlorinated graft copolymers of ethylene and maleic acid anhydride; and chlorinated copolymers of ethylene with propylene, butene, 3-methyl-1-pentene or octene. Copolymers can be higher order dipolymers, terpolymers or copolymers.
    [0031] In other embodiments, the plasticizer compositions of the invention may additionally comprise metal perchlorates. According to the invention, metal perchlorates can be used as powders, solids and the like; dissolved in the plasticizer compositions of the invention; or introduced into the solution. Suitable solvents to provide the solutions include alcohols, glycols, glycerols, esters, phosphites, water and the like. A preferred solvent is 2-(2-butoxyethoxy)ethanol.
    [0032] Representative examples of metal perchlorates include perchlorates of alkali metals, alkaline earth metals, aluminum, zinc, lanthanum or cerium metals. Are preferred alkali metal perchlorates; for example lithium, sodium and potassium perchlorate. Particularly preferred is sodium perchlorate.
    [0033] In some embodiments, metal perchlorates are provided as metal perchlorate hydrates, preferably in powder form. Exemplary hydrates are monohydrates, dihydrates, trihydrates and tetrahydrates.
    [0034] Perchlorate solutions are commercially available. For example, Galata Chemicals LLC manufactures Mark CE-350, a 2-(2-butoxyethoxy)ethanol solution of sodium perchlorate. 30 and 60 percent (by weight) of aqueous sodium perchlorate solutions are preferred.
    [0035] Examples of the amounts of metal perchlorates used are from about 0.01 to about 10 parts by weight, advantageously from about about 0.1 to about 5 parts by weight and in particular about 0.1 to about 3 parts by weight, based on 100 parts by weight of PVC. Of particular interest is a range of from about 0.1 to about 1 part, based on 100 parts by weight of PVC.
    In further embodiments, the plasticizer compositions of the invention may comprise mixtures comprising epoxidized acid monoesters and epoxy esters. Suitable examples include mixtures comprising 2-ethylhexyl talate epoxidized or 2-ethylhexyl soiate epoxidized and soy oil epoxidized, although the skilled person can readily conceive of more exemplary epoxidized combinations of fatty acid mono-esters and epoxy-esters. Also in certain modalities, the mixtures can be stable, homogeneous, liquid mixtures.
    [0037] Any of the known mixing processes, methods and techniques, for example admixture and mixing, can be used to prepare liquid mixtures in order to achieve homogeneity and/or stability. In some embodiments, the epoxidized fatty acid mono-esters and epoxy-esters are combined into an admixture, blend, and the like and held—with or without stirring—for a predetermined period of time at room temperature. In some modalities, the predetermined amount of time is in the range of 1 to 24 hours. Preferred are 1 to 10 hours, more preferred two to four hours. Also preferred are times of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 18, 22 hours.
    [0038] Still in one modality, the epoxidized fatty acid mono-esters and epoxy-esters are combined at a temperature in the range of 0-300°C. A temperature range of 0 - 250°C, 10300°C, 10-200°C, 10-100°C is preferred, more preferred is 20-80°C, 30-60°C.
    [0039] In one embodiment, the ratio of epoxy-esters to epoxidized fatty acid mono-esters is in the range of about 5 to about 95 percent by weight, based on the total weight of epoxy-esters and epoxidized of fatty acid monoesters. A ratio in the range of 10 to 50 percent by weight, based on the total weight of epoxy esters and epoxidized fatty acid monoesters, is preferred. The ratio of epoxy-esters to epoxidized fatty acid mono-esters can be in the range of about 10 to 90, 20 to 80, 30 to 70 and 40 to 60 weight percent, based on the total weight of the mixture.
    [0040] In still other embodiments, the plasticizer compositions of the invention can be incorporated into halogenated polymers. Plasticized halogenated polymer compositions can result from such incorporation.
    [0041] In one of these embodiments, the plasticizer compositions of the invention can be incorporated into halogenated polymers such as PVC, alone or in combination. with conventional plasticizers. Conventional plasticizers are known in the art.
    [0042] Exemplary conventional plasticizers are phthalates, hydrogenated phthalates, aliphatic dicarboxylic acid esters, polymeric dicarboxylic acid esters, citrates, sucrose esters, levulinic ketal esters, phosphates, alkyl phenol sulfonates, pyrrolidones of two or more, and mixtures of two or more of the same. Phthalates, substantially fully esterified mono, di and tribasic acids, adipates, azelates, succinates, glutarates, glycol esters, sucrose esters, levulinic ketal esters, citrates, phosphates, alkyl phenol sulfonates and mixtures of at least two thereof are preferred. . An overview of conventional plasticizers is found in PLASTICS ADDITIVES HANDBOOK, 4th edition, ed. Gachter/Müller, Hansa Gardner Publishers, Munich, 1993, p. 327-422, which is incorporated by reference herein in its entirety.
    [0043] Suitable examples of conventional plasticizers, used according to the invention in combination with the inventive plasticizer compositions, also include the following groups and mixtures thereof:
    [0044] A. Phthalate Plasticizers. Exemplary materials preferably include di-2-ethylhexyl, diisononyl and diisodecyl phthalate, also known by the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate) and DIDP (diisodecyl phthalate).
    [0045] B. Phthalate Ester Plasticizers. Examples include esters of aliphatic dicarboxylic acids, in particular esters of adipic, azelaic or sebacic acid; preferably di-2-ethylhexyl adipate and diisooctyl adipate and trimellitic acid esters such as tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), triisotridecyl trimellitate, triisooctyl trimellitate (mixture) and also tri-C6-C8-alkyl, tri-C6-C10-alkyl, tri-C7-C9-alkyl and tri-C9-C11-alkyl trimellitate. Common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIDTM (trisodecyl trimellitate) and TITDTM (trisotridecyl trimellitate). Other examples include glutarates, malonates, oxalates, suberates and glycolates.
    [0046] C. Polymeric Plasticizers. Common raw materials for preparing polyester plasticizers include dicarboxylic acids such as adipic, phthalic, azelaic or sebacic acid; diols such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol.
    [0047] D. Citric Acid Ester Plasticizers. A definition of these and other plasticizers and examples thereof are given in "Kunststoffadditive" ["plastic additives"], R. Gachter/H. Muller, Carl Hanser Verlag, 3rd ed., 1989, chapter 5.9.6, pp. 412-415, and in "PVC Technology", W.V. Titow, 4th Ed., Elsevier publ, 1984, pp. 165-170, each of which is incorporated herein by reference in its entirety.
    [0048] E. Epoxy Compound Plasticizers. Exemplary materials include epoxidized polybutadiene and polyisoprene, if desired also in a partially hydroxylated form, or glycidyl acrylate and glycidyl methacrylate as homo or copolymer.
    [0049] In one embodiment, plasticized halogenated polymer compositions having incorporated therein the plasticizer compositions of the invention provide reduced plasticizer extraction when compared to identical plasticized halogenated polymers except for the presence of the plasticizer compositions of the invention.
    [0050] In certain embodiments, the plasticizer compositions of the invention provide at least 15% reduced plasticizer extraction from plasticized halogenated polymers, compared to plasticized polymers otherwise identical except for the presence of the plasticizer compositions of the invention. In one embodiment, the plasticizer compositions can provide reduced plasticizer extraction of at least about 20%, 30%, 40%, 50% compared to otherwise identical plasticized halogenated polymers except for the presence of the plasticizer compositions of the invention.
    [0051] The plasticizer compositions of the invention can be added to halogenated polymers, such as PVC, in an effective amount for reduced extraction, low volatility and detectable plasticizing effect for which the invention also provides respective methods. Preferably, plasticizer compositions are added to halogenated polymers in the range of from about 1 to about 200 parts, based on 100 parts of halogenated polymers. More preferred is a range from about 10 to about 60 parts and from about 30 to about 60 parts, based on 100 parts of halogenated polymer. These ranges represent examples of effective amounts. Other examples of effective amounts: from about 2 to about 150 pieces; about 5 to about 100 parts; about 10 to about 60 parts; about 20 to about 50 parts, based on 100 parts of halogenated polymers.
    [0052] Plasticizer compositions can provide reduced volatility of at least about 25% compared to otherwise identical plasticized halogenated polymers except for the presence of the plasticizer compositions of the invention. Furthermore, the inventive compositions can reduce volatility by at least 30, 40, 50% relative to otherwise identical plasticized halogenated polymers except for the presence of the inventive plasticizer compositions
    [0053] In other embodiments, the plasticizer compositions of the invention can be incorporated into PVC articles, including flexible PVC.
    [0054] The plasticizer compositions of the invention can also be incorporated into PVC in combination with PVC stabilizers. PVC stabilizers are known in the art (see for example Plastics Additives Handbook, 5th edition, ed. Hans Zweifel, Hanser Publishers. Munich, 2001, pg 427-483, which is incorporated herein by reference in its entirety). Exemplary PVC stabilizers include zinc intermediates such as zinc salts, zinc acetylacetonate, liquid phosphite esters, and others.
    [0055] In some embodiments of the invention, plasticizer compositions also include one or more additives to improve or modify one or more chemical or physical properties, such as thermal stability, lubricity, color, viscosity, to name a few. Exemplary additives include, but are not limited to, heat stabilizers, lubricants, viscosity control agents, UV absorbers, antioxidants, antistatic agents, antimicrobial and antifungal compounds, among other compounds conventionally used in flexible PVC formulations. An overview of these can be found in the Plastics Additives Handbook, 4th edition, editors: R. Gachter and H. Müller, associate editor P.P. Klemchuk; Hanser Publishers, Munich, 1993 and Plastics Additives and Modifiers Handbook, ed. J. Edenbaum; Van Nostrand Reinhold, 1992, which is incorporated herein by reference in its entirety.
    [0056] A single additive can serve multiple purposes. For example, a single additive can serve as a lubricant and a heat stabilizer. Additives used in combination with the plasticizer compositions of the invention can be incorporated into halogenated polymers, including PVC, in any amount suitable to achieve the desired purpose.
    [0057] In various embodiments of the invention, use can be made of one or more of the following additives and/or mixtures thereof with the plasticizer compositions of the present invention in halogen-containing copolymers. I. Polyols and other organic components
    [0058] Exemplary compounds of this type include sorbitol, triethanolamine, polyethylene glycols, β-diketones such as dibenzoylmethane, uracils and others. Examples of the amounts of polyols used are from about 0.01 to 20 parts by weight, advantageously from 0.1 to about 10 parts by weight and in particular from about 0.1 to 5 parts by weight, based on 100 parts by weight of PVC. II. Hydrotalcite Co-stabilizers
    The chemical composition of these compounds is known to one of ordinary skill in the art (see for example, DE 3 843 581, US Pat. No. 4,000,100, EP 0 062 813 and WO 93/20135, each of which is hereby incorporated by reference in its entirety).
    [0060] Compounds of the hydrotalcite series can be described by the following general formula M2+1-xM3+x(OH)2(Ab-)x/b.dH2O, where M2 += one or more of the metals selected from the group consisting of Mg , Ca, Sr, Zn and Sn, M3+=Al or B, A is an anion of valence n, b is a number of 1-2, 0<x<0.5, and d is a number of 0-20,
    Preference is given to compounds with An=OH-, ClO4-, HCO3-, CH3COO-, C6H5COO-, CO32-, (CHOHCOO)22-, (CH2COO)22-, CH3CHOHCOO-, HPO3- or HPO42-;
    [0062] Examples of hydrotalcites include Al2O3.6MgO.CO2.12H2O, Mg4.5Al2(OH)13.CO3.3.5H2O, 4MgO.Al2O3.CO2.9H2O, 4MgO.Al2O3.CO2.6H2O, ZnO.3MgO.Al2O3. CO2.8-9H2O and ZnO.3MgO.Al2O3.CO2.5-6H2O. III. Metal Soap Stabilizers
    [0063] Metal soaps are primarily metal carboxylates, preferably relatively long chain carboxylic acids. Well known examples of these are stearates, oleates, palmitates, ricinolates, hydroxystearates, dihydroxy stearates and laurates.
    [0064] Exemplary metals include alkali, alkaline earth and rare earth metals. Na, K, Mg, Ca, Sr, Ba, Pb, Zn, Al, La and Ce are preferred. Use is often made of so-called synergistic mixtures, such as barium/zinc stabilizers, magnesium/zinc stabilizers, calcium/zinc stabilizers or calcium/magnesium/zinc stabilizers. Metal soaps can be used alone or in mixtures. An overview of common metal soaps is found in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A16 (1985), p. 361 et seq, which is incorporated herein by reference in its entirety.
    [0065] Metal soaps or mixtures thereof may be used in amounts of, for example, 0.001 to 10 parts by weight, expediently 0.01 to 8 parts by weight, particularly preferably 0.05 to 5 parts by weight , based on 100 parts by weight of PVC. IV. Alkaline Metal and Alkaline Earth Metal Compounds
    [0066] For the purposes of the present invention, examples of these materials include the carboxylates of the acids described above, but also corresponding oxides or, respectively, hydroxides or carbonates. Mixtures of these with organic acids are also possible. Examples include NaOH, KOH, CaO, Ca(OH)2, MgO, Mg(OH)2, BaO, Ba(OH)2, Sr(OH)2, Al(OH)3, CaCO3 and MgCO3 (and also basic carbonates ) and also selected salts of Na and K, including perchlorates. In the case of alkaline earth carboxylates and Zn carboxylates it is also possible to use adducts of these so-called as "overbasified" compounds. In addition to the stabilizers according to the invention, it is preferable to use alkaline earth metal carboxylates. V. Organotin Stabilizers
    [0067] Examples of possible compounds of this type include both mono- and dimethyl, butyl and octyltin mercaptides, maleates and others. SAW. Phosphites (Phosphorous Acid Triesters)
    [0068] Organic phosphites are known as chlorine-containing polymer stabilizers. Examples of these are triphenyl phosphite, diphenyl isodecyl phosphite, ethylhexyl diphenyl phosphite, phenyl diisodecyl phosphite, trilauryl phosphite, triisononyl phosphite, triisodecyl phosphite, triphenyl phosphite grade epoxy, diphenyl phosphite and tris(nonylphenyl) phosphite. Advantageous use can also be made of phosphites of various di- or polyols.
    [0069] Examples of the total amounts of organic phosphites used or their mixtures are from 0.01 to 10 parts by weight, advantageously from 0.05 to 5 and in particular from 0.1 to 3 parts by weight, based on 100 parts by weight of PVC. VII. Lubricants
    [0070] Examples of possible lubricants include fatty acids, fatty alcohols, montan wax, fatty acid esters, PE waxes, Amide waxes, chloroparaffins, glycerol esters and alkaline earth metal soaps and fatty ketones, and also lubricants, or combinations of lubricants, listed in EP0259783, incorporated herein by reference in their entirety. Stearic acid, stearic esters and calcium stearate are preferred. VIII. Fills
    [0071] Fillers such as calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, china clay, talc, fiberglass, glass granules, wood flour, mica, metal oxides or metal hydroxides , carbon black, graphite, rock flour, heavy stringer, fiberglass, talc, kaolin and chalk may be used in accordance with some embodiments of the present invention (see, for example, HANDBOOK OF PVC FORMULATING, EJ Wickson, John Wiley & Sons, Inc., 1993, pp. 393-449; see also TASCHENBUCH der Kunststoffadditive [Plastic Additives Manual], R. Gachter & H. Müller, Carl Hanser, 1990, pp. 549-615), each of which is hereby incorporated by reference in its entirety.
    The fillers can be used in amounts preferably at least one part by weight, for example 1 to 20 parts by weight, expediently 1 to 10 parts by weight and in particular 1 to 5 parts by weight, based in 100 parts by weight of PVC. IX. Pigments
    [0073] Suitable substances are known to those of ordinary skill in the art. Examples of inorganic pigments include TiO2, pigments based on zirconium oxide, BaSO4 and zinc oxide (zinc white). Mixtures of various pigments can also be used. A definition and further descriptions are found in the "Handbook of PVC Formulating", E.J. Wickson, John Wiley & Sons, New York, 1993, incorporated herein by reference in its entirety. X. Antioxidants
    Exemplary embodiments include alkylated monophenols, e.g., 2,6-di-tert-butyl-4-methylphenol, alkylthiomethylphenols, e.g., 2,4-dioctylthiomethyl-6-tert-butylphenol, alkylated hydroquinones, e.g. , 2,6-di-tert-butyl-4-methoxyphenol, hydroxylated thiodiphenyl ethers, eg 2,2'-thiobis(6-tert-butyl-4-methylphenol), alkylidenebisphenols, eg 2, 2'-methylene-bis(6-tert-butyl-4-methylphenol), benzyl compounds, eg 3,5,3',5'-tetratert-butyl-4,4'-dihydroxydibenzyl ether, hydroxybenzylated malonates, eg dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, hydroxybenzyl aromatics eg 1,3,5-tris(3,5-di-tert -butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, triazine compounds, eg 2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1, 3,5-triazine, phosphonates and phosphonites, eg dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, acylaminophenols eg 4-hydroxylauranilide, β-(3,5-diterc acid esters) -butyl-4-hydroxyphenyl) propionic, eg pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid, e-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid, 3,5-ditert-butyl-4-hydroxyphenylacetic acid esters with mono- or polyhydric alcohols, e-(3,5-ditert-butyl-4-hydroxyphenyl)propionic acid amides, such as, for example, N,N'-bis(3,5-ditert-butyl-4- hydroxyphenylpropionyl)hexamethylenediamine, vitamin E (tocopherol) and derivatives. Mixtures of antioxidants can also be used.
    [0075] Examples of the amounts of antioxidants used are from about 0.01 to about 10 parts by weight, advantageously from 0.1 to about 5 parts by weight and in particular from about 0.1 to 3 parts by weight , based on 100 parts by weight of PVC. XI. UV Absorbers and Light Stabilizers
    [0076] Examples of UV absorbers and light stabilizers include 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-hydroxybenzophenones, non-benzoic acid esters substituted or substituted such as 4-tert-butylphenyl salicylate, phenyl salicylate, acrylates, nickel compounds, oxalamides such as 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-ditert-butyloxanilide, 2 -(2-hydroxyphenyl)-1,3,5-triazines such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4 -octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, sterically hindered amines such as bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate and others. Mixtures of UV absorbers and/or light stabilizers can also be used.
    [0077] As provided above, the plasticizer compositions of the present invention may be incorporated into one or more halogen-containing polymers in, for example, a blending or formulation step. Examples of halogen-containing polymers include vinyl chloride (PVC) polymers, vinylidene chloride polymers, vinyl resins whose structure contains vinyl chloride units such as vinyl chloride copolymers and alkylglycidyl acrylates, vinyl chloride copolymers and vinyl esters of aliphatic acids, in particular vinyl acetate, vinyl chloride copolymers with acrylic or methacrylic acid esters and with acrylonitrile, vinyl chloride copolymers with diene compounds and with unsaturated dicarboxylic acids or anhydrides thereof, such as chloride copolymers vinyl with diethyl maleate, diethyl fumarate or maleic anhydride, post chlorinated polymers and vinyl chloride copolymers, vinyl chloride and vinylidene chloride copolymers with unsaturated aldehydes, ketones and others such as acrolein, crotonaldehyde, vinyl methyl ketone , vinyl methyl ether, vinyl isobutyl ether and others; vinylidene chloride polymers and copolymers thereof with vinyl chloride and other polymerizable compounds; vinyl chloracetate and dichlorodivinyl ether polymers; chlorinated vinyl acetate polymers, chlorinated polymeric esters of acrylic acid and α-substituted acrylic acid; chlorinated styrene polymers such as dichlorostyrene; chlorinated rubbers; chlorinated ethylene polymers; chlorinated powder polymers and polymers of chlorobutadiene and copolymers thereof with vinyl chloride, chlorinated natural or synthetic rubbers, and also mixtures of polymers mentioned with themselves or with other polymerizable compounds. For the purposes of the present invention, PVC includes copolymers with polymerizable compounds, such as acrylonitrile, vinyl acetate or ABS, where these can be suspension polymers, bulk polymers or else emulsion polymers.
    [0078] Preference is given to a homopolymer of PVC, post chlorinated PVC (C-PVC), also in combination with polyacrylates.
    [0079] Other suitable polymers are PVC graft polymers with EVA, ABS or MBS. Preferred substrates are mixtures of the aforementioned homo and copolymers, in particular vinyl chloride homopolymers, with other thermoplastics or/and elastomeric polymers, in particular mixtures with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM or with polylactones, in particular from the group consisting of ABS, NBR, NAR, SAN and EVA. The abbreviations used for copolymers are familiar to those skilled in the art and have the following meanings: ABS: acrylonitrile-butadiene-styrene; SAN: styrene-acrylonitrile; NBR: acrylonitrile-butadiene; NAR: acrylonitrile-acrylate; EVA: ethylene-vinyl acetate. Other possible polymers are, in particular, styrene-acrylonitrile copolymers based on acrylate (ASA).
    [0080] The plasticizer compositions of the invention, in particular in the form of flexible PVC formulations, are used in, and suitable for, wire and cable capping and insulation, decorative covering, forage membranes, agricultural and packaging films, hoses, pipes, floor coverings, shower curtains, carpet backing, interior and exterior trim, sealants and coatings, and automotive parts. Further examples of the use of the plasticizer compositions according to the invention include plastisols, e.g. plastisol for artificial leather, floors, textile coatings, wall coatings, coatings for coils, protective carpet coatings and carpets for motor vehicles.
    [0081] In some embodiments, conventional plasticizers can be used in combination with the plasticizer compositions of the invention, or in combination with fatty acid monoester epoxidized plasticizers, which the invention also provides. The weight ratio of epoxidized fatty acid monoesters to conventional plasticizers can be about 1:1, 1:2, 1:3, 1:5, 1:8, 1:10, 2:1, 3: 1, 5:1 or 8:1. A weight ratio in the range of from about 1:5 to about 3:1 is preferred. Representative conventional plasticizers that can be combined with the fatty acid monoester epoxy plasticizers are butylbenzyl phthalate, di-isononyl phthalate and dioctyl terephthalate.
    [0082] In yet some embodiments, the invention provides a method of reducing plasticizer extraction comprising adding an effective amount of the inventive plasticizer compositions to halogenated polymers such as PVC.
    [0083] In some embodiments, the invention provides a process for preparing plasticizer compositions for reduced plasticizer extraction from plasticized halogenated polymers comprising the steps of (i) providing a fatty acid monoester epoxidized; and (ii) mixing said fatty acid mono-ester epoxidate with an epoxy-ester and, optionally, a metal perchlorate and/or antioxidant, for a predetermined amount of time, at room temperature to achieve a stable homogeneous liquid mixture. . In some of these embodiments, a product made by said process is provided by the invention.
    [0084] In other embodiments, the invention provides a process for making a plasticized halogenated polymer composition for reduced plasticizer extraction from plasticized halogenated polymers comprising the steps of: (i) providing a fatty acid monoester epoxidate; (ii) mixing said fatty acid mono-ester epoxidate with an epoxy-ester and optionally a metal perchlorate and/or antioxidant, for a predetermined amount of time, at room temperature to achieve a stable homogeneous liquid mixture and (iii) addition of said stable homogeneous liquid mixture with a halogenated polymer. Examples of suitable halogenated polymers include polyvinyl chloride (PVC), which is preferred.
    [0085] The invention also provides product(s) made by any of the processes disclosed in this document.
    [0086] In other embodiments, the invention provides plasticized PVC compositions made by a process comprising the steps of providing a fatty acid mono-ester epoxidized, mixing said fatty acid mono-ester epoxidized with an epoxy-ester during a predetermined amount of time at room temperature to achieve a stable homogeneous liquid mixture and adding said stable homogeneous liquid mixture for PVC at a temperature in a range of 0-300°C. Preferred is a temperature range of 10-300°C, 0200°C, 10-200°C, 10-100°C, more preferred 20-80°C, 30-60°C. Other examples of mixing temperatures include 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 140, 150°C. These are also included as minimum temperatures.
    In certain embodiments, the inventive plasticizer compositions may provide lower cloud points than epoxidized fatty acid mono-esters and/or epoxy-esters, i.e. the individual components. It is well understood in the art that cloud points can be indicative of the stability of a particular liquid material, including the inventive plasticizer compositions. Without being bound by specific theory, cloud points can represent the lowest temperature at which a liquid matter, such as the inventive plasticizer compositions, remains free from ice crystal, gelling and cloudiness. When compared to epoxy-esters, the inventive plasticizer compositions can provide reduced cloud points of at least about 10%. Other examples of cloud point reduction, as provided by the inventive plasticizer compositions, include at least about 15%, 20%, 30%; compared to epoxy-ester cloud points.
    [0088] In certain embodiments, the invention provides compositions for improved electrical properties such as bulk resistivity. In some of these embodiments, the plasticizer compositions of the invention provide or impart such improved electrical properties. In yet some embodiments, the inventive plasticized halogenated polymer compositions provide improved electrical properties. Electrical properties including bulk resistivity may improve by at least 5-25% compared to identical plasticized halogenated compositions except for the inclusion of the inventive plasticizer compositions.
    [0089] The electrical property improvement compositions such as bulk resistivity that the invention provides may optionally include antioxidants. Suitable antioxidants that can be included for improved electrical properties are phenolic antioxidants such as alkylated monophenols, di-, tri- and tetraphenols. Exemplary antioxidants further include phosphites and thioesters.
    Also suitable are alkylated monophenols, eg 2,6-di-tert-butyl-4-methylphenol, alkylthiomethylphenols, eg 2,4-dioctylthiomethyl-6-tert-butylphenol, alkylated hydroquinones, eg. , 2,6-di-tert-butyl-4-methoxyphenol, hydroxylated thiodiphenyl ethers, eg 2,2'-thiobis(6-tert-butyl-4-methylphenol), alkylidenebisphenols, eg 2, 2'-methylene-bis(6-tert-butyl-4-methylphenol), benzyl compounds, eg 3,5,3',5'-tetratert-butyl-4,4'-dihydroxydibenzyl ether, hydroxybenzylated malonates, eg dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, hydroxybenzyl aromatics eg 1,3,5-tris(3,5-di-tert -butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, triazine compounds, eg 2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1, 3,5-triazine, phosphonates and phosphonites, eg dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, acylaminophenols eg 4-hydroxylauranilide, β-(3,5-diterc acid esters) -butyl-4-hydroxyphenyl)propionic , eg pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, acid β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid, e-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid, 3,5-ditert-butyl-4-hydroxyphenylacetic acid esters with mono- or polyhydric alcohols, e-(3,5-ditert-butyl-4-hydroxyphenyl)propionic acid amides, such as, for example, N,N'-bis(3,5-ditert-butyl-4-hydroxyphenyl) -propionyl)hexamethylenediamine, vitamin E (tocopherol) and derivatives.
    [0091] Mixtures of at least antioxidants can also be used. Examples of the amounts of antioxidants used are from about 0.01 to about 10 parts by weight, advantageously from about 0.1 to about 5 parts by weight and in particular from about 0.1 to about 3 parts by weight. weight, based on 100 parts by weight of PVC. Particularly preferably it is a range of from about 0.1 to about 1 part, based on 100 parts by weight of PVC.
    [0092] In order that the invention disclosed in this document may be more fully understood, the following examples are provided. These examples are for illustrative purposes only and are not to be construed as limiting the invention in any way. Like the rest of the description, parts and percentages are given on a weight basis unless otherwise indicated. EXAMPLES Materials:
    The materials listed below were obtained from Galata Chemicals, LLC (Southbury, CT): 2-Ethylhexyl talate epoxidized (designated EOT below) as Drapex ® 4.4; 2-ethylhexyl soiate (EOS) epoxidized such as Drapex ® 5.2; soy oil epoxiity (ESBO) such as Drapex ® 6.8.
    Butylbenzyl phthalate (BBP), dipropylene glycol dibenzoate (DPGDB) and dioctyl terephthalate (DOTP) were purchased from Sigma-Aldrich.
    The following compounds were obtained from Chemtura Corp (Middlebury, CT): 2,2'-methylene-bis(6-t-butyl-4-methylphenol) as Lowinox 22M46; pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) as Anox 20; octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate such as Anox PP18. Abbreviations:
    [0096] I.E.= inventive examples; PB = plasticizer mixture. Examples 1-3
    [0097] Plasticizer blends were prepared by mixing 75g 2-ethylhexyl talate epoxidized and 25g soybean oil epoxidized (PB 1); 62.5 g of 2-ethylhexyl talate epoxidized and 32.5 g of soybean oil exoxidized (PB 2); 50g 2-ethylhexyl talate epoxidized and 50g soy oil epoxidized (3 PB). Samples were mixed for 1 hour at room temperature to achieve a stable, homogeneous liquid mixture. Example 4 - Cloud Point Test Samples prepared in Examples 1-3, as well as the ESBO and EOT controls were cooled in order to determine the lowest temperature point at which the samples remain free of haze, gelling and cloudiness. As can be seen from Table 1, cloud points of the inventive plasticizer compositions, PB 1-PB 3, are surprisingly lower (41°F) than the cloud point for the controls, i.e. the individual blend components ESBO and EOT, at 49°F and 69°F, respectively. This represents a 16% reduction in cloud point vs EOT control (see Table 1). Table 1 - Cloud Points of Compositions/Mixtures of Plasticizer and its Components
    & (Temp.EOT-Temp.PBX)/Temp.EOT *100 Flexible Polyvinyl Chloride (PVC) Sample Preparation
    [0098] The formulations tested included the following: Oxy-450 PVC resin added at 100 phr; plasticizers: the blends according to Examples 1-3 and the following controls: di-isononyl ptalate (DINP), ESBO and EOT; BA/Zn Mark® 4781A stabilizer (sold by Galata Chemicals LLC) and stearic acid lubricant were added to all formulations at 2.5 and 0.2 phr, respectively (cf. Table 2).
    [0099] The above amounts are expressed in "phr", which means parts per 100 parts of PVC resin and indicates how many parts by weight of the particular substance are present in the PVC formulation based on 100 parts by weight of PVC. Table 2- Tested Formulations
    * Comparative B, a 37/3 (weight/weight). DINP/ESBO blend, represents a typical plasticizer composition in which ESBO is used as the smallest component.
    [00100] For converting the powder form of the PVC formulations into a usable form, a sheet was prepared under standard conditions using a two-roll mill (Dr. Collin GmbH, Ebersberg, Germany). The gap between the rollers was about 0.5 mm; roller temperature 165°C; preparation and homogenization time: 5 minutes; 0.5 mm sheet thickness. The PVC sheet was continuously moved from both sides towards the center and the enlargement thus obtained was distributed over the span with a wooden spatula on the roller with intense homogenization of all components.
    [00101] Similar formulations were prepared for the plasticizer blends containing BBP, DPGDB and DOTP esters. Plasticized Polyvinyl Chloride (PVC) Test Example 5 - Shore A Hardness
    [00102] Shore A hardness of the formulations was determined according to ASTM D2240, using a commercially available Type A Durometer hardness tester (Shore Instrument & Mfg Co, Jamaica, NY, USA). The analyzed samples were prepared according to the sample preparation technique described above. Shore A hardness characterization results were measured in triplicate; Table 3 contains an average of the three readings. A lower number indicates softer material. Softer materials are desirable. Table 3 - Shore A hardness of PVC formulations

    [00103] The data demonstrates that Shore A hardness values of PVC formulations containing the inventive plasticizer compositions give softer PVC (Shore A Hardness of 87 and 88, respectively, at equal plasticizer loading levels) than PVC which contains the phthalate controls (Shore A hardness of 91) and PVC containing the individual mix components (Shore A hardness of 92). Example 6 - Volatility of plasticizer mixtures incorporated in flexible PVC formulations
    [00104] Volatility of the plasticizer mixtures incorporated in the bleached flexible PVC sheets (thickness 0.5 mm) was calculated as a percentage of weight loss after exposing the prepared bleached PVC sheet chips (25 x 25 mm) at 135 °C of temperature for more than 24 hours of time. Weights were recorded using an analytical balance. Results were measured in triplicate. Table 4 shows an average of the three readings. Table 4 - Volatility of flexible PVC formulations
    *Cf. WO2011/143028, but no elastomeric compatibilizers
    [00105] The results in Table 4 demonstrate that the inventive PVC formulations (IE 1 - 3) are significantly less volatile (by 4179%) than a control formulation, Comparative B. The results in Table 4 show a significant reduction in volatility is unexpectedly achieved in the absence of any compatibilizers (including those described in WO2011/143028). Example 7 - Extraction of plasticizers from flexible PVC formulations
    [00106] Extraction of plasticizers from bleached flexible PVC sheets (thickness 0.5 mm) was measured by sinking the weighed samples of known surface area into a) sunflower oil at room temperature for 14 days and b) hexane at room temperature for 24 hours. Weight loss associated with plasticizer extraction was calculated in mg/dm2 after removing the oil samples, wiping away any excess oil, washing the samples with isopropanol to completely remove surface oil, and air drying the samples. Weights were recorded using an analytical balance. Results were measured in triplicate. Tables 5-7 contain an average of the three readings. Table 5 - Extraction of plasticized PVC formulations

    [00107] Table 5 shows the extraction results for flexible PVC formulations containing both the inventive plasticizer mixture and DINP/ESBO control. The inventive plasticizer blends (I.E.2) when incorporated into PVC result in lower extraction than the Control Comparative B.
    [00108] Tables 6-7 demonstrate that the inventive plasticizer blends gave lower extraction values for extraction out of a PVC matrix compared to the calculated extraction values for the individual components of the blends. The calculated extraction values are based on the extraction of the individual control components and their respective concentrations in the mixtures.
    [00109] The plasticizer compositions of the invention reduce extraction in the range of 33 to 52%, with amounts of epoxy ester ranging from 25% to 37.5 wt% based on the total weight of the plasticizer (Table 6). For fatty acid monoester epoxy plasticizer compositions, extraction reduction was 29 to 57%, with phthalate esters being added at 25% by weight based on the total weight of the plasticizer (Table 7). Table 6 - Reduced extraction of plasticizer compositions
    Plasticizer composition comprising fatty acid monoester epoxidized and conventional plasticizer: Table 7 - Reduced extraction of fatty acid monoester epoxidized plasticizer compositions (containing phthalate esters at 25% by weight based on total weight of the plasticizer)


    [00110] The results demonstrate a significant, unexpected reduction in actual extraction versus calculated extraction (in percent) for inventive examples, IE 4 - 6 vs. Controls. Thus, up to 57% reduction of actual extraction vs calculated extraction is achieved in IE 4. Example 8 — Volatility and Haze Tests Table 8 — Improved Volatility and Haze Characteristics of Plasticizer Compositions
    The results demonstrate synergism for volatility and haze characteristics of the plasticizer compositions of the invention, inventive examples, IE 8 - 10, when compared to controls made from individual blend components (Comparative J, K) and a control containing a conventional plasticizer (Comparative I). As can be seen, inventive example IE 9 gives less volatility and haze than Comparative J and K. Example 9 — Electrical Properties: Measurement of Volume Resistivity
    [00111] All antioxidants (AO1 - 3) were dissolved in the plasticizer composition mixtures according to Table 9, mixing the components at room temperature for 1 hour. Table 9 — Improved Bulk Resistivity for Plasticizer Compositions Containing Antioxidants

    AO1: 2,2'-Me1 ylene-bis(6-t-butyl-4-methylphenol) AO2: pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) AO3: octadecyl- 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate The results for volume (ie, electrical) resistivity in Table 9 demonstrate a significant and unexpected improvement for Inventive Examples IE 11-14 when compared to controls ( Comparative LM). As can be further noted, IE11-14 of the invention, composed of plasticizers and antioxidants, imparts much higher electrical/volume resistivity (as measured in Ohm meters) than an otherwise identical material except for the presence of antioxidants (EOT/ ESBO). Example 10 — Yellow Index Reduction with Metal Perchlorate
    [00112] All PVC compounds were plasticized by adding the inventive plasticizer compositions/blends at 40 phr to PVC. Sodium perchlorate (NaClO4), obtained as Mark CE-350 from Galata Chemicals LLC, was added to the inventive plasticizer blends at 0.8 percent by weight. Table 10 — Perchlorate-Based Yellow Reduction as Measured by Static Heat Stability Test at 190°C

    *in 40 phr
    [00113] The results in Table 10 demonstrate that inventive examples, IE 15 and 16 significantly and unexpectedly reduce the Yellow Index, as measured over time during exposure to 190°C, when compared to identical controls, except for the presence of NaClO4 (Comparative N, O).
    权利要求:
    Claims (13)
    [0001]
    1. Plasticizer composition, characterized by the fact that it comprises: i. a fatty acid monoester epoxidized, wherein the fatty acid monoester epoxidized is selected from 2-ethylhexyl talate epoxidized, 2-ethylhexyl soiate epoxidized, octyl talate epoxidized, octyl soiate epoxidized, octyl oleate epoxidized, methyl soiate epoxidized or mixtures thereof; ii. an epoxy-ester, wherein the epoxy-ester is selected from soy oil epoxidized, linseed oil epoxidized and mixtures thereof, the fatty acid mono-ester epoxidized and epoxy-ester being substantially free of mono - and/or diglycerides, and wherein the epoxy-esters and fatty acid mono-ester epoxidates are present in such amounts that a weight ratio of epoxy-esters/fatty acid mono-ester epoxidates ranges from 1/3 to 3/1; and iii. a metal perchlorate.
    [0002]
    2. Plasticizer composition according to claim 1, characterized in that it additionally comprises a conventional plasticizer selected from phthalates, hydrogenated phthalates, aliphatic dicarboxylic acid esters, polymeric dicarboxylic acid esters, citrates, sucrose esters, levulinic ketal esters, phosphates, alkyl phenol sulfonates, pyrrolidones or mixtures thereof, wherein the weight ratio of fatty acid monoester epoxidized to conventional plasticizer is from 1:5 to 3:1.
    [0003]
    3. Plasticizer composition according to claim 1 or 2, characterized in that the metal perchlorate is sodium perchlorate or potassium perchlorate.
    [0004]
    4. Plasticizer composition according to claim 3, characterized in that the metal perchlorate is sodium perchlorate.
    [0005]
    5. Plasticizer composition according to any one of claims 1 to 3, characterized in that it additionally comprises an antioxidant.
    [0006]
    6. Plasticizer composition according to claim 5, characterized in that the antioxidant is pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), octadecyl-3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate or 2,2'-methylene-bis(6-t-butyl-4-methylphenol).
    [0007]
    7. Plasticizer composition according to claim 6, characterized in that the antioxidant is pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).
    [0008]
    8. Plasticizer composition according to claim 6, characterized in that the antioxidant is octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
    [0009]
    9. Plasticizer composition according to claim 6, characterized in that the antioxidant is 2,2'-methylene-bis(6-t-butyl-4-methylphenol).
    [0010]
    10. Plasticized halogenated polymer composition, characterized in that it comprises a halogenated polymer and the plasticizer composition defined in any one of claims 1 to 3.
    [0011]
    11. Composition according to claim 10, characterized in that the halogenated polymer is PVC.
    [0012]
    12. PVC article, characterized in that it comprises the plasticizer composition defined in any one of claims 1 to 3.
    [0013]
    13. PVC article according to claim 12, characterized in that it additionally comprises flexible PVC.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-07-21| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-03-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-04| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161547427P| true| 2011-10-14|2011-10-14|
    US61/547,427|2011-10-14|
    US201261590204P| true| 2012-01-24|2012-01-24|
    US61/590,204|2012-01-24|
    PCT/US2012/059814|WO2013055961A1|2011-10-14|2012-10-11|Plasticizers derived from renewable feedstock|
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