Production and use of plasticizers based on 2,4-isomers of furandicarboxylic acid diesters

Abstract

The present disclosure generally relates to compounds of dialkyl esters of 2,4-furandicarboxylic acid, methods for preparing the compounds, polymer compositions including polymers and the compounds, methods for preparing the polymer compositions, polymer products including the polymer compositions, and methods for using the compounds as plasticizers in polymer products. The dialkyl esters of 2,4-furandicarboxylic acid of the present disclosure have higher plasticizing efficiency in polymer compositions than that of standard phthalic and terephthalic acid-based plasticizers. Polymer products plasticized with the dialkyl esters of 2,4-furandicarboxylic acid may have improved flexibility, durability, processability, and safety compared to the same polymer products plasticized with conventional phthalic and terephthalic acid-based plasticizers.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 031,949, filed May 29, 2020, the disclosure of which is incorporated herein by reference in its entirety for all purposes.

[0002] The present disclosure relates generally to compounds of dialkyl esters of 2,4-furandicarboxylic acid, methods for preparing the compounds, compositions including the compounds, methods for preparing compositions including the compounds, polymeric products including the compounds as plasticizers, and methods for preparing the polymeric products. [Background technology]

[0003] Plasticizers are widely used as additives in the polymer industry because it is easy to control the physical properties of polymer materials, such as flexibility, durability, and processability, by adding plasticizers to polymer materials and adjusting their content in the polymer material. This class of additives is particularly utilized in the polyvinyl chloride (PVC) resin industry, which accounts for approximately 90% of all plasticizer consumption worldwide, according to 2017 data. Therefore, plasticizers play an important role in the PVC industry, especially in terms of application, by transforming essentially rigid materials into highly flexible products.

[0004] Plasticizers are responsible for making PVC one of the most versatile thermoplastics from an application standpoint. For example, while PVC resins can have different levels of flexibility depending on the plasticizer content, rigid PVC materials (elongation at break <15%) typically have no plasticizer in the formulation, making them semi-rigid materials ( Elongation at break: Approximately 280% ) have up to one-quarter as much plasticizer by weight. Plasticizer content reaches surface levels in flexible and very flexible applications (elongation >380%), and PVC formulations can have more plasticizer than polymer by weight.

[0005] Within the class of molecules with favorable properties for acting as plasticizers, phthalate diesters have traditionally been exploited by combining technical and performance characteristics with low production costs. These traditional plasticizers include phthalate-derived plasticizers such as di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), and diisodecyl phthalate (DIDP). Phthalate-derived plasticizers currently comprise approximately 65% ​​of global plasticizer production. Despite their predominant historical use, phthalic anhydride-derived plasticizers face serious threats associated with the environmental and health issues they pose. Specifically, di(2-ethylhexyl) phthalate (DEHP) and its metabolite, mono-2-ethylhexyl phthalate, have been recognized as endocrine disruptors in several studies over the past 30 years, adversely affecting the male reproductive system and inducing problems during fetal development and obesity.

[0006] Faced with the risks documented by numerous independent studies, government agencies have imposed several regulations to control, reduce, or even ban the use of phthalate-derived plasticizers in certain items. For example, the European Commission included DEHP and other phthalate derivatives on the REACH list. Since 2007, DEHP and other phthalate derivatives, such as benzyl butyl phthalate (BBP), dibutyl phthalate (DBP), and diisobutyl phthalate (DIBP), have been banned in oral packaging for food, toys, and children's products. In 2015, these restrictions were extended to other general-purpose items, further pressuring the PVC market to develop alternative plasticizers. Similarly, the US Consumer Product Safety Commission, driven by a previous ruling by the California government, approved regulations in 2017 to warn consumers about the use of these compounds. Therefore, all materials containing more than 0.1% by weight of phthalates require labels warning about their presence in the formulation. For this reason, some of these phthalates are commonly referred to as "labeled plasticizers." Summary of the Invention

[0007] One aspect of the present disclosure is a compound of a dialkyl ester of 2,4-furandicarboxylic acid having the chemical structure of Formula I: [ka] In the formula, R1 and R2 are each 2-ethylhexanol, ethylhexanol, n-butanol, isononyl alcohol, isobutanol, isodecyl alcohol, 2-propylheptanol, C6 to C6 11 C4-C6 alcohols, including but not limited to straight chain alcohols, tridecyl alcohol, isooctyl alcohol, amyl alcohol, and other structural isomers of alcohols having the general structure above. 13 Represents the alkyl radical of a monohydric aliphatic primary alcohol.

[0008] In one embodiment, R1 and R2 are two different alkyl radicals. In another embodiment, R1 and R2 are preferably the same alkyl radical. In yet another embodiment, R1 is a straight-chain alkyl radical or a branched alkyl radical. In yet another embodiment, R2 is a straight-chain alkyl radical or a branched alkyl radical.

[0009] Another aspect of the present disclosure provides a process for preparing a compound of a dialkyl ester of 2,4-furandicarboxylic acid having the chemical structure of Formula I shown above, the process comprising: synthesizing 2,4-furandicarboxylic acid (2,4-FDCA) or a derivative thereof; and esterifying the 2,4-FDCA or a derivative thereof with an alcohol to obtain a dialkyl ester of 2,4-furandicarboxylic acid having the chemical structure of Formula I shown above, wherein R and R are each selected from the group consisting of 2-ethylhexanol, ethylhexanol, n-butanol, isononyl alcohol, isobutanol, isodecyl alcohol, 2-propylheptanol, C6-C8 11 C4-C6 alcohols, including but not limited to straight chain alcohols, tridecyl alcohol, isooctyl alcohol, amyl alcohol, and other structural isomers of alcohols having the general structure above. 13 represents the alkyl radical of a monohydric aliphatic primary alcohol. In one embodiment, R1 and R2 are the same alkyl radical or two different alkyl radicals. The properties of the 2,4-furandicarboxylic acid diester resulting from this process can be adjusted by changing the length and structure of the alkyl chain of the alcohol.

[0010] In another embodiment, the compound dialkyl ester of 2,4-furandicarboxylic acid is a C4-C 13 Contains dialkyl furandicarboxylates, isomers C4-C 13 Dialkyl groups are selected from unbranched, single, double, triple, and quadruple branched alkyl chains, and mixtures thereof.

[0011] In another embodiment, the 2,4-FDCA or derivatives of 2,4-FDCA are synthesized from renewable materials to produce biobased 2,4-FDCA or derivatives of 2,4-FDCA. In one embodiment, the biobased 2,4-FDCA or derivatives of 2,4-FDCA have from about 0.1% to about 99%, from about 0.1% to about 90%, from about 0.1% to about 75%, or preferably greater than 90% biobased carbon as determined by ASTM D6866.

[0012] In another embodiment, 2,4-furandicarboxylic acid (2,4-FDCA) is a 2,4-furandicarboxylic acid Dialkyl ester compounds is synthesized from renewable materials, allowing it to contain different levels of bio-based carbon, such as from about 0.1% to about 99%, greater than about 90%, or preferably from 29% to greater than 90%, typically measured according to ASTM D6866, depending on the source of the monohydric aliphatic primary alcohol.

[0013] In another embodiment, the process for preparing the compound dialkyl ester of 2,4-FDCA comprises using a stoichiometric excess (5 to 100% by mole) of plasticizing alcohol to react with 2,4-FDCA or a suitable derivative of 2,4-FDCA, optionally in the presence of an esterification catalyst such as Bronsted and Lewis acids, organic and inorganic acids, or metal catalysts such as tin(II) derivatives, and metal esters such as titanium and zirconium esters, and metal alkoxides such as antimony oxide and zeolites.

[0014] In another embodiment, the process for preparing a dialkyl ester of 2,4-FDCA further comprises, after complete conversion of 2,4-FDCA or a suitable derivative of 2,4-FDCA to a dialkyl ester of 2,4-FDCA, removing excess alcohol by vacuum evaporation.

[0015] In another embodiment, the process for preparing the compound dialkyl ester of 2,4-FDCA further comprises removing impurities, such as a titanium catalyst, from the resulting dialkyl ester of 2,4-FDCA. In one embodiment, the process for preparing the compound dialkyl ester of 2,4-FDCA further comprises dissolving the resulting compound in dichloromethane to form a solution, treating the solution with activated carbon to absorb impurities, such as a titanium catalyst, onto the charcoal, filtering the treated solution to remove the charcoal and impurities absorbed onto the charcoal, and evaporating the dichloromethane under vacuum.

[0016] Another embodiment of the present disclosure is a composition comprising a polymer and the compound of a dialkyl ester of 2,4-FDCA discussed above as a plasticizer, wherein the dialkyl ester of the 2,4-FDCA compound is present in the composition in an amount of 1 to 300, more preferably 10 to 150, and even more preferably 15 to 80 parts by weight of the compound per 100 parts by weight of the polymer.

[0017] In one embodiment, the composition exhibits a biobased carbon content, as determined by ASTM D6866, ranging from about 0.1% to about 90%, greater than about 90%, or preferably from about 0.1% to about 75%.

[0018] In another embodiment, the polymer is selected from the group consisting of PVC, polyvinyl butyral (PVB), thermoplastic polyurethane (PU), polylactic acid (PLA), polyhydroxybutyral (PHB), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polyethers, polysulfides, polysulfone homopolymers and copolymers of polystyrene (PS), polycarbonate (PC), polyalkyl methacrylate (PAMA), starch, thermoplastic starch (TPS), and combinations thereof.

[0019] In one embodiment, the polymer is polyvinyl chloride (PVC), hi another embodiment, the PVC is derived from a suspension, bulk, solution, emulsion, or microsuspension polymerization process.

[0020] In another embodiment, the composition further comprises one or more suitable additives typically used in polymer compositions, such as light stabilizers, acid stabilizers, heat stabilizers, UV stabilizers, fillers and reinforcing agents, biocides, blowing agents, demolding additives, lubricants, flow modifiers, impact modifiers, antiblocking agents, antistatic agents, slip agents, pigments, and flame retardants.

[0021] In another embodiment, the composition is 13 and further comprising an additional plasticizer selected from the group consisting of dialkyl phthalates, alkyl benzoates, trialkyl trimellitates, dialkyl adipates, alkyl 1,2-cyclohexanedicarboxylates, alkyl 1,3-cyclohexanedicarboxylates, alkyl 1,4-cyclohexanedicarboxylates, glyceryl esters, isosorbide esters, epoxidized vegetable oils, saturated and unsaturated fatty acid esters which may be fully or partially epoxidized, citric acid triesters, alkyl pyrrolidones, and combinations thereof.

[0022] In another embodiment, the additional plasticizer is preferably a non-phthalate diester (also called an orthoplasticizer).

[0023] Another aspect of the present disclosure is a method for preparing a composition comprising a polymer and the compound of dialkyl ester of 2,4-FDCA discussed above as a plasticizer, the method comprising mixing together the polymer in powder or pellet / granule form, the dialkyl ester of 2,4-FDCA, and other additives such as a Ca / Zn stabilizer and stearic acid to form a dry blend, loading the dry blend into a two-roll mill, and milling the mill for more than 3 minutes to facilitate incorporation of the plasticizer and homogenization of the composition.

[0024] Another aspect of the present disclosure provides a polymeric article comprising a composition comprising a polymer and the compound of a dialkyl ester of 2,4-FDCA discussed above as a plasticizer.

[0025] In one embodiment, the polymeric product is selected from the group consisting of a paint, an ink, an adhesive or adhesive component, a sealing compound, a coating composition, a lacquer, a plastisol, a synthetic leather, a solvent, a lubricant, a floor covering, an underbody protection material, a fabric coating, a cable or wire insulation, an extrusion, and a film. The polymeric product is produced by conventional means such as calendaring, extrusion, injection molding, or any other processing technique that can effectively melt and mix the additives in the composition.

[0026] In another embodiment, the polymeric product exhibits a biobased carbon content, as determined by ASTM D6866, ranging from about 0.1% to about 90%, greater than about 90%, or preferably from about 0.1% to about 75%.

[0027] Another aspect of the present disclosure is a method of making a polymeric product comprising a composition comprising a polymer and a compound of a dialkyl ester of 2,4-FDCA as a plasticizer as discussed above, the method comprising mixing together a polymer in powder or pellet / granule form, the dialkyl ester of 2,4-FDCA, and other additives such as a Ca / Zn stabilizer and stearic acid to form a dry blend, loading the dry blend into a two-roll mill, processing the mill for more than 3 minutes to facilitate incorporation of the plasticizer and homogenization of the composition, and processing the resulting homogenized composition into a polymeric product by calendaring, extrusion, injection molding, or any other processing technique suitable for converting a polymeric composition into a polymeric product. [Brief explanation of the drawings]

[0028] [Figure 1] 1 shows the Shore A hardness of test samples of compounds comprising dialkyl esters of 2,4-FDCA of the present disclosure as plasticizers compared to comparative control samples comprising standard phthalic and terephthalic acid plasticizers. [Figure 2]1 shows the thermogravimetric curves of test samples of compounds comprising dialkyl esters of 2,4-FDCA of the present disclosure as plasticizers compared to comparative control samples comprising standard phthalic and terephthalic acid plasticizers. [Figure 3] 1 shows weight loss curves obtained from migration tests using test samples of compounds comprising dialkyl esters of 2,4-FDCA of the present disclosure as plasticizers compared to comparative examples comprising DOP. DETAILED DESCRIPTION OF THE INVENTION

[0029] Described herein are new plasticizers based on the 2,4-isomer of furandicarboxylic acid diester that can be used in polymeric materials, including PVC. These plasticizers may overcome one or more of the aforementioned disadvantages of existing plasticizers, or at least provide a useful alternative. Also described is a cost-effective process for preparing plasticizers based on the 2,4-isomer of furandicarboxylic acid diester. This process can be more cost-effective than processes for existing plasticizers. Also disclosed are compositions containing plasticizers based on the 2,4-isomer of furandicarboxylic acid diester, as well as methods for preparing such compositions. Also disclosed are polymeric materials containing plasticizers based on the 2,4-isomer of furandicarboxylic acid diester that have improved, or at least equal, flexibility, durability, processability, and safety compared to the same materials plasticized with current existing plasticizers.

[0030] All percentages expressed herein are by weight of the total weight of the composition unless otherwise stated. When pH is referred to herein, the value corresponds to the pH measured at 25°C using standard equipment.

[0031] As used herein, "about," "approximately," and "substantially" are understood to refer to numbers within a range of numerical values, for example, from -10% to +10% of the referenced numerical value, preferably from -5% to +5% of the referenced numerical value, more preferably from -1% to +1% of the referenced numerical value, and most preferably from -0.1% to +0.1% of the referenced numerical value.

[0032] All numerical ranges herein should be understood to include all integers, whole numbers, or fractions within the range. Furthermore, these numerical ranges should be construed as providing support for claims directed to any number or subset of numbers within that range. For example, a disclosure of 1 to 10 should be construed as supporting ranges of 1 to 8, 3 to 7, 1 to 9, 3.6 to 4.6, 3.5 to 9.9, etc.

[0033] As used in this disclosure and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" or "the component" includes two or more components.

[0034] The terms "comprise," "comprises," and "comprising" are to be interpreted inclusively rather than exclusively. Similarly, the terms "include," "including," "containing," and "having" should all be interpreted as inclusive unless such a construction is clearly prohibited by the context. Further in this regard, these terms specify the presence of stated features, but do not exclude the presence of additional or further features.

[0035] Nevertheless, the compositions and methods disclosed herein may lack any element not specifically disclosed herein. Accordingly, disclosure of an embodiment using the term "comprising" is (i) a disclosure of an embodiment having the identified components or steps as well as additional components or steps, (ii) a disclosure of an embodiment "consisting essentially of" the identified components or steps, and (iii) a disclosure of an embodiment "consisting of" the identified components or steps. Any embodiment disclosed herein may be combined with any other embodiment disclosed herein.

[0036] The term "and / or" used in the context of "X and / or Y" should be interpreted as "X", or "Y", or "X and Y". Similarly, "at least one of X or Y" should be interpreted as "X", or "Y", or "X and Y".

[0037] As used herein, the terms "examples" and "e.g.," particularly when followed by a list of terms, are merely exemplary and illustrative and should not be considered exclusive or inclusive.

[0038] The term "substantially none" when used with respect to a particular component means that any of the components present constitutes less than about 2.0% by weight, such as less than about 1.0% by weight, preferably less than about 0.5% by weight, or more preferably less than about 0.1% by weight.

[0039] The term "plasticizer" as used herein refers to an additive that is added to a polymer, such as polyvinyl chloride (PVC), to change the physical properties of the polymer, such as decreasing the viscosity and increasing the flexibility of the polymer, thus softening the polymer. Softening occurs when the plasticizer dissolves in the polymer and increases the glass transition temperature (T g ) is brought about by reducing the plasticizer content. By varying the type and concentration of plasticizer in a polymer, the properties of the polymer can be tailored to requirements. Increasing the plasticizer concentration in a polymer increases flexibility, decreases tensile strength, and reduces the hardness of the polymer. Plasticizers also allow for improved compound processing properties to be achieved while also providing improved flexibility and durability of the end-use product. Plasticizers are generally organic molecules with a molecular weight of 100 to 1000 g / mol. Standard or conventional plasticizers generally include phthalate and terephthalate-based plasticizers.

[0040] The term "plasticizer efficiency" or "plasticizing efficiency" as used herein refers to the ability of a plasticizer to make a polymeric product softer, and is reported as the ratio of the slope of hardness versus plasticizer concentration to the slope of hardness found for dioctyl phthalate (DOP) in a polymeric product.

[0041] The term "derivative of 2,4-FDCA," as used herein, refers to a diester of 2,4-FDCA selected from the group consisting of dimethyl 2,4-furandicarboxylate (2,4-DMFDCA), diethyl 2,4-furandicarboxylate, and combinations thereof.

[0042] The term "suitable additives" as used herein refers to any one or more additives typically used in the polymer industry, such as light stabilizers, acid stabilizers, heat stabilizers, UV stabilizers, antioxidants (AOs), antistatic agents, fillers, reinforcing agents, biocides, blowing agents, demolding additives, lubricants, flow modifiers, impact modifiers, antiblocking agents, slip agents, pigments, flame retardants, additional plasticizers other than dialkyl esters of 2,4-FDCA, and combinations thereof. Additional plasticizers include those containing C4-C 13 These include, but are not limited to, dialkyl phthalates, alkyl benzoates, trialkyl trimellitates, dialkyl adipates, alkyl 1,2-cyclohexanedicarboxylates, alkyl 1,3-cyclohexanedicarboxylates, alkyl 1,4-cyclohexanedicarboxylates, glyceryl esters, isosorbide esters, epoxidized vegetable oils, fully or partially epoxidized saturated and unsaturated fatty acid esters, citric acid triesters, alkyl pyrrolidones, or combinations thereof.

[0043] In the context of the sustainable development of new plasticizers, 2,5-furandicarboxylic acid (2,5-FDCA) derivatives appear to be renewable building blocks that could bring a new dimension of competition to terephthalates. One of the main attractions of this platform is that these acids can be produced from sugars via fermentation routes. For example, WO2012 / 113609, WO2012 / 11360, DE102009028975A1, WO2011 / 023491, and U.S. Pat. No. 9,175,148 generally describe lateral alkyl C5, C7, C9, C6, C8, C9, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46, ​​C47, C48, C48, C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64, C65, C66, C67, C68, C69, C70, C71, C72, C73, C74, C75, C75, C76, C77, C78, ​​C79, C81, C82, C83, C84, C85, C86, C87, C88, C89, C90 10 and C 11 ~C 13 presents applications of 2,5-FDCA diesters ranging from 5 to 200 phr (parts per hundred parts of PVC resin). These furan plasticizers exhibit phthalate-like performance in terms of compatibility and migration. Similar results are found in Polym. Chem., 2019, 10, 5324-5332, and Journal of Polymer Science, Part A: Polymer Chemistry 54, 11-33, 2016. Regarding toxicity, a property that has driven the adoption of non-phthalate solutions, Matos et al. generally describe in their publication Materials 2019, 12, 2336 that diethylhexyl furanoate (also known as 2,5-DEHF), a 2,5-FDCA-based plasticizer, has metabolites that exhibit similar terephthalic acid toxicity. Regarding the use of other isomers of FDCA, U.S. Pat. No. 10,294,347 describes the production of 2,5 and 2,3-FDCA dialkyl esters and the use of C4 to C6 isomers in PVC. 22 and teach their use as plasticizers. However, to date, none of these diesters is mature enough to see commercialization in the near future.

[0044] Disclosed herein are new, preferably renewable, plasticizers for polymers, including PVC, that provide polymers with improved or at least equivalent properties, such as flexibility, durability, processability, and safety, compared to currently existing plasticizers, including phthalic acid-derived plasticizers, terephthalic acid-derived plasticizers, and 2,5-FDCA diester-derived plasticizers. The new plasticizers and processes for making the new plasticizers described herein may circumvent the barriers faced by plasticizer producers in the furan field and facilitate the production of affordable furan esters of 2,4-FDCA. Surprisingly, PVC compositions plasticized with these 2,4-FDCA diesters exhibited lower Shore A hardness at the same plasticizer concentration compared to those of currently existing plasticizers in PVC compositions, as shown in Figure 1 of the present disclosure. Experimental results demonstrated that some of the 2,4-FDCA diesters developed in accordance with the present disclosure have higher plasticizing efficiency than currently existing plasticizers. Surprisingly, these 2,4-FDCA diesters also demonstrated lower migration and advantageous safety profiles than currently existing plasticizers in polymer compositions.

[0045] Described herein are new plasticizers based on the 2,4-isomer of furandicarboxylic acid diester of the present disclosure that can be used in polymeric materials, including PVC. These plasticizers may overcome one or more of the aforementioned disadvantages of existing plasticizers, or at least provide a useful alternative. Also described are cost-effective processes for preparing plasticizers based on the 2,4-isomer of furandicarboxylic acid diester. These processes may be more cost-effective than those for existing plasticizers. Also disclosed are compositions containing plasticizers based on the 2,4-isomer of furandicarboxylic acid diester, as well as methods for preparing such compositions. Also disclosed are polymeric materials containing plasticizers based on the 2,4-isomer of furandicarboxylic acid diester that have improved, or at least equivalent, flexibility, durability, processability, and safety compared to the same materials plasticized with current existing plasticizers.

[0046] In one aspect of the present disclosure, innovative non-phthalic compounds of dialkyl esters of 2,4-furandicarboxylic acid are disclosed having the chemical structure of Formula I: [ka] wherein R1 and R2 each represent an alkyl radical of a C4 to C13 monohydric aliphatic primary alcohol, including, but not limited to, 2-ethylhexanol, ethylhexanol, n-butanol, isononyl alcohol, isobutanol, isodecyl alcohol, 2-methyl-1-pentanol, 2-propylheptanol, C6 to C11 straight chain alcohols, tridecyl alcohol, isooctyl alcohol, amyl alcohol, and other structural isomers of alcohols having the above general structure.

[0047] In one embodiment, R1 and R2 are two different alkyl radicals. In another embodiment, R1 and R2 are preferably the same alkyl radical. In yet another embodiment, R1 is a straight-chain alkyl radical. In yet another embodiment, R1 is a branched alkyl radical. In yet another embodiment, R2 is a straight-chain alkyl radical. In yet another embodiment, R2 is a branched alkyl radical. In yet another embodiment, each of R1 and R2 is an alkyl radical derived from ethylhexanol, and the resulting compound is di(ethylhexyl)-2,4-furanoate.

[0048] In another aspect of the present disclosure, a process for preparing an innovative non-phthalic acid compound of a dialkyl ester of 2,4-furandicarboxylic acid having the chemical structure of Formula I shown above is also described. The process includes synthesizing 2,4-furandicarboxylic acid (2,4-FDCA) or a derivative of 2,4-FDCA, and esterifying the 2,4-FDCA or the derivative of 2,4-FDCA with an alcohol to obtain a dialkyl ester of 2,4-furandicarboxylic acid having the chemical structure of Formula I discussed above, where R1 and R2 are each selected from the group consisting of 2-ethylhexanol, n-butanol, isononyl alcohol, isobutanol, isodecyl alcohol, 2-methyl-1-pentanol, 2-propylheptanol, C6-C6 11 C4-C6 alcohols, including but not limited to straight chain alcohols, tridecyl alcohol, isooctyl alcohol, amyl alcohol, and other structural isomers of alcohols having the general structure above. 13 R1 and R2 represent alkyl radicals derived from a monohydric aliphatic primary alcohol. In one embodiment, R1 and R2 are the same alkyl radical. In another embodiment, R1 and R2 are two different alkyl radicals. The properties of the 2,4-furandicarboxylic acid diester resulting from this process can be adjusted by changing the length and structure of the alkyl chain derived from the alcohol.

[0049] In another embodiment, a new furan isomer, i.e., 2,4-furandicarboxylic acid (2,4-FDCA), is synthesized from renewable sources through a fermentation process that has an inherently low environmental impact. Furthermore, this process can bring the production costs of this new isomer to a level comparable to that of terephthalic acid and phthalic anhydride. In another embodiment, 2,4-FDCA is produced via a catalytic route that includes several synthetic steps, as described in Org. Proc. Res. Dev. 2003, 7, 1, 74-81; Anti-Infective Agents, 2012, 10, 55-71; and ACS Sustainable Chem. Eng. 2016, 4, 3, 1707-1714. Esterification to yield the final diester can be adapted from the methodology discussed in Materials 2019, 12, 2336, where furan diacid (in this case, 2,5-FDCA) can be reacted with excess 2-ethyl-hexanol in the presence of sulfuric acid (1 wt%) at 160 °C for 6 hours. This step can be replicated using either bio-based or oil-based 2,4-FDCA.

[0050] In another embodiment, the compound dialkyl ester of 2,4-furandicarboxylic acid is a C4-C 13 Contains dialkyl furandicarboxylates, isomers C4-C 13 Dialkyl groups are selected from unbranched, single, double, triple, and quadruple branched alkyl chains, and mixtures thereof.

[0051] In another embodiment, 2,4-furandicarboxylic acid (2,4-FDCA) or a derivative thereof is synthesized from renewable materials, such as sugars, and the 2,4-furandicarboxylic acid Dialkyl ester compounds produces biobased 2,4-FDCA, which allows for different levels of biobased carbon, typically tested and measured according to ASTM D6866.

[0052] In another embodiment, the plasticizer exhibits a biobased carbon content. As discussed above, the total biobased or renewable carbon in the plasticizer can be contributed by biobased furan dicarboxylic acid and / or plasticizing alcohol, depending on the source of both components. ASTM D6866 distinguishes carbon originating from modern biomass-based inputs from carbon derived from fossil-based inputs. Biomass contains a well-characterized amount of carbon-14 that is easily distinguished from other materials, such as fossil fuels, that do not contain any carbon-14. Because the amount of carbon-14 in biomass is known, the percentage of carbon from renewable sources can be easily calculated from the total organic carbon in the sample.

[0053] In another embodiment, the compound exhibits a biobased carbon content, as determined by ASTM D6866, ranging from about 0.1% to about 99%, from about 0.1% to about 90%, from about 0.1% to about 75%, or preferably from about 29% to greater than 90%.

[0054] In another embodiment, 2,4-FDCA is produced by a recombinant microorganism capable of producing 2,4-FDCA from a feedstock comprising a carbon source, including hexose, pentose, glycerol, CO, sucrose, and / or combinations thereof, as described, for example, in U.S. Patent Application No. 16 / 806,728 (not yet published), the entire contents of which are incorporated herein by reference.

[0055] In another embodiment, 2,4-FDCA is obtained from renewable sources and catalytic routes, such as those described in U.S. Patent No. 9,284,290, Green Chem., 2014, 16, 1957-1966, ACS Sustainable Chem. Eng. 2016, 4, 3, 1707-1714, and U.S. Patent No. 8,455,668, the entire contents of which are incorporated herein by reference. A method for synthesizing 2,4-FDCA by the disproportionation pathway includes the following steps: a) oxidizing a furfural compound in the presence of a catalyst and an alkaline solution to obtain a bio-based furoate salt, where the catalyst is selected from the group consisting of Au / TiO, Au / C, Au / ZnO, Au / FeO, or other Au catalysts; b) heating the furoate salt in the presence of a metal-based catalyst under stirring to prepare a reaction mixture, and cooling the reaction mixture to room temperature; c) collecting furan from the reaction mixture obtained in item b) to obtain a mixture of 2,4-FDCA and 2,5-FDCA; and d) subjecting the mixture obtained in item c) to extraction or other separation methods to collect and purify 2,4-FDCA.

[0056] In another embodiment, 2,4-FDCA or its derivatives are obtained from renewable sources and catalytic routes, such as those described in ACS Sustainable Chem. Eng. 2016, 4, 3, 1707-1714 and U.S. Pat. No. 8,455,668. The entire contents of U.S. Pat. No. 8,455,668 are incorporated herein by reference. Starting from glycerol derivatives, glyceraldehyde, or dihydroxyacetone, 5-HMF or 4-HMF can be obtained through base-catalyzed condensation and acid-catalyzed dehydration steps in a batch process. 4-HMF oxidation will yield 2,4-FDCA.

[0057] In another embodiment, the process for preparing the compound dialkyl ester of 2,4-FDCA comprises using a stoichiometric excess (5 to 100% by mole) of plasticized alcohol to react with 2,4-FDCA or a suitable derivative of 2,4-FDCA, optionally in the presence of an esterification catalyst such as a metal catalyst, such as Bronsted and Lewis acids, organic and inorganic acids, or tin(II) derivatives, and metal esters, such as titanium and zirconium esters, and metal alkoxides, such as antimony oxide and zeolites. In another embodiment, the process for preparing the dialkyl ester of 2,4-FDCA further comprises removing the excess alcohol by vacuum evaporation after complete conversion of 2,4-FDCA or a suitable derivative of 2,4-FDCA to the dialkyl ester of 2,4-FDCA.

[0058] In another embodiment, the process for preparing the compound of dialkyl ester of 2,4-FDCA further includes dissolving the resulting compound in dichloromethane to form a solution, treating the solution with activated carbon to absorb impurities, such as titanium catalyst, onto the charcoal, filtering the treated solution to remove the charcoal and impurities absorbed onto the charcoal, and evaporating the dichloromethane under vacuum.

[0059] Another embodiment of the present disclosure provides a composition comprising a polymer and a dialkyl ester compound of 2,4-FDCA discussed above as a plasticizer in an amount of 1 to 300, more preferably 10 to 150, and even more preferably 15 to 80 parts by weight of the compound per 100 parts by weight of the polymer.

[0060] In one embodiment, the polymer is polyvinyl chloride (PVC).

[0061] In another embodiment, the polymer is selected from the group consisting of PVC, polyvinyl butyral (PVB), thermoplastic polyurethane (PU), polylactic acid (PLA), polyhydroxybutyral (PHB), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polyethers, polysulfides, polysulfone homopolymers and copolymers of polystyrene (PS), polycarbonate (PC), polyalkyl methacrylate (PAMA), starch, thermoplastic starch (TPS), and combinations thereof.

[0062] In another embodiment, the PVC is derived from a suspension, bulk solution, emulsion, or microsuspension polymerization process.

[0063] In another embodiment, the dialkyl ester of the 2,4-FDCA compound is present in the composition in an amount of from 1 to 300, more preferably from 10 to 150, and even more preferably from 15 to 80 parts by weight of the compound per 100 parts by weight of the polymer.

[0064] In another embodiment, the composition further comprises one or more suitable additives typically used in polymer compositions, such as light, acid, heat, and UV stabilizers, fillers and reinforcing agents, biocides, blowing agents, demolding additives, lubricants, flow modifiers, impact modifiers, antiblocking agents, antistatic agents, slip agents, pigments, and flame retardants.

[0065] In another embodiment, the composition is 13 and further comprising an additional plasticizer selected from the group consisting of dialkyl phthalates, alkyl benzoates, trialkyl trimellitates, dialkyl adipates, alkyl 1,2-cyclohexanedicarboxylates, alkyl 1,3-cyclohexanedicarboxylates, alkyl 1,4-cyclohexanedicarboxylates, glyceryl esters, isosorbide esters, epoxidized vegetable oils, saturated and unsaturated fatty acid esters which may be fully or partially epoxidized, citric acid triesters, alkyl pyrrolidones, and combinations thereof.

[0066] In another embodiment, the additional plasticizer is preferably a non-phthalate diester (also called an orthoplasticizer).

[0067] Another aspect of the present disclosure provides a method for preparing a composition comprising a polymer and the compound of dialkyl ester of 2,4-FDCA discussed above as a plasticizer, the method comprising mixing together the polymer in powder or pellet form, the dialkyl ester of 2,4-FDCA, and other additives such as a Ca / Zn stabilizer and stearic acid to form a dry blend, loading the dry blend into a two-roll mill, and milling the mill for more than 3 minutes to facilitate incorporation of the plasticizer and homogenization of the composition.

[0068] In yet another aspect, the present disclosure provides a polymeric article comprising a composition comprising a polymer and the compound of a dialkyl ester of 2,4-FDCA discussed above as a plasticizer.

[0069] In one embodiment, the polymeric product is selected from the group consisting of paints, inks, adhesives or adhesive components, sealing compounds, coating compositions, lacquers, plastisols, synthetic leather, solvents, lubricants, floor coverings, underbody protection, fabric coatings, cable or wire insulation, extrusions, and films. The polymeric product is produced by conventional means such as calendaring, extrusion, or any other technique that can effectively melt and mix the additives in the composition.

[0070] Yet another aspect of the present disclosure provides a method for making a polymeric product comprising a composition comprising a polymer and the above-discussed dialkyl ester of 2,4-FDCA compound as a plasticizer. First, the polymer in powder or pellet / granular form, the dialkyl ester of 2,4-FDCA, and other additives such as Ca / Zn stabilizers and stearic acid can be mixed together to form a dry blend. The dry blend can be placed in a mill, such as a two-roll mill. The dry blend can be processed in the mill for, for example, 3 minutes to facilitate the incorporation of the plasticizer and homogenization of the composition. The resulting homogenized composition can be processed into a polymeric product by calendaring, extrusion, injection molding, or any other processing technique suitable for converting a polymeric composition into a polymeric product.

[0071] The advantage of the present disclosure is that compounds of dialkyl esters of 2,4-FDCA as plasticizers can have higher plasticizing efficiency than phthalic acid-derived plasticizers and lower migration / exudation than aliphatic plasticizers, such as those derived from modified triglycerides. Thus, polymer products, such as PVC products, plasticized with compounds of dialkyl esters of 2,4-FDCA exhibit longer shelf life, lower additive requirements during compounding, lower hardness values, and more reliable and durable performance over time.

[0072] Another advantage of the present disclosure is that dialkyl ester compounds of 2,4-FDCA (2,4-DEHF) can have lower volatility. Based on structural parameters such as the dipole moment resulting from reduced symmetry and the presence of heteroatoms in the central molecular segment, 2,4-DEHF as a plasticizer in PVC compositions is expected to exhibit lower relative mobility in PVC compositions than phthalic acid and terephthalic acid plasticizers.

[0073] Another advantage of the present disclosure is that dialkyl esters of 2,4-FDCA (2,4-DEHF) in PVC compositions may exhibit lower relative mobility in PVC compositions than aliphatic plasticizers such as adipates, vegetable oils and their derivatives such as epoxidized vegetable oils, and their esters.

[0074] This advantage can be further expanded through the production of branched dialkyl esters of 2,4-FDCA. As a result, compositions prepared using branched dialkyl esters of 2,4-FDCA as plasticizers can exhibit reduced loss of plasticizer as a result of leaching or evaporation. This property can also translate into more reliable processing, as those skilled in the art can have greater control over the amount used during the preparation of the composition and more reliable control over properties over time. In this regard, 2,4-FDCA diesters can be incorporated into PVC resins to produce compositions by conventional means, such as calendaring, extrusion, injection molding, or any other technique that can effectively melt and mix additives in the formulation. [Example]

[0075] The present disclosure is further illustrated by the following non-limiting examples.

[0076] Example 1 In vivo production of 2,4-FDCA from glucose by the recombinant microorganism described in U.S. Patent Application No. 16 / 806,728 was performed using a 2.2 g / L KH2PO4, 9.4 g / L K2HPO4, 1.3 g / L (NH4)2SO4, 10 mg / L thiamine, 320 mg / L EDTA-NaOH, 2 mg / L CoCl2·6H2O, 10 mg / L MnSO4·H2O, 5 mg / L CuSO4·5H2O. 、The recombinant strain was evaluated in triplicate in shake flask fermentations using a defined medium containing 2 mg / L H3BO3, 2 mg / L Na2MoO4·2H2O, 54 mg / L ZnSO4·7H2O, 1 mg / L NiSO4·6H2O, 100 mg / L iron(III) citrate, 100 mg / L CaCl2·2H2O, and 0.3 g / L MgSO4·H2O. The carbon source was provided by 10 g / L glucose, and nitrogen sulfate was used as the nitrogen source for 2,4-FDCA production. Erlenmeyer flasks were inoculated with the recombinant strain to an initial optical density (OD600) of 0.1 and incubated at 37°C and 225 rpm for approximately 48 hours. Analysis of the 48-hour supernatant by high-performance liquid chromatography (HPLC) indicated the production of 14 ± 2 mg / L of 2,4-FDCA. As used herein, the term "EDTA-NaOH" refers to the soluble salt of ethylenediaminetetraacetic acid (EDTA) and sodium hydroxide (NaOH).

[0077] Example 2 Studies have investigated non-limiting examples of procedures for preparing 2,4-FDCA as a plasticizer of the present disclosure.

[0078] In this non-limiting example, a procedure for synthesizing 2,4-FDCA via a disproportionation pathway includes the following steps: a) oxidizing a furfural compound in the presence of a catalyst and an alkaline solution to obtain a biobased furoate salt, where the catalyst is selected from the group consisting of Au / TiO, Au / C, Au / ZnO, Au / FeO, or other Au catalysts; b) heating the furoate salt in the presence of a metal-based catalyst with stirring to prepare a reaction mixture and cooling the reaction mixture to room temperature; c) collecting furan from the reaction mixture obtained in item b) to obtain a mixture of 2,4-FDCA and 2,5-FDCA; and d) subjecting the mixture obtained in item c) to extraction or other separation methods to collect and purify 2,4-FDCA. The procedure is described in more detail below.

[0079] A procedure for preparing furoic acid from furfural: Oxidation of furfural

[0080] Furfural (3.00 grams, 31.22 mmol) was dissolved in 40 ml of water. One equivalent (31.75 mmol, 1.02 equivalents) of base (NaOH) and 0.012 grams of Au / TiO catalyst (ex-Strem-Autek; 1.2 wt.% Au, Au particle size 2-3 nm) were added to the furfural solution in water. A 100 ml reaction vessel (Buchi glass pipette) was closed and overhead stirring was applied. Oxygen pressure (303,974.99 Pa O) was applied to the reaction mixture. The reaction mixture was placed at 50 °C. After 1 hour of reaction, the pressure dropped to approximately 1 atmosphere, and the reaction vessel was repressurized to 303,974.99 Pa O and then stirred overnight. After stirring overnight, the reaction was stopped and the catalyst was filtered off. The solvent (water) was removed by rotary evaporation and vacuum was applied. The yield of sodium furoate was 94.9%.

[0081] The use of gold catalysts in the above reactions is often slightly more selective than other metal-based catalysts such as Pt or Pd, and under the conditions used in the reactions, a heterogeneous catalyst combination operating under the same basic conditions required for the subsequent disproportionation reaction would be advantageous.

[0082] This reaction demonstrates the efficiency of obtaining furoate salts from furfural, which can serve as input for subsequent disproportionation reactions.

[0083] Process for the production of a mixture of 2,4-FDCA and 2,5-FDCA 6.00 g of K-furoate (39.95 mmol) and 2.20 g of Cdl2 (6.01 mmol) were thoroughly ground together and charged into a three-neck, flat-flange reaction vessel. The mixture was then heated in a salt bath at 265 °C under a continuous (very slow) stream of nitrogen and stirring using a mechanical overhead stirrer. During the course of the reaction, the furan formed was collected via a Dean-Stark trap and a CO2 / acetone ice bath (-78 °C), yielding 1.35 grams (95% of theoretical) of furan. After 4 hours, the reaction was stopped and allowed to cool at room temperature for 1 hour. The black, hard solid material thus obtained was dissolved in water (50 mL). The remaining water-insoluble black material was filtered off, and the deep yellow filtrate was acidified (to pH 1) using 12 N HCl. 2,5-FDCA was precipitated and filtered off. 60.9% of the theoretical amount of 2,5-FDCA was isolated. NMR analysis of the reaction mixture after filtering off the insoluble black material showed that the K-furoate was over 90% converted and that a mixture of 2,4-FDCA and 2,5-FDCA was present in a ratio of 0.32:0.68. Based on this and the 60.9% of 2,5-FDCA isolated, it can be calculated that the K-furoate was disproportionated to a mixture of furandicarboxylic acids in 89% theoretical yield.

[0084] Procedure for the purification of 2,4-furandicarboxylic acid (2,4-FDCA) The crude reaction mixture (2,4-FDCA, 2,5-FDCA, 2-furoic acid, and Cdl2) underwent Soxhlet extraction using acetone for 8 hours. After cooling to room temperature, the acetone-insoluble white crystalline powder was analyzed by NMR, which showed no proton signals. The acetone-soluble portion was collected, and the solvent was evaporated under reduced pressure in a rotary evaporator. NMR analysis indicated the presence of 2,4-FDCA, 2,5-FDCA, and 2-furoic acid in the crude mixture. The mixture was then vigorously stirred with chloroform at room temperature for 10 minutes and filtered. This process was repeated until 2-furoic acid was completely removed from the mixture. The product was then dried in a vacuum oven at 40 °C for 12 hours. Because the solubility difference of 2,4-FDCA was relatively high in acetone at room temperature, the same technique (previously adapted with chloroform) was repeated with acetone to separate 2,4-FDCA from 2,5-FDCA. Therefore, the acetone soluble portions were separated, combined together, and evaporated under reduced pressure in a rotary evaporator, resulting in 2,4-FDCA that was not 100% qualitative but was greater than 85% pure, and research is ongoing to find a more accurate method for obtaining 100% pure compound of 2,4-FDCA.

[0085] Use of the process described herein allows for a 2,4-FDCA yield of at least 7% by weight, preferably at least 15-20% by weight, and more preferably at least 32% by weight (with the remaining fraction of the product being essentially 2,5-FDCA). 2,4-FDCA is produced from inexpensive, renewable feedstocks, such as furfural, through a simple two-step process that produces no harmful, toxic, or undesirable by-products (the primary by-product, furan, has extremely interesting practical applications).

[0086] Example 3 Studies have investigated non-limiting examples of procedures for preparing 2,4-FDCA for use as plasticizers in the present disclosure.

[0087] In a 250 mL jacketed glass reactor, dihydroxyacetone (10.0 g, 0.11 mol, 1 equivalent) was dissolved in deionized water (100 mL). The solution was cooled to 0°C, and Ambersep-900 basic ion exchange resin (27.8 g) was added. The mixture was then stirred at 0°C for 24 hours. After filtration to remove the resin, the product was freeze-dried.

[0088] The product was redissolved in DMSO (50 mL) in a 100 mL round-bottom flask and Amberlyst-15 acidic ion-exchange resin (5.0 g) was added. The setup was equipped with a Dean-Stark apparatus to collect the water produced during dehydration. The mixture was stirred at 110 °C for 5 h, then cooled to room temperature and filtered. The filtrate was concentrated under vacuum to remove most of the DMSO, maintaining the temperature below 50 °C. The product was then extracted by dichloromethane / NaHCO3 (1 M) partition. The organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The final product (a mixture of 4- and 5-HMF) was obtained as a brown viscous mass.

[0089] In a 250 mL round-bottom flask, 4-HMF was dissolved in aqueous sodium hydroxide (9.2 g NaOH in 100 mL deionized water). The mixture was cooled to 0 °C, and potassium permanganate (3.4 g, 22 mmol, 34 equiv.) was added. The solution was then stirred at 0 °C for 15 minutes. The manganese oxide precipitate was filtered off, and concentrated HCl solution was carefully added to the filtrate to bring the pH to 1, while maintaining the temperature below 5 °C. The resulting mixture was extracted with diethyl ether (×2). The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo. The product was obtained as a yellow powder.

[0090] Example 4 A study investigated the process for synthesizing the compounds of the present disclosure, dialkyl esters of 2,4-furandicarboxylic acid.

[0091] A novel dialkyl diester based on the 2,4-FDCA moiety was prepared via esterification of methyl furanoate with 2-ethylhexanol in the presence of a Ti catalyst, as described in Scheme 1 below. Dimethyl 2,4-furandicarboxylate (2,4-DMFDCA) (4.4 g, 23.9 mmol, 1 equiv.) and 2-ethylhexanol (9.34 g, 71.7 mmol, 3 equiv.) were charged into a 10 mL round-bottom flask. The setup was purged with argon gas. The reaction mixture was then heated to 115 °C for 15 min with constant stirring. After observing complete melting of the mixture, the catalyst Ti(OiPr)4 (0.34 g, 1.2 mmol) in 2.9 mL of toluene was added to the flask under a continuous flow of argon gas. The temperature was increased to 140 °C and stirred for 3 h. Excess 2-ethylhexanol was removed by vacuum evaporation. The resulting crude product was then dissolved in 20 mL of dichloromethane and treated with activated charcoal to eliminate the titanium catalyst and discolor the product. After filtration of the charcoal and evaporation of the dichloromethane under vacuum, the final product was obtained as an amber oil with a yield of 82% (7.5 g) and a purity of 98.0% by weight (H NMR titration).

[0092] The synthesis protocol and success of the synthesis were confirmed by FTIR (Fourier transform infrared) spectroscopy and 1 H NMR( 1 1H nuclear magnetic resonance (NMR). FTIR showed a shift in the carbonyl stretch (-C=O) (1500-1750 cm) characteristic of the resulting ester. -1 The success of the reaction was confirmed through detailed analysis of signals in the region related to (CCO-) and (OCC) stretching, and other signals characteristic of the ester product were observed at 1240 and 1050 cm, respectively. -1 Furthermore, 1 H NMR confirmed the attachment of alkyl residues at the furan moiety, confirming the formation of the targeted dialkyl ester through the presence of a characteristic signal at 4.2 ppm. Traces of residual alcohol were also observed in FTIR. 1 It was not found by 1 H NMR analysis. [ka]

[0093] Complementary properties such as thermal stability of the resulting dialkyl esters of 2,4-FDCA are investigated by thermogravimetric analysis (TGA) and dynamic scanning calorimetry (DSC). This property is compared to the processing window typically used for PVC and can be used to demonstrate the applicability of such plasticizers and benchmark the novel molecules against commercially available plasticizers with respect to stability.

[0094] Thermogravimetric analysis (TGA) has been performed. The TGA analysis and test results are detailed in Example 6 below and in FIG. 2.

[0095] The same synthetic protocol can be replicated starting from the diacid form of 2,4-FDCA, the only difference being the condensation of water instead of methanol in the reaction phase, derived from 2,4-FDCA and its derivatives from both fossil and biobased sources. Furthermore, the synthetic protocol allows for the synthesis of alcohols of different chain lengths (C4-C6), such as 1-butanol, 2-butanol, isobutanol, pentanol, hexanol, heptanol, octanol, 1-nonanol, isononanol, decanol, undecanol, dodecanol, tridecanol, and their mono-, di-, tri-, and tetra-branched structural isomers, as well as mixtures of the listed alcohols. 13 It can be adapted to alcohols with a range of

[0096] Example 5 A study investigated a process for preparing a dry blend of a polymer composition containing PVC and the dialkyl ester of 2,4-FDCA plasticizer of the present disclosure.

[0097] In a later stage, a dialkyl ester of 2,4-FDCA, specifically diethylhexyl 2,4-furanoate (2,4-DEHF), was prepared and used as a plasticizer to produce flexible PVC compositions, demonstrating the advantageous properties associated with the use of 2,4-DEHF in terms of processability and final performance. To that end, a dry blend was produced by adding a specific amount of the novel 2,4-DEHF plasticizer of the present disclosure, along with additives such as Ca / Zn stabilizers and stearic acid, to PVC resin powder (Braskem Norvic SP 700RA, nominal K value 57) in a beaker of suitable volume. The ingredients were thoroughly mixed with a spatula to form a dry blend. The dry blend was manually fed into a Mecanoplast two-roll mill and processed with manual mixing for 3 minutes to promote homogenization and facilitate plasticizer incorporation. Any other time suitable for causing plasticization of the mixture, as tracked by gelation behavior, can be used to produce flexible PVC compounds containing 2,4-DEHF. While the test samples of the present disclosure were prepared by calendering, any other processing technique suitable for converting PVC while simultaneously incorporating a plasticizer into the compound can be used. When calendering, the rolls were heated to 110°C and 140°C, respectively, but conditions can be adjusted to any other temperature and roll speed suitable for softening the PVC and effectively enabling processing / mixing.

[0098] The PVC compositions herein were specifically produced using 40 phr (parts per hundred parts of PVC resin) of plasticizer as an example, but plasticizer contents of 1 to 300 phr are suitable based on the expected relative lower migration of this 2,4-furanoate diester compared to its commercially available counterpart. In addition to the 2,4-DEHF plasticizer, phthalic and non-phthalic control plasticizers were used to prepare comparative control samples via the same methodology described above. Samples of DOTP from two suppliers were tested, hence DOTP_1 and DOTP_2.

[0099] The compositions of the test samples and control samples of the present disclosure are set forth in Table 1 below. [Table 1]

[0100] The chemical names of the plasticizers listed in Table 1 above are detailed below: DEHF (plasticizer of the present disclosure)—Diethylhexyl 2,4-furanoate (2,4-DEHF) (or bis(2-ethylhexyl) 2,4-furanoate), an example of a dialkyl ester of 2,4-FDCA of the present disclosure. ) , DOPT - diethylhexyl terephthalate (or bis(2-ethylhexyl) terephthalate) - the unit names 1 and 2 used after DOPT in Table 1 refer to different suppliers. DOP-diethylhexyl phthalate (or bis(2-ethylhexyl) phthalate), DOA-dioctyl adipate, DINP - Diisononyl phthalate, INBRAFLEX 5.0 - a commercially available blend of non-specific esters of epoxidized soybean oil, INBRAFLEX 3.8—a commercially available blend of non-specific epoxidized soybean oil, and DRAPEX 6.8 - A commercially available formulation of epoxidized soybean oil.

[0101] Example 6 A study investigated the thermal properties of PVC compositions plasticized with 2,4-DEHF.

[0102] The thermal performance of PVC compositions plasticized with the dialkyl esters of 2,4-FDCA of the present disclosure was determined by TGA (thermogravimetric analysis). Tests were performed using approximately 10 mg of compound sample, under a N2 atmosphere, from room temperature to 1000°C at a heating rate of 10°C / min. The resulting thermogravimetric curves of test samples of compounds containing the dialkyl esters of 2,4-FDCA of the present disclosure as plasticizers, compared to control samples containing the standard phthalic and terephthalic acid plasticizer DOP, are shown in Figure 2.

[0103] Figure 2 compares the thermal stability of compounds prepared with the dialkyl esters of the present invention with a comparative sample prepared with a commercially available DOP. The test results in Figure 2 demonstrate that the resulting compounds prepared with the plasticizers of the present invention (dialkyl esters of 2,4-FDCA) have superior thermal stability compared to compounds prepared with standard phthalic and terephthalic acid-based plasticizers.

[0104] Example 7 A study investigated the plasticizing efficiency of the plasticizers of the present disclosure using Shore A hardness.

[0105] The Shore A hardness test probes the softness of a given PVC composition by correlating the depth to which a standardized needle penetrates the sample with a hardness scale. In this regard, the plasticizing efficiency of a plasticizer can be understood as its ability to soften the PVC resin. Thus, the lower the hardness value, the higher the plasticizing efficiency of a given plasticizer. This is a very important aspect in the PVC sector, as hardness values ​​are used to characterize specific grades and formulations are typically designed to target Shore A value ranges.

[0106] The Shore A hardness of PVC compositions plasticized with different plasticizers was determined according to ASTM D2240 standard, and the test results are shown in Figure 1. As shown in Figure 1, test samples of PVC compositions plasticized with 2,4-DEHF of the present disclosure exhibited lower Shore A hardness values ​​than those observed for their phthalic and terephthalic acid-based counterparts. The experimental results clearly demonstrated that the novel 2,4-DEHF plasticizer exhibits higher plasticization efficiency in PVC compositions than that of standard phthalic and terephthalic acid-based plasticizers in PVC compositions. Thus, by using the diesters of the present disclosure described herein, compared to phthalic or terephthalic acid-based plasticizers, it is possible to reduce the plasticizer content and achieve a given PVC composition with a target hardness value.

[0107] Example 8 Studies have investigated the permanence of the plasticizers of the present disclosure in PVC compositions, which can be important in many applications.

[0108] Permanence is linked to the resistance of a given plasticizing molecule (or any other additive) to leaching out of the PVC composition onto food, packaging surfaces, or any other items that come into contact with the PVC composition. Apart from problems related to the user's exposure to contamination and harmful substances, a problem particularly associated with phthalates, this phenomenon is also responsible for negative changes in performance over time.

[0109] The migration test was conducted in an oven to simulate and accelerate potential exudation phenomena in accordance with standard ANBT-NBR NM-IEC 60811-3-2. Samples of Compound 1 of the present invention and Comparative Example 4 (shown in Table 1) were exposed to a temperature of 105°C, and weight loss measurements related to plasticizer migration were recorded at intervals of 24 hours (h), 48 hours, 72 hours, and 168 hours (1 week) after the start of the test. Comparative Example 4 was selected for this test because it is based on a phthalate plasticizer and is therefore a more significant comparison from an application standpoint and a structural standpoint. The resulting weight loss curves obtained from the migration test using test samples of a compound containing a dialkyl ester of 2,4-FDCA of the present disclosure as a plasticizer compared to a comparative example containing DOP are shown in Figure 3.

[0110] 3 demonstrates that PVC compounds prepared with the dialkyl esters of 2,4-FDCA of the present invention exhibited less overall weight loss throughout the experiment compared to PVC compounds prepared with DOP. Based on structural parameters such as reduced symmetry, the presence of branching units, and the dipole moment resulting from the presence of heteroatoms in the central molecular segment of 2,4-DEHF, 2,4-DEHF exhibits lower relative mobility in PVC compositions compared to phthalate plasticizers with comparable pendant alkyl side chains, such as in the comparisons above.

[0111] In summary, the inventors have surprisingly found that the Shore A hardness experimental results shown in Figure 1 demonstrate that the dialkyl esters of the 2,4-FDCA plasticizers of the present disclosure exhibit higher plasticizing efficiency in PVC compositions than those of standard phthalic and terephthalic acid-based plasticizers in PVC compositions. The inventors have also surprisingly found that compounds prepared using the plasticizers of the present invention (dialkyl esters of 2,4-FDCA) have superior thermal stability and better permanence compared to compounds prepared using standard phthalic and terephthalic acid-based plasticizers, as shown in Figures 2 and 3, respectively. The combined experimental results demonstrated in Figures 1-3 demonstrate the suitability of these new dialkyl esters for their performance as plasticizers in polymer compositions and products.

[0112] Various changes and modifications to the presently preferred embodiments disclosed herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present subject matter and without diminishing its intended advantages. It is therefore intended that such changes and modifications be covered by the appended claims.

Claims

1. A compound for plasticizing a polymeric material, said compound being a dialkyl ester of 2,4-furandicarboxylic acid (2,4-FDCA) having the chemical structure of Formula I: 【Chemistry 1】 In the formula, R １ and R ２ are respectively 2-ethylhexanol, ethylhexanol, isononyl alcohol, isodecyl alcohol, 2-methyl-1-pentanol, 2-propylheptanol, C ６ ~C １１ Compounds representing the alkyl radical of a C 5 -C 10 monohydric aliphatic primary alcohol, including but not limited to straight chain alcohols, isooctyl alcohol, amyl alcohol, and other structural isomers of alcohols having the above general structure.

2. 2. The compound of claim 1, wherein each of R1 and R2 is an alkyl radical derived from ethylhexanol, and the resulting compound is di(ethylhexyl)-2,4-furanoate.

3. 1. A process for preparing a compound of a dialkyl ester of 2,4-furandicarboxylic acid having the chemical structure of Formula I, comprising: 1) synthesizing 2,4-furandicarboxylic acid (2,4-FDCA) or a derivative of 2,4-FDCA; 2) esterifying the 2,4-FDCA or a derivative of the 2,4-FDCA with an alcohol to obtain a dialkyl ester of 2,4-furandicarboxylic acid having the chemical structure of Formula I; 【Chemistry 2】 In the formula, R １ and R ２ are respectively 2-ethylhexanol, ethylhexanol, isononyl alcohol, isodecyl alcohol, 2-methyl-1-pentanol, 2-propylheptanol, C ６ ~C １１ represents an alkyl radical of a C 5 -C 10 monohydric aliphatic primary alcohol, including but not limited to straight chain alcohols, isooctyl alcohol, amyl alcohol, and other structural isomers of alcohols having the above general structure.

4. 4. The process of claim 3, wherein the 2,4-FDCA or a derivative of 2,4-FDCA is synthesized from renewable materials to produce a bio-based 2,4-FDCA or a derivative of 2,4-FDCA.

5. 5. The process of claim 4, wherein the bio-based 2,4-FDCA or derivative of the 2,4-FDCA has greater than 90% bio-based carbon as determined by ASTM D6866.

6. 4. The process of claim 3, comprising using a stoichiometric excess (5 to 100% molar excess) of the alcohol to react with the 2,4-FDCA or a derivative of the 2,4-FDCA in the presence of an esterification catalyst selected from the group consisting of Bronsted acids, Lewis acids, organic acids, inorganic acids, metal catalysts and metal esters, metal alkoxides, and combinations thereof.

7. 7. The process of claim 6, further comprising removing excess alcohol by vacuum evaporation after substantially complete conversion of the 2,4-FDCA or the derivative of 2,4-FDCA to the dialkyl ester of 2,4-FDCA.

8. 4. The process of claim 3, further comprising removing a titanium catalyst from the resulting dialkyl ester of 2,4-FDCA using activated carbon.

9. A composition comprising a polymer and a compound of a dialkyl ester of 2,4-FDCA having the chemical structure of Formula I, 【Transformation 3】 In the formula, R １ and R ２ are respectively 2-ethylhexanol, ethylhexanol, isononyl alcohol, isodecyl alcohol, 2-methyl-1-pentanol, 2-propylheptanol, C ６ ~C １１ A composition representing the alkyl radical of a C 5 to C 10 monohydric aliphatic primary alcohol, including but not limited to straight chain alcohols, isooctyl alcohol, amyl alcohol, and other structural isomers of alcohols having the above general structure.

10. 10. The composition of claim 9, wherein the polymer is selected from the group consisting of PVC, polyvinyl butyral (PVB), thermoplastic polyurethane (PU), polylactic acid (PLA), polyhydroxybutyral (PHB), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polyethers, polysulfides, polysulfone homopolymers and copolymers of polystyrene (PS), polycarbonate (PC), polyalkyl methacrylate (PAMA), starch, thermoplastic starch (TPS), and combinations thereof.

11. 10. The composition of claim 9, wherein the dialkyl ester of 2,4-FDCA compound is present in the composition in an amount of 1 to 300 parts by weight, 10 to 150 parts by weight, or 15 to 80 parts by weight per 100 parts by weight of the polymer.

12. 10. The composition of claim 9, wherein the composition exhibits a biobased carbon content as determined by ASTM D6866 ranging from 0.1% to 75%.

13. 10. The composition of claim 9, further comprising an additive selected from the group consisting of light stabilizers, acid stabilizers, heat stabilizers, UV stabilizers, fillers, reinforcing agents, biocides, blowing agents, demolding additives, lubricants, flow modifiers, impact modifiers, pigments, flame retardants, and combinations thereof.

14. C ４ ~C １３ 10. The composition of claim 9, further comprising an additional plasticizer selected from the group consisting of dialkyl phthalates, alkyl benzoates, trialkyl trimellitates, dialkyl adipates, alkyl 1,2-cyclohexanedicarboxylates, alkyl 1,3-cyclohexanedicarboxylates, alkyl 1,4-cyclohexanedicarboxylates, glyceryl esters, isosorbide esters, epoxidized vegetable oils, fully or partially epoxidized saturated and unsaturated fatty acid esters, citric acid triesters, alkylpyrrolidones, and combinations thereof.

15. 1. A method for preparing a composition comprising a polymer and a compound of a dialkyl ester of 2,4-FDCA having the chemical structure of Formula I, comprising: mixing the polymer with the dialkyl ester of 2,4-FDCA to form a mixture; and processing the mixture to incorporate and homogenize the dialkyl ester of 2,4-FDCA; 【Chemistry 4】 In the formula, R １ and R ２ are respectively 2-ethylhexanol, ethylhexanol, isononyl alcohol, isodecyl alcohol, 2-methyl-1-pentanol, 2-propylheptanol, C ６ ~C １１ represents an alkyl radical of a C 5 -C 10 monohydric aliphatic primary alcohol, including but not limited to straight chain alcohols, isooctyl alcohol, amyl alcohol, and other structural isomers of alcohols having the above general structure.

16. mixing the polymer in powder or pellet form, the dialkyl ester of 2,4-FDCA, and suitable additives together to form a dry blend; and milling the dry blend until the dialkyl ester of 2,4-FDCA compound is incorporated into and homogenized with the polymer.

17. 17. The method of claim 16, wherein the milling is performed in a two-roll mill and the milling is for more than 3 minutes.

18. 1. A polymeric article comprising a polymer and a compound of a dialkyl ester of 2,4-FDCA having the chemical structure of Formula I: 【Transformation 5】 In the formula, R １ and R ２ are respectively 2-ethylhexanol, ethylhexanol, isononyl alcohol, isodecyl alcohol, 2-methyl-1-pentanol, 2-propylheptanol, C ６ ~C １１ A polymeric product representing the alkyl radical of a C 5 to C 10 monohydric aliphatic primary alcohol, including but not limited to straight chain alcohols, isooctyl alcohol, amyl alcohol, and other structural isomers of alcohols having the above general structure.

19. 20. The polymeric product of claim 18, wherein the polymeric product is selected from the group consisting of a paint, an ink, an adhesive or adhesive component, a sealing compound, a coating composition, a lacquer, a plastisol, a synthetic leather, a solvent, a lubricant, a floor finish, an underbody protection material, a fabric coating, a cable or wire insulation, an extrusion, and a film.

20. 1. A method for producing a polymer product, comprising: mixing a polymer in powder or pellet form and a compound of a dialkyl ester of 2,4-FDCA having the chemical structure of Formula I to form a dry blend; processing the dry blend to incorporate the dialkyl ester of 2,4-FDCA into the polymer to form a homogenized composition; and processing the homogenized composition by calendering, extrusion, or injection molding to form the polymeric article; 【Transformation 6】 In the formula, R １ and R ２ are respectively 2-ethylhexanol, ethylhexanol, isononyl alcohol, isodecyl alcohol, 2-methyl-1-pentanol, 2-propylheptanol, C ６ ~C １１ represents an alkyl radical of a C 5 -C 10 monohydric aliphatic primary alcohol, including but not limited to straight chain alcohols, isooctyl alcohol, amyl alcohol, and other structural isomers of alcohols having the above general structure.

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