Thermoplastic polyurethane composition containing nitro-substituted polyester diol

Abstract

The present invention relates to the field of polymers. More specifically, the present invention includes thermoplastic polyurethane elastomers comprising polyesters containing nitro-substituted dicarboxylic acids that are the product of polyethylene degradation. The thermoplastic polyurethane elastomers described herein exhibit higher glass transition temperatures and higher Shore A hardnesses than thermoplastic polyurethane elastomers synthesized from similar polyester diols made from virgin monomers that do not contain nitro substitution.

Description

[Technical Field]

[0001] The present invention relates to the field of polymers. More specifically, the present invention includes thermoplastic polyurethane (TPU) compositions comprising polyesters containing dicarboxylic acids and nitrosubstituted dicarboxylic acids from recycled raw materials. [Background technology]

[0002] All publications in this specification are incorporated by reference to the same extent as individual publications or patent applications are indicated to be incorporated by specific and individual reference. The following description contains information that may be useful in understanding the invention. It is not an assertion that any information provided herein is prior art, or relates to the invention currently claimed, or that any publication specifically or implicitly referenced is prior art.

[0003] TPU elastomers are used in a wide variety of applications, including footwear, automotive parts, tubes, hoses, and other uses. Typically, TPU elastomers are reaction products of one or more diisocyanate compounds, one or more high equivalent weight diols (polyesters or polyethers), and one or more chain extenders. In many applications, the selected high equivalent weight diols are polyester diols such as adipic acid polyester or polycaprolactone. Generally, cast elastomers prepared from polyester diols have superior mechanical properties compared to elastomers prepared from polyether diols. Polyester diols impart desirable mechanical properties and abrasion resistance to TPU, making TPU elastomers useful in footwear applications. TPU is expanding into new applications such as 3D printing. These applications require high hardness and tensile strength while maintaining the desirable flexibility of TPU elastomers.

[0004] Furthermore, environmental issues surrounding the petrochemical sources of polyester diols are creating a growing momentum among companies to offer more sustainable products. However, there remains a need for these products to offer performance equivalent to or better than conventional petroleum-based alternatives at a comparable price point.

[0005] U.S. Patent No. 5,844,165 discloses nitromalonate polyesters useful in high-energy propellants. According to this patent, preferred nitromalonate polyesters are both R-CH2ONO2. 1 base and R 2 The group is included. Therefore, the preferred nitromalonate described in this '165 patent is substituted with two nitromethane groups between the two carboxyl groups of the malonate, providing an energy composition.

[0006] U.S. Patent No. 3,745,076 discloses a reaction product of 4,4-dinitropimelic acid and diethylene glycol, which yields a polyester polyol containing hydroxyl groups that can react with polyisocyanates. According to this '076 patent, when nitro is a substituent, preferably there are at least two nitro groups on the substituted component. Since the object of this '076 patent is to produce a binder with a higher total energy content, multiple nitro groups are preferred. [Overview of the Initiative]

[0007] The following embodiments and aspects are described and illustrated in relation to systems, compositions, methods, and products, and are intended to be illustrative and illustrative, not limiting in scope.

[0008] Used polyethylene waste provides an abundant source of raw materials for producing new chemical substances. Nitro-functionalized diacids are products of chemically recycled polyethylene obtained via ATOD™ (Accelerated Thermal Oxidative Decomposition). These diacids can be used in the synthesis of nitro-functionalized polyester diols, which are the main building blocks of thermoplastic polyurethane. These nitro-functionalized polyester diols are the first polyols synthesized from monomers derived from chemically recycled used polyethylene.

[0009] It would be desirable to provide TPU elastomers made from polyester diols that are economical, produced from recycled components, and exhibit excellent mechanical properties.

[0010] Accordingly, the object of the present invention is to overcome the above-mentioned drawbacks of the prior art. Another object is to provide a polyester-based TPU elastomer with increased hardness and tensile strength while maintaining elasticity.

[0011] The present invention provides a TPU elastomer which is a polymer of: (1) at least one high-equivalent-weight polyester diol containing nitro functional groups on the main chain derived from a mixture of dicarboxylic acid and nitro-dicarboxylic acid, and a polymer of polyester diol not containing any nitro groups; (2) at least one chain extender; and (3) at least one diisocyanate. The presence of the polyester diol not containing any nitro groups provides non-energetic TPU useful for consumer goods.

[0012] In another embodiment, there is provided a TPU elastomer which is a polymer of: (1) 20 to 80 wt% of nitro-functionalized polyester diol (NO₂-PED) prepared from a mixture of dicarboxylic acid, nitro-dicarboxylic acid and 1,4-butanediol, or a mixture comprising said nitro-functionalized polyester diol and at least one chain extender; and (2) at least one polyisocyanate.

[0013] The present invention also includes NO₂-PED synthesized from chemically recycled monomers derived from the decomposition of waste polyethylene. The resulting TPU serves as a sustainable alternative to biologically or petrochemically based TPUs.

[0014] It has been found that the unique nitro functional groups on the high equivalent weight polyester diol component contribute to a high glass transition temperature, high tensile strength, and high Shore A hardness.

[0015] A thermoplastic polyurethane elastomer composition is provided, which comprises at least one nitro-substituted polyester diol (NO₂-PED) and at least one polyisocyanate, and further comprises a reaction product with at least one chain extender.

[0016] In some embodiments, the NO₂-PED has the formula:

Chemical Formula

[0017] In some embodiments, R is alkylenyl. In some embodiments, R is ethylenyl, propylenyl, isopropylenyl, butylenyl, pentylenyl, hexylenyl, heptylenyl, or octylenyl.

[0018] In some embodiments, R is alkylenyl, and one or more CH₂ groups are substituted with -O-.

[0019] In some embodiments, R is -(CH₂) O -O-(CH₂) O -, CH₃-O-(CH₂) O-O-(CH2) O The formulas are -CH3 and (CH3CH(OH)CH2)2O, where O is 2 to 4.

[0020] In some embodiments, R is an arylenyl or an aralkylenyl.

[0021] In some embodiments, the NO2-PED before the reaction has a molecular weight of 400 to 10,000 g / mol.

[0022] In some embodiments, the chain extender is a dihydroxyalkane or dihydroxycycloalkane. In some embodiments, the chain extender is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-dihydroxycyclohexane, or a mixture thereof.

[0023] In some embodiments, the chain extender is alkylene or aralkylenediamine. In some embodiments, the chain extender is ethylenediamine, hexamethylenediamine, 1,4-cyclohexanylenediamine, or a mixture thereof. In some embodiments, the chain extender is aromatic diamine. In some embodiments, the aromatic diamine is benzidine, dihydroxymethoxyhydroquinone, toluenediamine, diaminodiphenylmethane, phenylenediamine, or a mixture thereof.

[0024] In some embodiments, the chain extender is hydrazine.

[0025] In some embodiments, the chain extender is an amino alcohol. In some embodiments, the chain extender is ethanolamine, N-methylethanolamine, N-butylethanolamine, N-oleoylethanolamine, N-cyclohexylisopropanolamine, or a mixture thereof.

[0026] In some embodiments, the chain extender is a substituted aromatic diamine. In some embodiments, the chain extender is 4,4'-methylene-bis(o-chloroaniline), 4,4'-methylenebis(3-chloro-2,6-diethylaniline), or a mixture thereof.

[0027] In some embodiments, the thermoplastic polyurethane elastomer composition further comprises at least one crosslinking agent. In some embodiments, the crosslinking agent is glycerin, trimethylolpropane, diethanolamine, triethanolamine, or a mixture thereof.

[0028] In some embodiments, the ratio of polyisocyanate to active hydrogen-containing groups (NCO index) is 0.9 to 1.5.

[0029] In some embodiments, the isocyanate is 4,4'-diisocyanate diphenylmethane (4,4'-MDI), 2,4'-diisocyanate diphenylmethane (2,4'-MDI), p-phenylenediisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, 1,4-diisocyanate cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalenediisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diisocyanate dicyclohexylmethane, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, or a mixture thereof. In some embodiments, the isocyanate is 4,4'-MDI or 2,4'-MDI.

[0030] In some embodiments, the composition comprises one or more additives. In some embodiments, the one or more additives comprises at least one light stabilizer, UV stabilizer, or a mixture thereof. In some embodiments, the one or more additives are inorganic fillers, organic fillers, or a mixture thereof. In some embodiments, the one or more additives are at least one inorganic filler which is a silicate mineral, metal oxide, metal salt, clay, metal silicate, glass fiber, natural fiber material, synthetic fiber mineral, or a mixture thereof. In some embodiments, the additive is an organic filler which is carbon black, fullerene, carbon nanotube, biochar, melamine corophony, cellulose fiber, polyamide fiber, polyacrylonitrile fiber, polyurethane fiber, aromatic and / or aliphatic dicarboxylic acid ester-based polyester fiber, carbon fiber, or a mixture thereof. In some embodiments, the filler is present in an amount of 0.5 to 30 weight percent of the composition. In some embodiments, the filler comprises at least one flame retardant. In some embodiments, the at least one flame retardant is an organic phosphate, metal polyphosphate, metal oxide, metal salt, cyanuric acid derivative, or a mixture thereof. In some embodiments, at least one flame retardant is present in the composition at a concentration of 500 to 4000 ppm.

[0031] In some embodiments, the composition includes a foaming agent. In some embodiments, the foaming agent is at least one of water, pentane, cyclopentane, hydrofluorocarbon, or a mixture thereof.

[0032] In some embodiments, the nitrosubstituted polyester diol is a. Oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, C10-dicarboxylic acid, C11-dicarboxylic acid, C12-dicarboxylic acid, C13-dicarboxylic acid, C14-dicarboxylic acid, and C15-dicarboxylic acid, and b. Esters of at least one C8-C20 dicarboxylic acid substituted with a single nitro group; and at least one polyol.

[0033] In some embodiments, at least one polyol is C 1-8 It is a diol.

[0034] In some embodiments, the composition contains 20 to 80% by weight of a nitrosubstituted polyester diol.

[0035] In some embodiments, the composition further comprises a reaction product of at least one unsubstituted polyester diol and at least one polyisocyanate, and further comprises a reaction product with a chain extender.

[0036] A method for producing the composition is also provided, and this method is At least one nitrosubstituted polyester diol, At least one polyisocyanate, This includes reacting with at least one chain extender.

[0037] In some embodiments, the reaction conditions include a temperature of 25–120°C.

[0038] Thermoplastic polyurethane elastomer compositions prepared by the method described herein are also provided.

[0039] In some embodiments, the thermoplastic polyurethane elastomer composition is (a) A polyester comprising at least one nitrosubstituted polyester diol, (b) at least one isocyanate, (c) at least one chain extender, (d) at least one flame retardant, (e) at least one surfactant, (f) at least one blowing agent, and (g) In the form of a foam containing at least one urethane catalyst.

[0040] In some embodiments, the method further comprises reacting at least one polyester diol that is not substituted with a nitro group.

[0041] In some embodiments, the dicarboxylic acid used to produce polyester diols and nitropolyester diols is a. Oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, C10-dicarboxylic acid, C11-dicarboxylic acid, C12-dicarboxylic acid, C13-dicarboxylic acid, C14-dicarboxylic acid, and C15-dicarboxylic acid, and b. At least one C8-C20 dicarboxylic acid substituted with a single nitro group; and It is an ester of at least one diol.

[0042] In some embodiments, at least one diol is C 1-8 It is a diol.

[0043] Exemplary embodiments are shown in the reference figures. The embodiments and drawings disclosed herein are intended to be illustrative rather than restrictive. [Brief explanation of the drawing]

[0044] [Figure 1] This figure shows a bar graph indicating the weight percentage of dicarboxylic acid in a composition containing nitrosubstituted dicarboxylic acid. [Modes for carrying out the invention]

[0045] All references cited herein are incorporated by reference in their entirety as if they were fully cited. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this invention belongs.

[0046] Those skilled in the art will recognize many methods and materials similar or equivalent to those described herein that can be used in carrying out the present invention. Other features and advantages of the present invention will become apparent from the following detailed description, together with the accompanying drawings illustrating various features of embodiments of the present invention. In fact, the present invention is by no means limited to the methods and materials described. For convenience, specific terms used herein, in the examples and in the appended claims are set forth herein.

[0047] Unless otherwise stated or implied by the context, the following terms and phrases have the meanings set forth below. Unless otherwise stated or made clear by the context, the following terms and phrases do not exclude the meanings acquired in the art to which they relate. Unless otherwise defined, all technical and scientific terms used herein have the same meanings as commonly understood by those skilled in the art to which the present invention belongs. It should be understood that the present invention is not limited to and may vary from the specific methodologies, protocols, and reagents described herein. The definitions and terms used herein are provided to help illustrate specific embodiments and are not intended to limit the claimed invention, for the scope of the invention is limited only by the claims.

[0048] As used herein, the terms “comprising” or “comprises” are used in reference to compositions, methods, systems, products, and their respective components, which may include, but are useful to the embodiments, unspecified elements, whether useful or not. Generally, those skilled in the art will understand that the terms used herein are generally intended to be “open” terms (for example, “including” should be interpreted as “including but not limited to,” “having” as “having at least,” and “include” as “includes but is not limited to,” etc.). As used herein, the terms “comprising” or “comprise” mean that other elements may be present in addition to the defined elements presented. The use of “comprising” indicates inclusion, not limitation. The open-ended term "comprising," as a synonym for terms such as including, containing, or having, is used herein to describe and claim the present invention; however, the present invention or its embodiments may be described using alternative terms such as "consisting of" or "consisting essentially of."

[0049] Unless otherwise stated, the terms “a,” “an,” and “the” and similar references used in the context of describing a particular embodiment of this application (particularly in the context of the claims) can be interpreted as encompassing singular and plural forms and both. The enumeration of ranges of values ​​herein is merely intended to serve as a simple way to refer individually to each distinct value that falls within the range. Unless otherwise indicated herein, individual values ​​are incorporated herein as they are individually listed herein. All methods described herein may be carried out in any preferred order unless otherwise indicated herein or unless it is clearly inconsistent with the context. Any examples or exemplary language (e.g., “such as”) provided relating to a particular embodiment herein is merely intended to better illustrate this application and not to limit the scope of the application as otherwise claimed. The abbreviation “e.g.” is derived from the Latin “exempli gratia” and is used herein to indicate non-limiting examples. Therefore, the abbreviation "e.g." is synonymous with the term "for example." The language of this specification should not be construed as indicating any unclaimed elements essential to the practice of this application.

[0050] The grouping of alternative elements or embodiments of the Invention disclosed herein should not be construed as limiting. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. One member of a group may be included in or excluded from a group for convenience and / or patentability reasons. If such inclusion or exclusion occurs, the specification shall be deemed to include the group so as to satisfy the description of all Markush groups used in the appended claims.

[0051] "Optional" or "optionally" means that the situation described afterward may or may not occur, and therefore the description includes both cases where the situation occurs and cases where it does not.

[0052] As used herein, the term “substituted” means that one or more hydrogen atoms on a substituted moiety (typically 1, 2, 3, 4, or 5) are independently substituted with substituents independently selected from the group of substituents defined below or otherwise specified. In general, non-hydrogen substituents can be any substituent that can bond to an atom of a given moiety identified to be substituted. Examples of substituents, but not limited to these, include acyl, acylamino, acyloxy, aldehyde, alicyclic, aliphatic, alkanesulfonamide, alkanesulfonyl, alkaryl, alkenyl, alkoxy, alkoxycarbonyl, alkyl, alkylamino, alkylcarbanoyl, alkylene, alkylidene, alkylthio, alkynyl, amide, amide, amino, amidine, aminoalkyl, aralkyl, aralkylsulfonamide, allensulfonamide, allensulfonyl, aromatic, aryl, arylamino, arylcarbanoyl, aryloxy, azide, carbamoyl, carbonyl, and Examples of substituents include rubonyl, ketone, carboxy, carboxylate, CF3, cyano(CN), cycloalkyl, cycloalkylene, ester, ether, haloalkyl, halogen, halogen, heteroaryl, heterocyclyl, hydroxy, hydroxyalkyl, imino, iminoketone, ketone, mercapto, nitro, oxaalkyl, oxo, oxoalkyl, phosphoryl (phosphonate and phosphinate, etc.), silyl group, sulfonamide, sulfonyl (sulfate, sulfamoyl and sulfonate, etc.), thiol, and ureido moieties, each of which may be optionally substituted or unsubstituted. In some cases, two substituents together with the carbon(s) to which they are attached may form a ring. In some cases, two or more substituents together with the carbon(s) to which they are attached may form one or more rings.

[0053] The substituent may be protected as necessary, and any protecting group commonly used in the art may be used. Non-limiting examples of protecting groups can be found, for example, in Greene and Wuts, Protective Groups in Organic Synthesis, 4th Ed., Wiley&Sons, 2006.

[0054] The term "carboxy" refers to the radical -C(O)O-. It should be noted that the compounds described herein that comprise a carboxy moiety can include protected derivatives thereof, that is, derivatives wherein the oxygen is substituted with a protecting group. Suitable protecting groups for a carboxy moiety include benzyl, tert-butyl, methyl, ethyl and the like. The term "carboxyl" refers to -COOH.

[0055] The term "alkylenyl" refers to a divalent form of an alkyl group. In one embodiment, the alkyleneyl group is C 3-8 An alkyleneyl group. Examples of alkylenyl groups include methylenyl, ethylenyl, propylenyl, isopropylenyl, butylenyl, pentylenyl, and hexylenyl groups.

[0056] The term "arylenyl" refers to a divalent form of an optionally substituted aryl group. In one embodiment, arylenyl is a divalent form of optionally substituted phenyl. In one embodiment, arylenyl is a divalent form of phenyl. Non-limiting examples of alkylenyl groups include the following:

Chemical Formula

[0057] The term "cycloalkylenyl" refers to C 3-8This refers to the divalent form of a cycloalkyl group. Examples of cycloalkylenyl groups include 1,2-cyclobutenyl, 1,3-cyclobutenyl, 1,2-cyclopentenyl, 1,3-cyclopentenyl, 1,2-cyclohexenyl, 1,3-cyclohexenyl, and 1,4-cyclohexenyl.

[0058] The term "dihydroxycycloalkane" refers to a compound of C13 3-8 This refers to cycloalkyl groups. Examples of dihydroxycycloalkanes include 1,2-dihydroxycyclobutane, 1,3-dihydroxycyclobutane, 1,2-dihydroxycyclopentane, 1,3-dihydroxycyclopentane, 1,2-dihydroxycyclohexane, 1,3-dihydroxycyclohexane, and 1,4-dihydroxycyclohexane.

[0059] The term "polymer" refers to a substance, chemical compound, or mixture of compounds having a molecular structure consisting primarily or entirely of a large number of similar units (e.g., monomer units) bonded together. Of these, linear polymers are also called straight-chain polymers because they consist of a long series of carbon-carbon bonds. Branched polymers have branches at irregular intervals along the polymer chain. Crosslinked polymers include branches that connect polymer chains via covalent, ionic, or hydrogen bonds. Optionally substituted polymers are polymers that have functional groups at random points along the hydrocarbon chain backbone, where one or more of the hydrogen atoms bonded to the chain backbone may be substituents independently selected from the group of substituents provided herein or otherwise specified, but do not necessarily have to be substituents. Such polymers are generally said to be optionally substituted because they do not exhibit a regular substitution pattern along the chain backbone. Addition polymers are formed by adding monomers to a growing polymer chain. Condensation polymers are formed when small molecules condense during a polymerization reaction. Homopolymers are formed by the polymerization of a single monomer. Copolymers are formed by the polymerization of two or more monomers. Synthetic polymers are synthesized by chemical reactions. Natural polymers originate from nature and can be extracted. Biopolymers are produced by modified or naturally occurring organisms. Organic polymers are polymers that contain carbon atoms in the main chain of the polymer chain.

[0060] The term "oligomer" refers to a substance, chemical compound, or mixture of compounds having a molecular structure consisting primarily or entirely of several similar units (e.g., monomer units) that are bonded together.

[0061] The term "plastics" refers to synthetic materials, including a wide range of organic polymers such as polyolefins, polyesters, and polyamides, which can be molded into flexible shapes and then made into rigid, semi-elastic, or elastic forms.

[0062] The term "approximately" means within ±10% of the listed number. For example, "approximately 100" means between 90 and 110. Various non-limiting embodiments of the present invention

[0063] The object of the present invention is to provide a thermoplastic polyurethane elastomer produced starting from a dicarboxylic acid composition containing a nitrosubstituted dicarboxylic acid.

[0064] Nitro-substituted dicarboxylic acid composition Nitro-substituted dicarboxylic acid compositions can be prepared in accordance with U.S. Patent Nos. 10,519,292 and 10,557,011, the contents of which are fully incorporated by reference. The produced nitro-substituted dicarboxylic acid is mixed with other dicarboxylic acids. The process is as follows: a. Adding polyethylene (PE) to the reaction vessel; b. Adding an aqueous solution of nitric acid (HNO3) to a reaction vessel to obtain a mixture, wherein the weight ratio of PE to the aqueous solution of nitric acid is greater than 1:3; The method comprises subjecting the mixture obtained from cb to conditions effective for decomposing PE to produce dicarboxylic acids and nitro-substituted dicarboxylic acids.

[0065] Nitric acid may have a concentration of 10–90% by weight. In some embodiments, nitric acid has a concentration of about 67–90% by weight. In some embodiments, the weight ratio of PE to nitric acid is 1:10–1:100. In some embodiments, catalysts such as zeolite, alumina, silicoaluminophosphate, sulfated zirconia, zinc oxide, titanium oxide, zirconium oxide, niobium oxide, iron carbonate, calcium carbide, or combinations thereof are added to the reaction. In some embodiments, effective conditions include a temperature range of about 60°C–200°C. In some embodiments, effective conditions include an initial pressure of 0–1000 psi. In some embodiments, effective conditions include a batch process in which the residence time in the reaction vessel is about 1 hour–10 hours. In some embodiments, effective conditions include a continuous process. The dicarboxylic acid and nitro-dicarboxylic acid are then isolated, for example, by filtration of the mixture and evaporation of nitric acid (e.g., under reduced pressure). Next, the dicarboxylic acid and nitrodicarboxylic acid are subjected to an alcohol, such as C, in the presence of an acid catalyst, such as hydrochloric acid or sulfuric acid. 1-4 Esterilization occurs in the presence of alcohol to obtain the corresponding dicarboxylic acid and nitrodicarboxylic acid C 1-4 An ester may be obtained. In some embodiments, C 1-4 Esters are esters of methyl, ethyl, propyl, butyl, or pentyl compounds.

[0066] In some embodiments, succinic acid is present in an amount of about 10 to about 25% by weight. Glutaric acid is present in an amount of about 11 to about 25% by weight. Adipic acid is present in an amount of about 14 to about 22% by weight. Pimelic acid is present in an amount of about 10 to 20% by weight. Azelaic acid is present in an amount of about 3 to 10% by weight, or equivalent amounts of their esters. If present, oxalic acid is present in an amount of 10% by weight or less. If present, suberic acid is present in an amount of about 5 to about 16% by weight. If present, sebacic acid is present in an amount of about 1 to about 15% by weight. If present, undecanediic acid is present in an amount of about 1 to about 8% by weight. If present, dodecanediic acid is present in an amount of about 5% by weight or less. If present, tridecanediic acid is present in an amount of about 4% by weight or less. If present, tetradecanediic acid is present in an amount of about 2% by weight or less. If present, pentadecanediol is present in amounts of approximately 1% by weight or less. If present, hexadecanedioic acid is present in amounts of approximately 1% by weight or less. If present, heptadecanedioic acid is present in amounts of approximately 1% by weight or less. If present, octadecanediol is present in amounts of approximately 1% by weight or equivalent amounts of their esters.

[0067] In some embodiments, succinic acid is present in an amount of about 15 to about 19% by weight. Glutaric acid is present in an amount of about 17 to about 21% by weight. Adipic acid is present in an amount of about 16 to about 20% by weight. Pimelic acid is present in an amount of about 13 to 17% by weight. Azelaic acid is present in an amount of about 4 to 8% by weight, or equivalent amounts of their esters. If present, oxalic acid is present in an amount of 10% by weight or less. If present, suberic acid is present in an amount of about 9 to about 13% by weight. If present, sebacic acid is present in an amount of about 5 to about 9% by weight. If present, undecanediic acid is present in an amount of about 2 to about 4% by weight. If present, dodecanediic acid is present in an amount of about 1 to about 3% by weight or less. If present, tridecanediic acid is present in an amount of about 0.5 to about 1.5% by weight. If present, tetradecanediic acid is present in an amount of about 0.2% by weight or less. If present, pentadecanediol is present in amounts of approximately 0.2% by weight or less. If present, hexadecanedioic acid is present in amounts of approximately 0.2% by weight or less. If present, heptadecanedioic acid is present in amounts of approximately 0.2% by weight or less. If present, octadecanediol is present in amounts of approximately 0.2% by weight or equivalent amounts of their esters.

[0068] In some embodiments, succinic acid is present in an amount of about 5 to about 40% by weight. Glutaric acid is present in an amount of about 8 to about 27% by weight. Adipic acid is present in an amount of about 10 to about 29% by weight. Pimelic acid is present in an amount of about 10 to 20% by weight. Azelaic acid is present in an amount of about 1 to 13% by weight, or equivalent amounts of their esters. If present, oxalic acid is present in an amount of 10% by weight or less. If present, suberic acid is present in an amount of about 4 to about 20% by weight. If present, sebacic acid is present in an amount of 12% by weight or less. If present, undecanediic acid is present in an amount of 8% by weight or less. If present, dodecanediic acid is present in an amount of 5% by weight or less. If present, tridecanediic acid is present in an amount of 4% by weight or less. If present, tetradecanediic acid is present in an amount of 2% by weight or less. If present, pentadecanediol is present in amounts of approximately 0.4% by weight or less. If present, hexadecanedioic acid is present in amounts of approximately 0.4% by weight or less. If present, heptadecanedioic acid is present in amounts of approximately 0.4% by weight or less. If present, octadecanediol is present in amounts of approximately 0.4% by weight or equivalent amounts of their esters.

[0069] In some embodiments, the dicarboxylic acid is a C8-C substituted with a single nitro group. 20 Further comprising dicarboxylic acids or their esters. Nitro-substituted C8-C 20 The dicarboxylic acid may be substituted at the 2nd, 3rd, 4th, 5th, 6th, 7th, or 8th position of the dicarboxylic acid.

[0070] In some embodiments, at least one nitrosubstituted dicarboxylic acid is 2-nitro-suberic acid, 2-nitro-azelaic acid, 2-nitro-sebacic acid, 2-nitro-undecanedioic acid, 2-nitro-dodecanediic acid, 2-nitro-brassilicic acid, 2-nitro-tetradecanediic acid, 2-nitro-pentadecanedioic acid, 2-nitro-hexadecanedioic acid, 2-nitro-heptadecanedioic acid, 2-nitro-octadecanediic acid, 2-nitro-nonadecanedioic acid, or 2-nitroicosanedioic acid, or an ester thereof.

[0071] In some embodiments, the dicarboxylic acid includes: a. Oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, C10-dicarboxylic acid, C11-dicarboxylic acid, C12-dicarboxylic acid, C13-dicarboxylic acid, C14-dicarboxylic acid, and C15-dicarboxylic acid, or esters thereof, and b. At least one C8-C substituted with a single nitro group 20 Dicarboxylic acid, or its ester.

[0072] In some embodiments, at least one C8-C group substituted with a single nitro group 20 The dicarboxylic acid is nitro-suberic acid, nitro-azelaic acid, nitro-sebacic acid, nitro-undecanediic acid, nitro-dodecanediic acid, nitro-brassilicic acid, nitro-tetradecanediic acid, nitro-pentadecanedioic acid, nitro-hexadecanedioic acid, nitro-heptadecanedioic acid, nitro-octadecanediic acid, nitro-nonadecanedioic acid, or nitro-icosanedioic acid, or esters thereof. In some embodiments, C8-C 20 Dicarboxylic acids are 2-nitro-suberic acid, 2-nitro-azelaic acid, 2-nitro-sebacic acid, 2-nitro-undecanedioic acid, 2-nitro-dodecanedioic acid, 2-nitro-brassilicic acid, 2-nitro-tetradecanedioic acid, 2-nitro-pentadecanedioic acid, 2-nitro-hexadecanedioic acid, 2-nitro-heptadecanedioic acid, 2-nitro-octadecanedioic acid, 2-nitro-nonadecanedioic acid, or 2-nitroicosanedioic acid, or esters thereof. In some embodiments, the C8-C20 dicarboxylic acid is 3-nitro-suberic acid, 3-nitro-azelaic acid, 3-nitro-sebacic acid, 3-nitro-undecanedioic acid, 3-nitro-dodecanediic acid, 3-nitro-brassilicic acid, 3-nitro-tetradecanediic acid, 3-nitro-pentadecanedioic acid, 3-nitro-hexadecanedioic acid, 3-nitro-heptadecanedioic acid, 3-nitro-octadecanediic acid, 3-nitro-nonadecanedioic acid, or 3-nitroicosanedioic acid, or an ester thereof. In some embodiments, C8-C 20The dicarboxylic acids are 4-nitro-suberic acid, 4-nitro-azelaic acid, 4-nitro-sebacic acid, 4-nitro-undecanedioic acid, 4-nitro-dodecanediic acid, 4-nitro-brassilicic acid, 4-nitro-tetradecanediic acid, 4-nitro-pentadecanedioic acid, 4-nitro-hexadecanedioic acid, 4-nitro-heptadecanedioic acid, 4-nitro-octadecanediic acid, 4-nitro-nonadecanedioic acid, or 4-nitroicosanedioic acid, or esters thereof. In some embodiments, C8-C 20 The dicarboxylic acids are 5-nitro-suberic acid, 5-nitro-azelaic acid, 5-nitro-sebacic acid, 5-nitro-undecanediic acid, 5-nitro-dodecanediic acid, 5-nitro-brassilicic acid, 5-nitro-tetradecanediic acid, 5-nitro-pentadecanedioic acid, 5-nitro-hexadecanedioic acid, 5-nitro-heptadecanedioic acid, 5-nitro-octadecanediic acid, 5-nitro-nonadecanedioic acid, or 5-nitroicosanedioic acid, or esters thereof. In some embodiments, at least one C8-C substituted with a single nitro group 20 Dicarboxylic acids are present in the decomposition mixture at a concentration of approximately 70% by weight or less.

[0073] In some embodiments, the nitrodicarboxylic acid composition contains a dicarboxylic acid in the amount shown in Figure 1.

[0074] Dicarboxylic acid ester composition In some embodiments, dicarboxylic acids and nitrodicarboxylic acids are in ester form. These esters are prepared under esterification conditions. In some embodiments, the dicarboxylic acid is at least partially in ester form.

[0075] In some embodiments, the ester is a methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, sec-butyl ester, tert-butyl ester, pentyl ester, or hexyl ester, or a combination thereof. In some embodiments, the ester is a methyl ester. In some embodiments, the conversion is carried out by esterification or esterification.

[0076] Esters can be formed using any suitable esterification conditions known in the art. For example, dicarboxylic acids and nitrodicarboxylic acids can be mixed with at least one alcohol, and the mixture can be heated to induce esterification. Mineral acids or organic acids may be added as catalysts. In some embodiments, at least one alcohol is selected from the group consisting of linear alcohols, branched alcohols, cyclic alcohols, and combinations thereof. In some embodiments, at least one alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, and combinations thereof. In some embodiments, at least one alcohol is C1-C 10 It is an alcohol. In some embodiments, at least one alcohol is a C1-C4 alcohol. In some embodiments, at least one alcohol is methanol.

[0077] In some embodiments, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid are each independently in ester form.

[0078] In some embodiments, oxalic acid, suberic acid, sebacic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, 2-octenodioic acid, 2-nonenodioic acid, 2-decendioic acid, and 2-undecendioic acid are independently in ester form.

[0079] In some embodiments, 2-nitro-suberic acid, 2-nitro-azelaic acid, 2-nitro-sebacic acid, 2-nitro-undecanedioic acid, 2-nitro-dodecanediic acid, 2-nitro-brassilicic acid, 2-nitro-tetradecanediic acid, 2-nitro-pentadecanedioic acid, 2-nitro-hexadecanedioic acid, 2-nitro-heptadecanedioic acid, 2-nitro-octadecanediic acid, 2-nitro-nonadecanedioic acid, and 2-nitro-icosanedioic acid are independently in ester form.

[0080] In some embodiments, a single nitro group is substituted with C8-C 20 Dicarboxylic acids are in ester form. In some embodiments, they are in ester form, substituted with a single nitro group C8-C 20 The dicarboxylic acids are nitro-suberic acid, nitro-azelaic acid, nitro-sebacic acid, nitro-undecanediic acid, nitro-dodecanediic acid, nitro-brassilicic acid, nitro-tetradecanediic acid, nitro-pentadecanedioic acid, nitro-hexadecanedioic acid, nitro-heptadecanedioic acid, nitro-octadecanediic acid, nitro-nonadecanedioic acid, or nitro-icosanedioic acid. In some embodiments, C8-C 20The dicarboxylic acid is 2-nitro-suberic acid, 2-nitro-azelaic acid, 2-nitro-sebacic acid, 2-nitro-undecanedioic acid, 2-nitro-dodecanedioic acid, 2-nitro-brassilicic acid, 2-nitro-tetradecanedioic acid, 2-nitro-pentadecanedioic acid, 2-nitro-hexadecanedioic acid, 2-nitro-heptadecanedioic acid, 2-nitro-octadecanedioic acid, 2-nitro-nonadecanedioic acid, or 2-nitroicosanedioic acid, or esters thereof. In some embodiments, the ester form is selected from the group consisting of monoesters, diesters, multiesters, mixed diesters, mixed multiesters, and combinations thereof.

[0081] As used herein, the term "multiester" refers to an ester formed by converting one or more carboxyl groups from dicarboxylic acid to ester under esterification conditions.

[0082] In some embodiments, at least one ester is dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimephosphate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl undecanediate, dimethyl dodecanediate, dimethyl oxalate, dimethyl tridecanediate, dimethyl tetradecanediate, dimethyl pentadecanediate, dimethyl 2-octenodioate, dimethyl 2-nonenedioate, 2-decanedioate, dimethyl 2-undecanediate, dimethyl 2-nitro-suberate, 2-nitro-azelate Methyl, 2-nitro-sebacate dimethyl, 2-nitro-undecanediate dimethyl, 2-nitro-dodecanediate dimethyl, 2-nitro-brassylate dimethyl, 2-nitro-heptadecanedioate dimethyl, 2-nitro-octadecanedioate dimethyl, 2-nitro-tetradecanediate dimethyl, 2-nitro-pentadecanedioate dimethyl, 2-nitro-hexadecanedioate dimethyl, 2-nitro-heptadecanedioate dimethyl, 2-nitro-suberate dimethyl, 2-nitro-sebacate dimethyl, 2-nitro-undecanediate dimethyl, 2-nitro-dodecanediate dimethyl Dimethyl 2-nitro-tetradecanediate, dimethyl 2-nitro-pentadecanedioate, dimethyl 3-nitro-suberate, dimethyl 3-nitro-azelate, dimethyl 3-nitro-sebacate, dimethyl 3-nitro-undecanediate, dimethyl 3-nitro-dodecanediate, dimethyl 3-nitro-brasilate, dimethyl 3-nitro-heptadecanedioate, dimethyl 3-nitro-octadecanedioate, dimethyl 3-nitro-tetradecanediate, dimethyl 3-nitro-pentadecanedioate, dimethyl 3-nitro-hexadecanedioate, dimethyl 3-nitro-heptadecanedioate Dimethyl nitrate, 3-nitro-suberate, 3-nitro-sebacate, 3-nitro-undecanediate, 3-nitro-dodecanediate, 3-nitro-tetradecanediate, 3-nitro-pentadecanedioate, 4-nitro-suberate, 4-nitroazelate, 4-nitro-sebacate, 4-nitro-undecanediate, 4-nitro-dodecanediate, 4-nitro-brasilate, 4-nitroheptadecanedioate, 4-nitro-octadecanediate,4-Dimethyl 4-nitro-tetradecanediate, 4-Dimethyl 4-nitro-pentadecanedioate, 4-Dimethyl 4-nitro-hexadecanedioate, 4-nitro-heptadecanedioate, 4-Dimethyl 4-nitro-suberate, 4-Dimethyl 4-nitro-sebacate, 4-Dimethyl 4-nitro-undecanediate, 4-Dimethyl 4-nitro-dodecanediate, 4-Dimethyl 4-nitro-tetradecanediate, 4-Dimethyl 4-nitro-pentadecanedioate, 5-Dimethyl 5-nitro-suberate, 5-Dimethyl 5-nitroazelate, 5-Dimethyl 5-nitro-sebacate, 5-Dimethyl 5-nitro-undecanediate, 5-Dimethyl 5-nitro-dodecanediate This includes dimethyl 5-nitrobrasylate, dimethyl 5-nitroheptadecanedioate, dimethyl 5-nitrooctadecanediate, dimethyl 5-nitrotetradecanediate, dimethyl 5-nitropentadecanedioate, dimethyl 5-nitrohexadecanedioate, dimethyl 5-nitroheptadecanedioate, dimethyl 5-nitrosuberate, dimethyl 5-nitrosebacate, dimethyl 5-nitroundecanediate, dimethyl 5-nitrododecanediate, dimethyl 5-nitrotetradecanediate, and dimethyl 5-nitropentadecanedioate, and combinations thereof.

[0083] In some embodiments, at least one corresponding ester includes dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl undecanediate, dimethyl dodecanediate, and combinations thereof.

[0084] In some embodiments, at least one ester includes 5-50% dimethyl succinate, 5-50% dimethyl glutarate, 5-50% dimethyl adipate, 5-50% dimethyl pimelate, 0-30% dimethyl suberate, 0-30% dimethyl azelate, 0-20% dimethyl sebacate, 0-10% dimethyl undecanediate, 0-10% dimethyl dodecanediate, and combinations thereof.

[0085] In some embodiments, at least one corresponding ester includes 5-50% dimethyl succinate, 5-50% dimethyl glutarate, 5-50% dimethyl adipate, 5-50% dimethyl pimelate, 0-30% dimethyl suberate, 0-30% dimethyl azelate, 0-20% dimethyl sebacate, 0-10% dimethyl undecanediate, 0-10% dimethyl dodecanediate, and combinations thereof.

[0086] In some embodiments, the esterification mixture includes a composition comprising at least one of dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl undecanediate, dimethyl dodecanediate, and combinations thereof.

[0087] In some embodiments, the esterification mixture includes a composition comprising at least one of the following: 5-50% dimethyl succinate, 5-50% dimethyl glutarate, 5-50% dimethyl adipate, 5-50% dimethyl pimephosphate, 0-30% dimethyl suberate, 0-30% dimethyl azelate, 0-20% dimethyl sebacate, 0-10% dimethyl undecanediate, 0-10% dimethyl dodecanediate, and combinations thereof.

[0088] In some embodiments, the esterification mixture comprises at least one of about 5 to about 18% by weight of dimethyl succinate, about 8 to about 28% by weight of dimethyl glutarate, about 10 to about 29% by weight of dimethyl adipate, about 10 to about 20% by weight of dimethyl pimephosphate, and about 8 to about 13% by weight of dimethyl azelate, and combinations thereof.

[0089] In some embodiments, the esterification mixture comprises at least one of the following: dimethyl oxalate in an amount of 10% by weight or less, dimethyl suberate in an amount of about 9 to about 20% by weight, dimethyl sebacate in an amount of about 1 to about 10% by weight, dimethyl undecanediote in an amount of about 1 to about 8% by weight, dimethyl dodecanediote in an amount of about 5% by weight or less, dimethyl tridecanediote in an amount of about 4% by weight or less, dimethyl tetradecanediote in an amount of about 2% by weight or less, and dimethyl pentadecanediote in an amount of about 0.4% by weight or less, and combinations thereof.

[0090] In some embodiments, the esterification mixture comprises at least one of the following: about 5 to about 40% by weight of dimethyl succinate, about 8 to about 27% by weight of dimethyl glutarate, about 10 to about 29% by weight of dimethyl adipate, about 10 to about 20% by weight of dimethyl pimephosphate, and about 1 to about 13% by weight of dimethyl azelate, and combinations thereof.

[0091] In some embodiments, the esterification mixture comprises at least one of the following: dimethyl oxalate in an amount of 10% by weight or less; dimethyl suberate in an amount of about 4 to about 20% by weight; dimethyl sebacate in an amount of about 10% by weight or less; dimethyl undecanediote in an amount of about 8% by weight or less; dimethyl dodecanediote in an amount of about 5% by weight or less; dimethyl tridecanediote in an amount of about 4% by weight or less; dimethyl tetradecanediote in an amount of about 2% by weight or less; and dimethyl pentadecanediote in an amount of about 0.4% by weight or less; and combinations thereof.

[0092] In some embodiments, ester is a. Oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, C10-dicarboxylic acid, C11-dicarboxylic acid, C12-dicarboxylic acid, C13-dicarboxylic acid, C14-dicarboxylic acid, and C15-dicarboxylic acid, and b. Esters of at least one C8-C20 dicarboxylic acid substituted with a single nitro group; and at least one polyol.

[0093] In some embodiments, the method further includes separating at least one corresponding ester. In some embodiments, the separation is carried out by distillation. In some embodiments, the distillation is at least one selected from the group consisting of simple distillation, fractional distillation, vacuum distillation, azeotropic distillation, codistillation, and combinations thereof.

[0094] In some embodiments, the method further includes converting at least one compound containing at least one carboxyl group from an ester form to an acid form (e.g., a conversion from an ester form back to an acid form). In some embodiments, the conversion from an ester form to an acid form is carried out under ester hydrolysis conditions.

[0095] Nitrofunctionalized polyester diol (NO2-PED) composition The present invention also provides nitro-functionalized polyester diols (NO2-PED) by reacting dicarboxylic acids and nitro-dicarboxylic acids or their esters with diols.

[0096] Polyester diol is, formula: [ka] The formula has the following characteristics (wherein n is 0 to 14, y is 1 to 100, X is H or NO2, R is an alkylenyl, an alkylenyl having one or more CH2 groups substituted with -O-, a cycloalkylenyl, or arylenyl, and at least one X is NO2).

[0097] In some embodiments, R is ethylenyl, propyrenyl, isopropyrenyl, butyrenyl, pentyrenyl, hexylenyl, heptyrenyl, or octylenyl. In some embodiments, R is alkylenyl, and one or more CH2 groups are substituted with -O-. In some embodiments, R is -(CH2) O -O-(CH2) O -, CH3-O-(CH2) O -O-(CH2)O The formula is -CH3,(CH3CH(OH)CH2)2O, where O is 2 to 4. In some embodiments, the polyester diol before reaction with the isocyanate has a molecular weight of 300 to 10,000 g / mol.

[0098] Examples of diols include, for example, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, glycerol, trimethylolethane, trimethylolpropane, neopentyl glycol, pentaerythritol, dipentaerythritol, sorbitol, 2-methyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol. Examples include 2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-propyl-2-methyl-1,3-propanediol, 2-propyl-2-ethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol (BEPD), hydroxypivaloyl hydroxypivalate (HPHP), 2-cyclohexyl-2-methyl-1,3-propanediol, 2-phenyl-2-methyl-1,3-propanediol, 1,4-cyclohexanediol, 2,4-diethyl-1,5-pentanediol, dihydroxymethoxyhydroquinone, 1,4-cyclohexanedimethanol, and 1,4-dihydroxycyclohexane. In some embodiments, the diol is C 1-8 Diols, for example, or C 1-4 Diols, such as diethylene glycol, 1,2-propanediol, and 1,3-propanediol.

[0099] NO2-PED is prepared by reacting dicarboxylic acids and nitrocarboxylic acids or their esters under suitable reaction conditions. In some embodiments, NO2-PED is synthesized as shown in Scheme 1 according to the following general procedure: A dicarboxylic acid mixture is mixed with a diol (e.g., 1,6-hexanediol) and a catalytic amount of concentrated sulfuric acid or other suitable catalyst. The catalyst load can be varied from 0.2 mol% to 4 mol%. The mixture is heated with stirring in a preheated oil bath at 100-110°C under atmospheric pressure for 2-4 hours, followed by the application of reduced pressure (≤19 mbar) for 1-2 hours. The product is cooled under vacuum and characterized by ATR-FTIR analysis and end-group titration (total acid value and hydroxyl value). Titration is performed using a slightly modified version of Test Method A according to ASTM D-4274-99, and these results are used to calculate the approximate molecular weight of the polyester diol. Polyester diols stored outside a desiccator for extended periods should be dried before use by incubation overnight at 80°C in a vacuum oven or by bubbling a drying inert gas (such as argon) through the polyol at over 100°C, followed by simultaneous vacuuming for 1 hour, and then stored in a desiccator at ambient pressure. The reaction is typically carried out at atmospheric pressure, but other pressures may be used. [ka]

[0100] Scheme 1 In Scheme 1, n is between 0 and 20, and y is between 1 and 100. In some embodiments, y is between 1 and 30.

[0101] In another embodiment, NO2-PED is prepared by reacting dicarboxylic acid and nitro-dicarboxylic acid esters with a polyol, even in the presence of a suitable catalyst such as sulfuric acid or other mineral acid, according to Scheme 2. [ka]

[0102] Scheme 2 In scheme 2, n is between 0 and 20, and y is between 1 and 100. In some embodiments, y is between 1 and 30.

[0103] The catalyst may be hydrochloric acid, sulfuric acid, or other mineral acid. Alternatively, the catalyst may be dibutyltin(IV) dilaurate in an organic solvent such as heptane. The mixture is heated under atmospheric pressure at 100–130°C for 1–20 hours with stirring, and if used, alcohol by-products (e.g., methanol) and organic solvents (e.g., heptane) are evaporated and removed from the reactor. In some embodiments, this is followed by applying reduced pressure (≤19 mbar) for 1–20 hours. The alcohol by-products and organic solvents can also be removed by bubbling an inert gas through the mixture while applying vacuum for 1 hour.

[0104] The number-average molecular weight of NO2-PED is 300 to 10,000 g / mol. In some embodiments, the number-average molecular weight is approximately 500 to 4,000 g / mol.

[0105] Thermoplastic polyurethane (TPU) TPU can be prepared by a one-step or two-step method. In the one-step method, NO2-PED and a chain extender are blended in a reaction vessel. With vigorous stirring, the polyisocyanate is slowly added to the vessel. The reaction proceeds at a temperature of 60-120°C for 2.5 hours. The resulting TPU is then placed in a preheated silicone mold and cured at a temperature of, for example, 80-120°C for 20-48 hours. In the two-step method, NO2-PED is reacted with a polyisocyanate to obtain a TPU prepolymer, and then the chains are extended to obtain the finished TPU elastomer. NO2-PED is reacted with the polyisocyanate at a temperature of 80°C or less. Then, with rapid stirring, the catalyst and chain extender are added and the reaction is carried out at a temperature of 120°C or less. The catalyst may be any tin laurate or an amine catalyst such as DABCO or triethylamine, and may be 0.05-1.0% by weight relative to NO2-PED. NO2-PED may be present in 20-80% by weight of the chain-extended TPU. Polyisocyanate may be present in 20-80% by weight of the chain-extended TPU. Chain extender may be present in 1-20% by weight of the chain-extended TPU.

[0106] Next, the chain-extended TPU is poured into a mold and cured at a temperature of, for example, 80-120°C for 20-48 hours.

[0107] Examples of polyisocyanates include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, and 4,4'-biphenylene diisocyanate. Examples include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylenebis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanate ethyl) fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, and mixtures thereof. In one embodiment, the polyisocyanate includes an aromatic ring.

[0108] In some embodiments, the polyisocyanates are 4,4'-diisocyanate diphenylmethane (4,4'-MDI), 2,4'-diisocyanate diphenylmethane (2,4'-MDI), p-phenylenediisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, 1,4-diisocyanate-cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalenediisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diisocyanate dicyclohexylmethane, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and mixtures thereof.

[0109] In some embodiments, the ratio of polyisocyanate to active hydrogen-containing groups (NCO index) is 0.9 to 1.5. As is well known in the art, the NCO index is defined as the number of isocyanate equivalents divided by the total number of active hydrogen equivalents, multiplied by 100. The NCO index is expressed by the following formula:

number

[0110] Next, the TPU prepolymer is reacted with a chain extender. Examples of chain extenders include, for example, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, glycerol, trimethylolethane, trimethylolpropane, neopentyl glycol, pentaerythritol, dipentaerythritol, sorbitol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2 Examples of diols include ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-propyl-2-methyl-1,3-propanediol, 2-propyl-2-ethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol (BEPD), hydroxypivaloyl hydroxypivalate (HPHP), 2-cyclohexyl-2-methyl-1,3-propanediol, 2-phenyl-2-methyl-1,3-propanediol, 1,4-cyclohexanediol, 2,4-diethyl-1,5-pentanediol, dihydroxymethoxyhydroquinone, 1,4-cyclohexanedimethanol, and 1,4-dihydroxycyclohexane. In some embodiments, the polyol is C 1-8 Polyols, for example, C 1-8 Diol or C 1-4 These are diols, such as diethylene glycol, 1,2-propanediol, and 1,3-propanediol.

[0111] In some embodiments, the chain extender is a dihydroxyalkane or dihydroxycycloalkane. In other embodiments, the chain extender is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-dihydroxycyclohexane, or a mixture thereof. In some embodiments, the chain extender is an alkylene or aralkylenediamine. In some embodiments, the chain extender is ethylenediamine, hexamethylenediamine, 1,4-cyclohexanylenediamine, or a mixture thereof. In some embodiments, the chain extender is an aromatic diamine. In some embodiments, the chain extender is benzidine, dihydroxymethoxyhydroquinone, toluenediamine, diaminodiphenylmethane, phenylenediamine, or a mixture thereof. In some embodiments, the chain extender is hydrazine. In some embodiments, the chain extender is an amino alcohol. In some embodiments, the chain extender is ethanolamine, N-methylethanolamine, N-butylethanolamine, N-oleoylethanolamine, N-cyclohexylisopropanolamine, or a mixture thereof. In some embodiments, the chain extender is a substituted aromatic diamine. In some embodiments, the chain extender is 4,4'-methylene-bis(o-chloroaniline), 4,4'-methylenebis(3-chloro-2,6-diethylaniline), or a mixture thereof.

[0112] Scheme 3 Any additives The TPU composition of the present invention may contain several optional additives. Optional additives include further crosslinking agents, oligomers, light stabilizers, UV stabilizers, inorganic and organic fillers, flame retardants, dispersants, foaming agents, reactive diluents, free radical photoinitiators, cationic photoinitiators, and other additives.

[0113] In some embodiments, the crosslinking agent is glycerin, trimethylolpropane, diethanolamine, triethanolamine, or a mixture thereof.

[0114] In some embodiments, further oligomers include, for example, polyethers, polyesters, polycarbonates, polyacrylates, and copolymers thereof. The further oligomers may contain one or more (e.g., two or more) hydroxyl groups, one or more (e.g., two or more) ethylenically unsaturated groups, and / or one or more (e.g., two or more) epoxy groups. In one embodiment, the composition contains 0 to 60% by weight, for example, 5 to 40% by weight, of the further oligomers based on the total weight of the composition.

[0115] In some embodiments, examples of light and UV stabilizers include 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazine-4-one), and mixtures thereof.

[0116] In some embodiments, the inorganic filler includes silicate minerals, metal oxides, metal salts, clay, metal silicates, glass fibers, natural fiber materials, synthetic fiber minerals, or mixtures thereof.

[0117] In some embodiments, the organic filler includes carbon black, fullerene, carbon nanotubes, biochar, melamine corophony, cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, aromatic and / or aliphatic dicarboxylic acid ester-based polyester fibers, carbon fibers, or mixtures thereof.

[0118] In some embodiments, the filler is present in an amount of 0.5 to 30 percent by weight of the composition.

[0119] In some embodiments, the flame retardant is an organophosphate, a metal polyphosphate, a metal oxide, a metal salt, a cyanuric acid derivative, or a mixture thereof.

[0120] In some embodiments, the flame retardant is present in an amount of 10 to 35 percent by weight of the composition.

[0121] In some embodiments, the dispersant includes styrene, acrylic esters, di and triacrylate / methacrylates, ester acrylate / methacrylates, urethane or urea acrylate / methacrylates, or mixtures thereof.

[0122] In some embodiments, the foaming agent is at least one of water, pentane, cyclopentane, hydrofluorocarbon, or a mixture thereof.

[0123] Examples of reactive diluents include monofunctional and polyfunctional monomers. Examples of monofunctional monomers include: vinyl groups such as N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, and vinylpyridine; isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, and 2-hydro Xyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, caprolactone acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate Heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxyethyl Ethylene glycol (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, t-octyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate, 7-amino-3,7-dimethyloctyl(meth)acrylate, N,N-diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether; the following formula (2) CH2C(R, 6 )-COO(R 7 O) m -R 8 (2) Compound represented by ([wherein R 6 R represents a hydrogen atom or a methyl group; 7 is an alkylene group containing 2 to 8, preferably 2 to 5, carbon atoms; m is an integer from 0 to 12, preferably 1 to 8; R 8 is an alkyl group containing a hydrogen atom or 1 to 12, preferably 1 to 9, carbon atoms; or R 8 is a tetrahydrofuran group containing a hydrogen atom or an alkyl group containing 4 to 20 carbon atoms, which may optionally be substituted with an alkyl group containing 1 to 2 carbon atoms; or R 8 is a dioxane group containing an alkyl group having 4 to 20 carbon atoms, which may optionally be substituted with a methyl group; or R 8 is an aromatic group, and optionally C1~C 12 The alkyl group is preferably substituted with a C8-C9 alkyl group, or an alkoxylated aliphatic monofunctional monomer, such as ethoxylated isodecyl (meth)acrylate or ethoxylated lauryl (meth)acrylate.

[0124] Examples of polyfunctional monomers include monomers containing two or more (meth)acrylate groups, such as trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane trioxyethyl (meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, and tricyclodecanediyldimethyl di(meth)acrylate. Examples include di(meth)acrylates of diols which are ethylene oxide or propylene oxide adducts of bisphenol A, di(meth)acrylates of diols which are ethylene oxide or propylene oxide adducts of hydrogenated bisphenol A, epoxy(meth)acrylates which are (meth)acrylate adducts of diglycidyl ethers of bisphenol A, diacrylates of polyoxyalkylated bisphenol A, and triethylene glycol divinyl ether, adducts of hydroxyethyl acrylate, isophorone diisocyanate and hydroxyethyl acrylate (HIH), adducts of hydroxyethyl acrylate, toluene diisocyanate, and hydroxyethyl acrylate (HTH), and amide ester acrylates.

[0125] In one embodiment, the composition contains at least 10% by weight, for example, at least 20% by weight or at least 30% by weight of one or more reactive diluents based on the total weight of the composition. Generally, the composition contains less than 90% by weight, for example, less than 75% by weight or less than 50% by weight of one or more reactive diluents.

[0126] Examples of free radical photoinitiators include benzophenones (e.g., benzophenone, alkyl-substituted benzophenone, or alkoxy-substituted benzophenone); benzoins (e.g., benzoin, benzoin ethers (e.g., benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, benzoin phenyl ether, and benzoin acetate); acetophenones (e.g., acetophenone, 2,2-dimethoxyacetophenone, 4-(phenylthio)acetophenone, and 1,1-dichloroacetophenone); benzyl, benzyl ketals (e.g., benzyl dimethyl ketal, and benzyl diethyl ketal); anthraquinones (e.g., 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and 2-amyl anthraquinone); Examples include tetraquinones; triphenylphosphines; benzoylphosphine oxides, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; thioxanthones and xanthones, acridine derivatives, phenazene derivatives, quinoxaline derivatives or 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-aminophenyl ketones or 1-hydroxyphenyl ketones, such as 1-hydroxycyclohexylphenyl ketone, phenyl(1-hydroxyisopropyl) ketone and 4-isopropylphenyl(1-hydroxyisopropyl) ketone, or triazine compounds, such as 4'-methylthiophenyl-1-di(trichloromethyl)-3,5-S-triazine, S-triazine-2-(stilbene)-4,6-bis(trichloromethyl), and paramethoxystyryltriazine. Free radical photoinitiators are particularly useful when the composition contains ethylenically unsaturated components, such as acrylates or methacrylates. In one embodiment, the composition contains one or more free radical photoinitiators in an amount of 0 to 10% by weight, for example, 0.5 to 7.5% by weight, relative to the total weight of the composition.

[0127] Examples of cationic photoinitiators include, for example, onium salts having weakly nucleophilic anions. Examples include halonium, iodosyl, or sulfonium salts described in published European Patent No. 153904 and WO98 / 28663, sulfoxonium salts described in published European Patent Nos. 35969, 44274, 54509, and 164314, and diazonium salts described in U.S. Patent Nos. 3,708,296 and 5,002,856.

[0128] Examples of additional additives include antioxidants, dyes, wetting agents, defoamers, thickeners, photosensitizers, solvents (preferably in amounts less than 20% by weight, e.g., less than 10% by weight, less than 5% by weight, or about 0% by weight), and metal, organic, inorganic, or organic / inorganic hybrid fillers (e.g., silica particles, glass beads, or talc). The size of the fillers can vary, for example, in the nanometer or micrometer range. In one embodiment, the composition contains less than 20% by weight, e.g., less than 10% by weight, less than 5% by weight, or about 0% by weight of the fillers relative to the total weight of the composition.

[0129] Additional additives include colorants such as titanium dioxide and carbon black.

[0130] Manufacturing method In some embodiments, the TPU is provided under the following conditions: (a) A polyester comprising at least one nitrosubstituted polyester diol, (b) React with at least one polyisocyanate, (c) Manufactured by a process that includes condensation with at least one chain extender.

[0131] In some embodiments, the reaction conditions include a temperature of 25–120°C.

[0132] In some embodiments, the polyester comprising at least one nitro-substituted polyester diol further comprises at least one polyester diol that does not contain a nitro group.

[0133] In some embodiments, the TPU foam is reacted under the following conditions. (a) A polyester comprising at least one nitrosubstituted polyester diol, (b) at least one polyisocyanate, (c) at least one chain extender, (d) at least one flame retardant, (e) at least one surfactant, (f) at least one foaming agent, (g) Prepared by a process comprising reacting at least one urethane catalyst with the above.

[0134] Purpose TPU is useful in a variety of applications. In some embodiments, the composition is useful for preparing molded articles such as soles for footwear, rigid solid plastics for bezels and structural components of electronic devices, flexible plastics for straps and bands, and seals, gaskets, durable elastomers for wheels and tires, automotive suspension bushings, and electrical insulation components. In some embodiments, the composition is useful for 3D printing when extruded into a filament. In some embodiments, the composition can be pelletized and foamed to obtain foamed TPU foam for footwear applications.

[0135] It should be understood that the present invention is not limited to the specific methodologies, protocols, and reagents described herein, and that these themselves are subject to change. The terms used herein are intended solely to describe specific embodiments and do not limit the scope of the invention; they are defined solely by the claims.

[0136] Examples The present invention is further illustrated by the following examples, which are intended purely to illustrate the invention and should not be construed as limiting the invention. The following examples are for illustrative purposes only and are not intended in any way to limit any of the embodiments described herein. The following examples are provided to better illustrate the claimed invention and should not be construed as limiting the scope of the invention. To the extent that specific materials are mentioned, this is merely illustrative and not intended to limit the invention. Those skilled in the art can develop equivalent means or reactants without exercising their inventive ability and without departing from the scope of the invention.

[0137] General materials and methods The dicarboxylic acids (DCAs) used in the synthesis of polyester diols are obtained from the ATOD (accelerated thermal oxidative decomposition) of polyethylene plastics and consist of a mixture of linear aliphatic DCAs having carbon atoms ranging from 4 to 24. The mixture also includes DCAs having one or more nitro functional groups along the aliphatic linker. The average molecular weight of DCAs for chemical synthesis was determined by titration with aqueous sodium hydroxide solution using phenolphthalein as an indicator (acid value measurement). Unless otherwise indicated, other reagents and equipment were obtained from commercial sources and used as received. The materials used in the examples are as follows:

[0138] The following methods and criteria are used to evaluate and determine each TPU parameter.

[0139] Glass transition temperature: Glass transition temperature (T g The values ​​were measured by differential scanning calorimetry (DSC).

[0140] Shore A hardness: Shore A hardness is measured according to DIN 533505, with the hardness being measured 3 seconds after the pressure foot contacts the specimen. Hardness is referred to as Shore A hardness in the following text.

[0141] Tensile strength: Tensile strength is measured using an ASTM Type 4 test rod and an Instron Universal Tester.

[0142] Extension: Elongation is measured using an ASTM Type 4 test rod and an Instron Universal Tester.

[0143] The materials used in the examples are as follows: PED = Polyester Diol (a synthetic mixture of dicarboxylic acid and 1,6-hexanediol) NO2-PED = Nitrofunctionalized Polyester Diol (Synthesized from ATOD DCA) Emerox14801 = Bio-based polyester diol (commercial product) MDI = 4,4'-diphenylamine diisocyanate (commercial product) HDI = Hexamethylene diisocyanate (commercial product) HD = 1,6-Hexanediol (commercial product) MPD = 2-methylpropanediol (commercial product) 1,4-BD=1,4-butanediol (commercial product) DTBL = Dibutyltin dilaurate (commercial product) Irganox 1076 = Phenolic antioxidant (commercially available product) Irgafos168 = Phosphite antioxidant (commercially available product) Tinuvin 234 = Benzotrizole-based UV absorber (commercially available) Synthesis of nitropolyester diols

[0144] Nitro-substituted polyester diols were synthesized according to the following general procedure, as shown in Scheme 1: A dicarboxylic acid mixture was mixed with a diol (e.g., 1,6-hexanediol and a catalytic amount of concentrated sulfuric acid or other suitable catalyst; the catalytic load was varied from 0.2 mol% to 4 mol%). The mixture was heated with stirring in a preheated oil bath at 100–110°C under atmospheric pressure for 2–4 hours, followed by the application of reduced pressure (≤19 mbar) for 1–2 hours. The product was cooled under vacuum and characterized by ATR-FTIR analysis and end-group titration (total acid value and hydroxyl value). The titration was performed using a slightly modified version of Test Method A according to ASTM D-4274-99, and the approximate molecular weight of the polyester diol was calculated using these results. Polyester diols stored outside a desiccator for extended periods were dried before use either by incubation overnight at 80°C in a vacuum oven or by bubbling a drying inert gas (such as argon) through the polyol at over 100°C, followed by simultaneous vacuum application for 1 hour, and then stored in a desiccator under ambient atmospheric pressure. Specific and non-limiting examples of synthetic polyester diols, including reused portions, are shown in Examples 1-4.

[0145] Example 1 A mixture of dicarboxylic acids (DCA) obtained from ATOD of polyethylene waste having an average molecular weight of 178.14 g / mol (23.517 g, 0.5869 molar equivalents) was mixed at room temperature in a round-bottom flask equipped with a Teflon-coated magnetic stirring rod with 1,6-hexanediol (26.581 g, 1 molar equivalent) and a sulfuric acid catalyst (0.131 g, 1 mol% relative to the DCA mixture). The mixture was opened to air and heated to 105°C for 4 hours with stirring, at which point heating and stirring of the reaction molten material was applied under vacuum (≤19 mbar) for a further 2 hours. The reaction mixture was cooled under vacuum and stored in a desiccator. The nitro-containing polyester diol product (PE-1) was characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), 1H NMR, gel permeation chromatography (GPC), and end-group titration (total acid value and hydroxyl value, measured by acetylation method and test method A according to ASTMD-4274-99). The acid value was measured as a 4.6 ± 0.3 mg KOH / g sample, the hydroxyl value was 183 ± 9 mg KOH / g sample, and the number-average molecular weight was determined to be 614 ± 30 g / mol by titration.

[0146] Example 2 ATOD DCA mixture (42.803 g, 0.901 molar equivalent) was mixed with 1,6-hexanediol (31.513 g, 1 molar equivalent) and concentrated sulfuric acid (98%, 0.229 g, 1 mol% relative to the DCA mix) in a round-bottom flask equipped with a Teflon-coated magnetic stirring rod. The mixture was opened to air and heated to 105°C for 4 hours to produce a homogeneous molten product, after which a vacuum (≤19 mbar) was applied and heating was continued for a further 2 hours. The product was cooled under vacuum and stored in an atmospheric pressure desiccator. The nitro-containing polyesterdiol product PE-2 was characterized by ATRFTIR, GPC, and end-group titration as in Example 1. The acid value by titration was 6.3 ± 0.6 mg KOH / g, the hydroxyl value was 37.4 ± 8.1 mg KOH / g, and the number-average molecular weight was 2615 g / mol.

[0147] Table 1 shows further non-limiting examples of nitrosubstituted polyester diols (NO2-PE) prepared by the above method. [Table 1]

[0148] Nitro-substituted polyester diols can be optionally synthesized from the corresponding dimethyl esters of DCA obtained from ATOD of polyethylene plastic waste, as shown in Scheme 2 and described in Examples 3 and 4.

[0149] Example 3 (See RP1-139A) The starting diester mix is ​​estimated to have an average molecular weight of 177 g / mol. 100 parts by mass of the diester mix and 107 parts by mass of 1,6-hexanediol are placed in a reactor and heated to 120°C. To this mixture, 6 parts by weight of a 10% heptane solution containing dibutyltin(IV) dilaurate are added. The solution is stirred and reacted at 120°C for 17 hours, allowing the heptane and generated methanol to evaporate from the reactor. The reactants are then cooled to obtain 146 parts by weight of the isolated product as a clear yellow liquid. GPC analysis of THF versus polystyrene standard shows Mn 600 and PDI 3.49.

[0150] Example 4 (See RP1-139D) The starting diester mix is ​​estimated to have an average molecular weight of 177 g / mol. 100 parts by mass of the diester mix and 72 parts by mass of 1,6-hexanediol are placed in a reactor and heated to 120°C. 5.5 parts by weight of a 10% heptane solution containing dibutyltin(IV) dilaurate are added to this mixture. The solution is stirred and reacted at 120°C for 17 hours, allowing the heptane and generated methanol to evaporate from the reactor. The reactants are then cooled to obtain 119 parts by weight of the isolated product as a clear yellow liquid. GPC analysis of THF against polystyrene standard shows Mn 3200 and PDI 2.13.

[0151] Example 5 (See KK1-153B) Parts and percentages mentioned in the examples are percentages by weight (pbw) or height. All samples are prepared in the same manner. Diisocyanate, 4,4'-MDI is dried and supplied in excess directly to the reaction vessel. PED (composition shown in Table 2) is added to the excess diisocyanate and reacted completely at a temperature below 60°C to produce a TPU prepolymer. DTBL catalyst and 2-methylpropanediol (MPD) chain extender are added to the prepolymer and rapidly stirred and reacted completely at a temperature below 100°C. The chain-extended TPU is poured into a mold heated to a temperature below 125°C. The mold is placed in a 100°C oven for 24 hours, or until the TPU is completely cured. The cast elastomer is compression molded to produce test specimens. The cured TPU is characterized using FTIR, DSC, TGA, Instron Mechanical Testing, and Shore Hardness A Durometer. [Table 2] [Table 3]

[0152] TPU elastomer Example 5 and comparative sample A were prepared from the formulations listed in Table 2. The results in Table 3 show that the presence of nitro groups in the PED main chain resulted in a higher glass transition temperature, higher Shore A hardness, higher tensile strength, and lower elongation of the TPU compared to sample A. Example 6 (See KK2-53)

[0153] Example 6 and comparative sample B were prepared using the PEDs listed in Table 4. In Example 6, 1,4-BD and a DCA mixture obtained from ATOD with a number average molecular weight of 1.0 × 10⁻¹⁶ 3NO2-PED containing g / mol is dried and placed in a reaction vessel. Then, 2 wt% Sicopal Blue K pigment, 0.3 wt% Irganox 1076, and 0.15 wt% Irgafos 168 are added to the 1,4-BD / NO2-PED mixture. HDI is added slowly with vigorous stirring. The reaction proceeds at 80°C for 2.5 hours. The reaction mixture is poured into a preheated silicone mold and cured at 100°C for 24 hours. Next, the cast elastomer is compression molded to form test specimens. Comparative sample B has a number average molecular weight of 1.1 × 10⁶. 3 The same method was used to prepare a nitro-free polyester diol, Emerox 14801, with a concentration of g / mol. The results in Table 5 show that nitro-functionalized TPUs derived from NO2-PED yield higher Shore A hardness, higher tensile strength, and higher elongation compared to nitro-free PED.

[0154] Example 7 (See KK2-082) The number average molecular weight of 1.8 × 10⁻¹⁰ is derived from 1,4-BD and a transesterified NO2-diester mixture. 3 The NO2-PED containing g / mol is dried and placed in the reaction vessel. The HDI is slowly added while vigorously stirring. The reaction proceeds at 80°C for 2.5 hours. The reaction mixture is poured into a preheated silicone mold and cured at 100°C for 24 hours. Next, the cast elastomer is compression molded to form a test specimen. [Table 4] [Table 5]

[0155] Example 8 (See KK2-017) The HDI is dried and supplied in excess to the reaction vessel. Separately, the number average molecular weight is 1.3 x 10⁻⁶. 3NO2-PED in g / mol is blended with 2.0 wt% carbon black. Next, the blended NO2-PED is added to excess diisocyanate and reacted completely at a temperature below 60°C to obtain a TPU prepolymer. With rapid stirring, DTBL catalyst and MPD are added to the prepolymer and reacted completely at a temperature below 100°C. The chain-extended TPU is poured into a preheated silicone mold. The mold is placed in a 100°C oven for 24 hours, or until the TPU is completely cured. The cast elastomer is compression molded to produce test specimens.

[0156] Example 9 (See KK2-29) 4,4'-MDI is dried and supplied in excess to the reaction vessel. Separately, a number-average molecular weight of 1.3 x 10⁻¹⁶ is added. 3 g / mol NO2-PED is blended with 0.5 wt% Tinuvin 234, 0.17 wt% Irgafos 168, and 0.33 wt% Irganox 1076. Next, the blended NO2-PED is added to the excess diisocyanate and reacted completely at a temperature below 60°C to obtain a TPU prepolymer. With rapid stirring, the DTBL catalyst and 1,4-BD are added to the prepolymer and reacted completely at a temperature below 100°C. The chain-extended TPU is poured into a preheated silicone mold. The mold is placed in a 100°C oven for 24 hours, or until the TPU is completely cured. The cast elastomer is compression molded to produce test specimens.

[0157] Example 10 (See KK1-97) NO2-PED having a number-average molecular weight of 500 g / mol was blended and mixed in a flat-bottom polyethylene beaker with 3.0 wt% distilled water, 2 wt% silicone oil, and 1.0 wt% DTBL catalyst. MDI was added directly to the compound polyol and mixed vigorously for 15 seconds. The resulting foam was stabilized at room temperature for 24 hours before characterization. [Table 6]

[0158] The various methods and techniques described above provide many ways to carry out this application. Naturally, it should be understood that not all objectives or benefits described herein can necessarily be achieved according to every particular embodiment described herein. Therefore, for example, a person skilled in the art will recognize that a method can be carried out in a way that achieves or optimizes one benefit or set of benefits taught herein without necessarily achieving other objectives or benefits taught or suggested herein. Various alternatives are mentioned herein. It should be understood that some embodiments specifically include one, another, or several features, while other embodiments specifically exclude one, another, or several features, and yet another embodiment mitigates certain features by including one, another, or several advantageous features.

[0159] Furthermore, those skilled in the art will recognize the applicability of various features from different embodiments. Similarly, the various elements, features, and steps described above, as well as other known equivalents of each such element, feature, or step, can be used in various combinations by those skilled in the art to carry out the method according to the principles described herein. Some of the various elements, features, and steps are specifically included in various embodiments, while others are specifically excluded.

[0160] Although this application is disclosed in the context of specific embodiments and examples, it will be understood by those skilled in the art that the embodiments of this application extend beyond the specifically disclosed embodiments to other alternative embodiments and / or uses and modifications and their equivalents.

[0161] Various embodiments of this application are described herein, including the best mode known to the inventors for carrying out this application. Variations of these embodiments will become apparent to those skilled in the art by reading the preceding description. Those skilled in the art can appropriately adopt such modifications and it is intended that the application may be carried out in ways other than those specifically described herein. Accordingly, many embodiments of this application include all modifications and equivalents of the subject matter described in the claims attached herein, as permitted by applicable law. Furthermore, unless otherwise indicated herein or unless it is clearly inconsistent with the context, any combination of the above elements in all possible variations is incorporated herein.

[0162] All patents, patent applications, publications of patent applications, and other materials referenced herein, such as articles, books, specifications, publications, documents, and objects, are incorporated into this Specified in their entirety by this reference for all purposes, except for any indictment records relating to the same, any identical, any identical that does not conform to or contradicts this Document, or any identical that may have a limited effect on the broadest scope of the claims currently or hereafter relating to this Document. For example, if there is any inconsistency or contradiction between the descriptions, definitions, and / or use of terms relating to any of the incorporated materials and the terms relating to this Specified, the descriptions, definitions, and / or use relating to the terms relating to this Specified shall prevail.

[0163] It should be understood that the embodiments of the present application disclosed herein are illustrative of the principles of the embodiments of the present application. Other applicable modifications are within the scope of the present application. Therefore, alternative configurations of the embodiments of the present application can be utilized, not as an example but as an example, in accordance with the teachings herein. Accordingly, the embodiments of the present application are not limited to those precisely illustrated and described.

[0164] Various embodiments of the present invention are described in the detailed description above. While these descriptions directly illustrate the embodiments described above, it will be understood that those skilled in the art can recall and consider modifications and / or variations to the specific embodiments shown and described herein. Such modifications or variations that fall within the scope of this description are also intended to be included therein. Unless otherwise specified, the words and phrases in the specification and claims are intended to have the usual and customary meaning for those skilled in the art.

[0165] The above description of various embodiments of the invention known to the applicant at this point in time of filing is presented and intended for illustrative and explanatory purposes. This description is not intended to be exhaustive or to limit the invention to the exact forms disclosed, and many modifications and variations are possible in light of the above teachings. The embodiments described illustrate the principles of the invention and their practical application and help enable those skilled in the art to utilize the invention in various embodiments and to make various modifications suitable for specific intended uses. Accordingly, the invention is not intended to be limited to the specific embodiments disclosed for carrying out the invention.

[0166] While specific embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that modifications and alterations can be made based on the teachings herein without departing from the present invention and its broader embodiments. Accordingly, the appended claims shall encompass within their scope all such modifications and alterations as to be in the true spirit and scope of the present invention.

Claims

1. A thermoplastic polyurethane elastomer composition, (a) at least one nitrosubstituted polyester diol (NO ２ -PED) and the NO ２ - NO is a compound in which the nitro group between the two carboxyl groups of PED is substituted. ２ - A composition comprising PED and at least one polyester diol that is not substituted with a nitro group, wherein the NO ２ -PED is, formula: 【Chemistry 1】 (In the formula, n is 0 to 14, y is 1 to 100, and X is H or NO) ２ R is one or more CH groups substituted with alkylenyl, -O-. ２ An alkylenyl, cycloalkylenyl, or aryleniyl having a group, where at least one X is NO ２ A composition having (that is), (b) at least one polyisocyanate, (c) A composition comprising at least one chain extender and a reaction product thereof.

2. The composition according to claim 1, wherein R is alkylenyl.

3. The composition according to claim 1, wherein R is ethilenyl, propyrenyl, isopropyrenyl, butyrenyl, pentyrenyl, hexylenyl, heptyrenyl, or octyrenyl.

4. R is an alkylenyl group, and one or more CH ２ The composition according to claim 1, wherein the group is substituted with -O-.

5. R is -(CH ２ ) Ｏ -O-(CH ２ ) Ｏ -, and in the formula, o is from 2 to 4, the composition according to claim 1.

6. The composition according to claim 1, wherein R is alleleyl.

7. The NO before the reaction ２ - The composition according to claim 1, wherein the PED has a molecular weight of 400 to 10,000 g / mol.

8. The composition according to claim 1, wherein the chain extender is a dihydroxyalkane or a dihydroxycycloalkane.

9. The composition according to claim 8, wherein the chain extender is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-dihydroxycyclohexane, or a mixture thereof.

10. The composition according to claim 1, wherein the chain extender is alkylene or aralkylenediamine.

11. The composition according to claim 10, wherein the chain extender is ethylenediamine, hexamethylenediamine, 1,4-cyclohexanylenediamine, or a mixture thereof.

12. The composition according to claim 1, wherein the chain extender is an aromatic diamine.

13. The composition according to claim 12, wherein the aromatic diamine is benzidine, toluenediamine, diaminodiphenylmethane, phenylenediamine, or a mixture thereof.

14. The composition according to claim 1, wherein the chain extender is hydrazine.

15. The composition according to claim 1, wherein the chain extender is an amino alcohol.

16. The composition according to claim 15, wherein the chain extender is ethanolamine, N-methylethanolamine, N-butylethanolamine, N-oleoylethanolamine, N-cyclohexylisopropanolamine, or a mixture thereof.

17. The composition according to claim 1, wherein the chain extender is a substituted aromatic diamine.

18. The composition according to claim 17, wherein the chain extender is 4,4'-methylene-bis(o-chloroaniline), 4,4'-methylenebis(3-chloro-2,6-diethylaniline), or a mixture thereof.

19. The composition according to claim 1, wherein the thermoplastic polyurethane elastomer composition further comprises at least one crosslinking agent.

20. The composition according to claim 19, wherein the at least one crosslinking agent is glycerin, trimethylolpropane, diethanolamine, triethanolamine, or a mixture thereof.

21. The composition according to claim 1, wherein the ratio of active hydrogen-containing groups to polyisocyanate (NCO index) is 0.9 to 1.

5.

22. The composition according to claim 1, wherein the at least one polyisocyanate is 4,4'-diisocyanate diphenylmethane (4,4'-MDI), 2,4'-diisocyanate diphenylmethane (2,4'-MDI), p-phenylenediisocyanate, 1,3-bis(isocyanate-methyl)cyclohexane, 1,4-diisocyanate cyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalenediisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 4,4'-diisocyanate dicyclohexylmethane, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, or a mixture thereof.

23. The composition according to claim 1, (a) with a light stabilizer or UV stabilizer; (b) with inorganic or organic fillers; (c) silicate minerals, metal oxides, metal salts, clays, metal silicates, glass fibers, natural fiber materials, or synthetic fiber minerals; (d) carbon black, fullerenes, carbon nanotubes, biochar, melamine corophony, cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and / or aliphatic dicarboxylic acid esters, or carbon fibers; and (e) an organic phosphate, a metal polyphosphate, a metal oxide, a metal salt, or a cyanuric acid derivative; further comprising at least one additive, A composition in which the additive is present in an amount of 0.5 to 30 weight percent of the composition.

24. A composition according to claim 1, further comprising at least one flame retardant which is an organic phosphate, a metal polyphosphate, a metal oxide, a metal salt, a cyanuric acid derivative, or a mixture thereof, wherein the at least one flame retardant is present in the composition at a concentration of 500 to 4000 ppm.

25. The composition according to claim 1, further comprising a blowing agent which is water, pentane, cyclopentane, or hydrofluorocarbon, or a mixture thereof.

26. The at least one nitrosubstituted polyester diol is at least one C substituted with a single nitro group. ８－２０ The composition according to claim 1, comprising a reaction product of a dicarboxylic acid and at least one polyol.

27. The aforementioned at least one polyol is C １－８ The composition according to claim 26, wherein the composition is a diol.

28. The thermoplastic polyurethane elastomer composition according to claim 1, comprising 20 to 80% by weight of the nitrosubstituted polyester diol.

29. The composition according to claim 1, wherein the composition comprises at least one additive which is an antioxidant, a dye, a wetting agent, an antifoaming agent, a thickener, a photosensitizer, or a solvent, and the amount of the additive is less than 20% by weight of the total weight of the composition.

30. The composition according to claim 1, wherein the composition comprises a metallic, organic, inorganic, or organic / inorganic hybrid filler, and the filler is present in an amount of less than 20% by weight of the total weight of the composition.

31. at least one nitrosubstituted polyester diol (NO ２ A method for producing a thermoplastic polyurethane elastomer composition according to claim 1, comprising the step of reacting a PED, at least one polyisocyanate, and at least one chain extender.

32. The manufacturing method according to claim 31, wherein the reaction conditions include a temperature of 25 to 120°C.

33. A product comprising the thermoplastic polyurethane elastomer composition according to any one of claims 1 to 30.

34. The product according to claim 33, including molded products.

35. The product according to claim 34, including a sole for footwear.

36. The product according to claim 33, comprising a hard solid plastic.

37. The product according to claim 36 for use as a bezel and structural component of an electronic device.

38. The product according to claim 33, comprising a flexible plastic.

39. The product according to claim 38, for use as a strap or band.

40. The product according to claim 33, used for seals, gaskets, durable elastomer wheels and tires, automotive suspension bushings, and electrical insulation components.

41. A TPU foam for footwear comprising the thermoplastic polyurethane elastomer composition described in claim 1, wherein the thermoplastic polyurethane elastomer composition is pelletized and consumed.

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