WO2017058573A1 - Plasticizers containing esterified fatty acid phenyl ether esters and methods for making and using same - Google Patents

Abstract

A plasticizer can be or include one or more esterified fatty acid phenyl ether esters. The esterified fatty acid phenyl ether ester can have one or more fatty acid ester backbones, one or more phenyl ether moiety disposed on each fatty acid ester backbone, and one or more ester moiety disposed on each fatty acid ester backbone. The phenyl ether moiety and the ester moiety can be bonded to adjacent carbon atoms of the fatty acid ester backbone. In some examples, each fatty acid ester backbone of the esterified fatty acid phenyl ether ester can include two, three, four, or more pairs of the phenyl ether moiety and the ester moiety disposed thereon.

Description

PLASTICIZERS CONTAINING ESTERIFIED FATTY ACID PHENYL ETHER ESTERS AND METHODS FOR MAKING AND USING SAME

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Patent Application No. 62/234,369, filed on September 29, 2015, which is incorporated by reference herein.

BACKGROUND

Field

[0002] Embodiments described generally relate to plasticizers. More particularly, such embodiments relate to plasticizers containing esterified fatty acid phenyl ether esters and methods for making and using same.

SUMMARY

[0003] In one or more examples, a plasticizer can include one or more esterified fatty acid phenyl ether esters having a fatty acid ester backbone, one or more phenyl ether moieties and one or more ester moieties disposed on the fatty acid ester backbone. The phenyl ether moiety and the ester moiety can be bonded to adjacent carbon atoms of the fatty acid ester backbone.

[0004] For example, the plasticizer can include one or more esterified fatty acid phenyl ether esters that can include one or more reaction products of one or more fatty acid phenyl ether esters with one or more organic acid anhydrides. The fatty acid phenyl ether ester can include one or more reaction products of one or more epoxidized fatty acid esters with one or more aromatic alcohols.

[0005] In some examples, a method for making a plasticizer can include producing one or more epoxidized fatty acid esters from one or more unsaturated fatty acids, one or more esterification agents, and one or more epoxidation agents. The method can also include reacting the epoxidized fatty acid ester with one or more aromatic alcohols to produce one or more fatty acid phenyl ether esters and reacting the fatty acid phenyl ether ester with one or more organic acid anhydrides to produce one or more esterified fatty acid phenyl ether esters. In some examples, the method can include producing the epoxidized fatty acid ester by reacting the unsaturated fatty acid with the esterification agent to produce an unsaturated fatty acid ester, and reacting the unsaturated fatty acid ester with the epoxidation agent to produce the epoxidized fatty acid ester. In other examples, the method can include producing the epoxidized fatty acid ester by reacting the unsaturated fatty acid with the epoxidation agent to produce an epoxidized fatty acid, and reacting the epoxidized fatty acid with the esterification agent to produce the epoxidized fatty acid ester.

DETAILED DESCRIPTION

[0006] A plasticizer can be or include one or more esterified fatty acid phenyl ether esters that can have one or more fatty acid ester backbones, one or more phenyl ether moieties disposed on each fatty acid ester backbone, and one or more ester moieties disposed on each fatty acid ester backbone. The phenyl ether moiety and the ester moiety can be bonded to adjacent carbon atoms of the fatty acid ester backbone. In some examples, each fatty acid ester backbone of the esterified fatty acid phenyl ether ester can include one, two, three, four, or more pairs of the phenyl ether moiety and the ester moiety disposed thereon.

[0007] In one or more examples, the esterified fatty acid phenyl ether ester that can be used as or in the plasticizer can be produced according to reaction schemes illustrated in Schematic (I):

[0008] In some examples, one or more unsaturated fatty acids (A) can be reacted with one or more esterification agents to produce one or more unsaturated fatty acid esters (B). The unsaturated fatty acid ester (B) can be reacted with one or more epoxidation agents to produce one or more epoxidized fatty acid esters (D). In other examples, one or more unsaturated fatty acids (A) can be reacted with one or more epoxidation agents to produce one or more epoxidized fatty acids (C). The epoxidized fatty acid (C) can be reacted with one or more esterification agents to produce one or more epoxidized fatty acid esters (D). In either case, the epoxidized fatty acid ester (D) can be reacted with one or more aromatic alcohols to produce one or more fatty acid phenyl ether esters (E). The fatty acid phenyl ether ester (E) can be reacted with one or more organic acid anhydrides to produce one or more esterified fatty acid phenyl ether esters (F).

[0009] In one or more examples, for the esterified fatty acid phenyl ether ester (F), each R¹ and R² can independently be, but is not limited to, a substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group, and each X¹, X², X³, X⁴, and X⁵ can independently be, but is not limited to, hydrogen, a halide (e.g., F, CI, Br, or I), hydroxyl, and/or any substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group.

[0010] For illustrative purposes only, Schematic (I) depicts that the unsaturated fatty acid (A) can be or include a Ci₈-fatty acid with one site of unsaturation (unsaturated carbon-carbon double bond). It should be noted, however, that the unsaturated fatty acids can be or include one or more of a variety of unsaturated fatty acids. For example, the unsaturated fatty acid (A) can be or include, but is not limited to, Cio-C24-fatty acids that can have 1, 2, 3, 4, 5, 6, or more sites of unsaturation per molecule. Some sources of unsaturated fatty acids can be or include, but are not limited to, soybean oil, canola oil, vegetable oil, corn oil, sunflower oil, flaxseed oil, sesame oil, olive oil, peanut oil, cottonseed oil, safflower oil, rape seed oil, salts thereof, esters thereof, or any mixture thereof. Other illustrative unsaturated fatty acid sources can be or include, but are not limited to, tall oil fatty acids (TOFA), crude tall oils (CTO), distilled tall oils (DTO), depitched tall oil, tall oil pitches, portions thereof, fractions thereof, or any mixture thereof. The unsaturated fatty acids can be or include, but are not limited to, oleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, rumenic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, eicosatrienoic acid, arachidonic acid, docosatetraenoic acid, docosapentaenoic acid, docosahexaenoic acid, isomers thereof, salts thereof, esters thereof, or any mixture thereof. Representative tall oil products that can include unsaturated fatty acids used to produce the unsaturated fatty acid esters (B), the epoxidized fatty acids (C), and/or the epoxidized fatty acid esters (D), can be or include, but are not limited to, Ci6-Ci₈-unsaturated fatty acids, and can include XTOL® 100, XTOL® 300, XTOL® 304, XTOL® 520, and XTOL® 3030 tall oil products, all of which are commercially available from Georgia-Pacific Chemicals LLC, Atlanta, GA. In some examples, the unsaturated fatty acid can be or include unsaturated fatty acid esters, such as fatty acid methyl esters (FAME), fatty acid ethyl esters, or a mixture thereof.

[0011] Referring to Schematic (I), in some examples, the unsaturated fatty acid (A) can be reacted with one or more esterification agents to produce the unsaturated fatty acid ester (B), and in other examples, the epoxidized fatty acid (C) can be reacted with one or more esterification agents to produce the epoxidized fatty acid ester (D). For both esters (B) and (D), the R¹ can be or include, but is not limited to, a substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group. The esterification agent can be or include one or more alcohols R^OH, where R¹ can be or include, but is not limited to, a substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group. R¹ can be alkyl (e.g., C1-C24, C1-C18, or C1-C12), alkenyl, alkynyl, phenyl, aryl, alkanol, alkoxyl, amino, isomer thereof, or derivative thereof. In some examples, esterification agent can be one or more primary alcohols and R¹ can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, or isomers thereof. Illustrative esterification agents can be or include, but are not limited to, methanol, ethanol, butanol, pentanol, hexanol, 2-ethylhexanol, heptanol, octanol, nonanol, isononanol, decanol, isodecanol, benzyl alcohol, isomers thereof, salts thereof, ethers thereof, or any mixture thereof.

[0012] In other examples, the esterification agent can be or include one or more coupling agents, such as one or more polyols. Illustrative polyols can be or include diols, triols, tetraols, or have a greater order of alcohol groups disposed thereon. The esterification agent, therefore, can be or include one or more alcohols R^OH)!!, where n can be 2, 3, 4, 5, or greater, and R¹ can be the hydrocarbyl group as described above. If the esterification agent is or includes one or more coupling agents, then the esterification agent can be or include, but is not limited to, one or more of: ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane, pentaerythritol, isomers thereof, salts thereof, ethers thereof, or any mixture thereof.

[0013] The esterification agent can be combined and/or reacted with the unsaturated fatty acid or the epoxidized fatty acid in an amount of about 1 wt%, about 2 wt%, about 3 wt%, or about 4 wt% to about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 15 wt%, about 20 wt%, or greater, based on a combined weight of the unsaturated fatty acid and the esterification agent or based on a combined weight of the epoxidized fatty acid and the esterification agent. For example, the esterification agent can be combined and/or reacted with the unsaturated fatty acid or the epoxidized fatty acid in an amount of about 1 wt% to about 20 wt%, about 1 wt% to about 10 wt%, about 2 wt% to about 9 wt%, about 3 wt% to about 7 wt%, or about 4 wt% to about 6 wt%, based on a combined weight of the unsaturated fatty acid and the esterification agent or based on a combined weight of the epoxidized fatty acid and the esterification agent. [0014] In some examples, the unsaturated fatty acid or the epoxidized fatty acid can be in the presence of the esterification agent and one or more esterification catalysts to produce the epoxidized fatty acid ester (D). The esterification catalyst can be or include, but is not limited to, metal-containing catalysts, sulfuric acid, sulfonic acids, complexes thereof, salts thereof, or any mixture thereof. Illustrative metal-containing catalysts, can be or include, but are not limited to, metal alkoxides, metal oxides, metal halides, organometallic compounds, or any mixture thereof.

[0015] The esterification catalyst can be or include one or more metal-containing catalysts including tin compounds, titanium compounds, or mixtures thereof. The esterification catalyst can be or include, but is not limited to, stannous octoate, stannous 2-ethylhexanoate, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, isomers thereof, alkyl derivatives thereof, salts thereof, hydrates thereof, or any mixture thereof. Illustrative tin compounds can be or include, but is not limited to, tin-containing catalysts, tin alkoxides, organotin compounds, tin (II) compounds, tin (IV) compounds, or any mixture thereof. For example, the esterification catalyst can be or include a mixture of stannous octoate and stannous 2-ethylhexanoate, such as the FASCAT^® 2003 catalyst, commercially available from PMC Organometallix, Inc. Illustrative titanium compounds can be or include, but is not limited to, titanium-containing catalysts, titanium alkoxides, organotitanium compounds, titanium (II) compounds, titanium (IV) compounds, or any mixture thereof.

[0016] The esterification catalysts can be combined with the esterification agent and either the unsaturated fatty acid or the epoxidized fatty acid in an amount of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, or about 3 wt% to about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 15 wt%, about 20 wt%, or greater, based on a combined weight of the unsaturated fatty acid and the esterification agent or based on a combined weight of the epoxidized fatty acid and the esterification agent. For example, the esterification catalysts can be combined with the esterification agent and either the unsaturated fatty acid or the epoxidized fatty acid in an amount of about 0.1 wt% to about 20 wt%, about 0.5 wt% to about 15 wt%, about 1 wt% to about 10 wt%, about 2 wt% to about 9 wt%, about 3 wt% to about 7 wt%, or about 4 wt% to about 6 wt%, based on a combined weight of the unsaturated fatty acid and the esterification agent or based on a combined weight of the epoxidized fatty acid and the esterification agent. [0017] The mixture of the esterification agent, the optional esterification catalyst, and either the unsaturated fatty acid or the epoxidized fatty acid can be maintained at ambient temperature or heated to react and produce the epoxidized fatty acid ester. The mixture of the esterification agent, the optional esterification catalyst, and either the unsaturated fatty acid or the epoxidized fatty acid can be at a temperature of about 20°C, about 23°C, about 25°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, or about 100°C to about 110°C, about 120°C, about 130°C, about 150°C, about 170°C, about 190°C, about 200°C, about 210°C, about 230°C, about 250°C, about 300°C, or greater to produce the epoxidized fatty acid ester. For example, the mixture of the esterification agent, the optional esterification catalyst, and either the unsaturated fatty acid or the epoxidized fatty acid can be at a temperature of about 20°C to about 300°C, about 25°C to about 200°C, about 25°C to about 150°C, about 25°C to about 125°C, about 25°C to about 120°C, about 25°C to about 110°C, about 25°C to about 100°C, about 25°C to about 90°C, about 25°C to about 75°C, about 25°C to about 50°C, about 50°C to about 200°C, about 50°C to about 150°C, about 50°C to about 125°C, about 50°C to about 120°C, about 50°C to about 110°C, about 50°C to about 100°C, about 50°C to about 90°C, about 50°C to about 75°C, about 75°C to about 200°C, about 75°C to about 150°C, about 75°C to about 125°C, about 75°C to about 120°C, about 75°C to about 110°C, about 75°C to about 100°C, or about 75°C to about 90°C to produce the epoxidized fatty acid ester.

[0018] The mixture of the esterification agent, the optional esterification catalyst, and either the unsaturated fatty acid or the epoxidized fatty acid can be reacted, heated, or maintained at the temperature for a period of about 0.5 hr, about 1 hr, about 1.5 hr, about 2 hr, about 2.5 hr, about 3 hr, about 4 hr, about 5 hr, or about 7 hr to about 8 hr, about 10 hr, about 12 hr, about 15 hr, about 20 hr, about 24 hr, or longer to produce the epoxidized fatty acid ester. For example, the mixture of the esterification agent, the optional esterification catalyst, and either the unsaturated fatty acid or the epoxidized fatty acid can be reacted, heated, or maintained at the temperature for a period of about 0.5 hr to about 24 hr, about 0.5 hr to about 12 hr, about 0.5 hr to about 6 hr, about 0.5 hr to about 4 hr, about 0.5 hr to about 3 hr, about 0.5 hr to about 2 hr, about 0.5 hr to about 1 hr, about 1 hr to about 12 hr, about 1 hr to about 6 hr, about 1 hr to about 4 hr, about 1 hr to about 3 hr, about 1 hr to about 2 hr, about 1.5 hr to about 6 hr, about 1.5 hr to about 4 hr, about 1.5 hr to about 3 hr, or about 1.5 hr to about 2 hr to produce the epoxidized fatty acid ester. [0019] In some examples, the mixture of the esterification agent, the optional esterification catalyst, and either the unsaturated fatty acid or the epoxidized fatty acid can be reacted, heated, or maintained at a temperature of about 25°C to about 200°C for a period of about 0.5 hr to about 8 hr to produce the epoxidized fatty acid ester. In other examples, the mixture of the esterification agent, the optional esterification catalyst, and either the unsaturated fatty acid or the epoxidized fatty acid can be reacted, heated, or maintained at a temperature of about 90°C to about 150°C for a period of about 0.5 hr to about 4 hr to produce the epoxidized fatty acid ester. In other specific examples, the mixture of the esterification agent, the optional esterification catalyst, and either the unsaturated fatty acid or the epoxidized fatty acid can be reacted, heated, or maintained at a temperature of about 110°C to about 130°C for a period of about 1 hr to about 3 hr to produce the epoxidized fatty acid ester.

[0020] Referring back to Schematic (I), in some examples, the unsaturated fatty acid ester (B) can be reacted with one or more epoxidation agents to produce the epoxidized fatty acid ester (D), and in other examples, the unsaturated fatty acid (A) can be reacted with one or more epoxidation agents to produce the epoxidized fatty acid (C). The epoxidation agent can be generated ex-situ or in-situ the mixture with the unsaturated fatty acid ester or the unsaturated fatty acid. The epoxidation agent can be or include hydrogen peroxide, ozone, inorganic peroxides, organic peroxides, peroxycarboxylic acids, alkyl hydroperoxides, any atomic oxygen source, or any mixture thereof. Illustrative epoxidation agents can be or include, but are not limited to, one or more of: hydrogen peroxide, calcium peroxide, magnesium peroxide, peracetic acid, weto-chloroperoxybenzoic acid (mCPBA), tert-butyl hydroperoxide (TBHP), dimethyldioxirane, salts thereof, or any mixture thereof. One or more epoxidation catalysts can optionally be used to generate the epoxidation agent. The epoxidation agent can be generated by the epoxidation catalyst ex-situ or in-situ the epoxidation mixture. In some examples, metal- catalyzed epoxidation can be utilized to produce the epoxidized fatty acid ester or the epoxidized fatty acid.

[0021] The epoxidation agent can be mixed, blended, or otherwise combined with either the unsaturated fatty acid or the unsaturated fatty acid ester in an amount of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, or about 3 wt% to about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 15 wt%, about 20 wt%, or greater, based on a combined weight of the unsaturated fatty acid and the epoxidation agent or based on a combined weight of the unsaturated fatty acid ester and the epoxidation agent. For example, epoxidation agent can be combined with either the unsaturated fatty acid or the unsaturated fatty acid ester in an amount of about 0.1 wt% to about 20 wt%, about 0.5 wt% to about 15 wt%, about 1 wt% to about 10 wt%, about 2 wt% to about 9 wt%, about 3 wt% to about 7 wt%, or about 4 wt% to about 6 wt%, based on a combined weight of the unsaturated fatty acid and the epoxidation agent or based on a combined weight of the unsaturated fatty acid ester and the epoxidation agent.

[0022] The mixture of the epoxidation agent with either the unsaturated fatty acid or the unsaturated fatty acid ester can be maintained at ambient temperature or heated to react and produce the epoxidized fatty acid or the epoxidized fatty acid ester. The mixture of the epoxidation agent with either the unsaturated fatty acid or the unsaturated fatty acid ester can be at a temperature of about 20°C, about 23°C, about 25°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, or about 100°C to about 110°C, about 120°C, about 130°C, about 150°C, about 170°C, about 190°C, about 200°C, or greater to produce the epoxidized fatty acid or the epoxidized fatty acid ester. For example, the mixture of the epoxidation agent with either the unsaturated fatty acid or the unsaturated fatty acid ester can be at a temperature of about 20°C to about 200°C, about 25°C to about 200°C, about 25°C to about 150°C, about 25°C to about 125°C, about 25°C to about 120°C, about 25°C to about 110°C, about 25°C to about 100°C, about 25°C to about 90°C, about 25°C to about 75°C, about 25°C to about 50°C, about 50°C to about 200°C, about 50°C to about 150°C, about 50°C to about 125°C, about 50°C to about 120°C, about 50°C to about 110°C, about 50°C to about 100°C, about 50°C to about 90°C, about 50°C to about 75°C, about 75°C to about 200°C, about 75°C to about 150°C, about 75°C to about 125°C, about 75°C to about 120°C, about 75°C to about 110°C, about 75°C to about 100°C, or about 75°C to about 90°C to produce the epoxidized fatty acid or the epoxidized fatty acid ester.

[0023] The mixture of the epoxidation agent with either the unsaturated fatty acid or the unsaturated fatty acid ester can be reacted, heated, or maintained at the temperature for a period of about 0.5 hr, about 1 hr, about 1.5 hr, about 2 hr, about 2.5 hr, about 3 hr, about 4 hr, about 5 hr, or about 7 hr to about 8 hr, about 10 hr, about 12 hr, about 15 hr, about 20 hr, about 24 hr, or longer to produce the epoxidized fatty acid or the epoxidized fatty acid ester. For example, the mixture of the epoxidation agent with either the unsaturated fatty acid or the unsaturated fatty acid ester can be reacted, heated, or maintained at the temperature for a period of about 0.5 hr to about 24 hr, about 0.5 hr to about 12 hr, about 0.5 hr to about 6 hr, about 0.5 hr to about 4 hr, about 0.5 hr to about 3 hr, about 0.5 hr to about 2 hr, about 0.5 hr to about 1 hr, about 1 hr to about 12 hr, about 1 hr to about 6 hr, about 1 hr to about 4 hr, about 1 hr to about 3 hr, about 1 hr to about 2 hr, about 1.5 hr to about 6 hr, about 1.5 hr to about 4 hr, about 1.5 hr to about 3 hr, or about 1.5 hr to about 2 hr to produce the epoxidized fatty acid or the epoxidized fatty acid ester.

[0024] Referring back to Schematic (I), the epoxidized fatty acid ester (D) can be reacted with one or more aromatic alcohols to produce the one or more fatty acid phenyl ether esters (E). For the fatty acid phenyl ether ester (E), the phenyl ether motif can be substituted with X¹, X², X³, X⁴, and X⁵, depending on the aromatic alcohol. Each X¹, X², X³, X⁴, and X⁵ can independently be, but is not limited to, hydrogen, a halide (e.g., F, CI, Br, or I), hydroxyl, and/or any substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group. In some examples, each X¹, X², X³, X⁴, and X⁵ can independently be any of the chemical groups discussed and described above for R¹. Illustrative aromatic alcohols can be or include, but are not limited to, phenol, naphthol, cresol, xylenol, guaiacol, bisphenol A (BP A), polyphenol, isomers thereof, halides thereof, substituted derivatives thereof, or any mixture thereof.

[0025] The aromatic alcohol can be mixed, blended, or otherwise combined with the epoxidized fatty acid ester in a molar excess. In some examples, for each mole of epoxide sites on the epoxidized fatty acid ester, about 1, about 1.2, or about 1.5 to about 2, about 2.5, about 3, about 4, about 5, or more moles of the aromatic alcohol can be mixed, blended, combined, and/or reacted with the epoxidized fatty acid ester. For example, for each mole of epoxide sites on the epoxidized fatty acid ester, about 1 to about 5, about 1 to about 4, about 1 to about 3, about 1 to about 2.5, about 1 to about 2, about 1.2 to about 5, about 1.2 to about 4, about 1.2 to about 3, about 1.2 to about 2.5, about 1.2 to about 2, about 1.5 to about 5, about 1.5 to about 4, about 1.5 to about 3, about 1.5 to about 2.5, or about 1.5 to about 2 moles of the aromatic alcohol can be mixed, blended, combined, and/or reacted with the epoxidized fatty acid ester.

[0026] The aromatic alcohol can be combined and/or reacted with the epoxidized fatty acid ester in an amount of about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, or about 30 wt% to about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 60 wt%, about 70 wt%, about 80 wt%, about 90 wt%, about 100 wt%, about 120 wt%, about 150 wt%, or greater, based on the weight of the epoxidized fatty acid ester. For example, the aromatic alcohol can be combined and/or reacted with the epoxidized fatty acid ester in an amount of about 10 wt% to about 150 wt%, about 10 wt% to about 100 wt%, about 10 wt% to about 80 wt%, about 10 wt% to about 50 wt%, about 10 wt% to about 40 wt%, about 10 wt% to about 30 wt%, about 10 wt% to about 20 wt%, about 20 wt% to about 150 wt%, about 20 wt% to about 100 wt%, about 20 wt% to about 80 wt%, about 20 wt% to about 50 wt%, about 20 wt% to about 40 wt%, or about 20 wt% to about 30 wt%, based on the weight of the epoxidized fatty acid ester.

[0027] In some examples, the epoxidized fatty acid ester can be mixed, blended, combined, and/or reacted with the aromatic alcohol in the presences of one or more catalysts to produce the fatty acid phenyl ether ester. The catalyst can be or include, but is not limited to, pyridine, 4-dimethylaminopyridine (DMAP), pyrrolidone, N-methyl-2-pyrrolidone ( MP), succinimide, N-bromosuccinimide, pyridine derivatives thereof, pyrrolidone derivatives thereof, succinimide derivatives thereof, salts thereof, hydrates thereof, complexes thereof, halogen derivatives thereof, or any mixture thereof.

[0028] The mixture of the epoxidized fatty acid ester, the aromatic alcohol, and the optional catalyst can be maintained at ambient temperature or heated to react and produce the fatty acid phenyl ether ester. The mixture of the epoxidized fatty acid ester, the aromatic alcohol, and the optional catalyst can be at a temperature of about 20°C, about 23°C, about 25°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, or about 90°C to about 100°C to about 110°C, about 120°C, about 125°C, about 130°C, about 140°C, about 150°C, about 170°C, about 190°C, about 200°C, about 210°C, about 220°C, or greater to produce the fatty acid phenyl ether ester. For example, the mixture of the epoxidized fatty acid ester, the aromatic alcohol, and the optional catalyst can be at a temperature of about 20°C to about 220°C, about 20°C to about 200°C, about 20°C to about 150°C, about 50°C to about 200°C, about 50°C to about 150°C, about 50°C to about 120°C, about 50°C to about 100°C, about 80°C to about 200°C, about 80°C to about 150°C, about 80°C to about 120°C, or about 80°C to about 100°C to produce the fatty acid phenyl ether ester.

[0029] The epoxidized fatty acid ester, the aromatic alcohol, and the optional catalyst can be reacted, heated, or maintained at a desired temperature for a period of about 0.2 hr, about 0.5 hr, about 1 hr, about 1.5 hr, or about 2 hr to about 2.5 hr, about 3 hr, about 3.5 hr, about 4 hr, about 5 hr, about 6 hr, about 8 hr, or longer to produce the fatty acid phenyl ether ester. For example, the epoxidized fatty acid ester, the aromatic alcohol, and the optional catalyst can be reacted, heated, or maintained at the temperature for a period of about 0.2 hr to about 8 hr, about 0.5 hr to about 8 hr, about 1 hr to about 8 hr, about 2 hr to about 8 hr, about 0.2 hr to about 5 hr, about 0.5 hr to about 5 hr, about 1 hr to about 5 hr, about 2 hr to about 5 hr, about 0.5 hr to about 3 hr, about 1 hr to about 3 hr, or about 2 hr to about 3 hr to produce the fatty acid phenyl ether ester.

[0030] Referring back to Schematic (I), the fatty acid phenyl ether ester (E) can be reacted with one or more organic acid anhydrides to produce the one or more esterified fatty acid phenyl ether esters (F). The R² of the ester moiety disposed on the fatty acid ester backbone of the esterified fatty acid phenyl ether ester can be or include, but is not limited to, a substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group. The R² can be alkyl (e.g., C1-C24, C1-C18, or C1-C12), alkenyl, alkynyl, phenyl, aryl, alkanol, alkoxyl, amino, isomer thereof, or derivative thereof. In some examples, R² can be one or more primary alcohols. For example, R² can be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, or isomers thereof. Illustrative esterification agents can be or include, but are not limited to, methanol, ethanol, butanol, pentanol, hexanol, 2-ethylhexanol, heptanol, octanol, nonanol, isononanol, decanol, isodecanol, benzyl alcohol, isomers thereof, salts thereof, ethers thereof, or any mixture thereof.

[0031] It should be noted, however, that the one or more ester moieties disposed on the fatty acid ester backbone can be derived from one or more organic acid anhydrides that can be or include, but are not limited to, one or more organic acids, one or more esters, one or more acylation agents, or any mixture thereof. The R² can be derived from the remaining hydrocarbyl group of the organic acid anhydride, the organic acid, or the ester. For example, the organic acid anhydride can have the formula R²OR² and/or the organic acid can have the formula R²0₂H, where R² can be or include, but is not limited to, a substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group. In some examples, the fatty acid phenyl ether ester can be reacted with one or more acylation agents (e.g., acetic anhydride) to produce the esterified ester, more specifically, the acylated fatty acid phenyl ether ester.

[0032] Illustrative organic acid anhydrides can be or include, but are not limited to, one or more of: acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, caproic anhydride, benzoic anhydride, succinic anhydride, maleic anhydride, succinic anhydride, maleic anhydride, fumaric anhydride, isomers thereof, acids thereof, halides thereof, salts thereof, esters thereof, or any mixture thereof. Illustrative organic acid anhydrides also can be or include, but are not limited to, one or more of: acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, benzoic acid, succinic acid, maleic acid, succinic acid, maleic acid, fumaric acid, acetic halide, propionic halide, butyric halide, valeric halide, caproic halide, benzoic halide, succinic halide, maleic halide, succinic halide, maleic halide, fumaric halide, isomers thereof, salts thereof, esters thereof, or any mixture thereof. In some examples, the halides can be, but not limited to, chlorides and/or bromides.

[0033] The organic acid anhydride can be mixed, blended, or otherwise combined with the fatty acid phenyl ether ester in a molar excess. In some examples, for each mole of hydroxyl groups on the backbone of the fatty acid phenyl ether ester, about 1, about 1.2, or about 1.5 to about 2, about 2.5, about 3, about 4, about 5, or more moles of the organic acid anhydride can be mixed, blended, combined, and/or reacted with the fatty acid phenyl ether ester. For example, for each mole of hydroxyl groups on the backbone of the fatty acid phenyl ether ester, about 1 to about 5, about 1 to about 4, about 1 to about 3, about 1 to about 2.5, about 1 to about 2, about 1.2 to about 5, about 1.2 to about 4, about 1.2 to about 3, about 1.2 to about 2.5, about 1.2 to about 2, about 1.5 to about 5, about 1.5 to about 4, about 1.5 to about 3, about 1.5 to about 2.5, or about 1.5 to about 2 moles of the organic acid anhydride can be mixed, blended, combined, and/or reacted with the fatty acid phenyl ether ester.

[0034] The organic acid anhydride can be combined and/or reacted with the fatty acid phenyl ether ester in an amount of about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, or about 30 wt% to about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 60 wt%, about 70 wt%, about 80 wt%, about 90 wt%, about 100 wt%, about 120 wt%, about 150 wt%, or greater, based on the weight of the fatty acid phenyl ether ester. For example, the organic acid anhydride can be combined and/or reacted with the fatty acid phenyl ether ester in an amount of about 10 wt% to about 150 wt%, about 10 wt% to about 100 wt%, about 10 wt% to about 80 wt%, about 10 wt% to about 50 wt%, about 10 wt% to about 40 wt%, about 10 wt% to about 30 wt%, about 10 wt% to about 20 wt%, about 20 wt% to about 150 wt%, about 20 wt% to about 100 wt%, about 20 wt% to about 80 wt%, about 20 wt% to about 50 wt%, about 20 wt% to about 40 wt%, or about 20 wt% to about 30 wt%, based on the weight of the fatty acid phenyl ether ester. [0035] In some examples, the fatty acid phenyl ether ester can be mixed, blended, combined, and/or reacted with the organic acid anhydride in the presences of one or more catalysts to produce the esterified fatty acid phenyl ether ester. The catalyst can be or include, but is not limited to, pyridine, DMAP, pyrrolidone, MP, succinimide, N-bromosuccinimide, pyridine derivatives thereof, pyrrolidone derivatives thereof, succinimide derivatives thereof, salts thereof, hydrates thereof, complexes thereof, halogen derivatives thereof, or any mixture thereof.

[0036] The mixture of the fatty acid phenyl ether ester, the organic acid anhydride, and the optional catalyst can be maintained at ambient temperature or heated to react and produce the fatty acid phenyl ether ester. The mixture of the fatty acid phenyl ether ester, the organic acid anhydride, and the optional catalyst can be at a temperature of about 20°C, about 23 °C, about 25°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, or about 90°C to about 100°C to about 110°C, about 120°C, about 125°C, about 130°C, about 140°C, about 150°C, about 170°C, about 190°C, about 200°C, about 210°C, about 220°C, or greater to produce the esterified fatty acid phenyl ether ester. For example, the mixture of the fatty acid phenyl ether ester, the organic acid anhydride, and the optional catalyst can be at a temperature of about 20°C to about 220°C, about 20°C to about 200°C, about 20°C to about 150°C, about 50°C to about 200°C, about 50°C to about 150°C, about 50°C to about 120°C, about 50°C to about 100°C, about 80°C to about 200°C, about 80°C to about 150°C, about 80°C to about 120°C, or about 80°C to about 100°C to produce the esterified fatty acid phenyl ether ester.

[0037] The fatty acid phenyl ether ester, the organic acid anhydride, and the optional catalyst can be reacted, heated, or at the temperature for a period of about 0.2 hr, about 0.5 hr, about 1 hr, about 1.5 hr, or about 2 hr to about 2.5 hr, about 3 hr, about 3.5 hr, about 4 hr, about 5 hr, about 6 hr, about 8 hr, or longer to produce the esterified fatty acid phenyl ether ester. For example, the fatty acid phenyl ether ester, the organic acid anhydride, and the optional catalyst can be reacted, heated, or at the temperature for a period of about 0.2 hr to about 8 hr, about 0.5 hr to about 8 hr, about 1 hr to about 8 hr, about 2 hr to about 8 hr, about 0.2 hr to about 5 hr, about 0.5 hr to about 5 hr, about 1 hr to about 5 hr, about 2 hr to about 5 hr, about 0.5 hr to about 3 hr, about 1 hr to about 3 hr, or about 2 hr to about 3 hr to produce the esterified fatty acid phenyl ether ester.

[0038] In some examples, the mixture of the fatty acid phenyl ether ester, the organic acid anhydride, and the optional catalyst can be reacted, heated, or at a temperature of about 50°C to about 200°C and for a period of about 1 hr to about 8 hr to produce the esterified fatty acid phenyl ether ester. In other examples, the mixture of the fatty acid phenyl ether ester, the organic acid anhydride, and the optional catalyst can be reacted, heated, or at a temperature of about 80°C to about 150°C and for a period of about 2 hr to about 6 hr to produce the esterified fatty acid phenyl ether ester. In other examples, the mixture of the fatty acid phenyl ether ester, the organic acid anhydride, and the optional catalyst can be reacted, heated, or at a temperature of about 100°C to about 130°C and for a period of about 2 hr to about 4 hr to produce the esterified fatty acid phenyl ether ester.

[0039] In one or more examples, one or more esterified fatty acid phenyl ether polyesters can be produced by coupling two or more fatty acids, of the same or different fatty acids, by using one or more coupling agents as esterification agents, as discussed and described above. In some examples, one or more esterified fatty acid phenyl ether diesters can be produced by coupling two fatty acid ester backbones with a diol coupling agent, such as ethylene glycol, propylene glycol, butylene glycol, or others. In some examples, one or more esterified fatty acid phenyl ether triesters can be produced by coupling three fatty acid ester backbones with a triol coupling agent, such as glycerol. In other examples, one or more esterified fatty acid phenyl ether tetraesters can be produced by coupling four fatty acid ester backbones with a tetraol coupling agent, such as pentaerythritol.

Plastic Composition

[0040] One or more plastic compositions can be made or produced with the plasticizers discussed and described herein. The plasticizer can be or include one or more of the esterified fatty acid phenyl ether ester, one or more of the esterified fatty acid phenyl ether polyester, or a mixture thereof. In some examples, one or more polymers and one or more plasticizers can be mixed, blended, extruded, or otherwise combined to produce the plastic composition. The polymers and/or the plasticizers can be in a molten state, a liquid state, a solid state, or any mixture thereof. The polymer can be or include, but is not limited to, one or more homogeneous polymers, one or more heterogeneous polymers, one or more copolymers, or any mixture thereof. In some specific examples, the polymer can be or include, but is not limited to, polyvinylchloride (PVC), polyvinylacetate (PVAc), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVF), cellulose esters, cellulose ethers, cellulose nitrates, polyacrylates, polyesters, nitrile rubber, acetonitrile-butadiene-styrene (ABS), polymeric derivatives thereof, or any mixture thereof.

[0041] In some examples, one or more polymers and one or more plasticizers can be mixed, blended, extruded, or otherwise combined in a molten state to produce the plastic composition. For example, a molten mixture of the polymers and plasticizers can be extruded in a single screw extruder, a twin screw extruder, or other types of extruders. In some examples, roll mills can be used to blend the mixture of the polymers and plasticizers in a molten state to produce the plastic composition.

[0042] In other examples, the plastic composition can be produced by solvent casting. For example, one or more polymer solutions and one or more plasticizer solutions can be mixed, blended, or otherwise combined to produce a polymer-plasticizer solution. The polymer solution can include a first solvent and one or more polymers and the plasticizer solution can include a second solvent and one or more plasticizers. The first solvent and the second solvent can be removed from the polymer-plasticizer solution to produce a plastic composition. Each of the first solvent and the second solvent independently can be or include, but is not limited to, tetrahydrofuran, pyridine, N-methyl-2-pyrrolidone ( MP), benzene, toluene, hexanes, isomers thereof, or any mixture thereof.

[0043] In some examples, the polymer solution can include the polymer in an amount of about 1 wt% to about 50 wt%, based on a combined weight of the polymer and the first solvent. The plasticizer solution can include the plasticizer in an amount of about 1 wt% to about 50 wt%, based on a combined weight of the plasticizer and the second solvent. In other examples, the polymer solution can include the polymer in an amount of about 5 wt% to about 20 wt%, based on a combined weight of the polymer and the first solvent. The plasticizer solution can include the plasticizer in an amount of about 5 wt% to about 20 wt%, based on a combined weight of the plasticizer and the second solvent.

[0044] The polymer-plasticizer solution can include a weight ratio of the plasticizer solution to the polymer solution of about 20:80 to about 40:60. Also, the polymer-plasticizer solution can include a weight ratio of the plasticizer to the polymer of about 20:80 to about 40:60. In some examples, the plastic composition can include the plasticizer in an amount of about 10 wt% to about 60 wt%, based on a combined weight of the plasticizer and the polymer. In other examples, the plastic composition can include the plasticizer in an amount of about 20 wt% to about 40 wt%, based on a combined weight of the plasticizer and the polymer.

Prophetic Examples

[0045] In order to provide a better understanding of the foregoing discussion, the following non- limiting prophetic examples are offered. Although the prophetic examples can be directed to specific embodiments, they are not to be viewed as limiting the invention in any specific respect.

[0046] Prophetic Example 1: Preparation of esterified fatty acid phenyl ether ester. To a 250 mL 3-neck flask is added about 70 g of phenol, about 155 g of epoxidized TOFA 2-ethylhexyl ester, and about 0.2 g of 4-dimethylaminopyridine (DMAP) to produce a mixture. After the flask is degassed and filled with nitrogen, the mixture is stirred at about 120°C for about 2 hr. The reaction mixture is vacuum distilled to remove excess amount of phenol. To the distillation residue is added about 75 g of acetic anhydride, and the mixture is heated at about 120°C for about 3 hr. The mixture is then distilled to remove acetic acid and excess amount of acetic anhydride to make the final product.

[0047] Prophetic Example 2: Preparation of esterified fatty acid phenyl ether ester with epoxide functional group. To a 250 mL 3-neck flask is added about 35.5 g of phenol, about 155 g of epoxidized TOFA 2-ethylhexyl ester, and about 0.2 g of DMAP to produce a mixture. After the flask is degassed and filled with nitrogen, the mixture is stirred at about 120°C for about 2 hr. To the reaction mixture is added about 50 g of acetic anhydride, and the mixture is heated at about 120°C for about 3 hr. The mixture is then distilled to remove acetic acid and excess amount of acetic anhydride to make the final product.

[0048] Prophetic Example 3: Properties of polyvinyl chloride) plasticized with esterified fatty acid phenyl ether ester by solvent blending. Esterified fatty acid phenyl ether ester (sample from Ex. 1) and PVC are dissolved in THF respectively to make about 10 wt% solutions. The plasticizer and PVC solutions are mixed at about 20:80 and about 40:60 weight ratios. The solution mixtures are casted onto glass slides to make solution films. The films are air dried overnight, and further vacuum dried in a vacuum oven at about 60°C to about 70°C for about 3 hr. The films are analyzed by DSC and TGA. [0049] Prophetic Example 4: Properties of polyfvinyl chloride) plasticized with esterified fatty acid phenyl ether ester by thermal compounding. Esterified fatty acid phenyl ether ester (sample from Ex. 3) is heated to about 140°C before being weighed and mixed. About 70 g of the plasticizer is weighed and inserted into a Brabender mixing head to achieve fusion. Bowl temperature is set at about 160°C to about 185°C a rotor speed ranging from about 60 rpm to about 85 rpm. Samples are then removed from the mixing head and pressed in a 120-ton Wabash press. The conditions for the press are: preheat at about 179°C (about 355°F) for about 30 sec; ramp for about 60 sec; hold for about 120 sec; cool for about 800 sec; and pressure at about 136 tonne (about 150 ton). The samples are analyzed by DMA.

[0050] Embodiments of the present disclosure further relate to any one or more of the following paragraphs:

[0051] 1. A plasticizer comprising an esterified fatty acid phenyl ether ester having a fatty acid ester backbone, a phenyl ether moiety disposed on the fatty acid ester backbone, and an ester moiety disposed on the fatty acid ester backbone, wherein the phenyl ether moiety and the ester moiety are bonded to adjacent carbon atoms of the fatty acid ester backbone.

[0052] 2. A plasticizer comprising an esterified fatty acid phenyl ether ester, wherein the esterified fatty acid phenyl ether ester comprises a reaction product of a fatty acid phenyl ether ester with an organic acid anhydride, and wherein the fatty acid phenyl ether ester comprises a reaction product of an epoxidized fatty acid ester with an aromatic alcohol.

[0053] 3. A method for making a plasticizer, comprising: producing an epoxidized fatty acid ester from an unsaturated fatty acid, an esterification agent, and an epoxidation agent; reacting the epoxidized fatty acid ester with an aromatic alcohol to produce a fatty acid phenyl ether ester; and reacting the fatty acid phenyl ether ester with an organic acid anhydride to produce an esterified fatty acid phenyl ether ester.

[0054] 4. The method of paragraph 4, wherein the producing the epoxidized fatty acid ester from the unsaturated fatty acid, the esterification agent, and the epoxidation agent, further comprises: reacting the unsaturated fatty acid with the esterification agent to produce an unsaturated fatty acid ester; and reacting the unsaturated fatty acid ester with the epoxidation agent to produce the epoxidized fatty acid ester. [0055] 5. The method of paragraph 4, wherein the producing the epoxidized fatty acid ester from the unsaturated fatty acid, the esterification agent, and the epoxidation agent, further comprises: reacting the unsaturated fatty acid with the epoxidation agent to produce an epoxidized fatty acid; and reacting the epoxidized fatty acid with the esterification agent to produce the epoxidized fatty acid ester.

[0056] 6. A method for making a plasticizer, comprising: reacting an unsaturated fatty acid with an esterification agent to produce an unsaturated fatty acid ester; reacting the unsaturated fatty acid ester with an epoxidation agent to produce an epoxidized fatty acid ester; reacting the epoxidized fatty acid ester with an aromatic alcohol to produce a fatty acid phenyl ether ester; and reacting the fatty acid phenyl ether ester with an organic acid anhydride to produce an esterified fatty acid phenyl ether ester.

[0057] 7. A method for making a plasticizer, comprising: reacting an unsaturated fatty acid with an epoxidation agent to produce an epoxidized fatty acid; reacting the epoxidized fatty acid with an esterification agent to produce an epoxidized fatty acid ester; reacting the epoxidized fatty acid ester with an aromatic alcohol to produce a fatty acid phenyl ether ester; and reacting the fatty acid phenyl ether ester with an organic acid anhydride to produce an esterified fatty acid phenyl ether ester.

[0058] 8. The plasticizer or the method according to any one of paragraphs 1 to 7, wherein the esterified fatty acid phenyl ether ester comprises 2 to 4 pairs of the phenyl ether moiety and the ester moiety disposed on the fatty acid ester backbone, and wherein each pair of the phenyl ether moiety and the ester moiety is independently bonded to adjacent carbon atoms of the fatty acid ester backbone.

[0059] 9. The plasticizer or the method according to any one of paragraphs 1 to 8, wherein the esterified fatty acid phenyl ether ester comprises 2 to 4 of the fatty acid ester backbones coupled together by a coupling motif derived from a coupling agent.

[0060] 10. The plasticizer or the method according to any one of paragraphs 1 to 9, wherein the phenyl ether moiety is derived from an aromatic alcohol, and the aromatic alcohol comprises phenol, naphthol, cresol, xylenol, guaiacol, bisphenol A, polyphenol, isomers thereof, or any mixture thereof. [0061] 11. The plasticizer or the method according to any one of paragraphs 1 to 10, wherein the ester moiety is derived from an organic acid anhydride comprising acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, caproic anhydride, benzoic anhydride, succinic anhydride, maleic anhydride, succinic anhydride, maleic anhydride, fumaric anhydride, isomers thereof, acids thereof, halides thereof, salts thereof, esters thereof, or any mixture thereof.

[0062] 12. The plasticizer or the method according to any one of paragraphs 1 to 11, wherein the ester moiety is derived from an organic acid anhydride and/or an organic acid comprising acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, caproic anhydride, benzoic anhydride, succinic anhydride, maleic anhydride, succinic anhydride, maleic anhydride, fumaric anhydride, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, benzoic acid, succinic acid, maleic acid, succinic acid, maleic acid, fumaric acid, acetic halide, propionic halide, butyric halide, valeric halide, caproic halide, benzoic halide, succinic halide, maleic halide, succinic halide, maleic halide, fumaric halide, isomers thereof, salts thereof, acids thereof, anhydrides thereof, esters thereof, or any mixture thereof.

[0063] 13. The plasticizer or the method according to any one of paragraphs 1 to 12, wherein the fatty acid ester backbone is derived from an epoxidized fatty acid ester that is a reaction product of an unsaturated fatty acid, an esterification agent, and an epoxidation agent.

[0064] 14. The plasticizer or the method of paragraph 13, wherein the unsaturated fatty acid is derived from tall oil, soybean oil, canola oil, vegetable oil, corn oil, sunflower oil, flaxseed oil, sesame oil, olive oil, peanut oil, cottonseed oil, safflower oil, rape seed oil, or any mixture thereof.

[0065] 15. The plasticizer or the method of paragraph 13, wherein the unsaturated fatty acid comprises oleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, rumenic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, eicosatrienoic acid, arachidonic acid, docosatetraenoic acid, docosapentaenoic acid, docosahexaenoic acid, isomers thereof, salts thereof, esters thereof, or any mixture thereof.

[0066] 16. The plasticizer or the method of paragraph 13, wherein the epoxidation agent comprises hydrogen peroxide, calcium peroxide, magnesium peroxide, peracetic acid, meta- chloroperoxybenzoic acid, tert-butyl hydroperoxide, dimethyldioxirane, salts thereof, or any mixture thereof.

[0067] 17. The plasticizer or the method of paragraph 13, wherein the esterification agent comprises methanol, ethanol, butanol, pentanol, hexanol, 2-ethylhexanol, heptanol, octanol, nonanol, isononanol, decanol, isodecanol, benzyl alcohol, isomers thereof, salts thereof, ethers thereof, or any mixture thereof.

[0068] 18. The plasticizer or the method of paragraph 13, wherein the esterification agent comprises a coupling agent comprising ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane, pentaerythritol, isomers thereof, salts thereof, ethers thereof, or any mixture thereof.

[0069] 19. The plasticizer or the method according to any one of paragraphs 1 to 18, wherein the epoxidized fatty acid ester comprises a reaction product of an unsaturated fatty acid ester with an epoxidation agent, and wherein the unsaturated fatty acid ester comprises a reaction product of an unsaturated fatty acid ester and an esterification agent.

[0070] 20. The plasticizer or the method according to any one of paragraphs 1 to 19, wherein the epoxidized fatty acid ester comprises a reaction product of an epoxidized fatty acid with an esterification agent, and wherein the epoxidized fatty acid comprises a reaction product of an unsaturated fatty acid ester and an epoxidation agent.

[0071] 21. The plasticizer or the method according to any one of paragraphs 1 to 20, wherein the fatty acid phenyl ether ester is reacted with an acylation reagent to produce an acylated fatty acid phenyl ether ester as the esterified fatty acid phenyl ether ester.

[0072] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges including the combination of any two values, e.g., the combination of any lower value with any upper value, the combination of any two lower values, and/or the combination of any two upper values are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are "about" or "approximately" the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art. [0073] Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0074] While the foregoing is directed to embodiments, other and further embodiments of the invention can be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims

Claims: What is claimed is:

1. A plasticizer comprising an esterified fatty acid phenyl ether ester having a fatty acid ester backbone, a phenyl ether moiety disposed on the fatty acid ester backbone, and an ester moiety disposed on the fatty acid ester backbone, wherein the phenyl ether moiety and the ester moiety are bonded to adjacent carbon atoms of the fatty acid ester backbone.

2. The plasticizer of claim 1, wherein the esterified fatty acid phenyl ether ester comprises 2 to 4 pairs of the phenyl ether moiety and the ester moiety disposed on the fatty acid ester backbone, and wherein each pair of the phenyl ether moiety and the ester moiety is independently bonded to adjacent carbon atoms of the fatty acid ester backbone.

3. The plasticizer of claim 1, wherein the phenyl ether moiety is derived from an aromatic alcohol, and the aromatic alcohol comprises phenol, naphthol, cresol, xylenol, guaiacol, bisphenol A, polyphenol, isomers thereof, or any mixture thereof.

4. The plasticizer of claim 1, wherein the ester moiety is derived from an organic acid anhydride comprising acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, caproic anhydride, benzoic anhydride, succinic anhydride, maleic anhydride, succinic anhydride, maleic anhydride, fumaric anhydride, isomers thereof, acids thereof, halides thereof, salts thereof, esters thereof, or any mixture thereof.

5. The plasticizer of claim 1, wherein the fatty acid ester backbone is derived from an epoxidized fatty acid ester that is a reaction product of an unsaturated fatty acid, an esterification agent, and an epoxidation agent.

6. The plasticizer of claim 5, wherein the unsaturated fatty acid is derived from tall oil, soybean oil, canola oil, vegetable oil, corn oil, sunflower oil, flaxseed oil, sesame oil, olive oil, peanut oil, cottonseed oil, safflower oil, rape seed oil, or any mixture thereof.

7. The plasticizer of claim 5, wherein the unsaturated fatty acid comprises oleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, rumenic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, eicosatrienoic acid, arachidonic acid, docosatetraenoic acid, docosapentaenoic acid, docosahexaenoic acid, isomers thereof, salts thereof, esters thereof, or any mixture thereof.

8. The plasticizer of claim 5, wherein the epoxidation agent comprises hydrogen peroxide, calcium peroxide, magnesium peroxide, peracetic acid, weto-chloroperoxybenzoic acid, tert- butyl hydroperoxide, dimethyldioxirane, salts thereof, or any mixture thereof.

9. The plasticizer of claim 5, wherein the esterification agent comprises methanol, ethanol, butanol, pentanol, hexanol, 2-ethylhexanol, heptanol, octanol, nonanol, isononanol, decanol, isodecanol, benzyl alcohol, isomers thereof, salts thereof, ethers thereof, or any mixture thereof.

10. The plasticizer of claim 5, wherein the esterification agent comprises a coupling agent comprising ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane, pentaerythritol, isomers thereof, salts thereof, ethers thereof, or any mixture thereof.

11. A plasticizer comprising an esterified fatty acid phenyl ether ester, wherein the esterified fatty acid phenyl ether ester comprises a reaction product of a fatty acid phenyl ether ester with an organic acid anhydride, and wherein the fatty acid phenyl ether ester comprises a reaction product of an epoxidized fatty acid ester with an aromatic alcohol.

12. The plasticizer of claim 11, wherein the epoxidized fatty acid ester comprises a reaction product of an unsaturated fatty acid ester with an epoxidation agent, and wherein the unsaturated fatty acid ester comprises a reaction product of an unsaturated fatty acid ester and an esterification agent.

13. The plasticizer of claim 11, wherein the epoxidized fatty acid ester comprises a reaction product of an epoxidized fatty acid with an esterification agent, and wherein the epoxidized fatty acid comprises a reaction product of an unsaturated fatty acid ester and an epoxidation agent.

14. A method for making a plasticizer, comprising:

producing an epoxidized fatty acid ester from an unsaturated fatty acid, an esterification agent, and an epoxidation agent;

reacting the epoxidized fatty acid ester with an aromatic alcohol to produce a fatty acid phenyl ether ester; and

reacting the fatty acid phenyl ether ester with an organic acid anhydride to produce an esterified fatty acid phenyl ether ester.

15. The method of claim 14, wherein the producing the epoxidized fatty acid ester from the unsaturated fatty acid, the esterification agent, and the epoxidation agent, further comprises: reacting the unsaturated fatty acid with the esterification agent to produce an unsaturated fatty acid ester; and

reacting the unsaturated fatty acid ester with the epoxidation agent to produce the epoxidized fatty acid ester.

16. The method of claim 14, wherein the producing the epoxidized fatty acid ester from the unsaturated fatty acid, the esterification agent, and the epoxidation agent, further comprises: reacting the unsaturated fatty acid with the epoxidation agent to produce an epoxidized fatty acid; and

reacting the epoxidized fatty acid with the esterification agent to produce the epoxidized fatty acid ester.

17. The method of claim 14, wherein the aromatic alcohol comprises phenol, naphthol, cresol, xylenol, guaiacol, bisphenol A, polyphenol, isomers thereof, or any mixture thereof.

18. The method of claim 14, wherein the organic acid anhydride comprises acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, caproic anhydride, benzoic anhydride, succinic anhydride, maleic anhydride, succinic anhydride, maleic anhydride, fumaric anhydride, isomers thereof, acids thereof, halides thereof, salts thereof, esters thereof, or any mixture thereof.

19. The method of claim 14, wherein the epoxidation agent comprises hydrogen peroxide, calcium peroxide, magnesium peroxide, peracetic acid, weto-chloroperoxybenzoic acid, tert- butyl hydroperoxide, dimethyldioxirane, salts thereof, or any mixture thereof.

20. The method of claim 14, wherein the esterification agent comprises methanol, ethanol, butanol, pentanol, hexanol, 2-ethylhexanol, heptanol, octanol, nonanol, isononanol, decanol, isodecanol, benzyl alcohol, ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane, pentaerythritol, isomers thereof, salts thereof, ethers thereof, or any mixture thereof.

21. A method for making a plasticizer, comprising:

reacting an unsaturated fatty acid with an esterification agent to produce an unsaturated fatty acid ester;

reacting the unsaturated fatty acid ester with an epoxidation agent to produce an epoxidized fatty acid ester;

reacting the epoxidized fatty acid ester with an aromatic alcohol to produce a fatty acid phenyl ether ester; and

reacting the fatty acid phenyl ether ester with an organic acid anhydride to produce an esterified fatty acid phenyl ether ester.

22. A method for making a plasticizer, comprising:

reacting an unsaturated fatty acid with an epoxidation agent to produce an epoxidized fatty acid;

reacting the epoxidized fatty acid with an esterification agent to produce an epoxidized fatty acid ester;

reacting the epoxidized fatty acid ester with an aromatic alcohol to produce a fatty acid phenyl ether ester; and reacting the fatty acid phenyl ether ester with an organic acid anhydride to produce an esterified fatty acid phenyl ether ester.