MX2008006565A - Adducts of levulinic derivatives with epoxidized fatty acid esters and uses thereof - Google Patents

Abstract

The present disclosure relates to methods of preparation of compounds resulting from the reaction of levulinic esters and epoxidized unsaturated fatty acid esters. The compounds are useful as renewable biomass-based plasticizers for a variety of polymers. Mono-, di- and tri-ketal adducts formed in a reaction between alkyl esters of levulinate and epoxidized unsaturated fatty acid esters derived from vegetable oils are also disclosed.

Description

ADDITIVES OF LEVULIN DERIVATIVES WITH EPOXY FATTY ACID ESTERS AND THEIR USES FIELD OF THE INVENTION The present invention relates to methods for the preparation of epoxidized unsaturated fatty acid ester and levulin ester compounds. The compounds are useful as renewable biomass-based plasticizers for a variety of polymers. BACKGROUND OF THE INVENTION Plasticizers for various polymers are widely known in the art. Most plasticizer compounds are produced from petroleum-based raw materials that are expensive and non-renewable. Certain plasticizer compounds are prepared from analysable raw materials such as triglycerides or from vegetable oils, typically through the epoxidation of unsaturated fatty acid fragments. However, epoxidized triglycerides have significant limitations and can not be used satisfactorily as primary plasticizers, because their compatibility with polyvinyl chloride (PVC) polymers is limited. Certain esters of aliphatic dicarboxylic acids such as esters of sebacid and azelaic acids are produced from various unsaturated fatty acid compounds. Dicarboxylic acids have excellent plasticizing properties. Ref .: 193421 However, due to the complexity of the synthesis involved or the costs of raw materials, dicarboxylic acids are relatively expensive and are used as premium products in applications provided for use at low temperatures. Certain known plasticizer compounds used in industrial practice, such as esters of phosphoric acid and alkylated phenols, are harmful to the environment and confer unpleasant odors on the finished products and cause harmful air pollution. Commonly used in plasticizing PVC, esters of italic acid have recently been implicated as endocrine disrupters responsible for the harmful reproductive effects in animals and humans, and for the reproductive toxicity of humans in humans, in particular. Accordingly, it is desirable to provide plasticizing compounds that are non-expensive, non-toxic, made from abundant renewable raw materials, and that have products that are distributed in the environment substantially devoid of harmful effects. BRIEF DESCRIPTION OF THE INVENTION The ester compounds described are versatile plasticizers with good compatibility with many polymers. These ester compounds reproduce abundant and inexpensive raw materials such as esters of unsaturated fatty acids and esters of levulinic acid.

The epoxide groups of monoepoxidated unsaturated fatty acid esters react with levulinic esters in the presence of a suitable catalyst, typically an aprotic acid or a Lewis acid, to form ketals of levulin esters of dihydric fatty acid esters. Similarly, levulinic acid esters react with esters of bis-epoxidized and tris-epoxidized unsaturated fatty acid esters of unsaturated fatty acid esters having two or three double bonds, thereby producing the corresponding bis-ketals and tris-ketals. Additionally, levulinic acid and angelicalactone can be used in combination or in place of the levulinic acid ester in the reactions with epoxidized unsaturated fatty acid esters. The adducts of the levulinic fatty acid ester and the epoxidized unsaturated fatty acid are useful as plasticizers for a range of industrial polymers. Examples of compounds prepared from levulinic acid ester, levulinic acid, and / or angelicalactone and an epoxidized unsaturated fatty acid may include the formula: and the formula where X is selected from the following: and wherein R1 and R2 are independently linear or branched Ci-Cio alkyl or alkoxyalkyl; one of A or B is hydrogen and the other is an esterified carboxy group; and n and m are independently integers from 0 to 20, and the value of the sum of m + n is in the range of 8 to 21. The reaction product can also have the formula: wherein R1 and R2 are independently linear or branched alkyl or alkoxyalkyl of Ci-Cio- When the ester of levulinic acid, levulinic acid, and / or angelicalactone are reacted with a bis-epoxidized or tris-epoxidized unsaturated fatty acid ester, Examples of the resulting compounds may include the following: wherein R1 and R2 are independently C1-C10 linear or branched alkyl or alkoxyalkyl. In some embodiments, R1 and R2 may be methyl, ethyl, n-butyl, isobutyl, isoamyl, or 2-ethylhexyl. The compounds can also be used as a plasticizer with a base polymer in a plasticized polymer composition. A base polymer may include polymers of vinyl chloride, poly (3-hydroxyalkanoate), poly (lactate), and polysaccharide polymers. BRIEF DESCRIPTION OF THE FIGURES Details of one or more of the embodiments of the invention are set forth in the appended figures and the following description. Other features, objects and advantages of the invention will be apparent from the description and the figures and from the claims. Figures 1A-1B demonstrate a mass spectrum The representative of the compounds (4) (Figure 1A) and (11) (Figure IB), obtained in the course of a GC-MS analysis, for example 6. (Electron ionization at 70 eV). Figures 2Ai and 2A2 are mass spectra representative of compounds (4) (Figure 2Ai) and (11) (Figure 2A2), obtained in the course of GC-MS analysis, for example 7 (Sample B). Figure 2B is a mass spectrum IE representative of the mixture of isomers of the epoxy ketal compound (13a) and (13b) (Sample A, Example 7). Figures 3A-3B show a mass spectrum IE representative of mixtures of isomers of the monoketal compound (4) wherein R1 = R2 = ethyl (Example 24) (Figure 3A), and a mass spectrum IE representative of the mixture of isomers of the diketal compound (11) wherein R1 = R2 = ethyl (Example 24) (Figure 3B). Figures 4A-4B show a mass spectrum IE representative of mixtures of isomers of the monoketal compound (4) wherein R1 = R2 = n-butyl (Example 25) (Figure 4A), and a mass spectrum IE representative of the mixture of isomers of the diketal compound (Figure 4B) wherein R1 = R2 = n-butyl (Example 25). DETAILED DESCRIPTION OF THE INVENTION The following terms apply: Unsaturated fatty acids means linear monocarboxylic acids having from 10 to 24 carbon atoms and at least one double bond. The double bonds can be in any position, conjugated to each other or non-conjugated, but not in alénic configurations, and any of the double bonds can independently be cis or trans. Preferably, the unsaturated fatty acids have from 1 to 3 double bonds. The fatty acids may also be composed of a mixture of several unsaturated and saturated fatty acids, for example, as in the triglycerides of various vegetable oils, fish oils, and palm oils. Esters of unsaturated fatty acids means esters of the fatty acids described above with monohydric or polyhydric alcohols. Monohydric alcohols are linear or branched primary or secondary alkanoles or alkoxyalkanols having from 1 to 12 carbon atoms. Preferred examples of alkanols are ethanol, propanol, isopropanol, butanol, secondary butanol, isobutanol, isoamyl alcohol, 2-ethexanol. Preferred alkoxyalkanols are primary or secondary alcohols having from 3 to 12 carbon atoms, wherein a linear, branched or cyclic alkoxy group having from 1 to 8 carbon atoms is located in a position adjacent to the hydroxyl group. Alkoxyalkanols are typically derived through the opening of an alkyl oxirane with an alkanol. Another suitable example of an alkoxyalkanol is the tetrahydrofurfuryl alcohol easily accessible through the hydrogenation of furfural. Monohydric alcohols are most preferred due to their availability, cost and satisfactory stability of its esters. Polyhydric alcohols are linear or branched polyhydric alkanes having from 1 to 6 hydroxyl groups. Typical examples are ethylene glycol, 1,2- and 1,3-diols of propylene, isomers of butylene glycol, glycerol, 1,2,4-trihydroxybutane, pentaerythritol, xylitol, ribitol, sorbitol, mannitol, and galactitol. The polyhydric alcohols may optionally contain one or more ether linkages, and suitable examples of the polyhydric alcohols are isosorbide, sorbitan isomers, and diglycerol. It is preferred that substantially all of the hydroxyl groups of the polyhydric alcohols are esterified with an unsaturated fatty acid group. It is understood that in industrial practice it may not be practical to achieve complete esterification. It is also understood that in industrial practice, when mixed fatty acid compositions are used, not all fatty acid groups can be introduced and some groups of fully saturated fatty acids can be present. In fact, it is advantageous in terms of cost to use mixtures of unsaturated and saturated fatty acid esters such as those present in triglycerides of typical vegetable oils (for example, soybean oil, flaxseed oil, canola oil, olive oil). safflower, sunflower oil, corn oil, castor oil, mixtures thereof and the like).

It is preferred, however, that the mixed fatty acid esters contain predominantly unsaturated fatty acid esters. It is also preferred that the fatty acid ester with a high content of mono-unsaturated fatty acid ester be used, such as compositions found in highly oleic cane oil. 10-undecylenic acid esters are also preferred. Another preferred starting material is a mixture of methyl esters of fatty acids derived through the trans-esterification of plant acids (for example, soybean oil, canola oil and other unsaturated triglycerides commonly used in the industrial production of several biodiesel fuels). Various esters of unsaturated fatty acids can optionally be mixed, partially hydrogenated, or on the contrary isomerized to change the position or stereochemistry of the double bonds. Ester of epoxidized unsaturated fatty acid means that at least one of the double bonds of the unsaturated fatty acid ester is oxidized to an epoxy group. Oxidations are well known in the art and can be easily achieved on an industrial scale, for example, through the use of acid peroxide and a carboxylic acid (eg, formate or acetate), or through the halohydrin method. It is preferred, however, that the epoxidation of most or all of the double bonds present in the unsaturated fatty acid esters be achieved. It is understood that in practice, the epoxidized fatty acid esters may contain various amounts of by-products that arise from the hydrolysis or reconfiguration of the epoxides and the entanglements of the fatty acid chains. The use of epoxidized fatty acid esters containing small amounts of epoxidation by-products and epoxide decomposition byproducts are completely within the scope of the present disclosure. Levulinic esters are esters of (4-oxopentanoic) levulinic acid and a monohydric alcohol. However, the monohydric alcohol fragment in the levulinic ester is independently selected from the monohydric alcohol moiety of the esters of unsaturated fatty acids, and thus may be the same or different. The levulinic esters can optionally be mixtures of levulinic esters with more than one monohydric alcohol. Polymers Poly (vinyl chloride) polymers, PVC, are homopolymers or co-polymers of vinyl chloride. Many PVC compounds of various degrees of polymerization, crosslinking and co-polymer compositions are known in the art and are produced industrially. The poly (3-hydroxyalkanoate), PHA, are homopolymers or co-polymers of polyester of 3-hydroxyalkanoic acids. Preferably, PHA is composed of linear 3-hydroxyalkanoic fragments having from 3 to 18 carbon atoms. The poly (3-hydroxybutyrate), PHB, is a homopolymer that is produced biologically, for example through various microorganisms. A pure PHB polymer is a brittle polymer that has a narrow range of processing temperatures, and easily decomposes at temperatures that are only 20-30 ° C above its melting temperature. The poly (lactate), or poly (lactide), PLA, is a known polyester homopolymer comprising repeat units of lactic acid of various stereochemistries. The polysaccharides are homopolymers and co-polymers, linear or branched, comprising hexose or pentose fragments connected through glycosyl bonds. The polysaccharides may optionally contain several additional groups such as acylamido groups, sulfate ester groups, carboxylic ester groups, alkyl ether and hydroxyalkyl groups, and the like. Additional groups may be present in polysaccharides derived from natural sources or may be artificially introduced (i.e., through acylation of cellulose). Examples of polysaccharides include acylated cellulose and starch derivatives, as well as native or acylated chitin and pectin.

Plasticizers are chemical compounds added to a base composition comprising one or more of the above polymers for the purpose of lowering the glass transition temperature of the polymer composition, thereby making the composition more flexible and manageable for processing, example, through melt extrusion or molding. The plasticizers are typically used at various effective concentrations, and depending on the polymer used and the desired properties of the polymer formulation formed in the composite, the plasticizers can be used at concentrations between 1 and 80% by weight of the unplasticized polymer. It is understood that, depending on the polymer-plasticizer used, plasticizers can also confer other changes in the physical and mechanical properties of the polymer formed into compounds, as well as changes in the barrier properties of the polymer formed in compounds with respect to their permeability to several glasses, water, water vapor, or organic compounds. It is also understood that one or more different plasticizers can be used in various blends with additional compounds for the preparation of an extrudable or moldable polymer composition. Additional compounds may include various inorganic and organic filler compounds, wood powder, reinforcing fibers, dyes, pigments, stabilizers, lubricants, antiracrobial additives and the like. The plasticizers are typically mixed with polymer and other optional components of the base composition through mixing in various forming equipment of compounds well known in the art at temperatures that are above or below the melting temperature of the polymer. Plasticizers can also be introduced with the help of an optional volatile solvent. The ketal derivatives of levulinic acid are prepared through the reaction of an epoxidized unsaturated fatty acid ester with a sufficient amount of levulinic ester in the presence of a suitable catalyst, thereby resulting in a variety of compounds which are covalent adducts between the fragments of fatty acid ester and levulin fragment. According to the reaction, the ketal ester compound of the formula (3) is formed rapidly: (2) (1) (3) (Reaction 1), wherein (2) is a levulinate ester, (1) is an epoxidized unsaturated fatty acid ester showing the epoxy group, (3) is an ester adduct of ketal, and R 1 is a linear or branched C 1 -C 10 alkyl or alkoxyalkyl. For example, according to this reaction, an easily available ester of 9,10-epoxidized oleic ester is converted into the ketal of the formula (4): wherein R1 and R2 are independently a linear or branched alkyl or alkoxyalkyl of Ci-Cio. Typically, catalysts for reacting epoxides with ketones include various acids. The conditions generally apply to reactions of levulinate esters with epoxidized unsaturated fatty acid esters. Non-limiting examples of the catalysts include strong mineral acids, such as sulfuric, hydrochloric, hydrofluoroboric, hydrobromic, p-toluenesulfonic acid, camphor sulfonic acid, methanesulfonic acid, and the like. Various resins containing protonated sulfonic acid groups are also useful and can be easily recovered after completion of the reaction. Examples of acids also include Lewis acids. For example, boron trifluoride and various BF3 complexes, exemplified by diethyl etherate BF3, are also useful. Silica, acidic albumin, titania, zirconia, various acid clays, mixed aluminum or magnesium oxides can also be used. Activated carbon derivatives comprising mineral acid, sulfonic acid or Lewis acid derivatives can also be used. A person skilled in the art can practice many variations in the part of the catalyst composition and the amounts used in the preparation of the compound described herein. High temperatures can be used to accelerate the reaction with fewer reactive catalysts. However, the temperature of the reaction mixture does not criticize for the success in the manufacture of a quantity of a product levulinic ketal, even with less active catalyst the reaction still progresses to produce the desired compounds. The amount of catalyst type depends on the specific chemical composition of the epoxide and the levulinate ester used in the reaction and can be easily established by one skilled in the art. The reaction can be carried out in the presence of an optional co-solvent which is inert under reaction conditions and is typically removed at the end of the reaction through distillation. Typically, it is desired to use a sufficient amount of a co-solvent (or a sufficient excess of levulinate ester) to miniaturize the entanglement of the epoxidized fatty acid esters through the formation of an ether linkage. Preferred non-limiting examples of suitable co-solvents include saturated hydrocarbons, ethers and carboxylic esters of simple alkanes and alkanoic acids. Similarly to mono-epoxides, the bis-epoxides of unsaturated acid esters are converted into a mixture of stereoisomers comprising bis-ketals of levulinic ester. When mono- or bis-epoxides of unsaturated fatty acid esters are reacted with ethyl levulinate, the reaction of the fatty acid bis-epoxides may be accompanied by other competition reactions. These competition reactions have been found to be advantageous for making useful compounds. In particular, when an amount of free alkanol is present and / or when the protic acid catalyst which favors the trans-esterification reaction is used, the formation of an alkoxyalkanol derivative of an unsaturated fatty acid ester favors the formation of ketal After the use of the conditions which allow the removal of the alkanol after the epoxide opening, the product of the levulinlated trans-esterification of the formula (5) is formed: (CH2) m-B wherein R3 may be linear or branched C1-C10 alkyl or alkoxyalkyl; one of A or B is hydrogen and the other is an esterified carboxyl group; ynym are each integer having values from 0 to 20, and the value of the sum of m + n is in the range of 8 to 21. In a variation the known alkoxyalkanol derivatives of unsaturated fatty acid esters can be prepared through of the epoxide group of an unsaturated fatty acid ester epoxidized with an alkanol. The hydroxyl groups of the alkoxyalkanol derivatives are then esterified with a free levulinic ester or free levulinic acid, or with gamma-angelicalactone thereby providing adjacent alkoxy-levulinoyl derivatives of unsaturated fatty acid esters: wherein (6) is an epoxidized unsaturated fatty acid ester; (7) is a derivative of alkoxyalkanol; (5a) is an alco-levulinoyl derivative; R3 may be a straight or branched alkyl or alkoxyalkyl of Ci_io; one of A or B is hydrogen and the other is an esterified carboxyl group; ynym are integers each having values from 0 to 20, and the value of the sum of m + n is in the range of 8 to 21. When bis-epoxides or tris-epoxies of unsaturated fatty acid esters are used having groups Epoxy placed in close proximity to each other, an intra-molecular epoxide opening reaction also takes place, thereby resulting in the formation of one or more ether bonds each connecting two carbon in the fatty acid carbon chain continuous. Typically, ether linkages result in the formation of a tetrahydrofuran (major) and tetrahydropyran (minor) ring. Complex mixtures of stereoisomers of oxygenated derivatives of unsaturated fatty acid esters are then formed. For example, representative isomers of the products of a bis-epoxide derived from a di-unsaturated fatty acid having two double bonds separated through a methylene group can have the formulas (8a) and (8b) wherein R3, A, B, n, and m are as defined above.

Typically, after removal or neutralization of the catalyst, and typically through distillation under reduced pressure, removal of any excess levulinate ester, solvent, and where applicable, any unsaturated fatty acid ester, which can be removed, is accomplished. being present as impurities in the starting materials of the epoxidized fatty acid ester, resulting in the formation of a stable, transparent and virtually odorless, pure liquid. Depending on the specific conditions used, the liquid comprises the levulinic ketals of vicinal dihydroxy derivatives of unsaturated fatty acid esters and / or mixtures of alkyloxy-levulinoyl compounds. These above compounds may comprise ether linkages connecting two carbon atoms of the unsaturated fatty acid chain (thus forming a tetrahydrofuran or tetrahydropyran ring). Levulinic adducts are useful as plasticizer compounds for PVC, poly (3-hydroxyalkanoates), poly (lactate), and various polysaccharide polymers. These are compatible with those polymers through a wide range of concentrations. By selecting several alkanol fragments present in the reagents used in the synthesis of these adducts, it is possible to adjust the properties of the plasticizer not only with respect to the best plasticizing properties and better compatibility, but also with respect to the barrier properties of the polymer resulting, such as permeability of moisture, gases, solvents, water filtration, and retention of odor and dirt. Also provided herein is a group of similar plasticizer compounds that are substantially devoid of free carbonyl groups, and thus can be mixed with levulinoyl derivatives described herein to give desirable plasticized polymer compositions. Useful plasticizer compounds are produced through the use of an ester of a lower alkanoic acid in place of the levulinic ester. In this modality, the free hydroxyl groups of the alkoxyalkanol derivatives (7) are acylated with lower alkanoic acids or their anhydrides through the trans-esterification, to produce alkaloid esters and lower alkanoic acids. The alkanoic acids used in this embodiment are linear or branched monocarboxylic acids having from 2 to 8 carbon atoms. Preferred examples of the acids are acetic, propionic, butyric, and 2-ethylhexanoic. Preferred esters for the transesterification reactions in this embodiment are esters of the above alkanoic acids and linear or branched primary or secondary alkanols having from 1 to 4 carbon atoms. The alcohol fragment is typically selected with consideration of a desire to have a lower boiling point of the alcohol released in the trans-esterification reaction such that it can be easily removed by distillation as formed during the reaction. Trans-esterification is typically achieved under ordinary conditions well known in the art and involves the acid of an acid or base catalyst. The resulting alkyloxy acyloxy derivatives of mono-epoxides of monounsaturated fatty acid esters have the formula (9): wherein R3 may be a linear or branched alkyl or alkoxyalkyl of Ci-i0; and R 4 may be a linear or branched C 1 -C alkyl; one of A or B is hydn and the other is an esterified carboxyl group; ynym are integers that have values from 0 to 20, and the value of the sum of m + n is in the range of 8 to 21. Similar to the levulin derivatives of the formulas (8a) and (8b), · the derivatives of alkyloxy acyloxy resulting from fatty acid esters of bis-epoxides of dieno fatty acid esters have double bonds separated with a butylene group having the representative structures (10a) and (10b): (10a) (10b) wherein R3, R4, A, B, n, and m are as defined above. The resulting alkyloxy acyloxy derivatives of fatty acid esters and lower alkanoic esters have excellent plasticizing properties similar to the levulinic ester adducts described above. Accordingly, they can be used in a substantially similar manner for the polymer formulations as primary plasticizers or as mixtures with levulinoyl derivatives described herein to control the presence of free carbonyl groups in the plasticized polymer composition. In another embodiment, when the provision of a plasticizing composition for use in various articles containing PVC is desired, the synthesis of the adducts of levulinic esters, and esters of unsaturated epoxidized fatty acids can be carried out using esters of epoxidized unsaturated fatty acid esters. with a contiguous carbon chain of typical fatty acid ester of 18 carbon atoms. The adduct may include compounds containing predominant ketals of the formula (4), and, wherein the bis-epoxides and the tris-epoxides of the unsaturated fatty acid esters are present in the starting materials, they may also be converted to levulinic ketal ester adducts exemplified by bis-ketals of the formula (11) and tris-ketals of the formula (12): wherein R1 and R2 may be a straight or branched alkyl or alkoxyalkyl of Ci-Cio. It is understood that in the embodiments, other reaction products may be formed and may be present in various amounts. The other reaction products may comprise, for example, stereoisomers of epoxy ketals of the formula (13a) and (13b): The reaction products may also include combinations of the compounds of the formulas (5) to (10). Additionally, various amounts of interlaced modified unsaturated fatty acid ester derivatives, wherein two or more contiguous carbon bonds of the unsaturated fatty acid ester are connected through an ether link may also be present. Other compounds that may be present include amounts of saturated fatty acid esters that do not substantially react with levulinic esters and therefore remain unchanged in the resulting product mixtures. In further embodiments, the product mixture comprising any combination of ketal adducts produced from levulinic ester and an epoxidized unsaturated fatty acid ester (typically exemplified by ketal (4), (11), (12), and (13) adducts )), and one or more saturated fatty acid esters (typically employed by hexadecanoic or octadecanoic acid esters and a monohydric alcohol R3-OH), are subjected to additional treatment allowing partial or substantially complete removal of the acid esters saturated fatty acids from the mixture of ketal adducts. The removal is typically achieved through the distillation of saturated acid esters under reduced pressure and high enough temperature to initiate distillation of saturated esters but not of ketal adducts. The conditions for distillation may vary, depending on the temperature and vacuum used, as well as the type of distillation hardware known in the art. It has been found that ketal adducts, such as compounds (4), (11), (12), and (13), have high boiling temperatures that are typically 25-100 ° C higher than those of the corresponding fatty acid esters, and the large Difference in boiling point allows the efficient removal of saturated fatty esters using simple distillation equipment such as descending film columns or other distillation columns with a relatively low number of theoretical plates. It has been found that the partial or substantial removal of the saturated acid esters of the mixtures of levulin ester adducts with epoxidized unsaturated fatty acid esters results in the formation of a mixture of ketal adducts with improved plasticizing properties, improved compatibility and a minimized or insignificant exudation, and a reduced or absent odor. It has also been found that the monoketal adducts of levulinic esters with epoxidized unsaturated fatty acid esters (typically exemplified by the ketals of the formula (4)) can be effectively distilled from the reaction mixtures comprising bis- and tris-ketal adducts. (typically, exemplified by ketals of formulas (11) - (13)) Distillations are typically carried out under vacuum or under reduced pressure, and can provide a high purity monocetal compound in a virtually colorless and odorless form. purified ketals of the formula (4) were found to be excellent PVC plasticizers comparable with the plasticizing properties of PVC to the esters of sebasic and azelaic acids known in the art.The plasticizing compounds can be used alone or in various mixtures, including many other plasticizers known in the art, such as esters of dicarboxylic acids, citric acid, and this of aromatic dicarboxylic acids (for example, esters of italic acid). Particularly useful are mixtures comprising plasticizer compounds prepared with epoxidized triglycerides with a high degree of epoxidation for plasticizing PVC. The epoxidized triglycerides can typically be exemplified through epoxidized soy bean oil and epoxidized linseed oil, while other epoxidized vegetable oils are also useful. In the formulations, the epoxidized fatty acid fragments provide a desired stabilizing effect through the action as scavengers of the acid polymer decomposition products. Plasticizer compounds are useful for making various industrial and consumer items, including flooring materials, side elements for exteriors and interiors of buildings, window frames, flexible and rigid pipes, tubing, reinforced hoses, artificial skin, consumer product packaging , interior and exterior automotive parts, electronic-type housings, several individual and multi-layer films, vinyl office supplies, and the like. A number of embodiments of the invention have been described. However, it is understood that various modifications can be made without departing from the spirit and scope of the description. Accordingly, other embodiments are within the scope of the following claims. EXAMPLES EXAMPLE 1A 506.2 grams of a fully epoxidized soy bean oil (Vicoflex brand 7170, Arkema) were mixed with 1 L of anhydrous methanolic solution containing 2.1 g of sodium methoxide, and the resulting mixture was stirred magnetically at room temperature (18). C) for 6 hours The progression of trans-esterification over time was followed by gas chromatography After the trans-esterification reaction was found to be substantially complete, the reaction mixture was neutralized by the addition of 12.8 grams of anhydrous potassium dihydrogen phosphate powder, followed by further stirring overnight (12 hours) The resulting mixture was filtered and the methanol was evaporated under reduced pressure using a rotary evaporator with a water bath set at 40 °. C. The resulting oil was dissolved in 1 liter of hexanes, filtered and the hexanes were removed under reduced pressure using a rotary evaporator. Therefore, a clear clear product with a weak oily odor (485 g) was obtained and analyzed by GC-MS (gas chromatography - mass spectrometry). When the TIC integration method was used, the oil was found to contain approximately 9% methyl hexadecanoate, 5% methyl octadecanoate, 42% methyl 9,10-epoxy-9-octadecenoate, 40% isomer , 10, -12, 13-bisepoxy-9, 12-octadecenoate methyl, and small amounts of esters of other epoxidized unsaturated fatty acids.

EXAMPLE IB Alternately, soybean oil fatty acids from an edible soy bean oil (supplier Archer Daniels Midland Company) were prepared by trans-esterification and epoxidation reactions. 0.950, kg of soybean oil was stirred with 0.5 L of methanol containing 6 g of sodium hydroxide at 40-45 ° C for about 6 hours. The reaction mixture was neutralized through the addition of 40 g of anhydrous potassium dihydrogen phosphate powder, followed by stirring for 10 hours at room temperature. The methanol was distilled from the resulting mixture under reduced pressure using a rotary evaporator and the remaining solution was mixed with 1 L of hexanes and allowed to stand in a separatory funnel for 2 hours. The lower layer (crude glycerol) was discarded. The upper layer (containing hexane soluble materials) was collected and filtered, and the hexanes were distilled under reduced pressure using a separating funnel. The resulting fatty acid methyl ester mixture (922 g, pale yellowish transparent oil with a weak oily odor) was analyzed through GC-MS and found to be in accordance with a typical soybean oil fatty acid composition. . The oil was dissolved in 0.5 L of hexane, mixed with 100 g of formic acid in 10% solution containing 500 mg of Tween 80 surfactant, and settled in vigorous agitation by means of a magnetic stirrer. While the mixture was continuously stirred, 50% acidic peroxide (a total of 380 ml) was carefully introduced in small portions (20-40 ml) over a period of 8 hours in order to maintain an exothermic reaction mixture at a temperature below the boiling point of the hexanes. The progression of the epoxidation was monitored by GC-MS. After the epoxidation was found to be complete, the reaction mixture was separated in a separatory funnel, and the lower aqueous layer was discarded. The hexane layer was dried over anhydrous sodium sulfate, filtered and the hexane was distilled under reduced pressure. The resulting oil (1.06 kg) was analyzed by GC-MS and found to be practically identical to that obtained in Example IA. EXAMPLES 2-5 The synthesis of the epoxidized fatty acid esters was carried out according to Example IB using samples of olive oil, canola oil, or corn oil obtained from a local grocery store instead of oil of soybeans, or according to Example 1A using an epoxidized linseed oil (Vicoflex brand 7170, Arkema) in place of an epoxidized soy bean oil. All examples were carried out on a 25% scale of the procedures described in Example 1, and all the materials were reduced accordingly. EXAMPLE 6 0.2 g of fatty acid methyl ester of epoxidized soy bean oil from soybean oil according to Example 1, and 1 g of anhydrous ethyl levulinate in 5 ml of tert-butyl methyl ether were dissolved. . While the reaction was stirred at room temperature by means of a magnetic stirrer, 0.01 ml of boron trifluoride etherate was added to the reaction solution, and a mild exothermic effect was observed. After stirring for 20 minutes, the temperature of the reaction mixture was returned to room temperature (18 ° C), and an additional 0.01 ml of boron trifluoride etherate was added, and the reaction mixture was stirred for an additional 30 minutes. , and the reaction products were analyzed by GC-MS. The reaction mixture was found to contain stereoisomers of levulin ketals of the formula (4) and (11) as main reaction products: wherein R1 is methyl and R2 is ethyl. The representative mass spectrum of the isomers is shown in Figs. 1A-1B. The reaction mixture was also found to contain. unreacted ethyl levulinate and unchanged saturated fatty acid ester which was present in the starting material originated from soybean oil. The reaction mixture was found to contain small amounts of the compound (12): wherein R1 is methyl and R2 is ethyl. EXAMPLE 7 1 ml of epoxidized soybean oil fatty acid ester (prepared according to Example 1) was dissolved in 4 ml of dry methyl levulinate, and the reaction mixture was stirred magnetically under nitrogen. While the solution was stirred, the reaction was initiated by the addition of 0.02 ml of boron trifluoride etherate (an exothermic effect was observed). The progress of the reaction was followed by GC-MS. After 30 min, a sample was taken for GC-MS analysis (sample A), and an additional 0.02 ml of boron trifluoride etherate was added. After stirring 30 min more, another sample was taken for GC-MS analysis (sample B). The GC-MS analysis of sample A showed that the main reaction products were compound (4): and stereoisomers of a ketal epoxide compound having the formula (13a) and (13b): wherein R1 = R2 = methyl. The GC-MS analysis of sample B showed that the main reaction products were compound (4) and (11), and only traces of the compounds of (13a) and (13b) were observed, therefore indicating that the compounds (13a) and (13b) are intermediates in the formation of compound (4) resulting from a step of adding a levulinic ester to the bis-epoxide present in the starting material. The representative mass spectrum of the compounds (4), (11), (13) formed in this example is shown in Figures 2AX and 2B. EXAMPLES 8-12 The reactions were carried out as described in Example 7, with the exception of instead of boron trifluoride, one of the following catalysts was used: SnCl 2 (50 mg), SnCl 4 (50 mg), TiCl 4 (50 mg), or p-toluenesulfonic acid (20 mg) anhydrous. The reactions were carried out at 60-80 ° C for 3 hours. The characteristics of the GC and the MS spectrum of the products observed in these examples were in all respects identical to those observed in Example 7. EXAMPLE 13 The reaction was carried out as described in Example 7, except that instead of epoxidized fatty acids of Example 1, 1.2 g of epoxidized soy bean oil (Vicoflex 7170, Arkema) were used, and the amount of boron trifluoride etherate catalyst used was 0.05 ml (introduced all at once) . After completion of the reaction, methyl levulinate was distilled off under reduced pressure. The resulting oil was dissolved in 50 ml of hexanes and washed once with 10 ml of 1% aqueous sodium fluoride, and then twice with 20 ml of water. The hexane solution was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure. A pale yellow oil (1.32 g) was obtained which contained the ketal adducts of methyl levulinate and epoxidized oil. Half of this oil (0.66 g) was dissolved in 10 ml of methanol containing 0.2% w / w of sodium methoxide, and all this was stirred for 2 hours. The reaction mixture was then neutralized by stirring with 0.8 g of potassium dihydrogen phosphate in anhydrous fine powder for 3 hours, filtered, and the methanol was distilled under reduced pressure. The residue was dissolved in 10 ml of hexanes and filtered. The hexanes were removed under reduced pressure, and the resulting oil (0.46 g) was analyzed through GC-MS. The composition of this oil was found to be substantially identical to that obtained in Example 7. EXAMPLES 14-17 The synthesis was carried out in accordance with the Example 7, except that instead of the epoxidized esters of Example 1, epoxidized esters prepared according to Examples 2-5 were used. It was found that all products contained variable amounts of compound (4) and (11), wherein R1 = R2 = methyl, in portions reflecting the abundance of methyl-9-octadecenoate and methyl 9,12-octadecandienate in the starting materials. In addition, the product obtained from the methyl esters of epoxidized linseed oil fatty acids was found to contain copious amounts (about 35-45%) of the tricetal compound (12), wherein R1 = R2 = methyl. EXAMPLE 18 252 grams of epoxidized fatty acid esters of soybean oil were dissolved in 745 g of dry methyl levulinate, and all this was stirred magnetically under nitrogen, and then heated to 70 ° C by means of a water bath. oil. Boron trifluoride etherate (1.2 ml) was introduced in 4 portions (0.3 ml each) at 20 min intervals, while the reaction was magnetically stirred and maintained at 65-70 ° C by means of an oil bath. The progress of the reaction was monitored through GC-MS. After all the catalyst was introduced, stirring was continued for 1 hour at 70 ° C, and then for another hour at room temperature. The methyl levulinate was distilled under reduced pressure by means of a rotary evaporator, with the heating bath set at 105-110 ° C, and using a vacuum pump capable of providing 6 mm of eventual vacuum. The resulting oil was dissolved in 600 ml of hexanes and washed with 100 ml of 2% aqueous sodium fluoride, and then washed twice with 150 ml of water. The washed hexane solution was then dried over anhydrous sodium sulfate and filtered. The filtrate was collected and the hexane was distilled under reduced pressure until a constant weight was reached. The resulting viscous oil (336 g) was pale yellow-amber in color and had a faint oily odor typical of methyl hexadecanoate. The oil was analyzed by GC-MS and found to be practically identical in composition to the product obtained in Example 6. EXAMPLES 19-22 75 g of the product obtained in Example 18 were placed in a 500-ml round bottom flask my coupling to a Kugelrohr rotary type apparatus, and vacuum was applied using a pump capable of providing an eventual vacuum of 0.1 millibars. The rotating flask containing the starting material was heated slightly by means of an established heat gun to provide an air stream heated to 250 ° C, to allow the start of a stable distillation of methyl hexadecanoate and methyl octadecanoate. The distillation was stopped after collecting approximately 5-10 g of methyl hexadecanoate and methyl octadecanoate in the receiving flask, and the content of the undistilled material was evaluated for the presence of methyl hexadecanoate and residual methyl octadecanoate. The procedure for the removal of methyl hexadecanoate and methyl octadecanoate was repeated several times, each time with a fresh batch of starting material. The resulting materials were found to contain mainly stereoisomers of monoketal (4) and dictal (11), and small amounts of tricetal (12), where R1 = R2 = methyl. The resulting mixtures of the compounds were also found to contain small amounts of methyl hexadecanoate and methyl octadecanoate in varying proportions. The total content of methyl hexadecanoate and methyl octadecanoate, when taken together, was found to be less than 0.1% (Example 19), about 1.5% (Example 20), about 2.9% (Example 21), and about 5.1% ( Example 22) by weight. EXAMPLE 23 96 grams of the mixture of compounds prepared according to Example 19 were placed, predominantly containing ketals (4) and (11), wherein R1 = R2 = methyl, in a 500 ml round bottom flask coupled to a Kugelrohr rotary type apparatus, and vacuum was applied using a pump capable of providing an eventual vacuum of 0.1 millibars. The rotating flask containing the starting material was heated slightly by means of an established heat gun to provide an air stream heated to 350 ° C. A slight distillation started, and approximately 32 grams of distillate were collected in the receiving flask, and the distillation was stopped by quenching the heat, and the materials allowed to cool to room temperature under vacuum. The distillate (Example 23A) was a practically colorless and odorless oil. It was analyzed through GC-MS and found to be a 96% pure monocetal compound (4), where R1 = R2 = methyl. Traces of compound (11), (13a) and (13b) were also found (Example 23?). The residual oily material that remained in the distillation flask (Example 23B) was analyzed through GC-MS and found to contain approximately 80% of the stereoisomers of the diketal compound (11), 12% of the monoketal (4), and small quantities of tricetal (12), where R1 = R2 = methyl. EXAMPLES 24-28 16 grams of the mixture containing ketal (4) and dictal (11), R1 = R2 = methyl, were dissolved as main congeners according to Example 19, in 40 ml of one of the following: (24) absolute ethanol with approximately 0.2% w / w sodium ethoxide, (25) n-butanol anhydrous with approximately 0.2% w / w sodium n-butoxide, (26) anhydrous isobutanol with approximately 0.4% sodium isobutoxide, ( 27) anhydrous isoamyl alcohol with 0.3% sodium 3-methylbutoxide, (28) 2-ethylhexyl alcohol with 0.3% sodium 2-ethylhexoxide. The solutions were stirred for 12 hours by means of magnetic stirring at room temperature (26 ° C). The progression of the trans-esterification reaction was monitored by analyzing small aliquots of the reaction mixture by GC-MS. The mixtures of the compounds (4) and (11), wherein R1 or R2 are each methyl and wherein one of R1 or R2 is methyl and the other is ethyl, n-butyl, isobutyl, isoamyl or 2-ethylhexyl is they detected The representative mass spectrum of monoketal (4) and dictal (11) prepared and observed in Examples 24 and 25 is shown in Figures 3a-3B and 4A-4B, respectively. After the trans-esterification reaction was substantially complete, as evaluated by GC-MS analysis, the reaction mixtures were neutralized by the addition of 0.4-0.5 g of powdered anhydrous potassium diacid phosphate followed by vigorous stirring at room temperature for 24 hours. The solutions were then filtered, and the excess alcohol in each sample was distilled under reduced pressure in a rotary evaporator until a constant weight was reached for each of the samples. The resulting oil and products were analyzed through GC-MS and found to contain predominantly compounds (4) and (11), wherein R1 = R2, and R1 and R2 were selected from ethyl, n-butyl, isobutyl , isoamyl, 2-ethylhexyl. EXAMPLES 29-40 The trans-esterification reactions were carried out according to Examples 24 and 25, except that the starting materials comprising levulin ketal adducts (4) and (11) were prepared according to Examples 18 , 20, 21, 22, 23 A and 23B, the resulting product mixtures had R1-R2 selected from ethyl or n-butyl and contained several small amounts of ethyl or n-butyl esters of hexadecanoic or octadecanoic acids in amounts consistent with its abundance in the starting materials before trans-esterification. EXAMPLE 41 Plasticized PVC compositions comprising the compounds (4) and (11) were prepared. Samples of pure plasticizer mixtures comprising varying amounts of ketals (4) and (11), prepared according to Examples 18-40, were vigorously pre-mixed in 20 ml glass jars with dry PVC powder (Nm average of about 55,000, average Pm 97,000, inherent viscosity 0.92, relative viscosity 2.23, supplier Sigma-Aldrich Company, Cat. No. 34,677-2), in proportions to provide a final plasticizer content of 20%, 40 or 60 % in weigh. Bis- (2-ethylhexyl) phthalate, bis- (2-ethylhexyl) sebacate and epoxidized soy bean oil (Vicoflex bry) were used., Arkema) as reference plasticizers. Each of the resulting mixtures was fed individually into a double screw-extruder chamber of Daca Microcompounder (Daca Instruments) under nitrogen, with the mixing chamber heated to 160 ° C, and the engine speed set at 100 rpm. The mixture was then mixed for about 5 minutes. The resulting melt was then extruded from the mixing chamber as a flexible rod (3 mm diameter), which was immediately cooled to room temperature in ambient air. The glass transition data (by differential scanning calorimetry) and the plasticizer exudation data were collected using plasticized PVC specimens from the extruded bars. All mixtures of the compound were cut extruded bars. All mixtures of the compound comprising compounds (4) and / or (11) were found to have satisfactory plasticizing properties, as analyzed by observing the decreased glass transition temperatures compared to the unplasticized polymer. The compounds were also found to have excellent polymer compatibility properties, with minimal or negligible exudation after the stress exudation test. The plasticization efficiency of the compound mixtures prepared according to Examples 18-40 was found to be superior to or comparable to that of bis- (2-ethylhexyl) phthalate. The compatibility and exudation properties of PVC were also found to be superior to epoxidized soybean oil and bis- (2-ethylhexyl) phthalate at the plasticizer concentrations tested. An optimum combination of the effectiveness and compatibility of the plasticizer was observed under the conditions tested when the plasticizer compound mixtures comprised predominantly monoketal (4) and / or diketal (11) having R 1 = R 2 = ethyl or n-butyl. In addition, samples of the plasticizer mixtures comprising monoketal (4) and dictal (11), wherein the concentration of alkyl hexadecanoate and alkyl octadecanoate was about 5% or less by weight of the plasticizer, exhibited better plasticizer compatibility with PVC and showed virtually no exudation as compared to those samples where the concentration of alkyl hexadecanoate and alkyl octadecanoate was in excess of about 5%.

EXAMPLE 42 Samples of plasticized PHB, (poly (3-hydroxybutyrate, of natural origin, Tm 172 ° C, supplied by Sigma-Aldrich Cat. No. 36,350-2) were prepared according to Example 41, except that the temperature of the mixing chamber was set at 180 ° C, the mixing time was set to 3 minutes, and the mixtures of the plasticizer compounds of Examples 18-40 comprising ketals (4) and (11) were prepared at 5, 10, 20 and 30% by weight The mixtures of plasticizer compounds in which R1 = R2 = methyl or ethyl were found to have satisfactory plasticizer efficiency and compatibility under the conditions tested when the plasticizer concentration was at or below about 20% by weight, and when the content of the alkyl hexadecanoate and alkyl octadecanoate was at or below about 1.5% by weight of the plasticizer EXAMPLE 43 The plasticizer polymer compositions were prepared in accordance with Example 42, except that a cellulose acetate polymer with 39.8% acetyl content and Nm of about 30,000 (Sigma-Aldrich Cat. No. 18,095-5) was used. The results obtained were similar to those obtained with the polyester PHB used in Example 42.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (14)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A compound having the formula: characterized in that: R1 is a linear or branched alkyl or alkoxyalkyl of Ci-Cio; one of A or B is hydrogen and the other is an esterified carboxy group; and m and n are independently integers from 0 to 20, where the sum of m + n is in the range of 8 to 21.
2. 2. A compound having the formula: characterized because X is wherein: R 3 is a linear branched C 1 -C 10 alkoxyalkyl alkyl; one of A or B is hydrogen and the other is an esterified carboxy group; and m and n are independently integers from 0 to 20, where the sum of m + n is in the range of 8 to 21.
3. 3. A compound having the formula: characterized because X is selected as: Y wherein: R 3 is a linear or branched C 1 -C 10 alkyl or alkoxyalkyl; one of A or B is hydrogen and the other is an esterified carboxy group; and m and n are independently integers from 0 to 20, where the sum of m + n is in the range of 8 to 21.
4. 4.- A compound having the formula: characterized in that: R1 and R2 are independently alkyl or linear or branched alkoxyalkyl of Ci-Cio-
5. 5. A compound having the formula characterized in that R1 and R2 are independently linear or branched C1-C10 alkoxyalkyl.
6. 6.- A compound that has the formula characterized in that: R1 and R2 are independently linear or branched alkoxyalkyl CL-Cio alkyl.
7. 7. - A compound that has the formula characterized in that: R1 and R2 are independently linear or branched alkyl or alkoxyalkyl of Ci-Cio.
8. 8. A compound that has the formula: characterized in that R1 and R2 are independently straight or branched alkyl or alkoxyalkyl of CI-CIQ.
9. 9. The compound according to any of claims 4-8, characterized in that R1 and R2 are independently selected from the group consisting of methyl, ethyl, n-butyl, isobutyl, isoamyl, and 2-ethylhexyl.
10. 10. The compound according to claim 9, characterized in that R1 and R2 are independently selected from the group consisting of methyl, ethyl, and n-butyl.
11. 11. A method for preparing a compound according to any of claims 1-8, or mixtures thereof, characterized in that it comprises: a) providing an epoxidized fatty acid ester derivative and one or more levulinate esters, acid levulinic and angelicalactone; b) effecting the reaction between the compounds of a) in the presence of an acid catalyst, wherein the reaction results in the formation of a compound according to claim 1-8, or mixtures thereof.
12. 12. A plasticized polymer composition, characterized in that it comprises: a) a base polymer; and b) a compound according to any of claims 1-8.
13. 13. The plasticized polymer composition according to claim 12, characterized in that the base polymer is selected from the group consisting of vinyl chloride polymer, a poly (3-hydroxyalkanoate) polymer, and a polysaccharide polymer.
14. 14. The plasticized polymer composition according to claim 13, characterized in that the base polymer is vinyl chloride polymer.