Thermoplastic polyurethane composition comprising a nitro-substituted polyester diol

Abstract

The present invention relates to the field of polymers. More specifically, the present invention includes a thermoplastic polyurethane elastomer that includes a polyester containing a nitro-substituted dicarboxylic acid that is a product of polyethylene decomposition. The thermoplastic polyurethane elastomer described herein exhibits a higher glass transition temperature and a higher Shore A hardness compared to a thermoplastic polyurethane elastomer synthesized from a similar polyester diol made from virgin monomers that do not contain a nitro-substituent.

Description

Invention Field

[0001] This invention relates to the field of polymers. More specifically, the invention includes thermoplastic polyurethane (TPU) compositions comprising polyesters containing dicarboxylic acids and nitro-substituted dicarboxylic acids derived from recycled raw materials. Background Technology

[0002] All publications herein are incorporated herein by reference, just as individual publications or patent applications are incorporated herein by reference specifically and separately. The following description includes information useful for understanding the invention. This is not an admission that any information provided herein is prior art or related to the claimed invention, or that any specific or implied reference in any publication is prior art.

[0003] TPU elastomers are used in a variety of applications, such as footwear, automotive parts, piping, hoses, and others. TPU elastomers are typically the product of a reaction of one or more diisocyanate compounds, one or more high-equivalent weight diols (polyesters or polyethers), and one or more chain extenders. For many applications, the high-equivalent weight diol is often a polyester diol, such as polyester adipate or polycaprolactone. Cast elastomers made from polyester diols generally have better mechanical properties than those made from polyether diols. Polyester diols impart ideal mechanical properties and abrasion resistance to TPU, making TPU elastomers suitable for footwear applications. TPU is expanding into emerging applications such as 3D printing. This application requires high stiffness and tensile strength while maintaining the desired flexibility of the TPU elastomer.

[0004] Furthermore, due to environmental concerns surrounding the petrochemical sources of polyester glycol, many companies are increasingly seeking products with improved sustainability. However, these products still need to offer the same or better performance than traditional petroleum-based alternatives at comparable prices.

[0005] U.S. Patent No. 5,844,165 discloses nitromalonate polyesters that can be used in high-energy propellants. According to this '165 patent, preferred nitromalonate polyesters contain R... 1 and R 2 Group, the R 1 and R 2 All groups are –CH2ONO2. Therefore, the preferred nitromalonate described in this '165 patent is provided by replacing the two carboxyl groups between the two carboxyl groups of the malonate with two nitromethane groups, thereby providing a high-energy composition.

[0006] U.S. Patent No. 3,745,076 discloses the reaction product of 4,4-dinitro-pimelic acid and diethylene glycol, which produces a hydroxyl-containing polyester polyol that can be reacted with a polyisocyanate. According to the '076 patent, when the nitro group is a substituent, it is preferred that there be at least two nitro groups present on the substituted component. Multiple nitro groups are preferred because the purpose of the '076 patent is to produce adhesives with a higher total energy content. SUMMARY

[0008] The following embodiments and aspects thereof are described and illustrated in conjunction with systems, compositions, methods and articles of manufacture, which are meant to be exemplary and illustrative, not limiting in scope.

[0009] Post-consumer polyethylene waste provides a rich source of raw material for the manufacture of new chemicals. Nitro-functionalized diacids are chemical recycling polyethylene products that accelerate the autothermal oxidative decomposition (ATOD TM ) of post-consumer polyethylene. These diacids can be used to synthesize nitro-functionalized polyester diols, which are the primary building blocks of thermoplastic polyurethanes. These nitro-functionalized polyester diols are the first polyols synthesized from chemical recycling post-consumer polyethylene derived monomers.

[0010] It is desirable to provide a TPU elastomer made from polyester diols that is economical, made from recycled components, and exhibits excellent mechanical properties.

[0011] It is therefore an object of the present invention to overcome the deficiencies in the prior art described above. Another object is to provide a polyester-based TPU elastomer that has improved hardness and tensile strength while maintaining elasticity.

[0012] The present invention provides a TPU elastomer that is a polymer of (1) at least one high equivalent weight polyester diol containing nitro functional groups on the backbone derived from a mixture of dicarboxylic acids and nitro dicarboxylic acids and a polyester diol that does not contain any nitro groups, (2) at least one chain extender, and (3) at least one diisocyanate. The presence of a polyester diol that does not contain any nitro groups provides a non-energy TPU that can be used in consumer products.

[0013] In another embodiment, a TPU elastomer is provided that is a polymer of (1) 20-80 wt% of a nitro-functionalized polyester diol (NO2-PED) made from a mixture of dicarboxylic acids, nitro dicarboxylic acids, and 1,4-butanediol or a mixture thereof with at least one chain extender mixture, and (3) at least one polyisocyanate.

[0014] The present invention also includes NO2-PEDs synthesized from chemical recycling monomers derived from the decomposition of post-consumer polyethylene. The resulting TPU provides a sustainable alternative to bio-based or petrochemical-based TPU.

[0015] We have found that the unique nitro functionality on the high equivalent weight polyester diol component contributes to higher glass transition temperatures, higher tensile strength, and better Shore A hardness.

[0016] A thermoplastic polyurethane elastomer composition is provided comprising the reaction product of:

[0017] at least one nitro-substituted polyester diol (NO2-PED), and

[0018] at least one polyisocyanate, and further comprising the reaction product of

[0019] at least one chain extender.

[0020] In some embodiments, the NO2-PED has the formula:

[0021]

[0022] where n is 0-14, y is 1-100, X is H or NO2, and R is an alkylene group, an alkylene group in which one or more CH2groups are replaced by -O-, a cycloalkylene group, or an arylene group, wherein at least one X is NO2.

[0023] In some embodiments, R is an alkylene group. In some embodiments, R is an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, or an octylene group.

[0024] In some embodiments, R is an alkylene group in which one or more CH2groups are replaced by -O-.

[0025] In some embodiments, R is -(CH2) o -O-(CH2) o -, o -O-(CH2) o -CH3, (CH3CH(OH)CH2)2O, where o is 2 to 4.

[0026] In some embodiments, R is an arylene group or an aromatic alkylene group.

[0027] In some embodiments, the NO2-PED has a molecular weight of 400 to 10,000 g / mol prior to reaction.

[0028] In some embodiments, the chain extender is a dihydroxyalkane or a dihydroxycycloalkane. In some embodiments, 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.

[0029] In some embodiments, the chain extender is an alkylene or aralkylene diamine. In some embodiments, the chain extender is ethylenediamine, hexamethylenediamine, 1,4- cyclohexanediamine, or a mixture thereof. In some embodiments, the chain extender is an aromatic diamine. In some embodiments, the aromatic diamine is benzidine, dihydroxymethoxyhydroquinone, toluenediamine, diaminodiphenylmethane, phenylenediamine, or a mixture thereof.

[0030] In some embodiments, the chain extender is a hydrazine.

[0031] In some embodiments, the chain extender is an amino alcohol. In some embodiments, the chain extender is ethanolamine, N-methylethanolamine, N-butylethanolamine, N- oleoyl ethanolamine, N-cyclohexylisopropanolamine, or a mixture thereof.

[0032] In some embodiments, the chain extender is a substituted aromatic diamine. In some embodiments, the chain extender is 4,4'-methylenebis(o-chloroaniline), 4,4'- methylenebis(3-chloro-2,6-diethylaniline), or a mixture thereof.

[0033] In some embodiments, the thermoplastic polyurethane elastomer composition further comprises at least one crosslinking agent. In some embodiments, the crosslinking agent is glycerol, trimethylolpropane, diethanolamine, triethanolamine, or a mixture thereof.

[0034] In some embodiments, the ratio of polyisocyanate to active hydrogen containing groups (NCO index) is 0.9-1.5.

[0035] In some embodiments, the isocyanate is 4,4'-diisocyanatodiphenylmethane (4,4'-MDI), 2,4'-diisocyanatodiphenylmethane (2,4'-MDI), p-phenylene diisocyanate, 1,3- bis(isocyanatomethyl)cyclohexane, 1,4-diisocyanatocyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4'- diphenyl diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, 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.

[0036] In some embodiments, the composition comprises one or more additives. In some embodiments, the one or more additives include at least one light stabilizer, UV stabilizer, or a mixture thereof. In some embodiments, the one or more additives is an inorganic filler, an organic filler, or a mixture thereof. In some embodiments, the one or more additives is at least one inorganic filler that is a silicate mineral, a metal oxide, a metal salt, a clay, a metal silicate, a glass fiber, a natural fibrous material, a synthetic fibrous mineral, or a mixture thereof. In some embodiments, the additive is an organic filler that is carbon black, fullerene, carbon nanotube, biochar, melamine resin, cellulose fiber, polyamide fiber, polyacrylonitrile fiber, polyurethane fiber, polyester fiber based on aromatic and / or aliphatic dicarboxylic ester, carbon fiber, or a mixture thereof. In some embodiments, the filler is present at 0.5-30 wt% of the composition. In some embodiments, the filler includes at least one flame retardant. In some embodiments, the at least one flame retardant is an organophosphate, a metal polyphosphate, a metal oxide, a metal salt, a cyanuric acid derivative, or a mixture thereof. In some embodiments, the at least one flame retardant is present in the composition at 500 to 4000 ppm.

[0037] In some embodiments, the composition comprises a blowing agent. In some embodiments, the blowing agent is at least one of water, pentane, cyclopentane, hydrofluorocarbon, or a mixture thereof.

[0038] In some embodiments, the nitro-substituted polyester diol is an ester of:

[0039] 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

[0040] b. at least one C8-C 20 dicarboxylic acid substituted with a single nitro group;

[0041] and at least one polyol.

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

[0043] In some embodiments, the composition comprises 20-80 wt% of the nitro-substituted polyester diol.

[0044] In some embodiments, the composition further comprises a reaction product of:

[0045] at least one polyester diol that is not substituted with a nitro group, and

[0046] at least one polyisocyanate, and further comprising a reaction product of

[0047] at least one chain extender.

[0048] Also provided is a method of making a composition, the method comprising: reacting:

[0049] at least one nitro-substituted polyester diol,

[0050] at least one polyisocyanate, and

[0051] at least one chain extender.

[0052] In some embodiments, the reaction conditions comprise a temperature of 25 °C to 120 °C.

[0053] Also provided is a thermoplastic polyurethane elastomer composition made by the method described herein.

[0054] In some embodiments, the thermoplastic polyurethane elastomer composition is in a foam form comprising:

[0055] (a) a polyester comprising at least one nitro-substituted polyester diol,

[0056] (b) at least one isocyanate,

[0057] (c) at least one chain extender,

[0058] (d) at least one flame retardant,

[0059] (e) at least one surfactant,

[0060] (f) at least one blowing agent, and

[0061] (g) at least one urethane catalyst.

[0062] In some embodiments, the method further comprises: reacting at least one polyester diol that is not nitro-substituted.

[0063] In some embodiments, the dicarboxylic acid used to make the polyester diol and the nitro polyester diol is an ester of:

[0064] a. oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, a C10 dicarboxylic acid, a C11 dicarboxylic acid, a C12 dicarboxylic acid, a C13 dicarboxylic acid, a C14 dicarboxylic acid, and a C15 dicarboxylic acid, and

[0065] b. at least one C8-C 20 dicarboxylic acid that is substituted with a single nitro group; and

[0066] at least one diol.

[0067] In some embodiments, the at least one diol is a C 1-8 diol.

[0068] BRIEF DESCRIPTION OF DRAWINGS

[0069] Exemplary embodiments are shown in the reference drawings. It is intended that the embodiments disclosed herein and the drawings be considered illustrative only and not restrictive in nature.

[0070] Figure 1 Bar graphs are depicted showing the weight % of dicarboxylic acid in compositions comprising nitro-substituted dicarboxylic acids. DETAILED DESCRIPTION

[0072] All references cited herein are incorporated by reference in their entirety as if each had been individually incorporated. The nomenclature used herein and the nomenclature used in the description and claims sections below are intended to conform to International Patent Classification (IPC) standards as close as practicable. The use of the singular is intended to include the plural unless otherwise clear from the context. The use of "and / or" means "and" or "or", unless otherwise indicated. The use of "or" means "and / or", unless otherwise indicated. The use of "comprise", "comprises", "comprising", "contain", "contains", "containing", "include", "includes", "including" and "has" are not intended to be limiting. It is contemplated that the application can be practiced with the except of the details of the methods and materials described herein. The omission of such details does not preclude the application from practicing the application.

[0073] Those skilled in the art will appreciate that many methods and materials similar or equivalent to those described herein can be used in the practice of the present application. The present application is directed to each feature and embodiment of the application in combination with every other feature and embodiment of the application. Other features and advantages of the application will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, various features of the application. In fact, the application is not limited by the method and materials described herein, but can extend to whatever method and materials would operate according to the principles of the application and similar methods and materials will become apparent to those skilled in the art in view of the teachings herein. The present application has been described in terms of particular embodiments and applications, and it is recognized that those skilled in the art might conceive and adapt variations, modifications, and alternative embodiments within the scope and spirit of the application. Accordingly, the application is not intended to be limited to the particular methods and materials described herein but extend to all alternatives consistent with the principles of the application.

[0074] Unless the context clearly indicates otherwise, the following terms and phrases include the definitions provided below. The following terms and phrases do not exclude meanings of the term or phrase that are acquired in the art to which the term or phrase belongs, unless otherwise explicitly stated or clearly apparent from the context. Unless otherwise defined, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the application belongs. It should be understood that the application is not limited to the particular methods, protocols, reagents, etc. described herein as these can vary. The definitions and terms used herein are intended to help describe the specific embodiments and are not intended to limit the claimed application as the scope of the application is limited only by the claims.

[0075] As used herein, the terms “comprising” or “including,” when used in the context of compositions, methods, systems, articles of manufacture, and the like, are used open- ended and do not exclude additional elements / elements. Those skilled in the art will understand that, in general, the terms used herein are intended to be synonymous with the open-ended terms “comprising” and “including,” unless the context clearly indicates otherwise. As used herein, the terms “comprising” or “including” means that other elements / elements can be present in addition to the defined elements / elements. The use of “including” indicates that the elements / elements are included but not limited to. Although the present application is described and claimed using the open-ended term “comprising” as synonyms for terms like comprising, containing, or having, the present application or embodiments thereof can also be described using alternative terms like “consisting of’ or “consisting essentially of.”

[0076] The terms “a,” “an,” and “the” and similar referents on the context of describing the specific embodiments of the application, particularly in the claims (especially as capitalized) can be interpreted to cover both singular and plural unless otherwise indicated by context. Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein unless otherwise indicated by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the application and does not pose a limitation on the scope of the application otherwise claimed. The abbreviation "e.g." is derived from the Latin expression "exempli gratia," and is used herein to mean "for example." Thus, the abbreviation "e.g." is synonymous with "for example." No language herein is to be construed as indicating any non-claimed element essential to the practice of the application.

[0077] Groupings of alternative elements or embodiments of the application disclosed herein are not to be construed as limitations. Each group member can be referred to and claimed individually or in any combination with other members of the group or other elements found herein. One or more members of a group can be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified thus fulfilling the written description requirement under 35 U.S.C. § 112.

[0078] ​“Optional” or “optionally” means that the subsequently described event or circumstance can or can not occur, and, thus, the description includes instances where the event occurs and instances where it does not.

[0079] As used herein, the term “substituted” means the replacement of one or more (typically 1, 2, 3, 4, or 5) hydrogen atoms on a substituted moiety with a substituent independently selected from the substituents listed in the “Substituent” definition or otherwise specified. Typically, a non-hydrogen substituent can be any substituent that can be bonded to an atom of the given moiety that is specified to be substituted. Examples of substituents include, but are not limited to: acyl, acylamino, acyloxy, aldehyde, alicyclic, aliphatic, alkansulfonamido, alkansulfonyl, alkaryl, alkenyl, alkoxy, alkoxycarbonyl, alkyl, alkylamino, alkylcarbonyl, alkylidene, alkylidene, alkylthio, alkynyl, amide, amido, amino, amidine, aminoalkyl, aralkyl, aralkylsulfonamido, aransulfonamido, arenesulfonyl, aromatic, aryl, arylamino, arylcarbonyl, aryloxy, azido, carbamoyl, carbonyl, ketone containing, carboxy, carboxylate, CF3, cyano (CN), cycloalkyl, cycloalkylidene, ester, ether, haloalkyl, halogen, halogen, heteroaryl, heterocyclyl, hydroxyl, hydroxyalkyl, imino, imino ketone, ketone, mercapto, nitro, oxoalkyl, oxo, oxoalkyl, phosphoryl (including phosphonate and phosphinite), silyl, sulfonamido, sulfonyl (including sulfate, sulfonamidyl, and sulfonate), thiol, and urea moieties, each of which can also be optionally substituted or not. In some cases, two substituents can form a ring together with the carbon atom to which they are attached. In some cases, two or more substituents can form one or more rings together with the carbon atoms to which they are attached.

[0080] Substituents can be protected, if desired, and any protecting group commonly used in the art can be used. Non-limiting examples of protecting groups can be found in, for example, Greene and Wuts, Protecting Groups in Organic Synthesis, 4th Ed., Wiley & Sons (2006).

[0081] The term “carboxy” refers to the group —C(O)O—. Note that compounds described herein that contain a carboxy moiety can include protected derivatives thereof, i.e., the oxygen atom is replaced with a protecting group. Suitable protecting groups for carboxy moieties include: benzyl, t-butyl, methyl, ethyl, and the like. The term “carboxyl” refers to —COOH.

[0082] The term "alkylene" refers to a divalent alkyl group. In one embodiment, the alkylene group is C10. 3-8 Alkylenes. Examples of alkylenes include: methylene, ethylene, propylene, isopropylene, butylene, pentylene, and hexylene.

[0083] The term "arylene" refers to an optionally substituted aryl group in a divalent form. In one embodiment, the arylene is an optionally substituted phenyl group in a divalent form. In one embodiment, the arylene is a phenyl group in a divalent form. Non-limiting exemplary alkylene groups include:

[0084]

[0085] The term "cycloalkylene" refers to the divalent form of C 3-8 Cycloalkyl. Examples of cycloalkylene compounds include: 1,2-cyclobutylene, 1,3-cyclobutylene, 1,2-cyclopentane, 2,3-cyclopentane, 1,4-cyclohexane, 1,3-cyclohexane, and 1,4-cyclohexane.

[0086] The term "dihydroxycycloalkanes" refers to C4 hydrocarbons that have been substituted with two hydroxyl groups. 3-8 Cycloalkyl. 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.

[0087] The term "polymer" refers to a substance, compound, or mixture of compounds whose molecular structure is mainly or entirely composed of a large number of similar units (such as monomer units) bonded together. Linear polymers are also called straight-chain polymers because they consist of a long chain of carbon-carbon bonds; branched polymers have irregularly spaced branches along the polymer chain; crosslinked polymers contain branches that are linked by covalent, ionic, or H bonds; and optionally substituted polymers are polymers containing functional groups at random points along the hydrocarbon backbone, wherein one or more hydrogen atoms attached to the backbone may (but are not required to) be substituted with substituents selected independently of the term "substituent" as defined herein or otherwise specified. These polymers are considered to be optionally substituted because they do not typically 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 polymerization; homopolymers are formed by polymerizing a single monomer; copolymers are formed by polymerizing more than one monomer; synthetic polymers are synthesized through chemical reactions; natural polymers are derived from nature and can be extracted; biopolymers are produced, modified, or naturally occurring by living organisms; organic polymers are polymers containing carbon atoms in the polymer chain backbone.

[0088] The term "oligomer" refers to a substance, compound, or mixture of compounds whose molecular structure consists primarily or entirely of a few similar units (e.g., monomeric units) bound together.

[0089] The term "plastic" refers to a synthetic material comprising a variety of organic polymers (e.g., polyolefins, polyesters, polyamides, etc.) that can be molded into shape while soft and then solidified into a rigid, semi-elastic, or elastic form.

[0090] The term "about" refers to ±10% of the recited number. For example, "about 100" refers to 90-110, inclusive.

[0091] Various non-limiting embodiments of the present invention

[0092] It is an object of the present invention to provide a thermoplastic polyurethane elastomer that is prepared starting from a dicarboxylic acid composition containing a nitro-substituted dicarboxylic acid.

[0093] Nitro-substituted dicarboxylic acid composition

[0094] The nitro-substituted dicarboxylic acid composition can be prepared according to U.S. Patents 10,519,292 and 10,557,011, the contents of which are incorporated by reference in their entirety. The produced nitro-substituted dicarboxylic acid is mixed with other dicarboxylic acids. The method comprises:

[0095] a. adding polyethylene (PE) to a reaction vessel;

[0096] b. adding aqueous nitric acid (HN03) to the reaction vessel to provide a mixture, wherein the weight ratio of PE to aqueous nitric acid is greater than 1:3; and

[0097] c. subjecting the mixture obtained in step b to effective conditions to decompose the PE to produce a dicarboxylic acid and a nitro-substituted dicarboxylic acid.

[0098] The concentration of nitric acid can be 10 to 90 wt.%. In some embodiments, the concentration of nitric acid is about 67 to 90 wt.%. In some embodiments, the weight ratio of PE to nitric acid is 1 : 10 to 1 : 100. In some embodiments, a catalyst is added to the reaction, such as a zeolite, alumina, silicoaluminophosphate, sulfated zirconia, zinc oxide, titanium oxide, zirconium oxide, niobium oxide, iron carbonate, calcium carbide, or a combination thereof. In some embodiments, the effective conditions include a temperature range of about 60 °C to about 200 °C. In some embodiments, the effective conditions include an initial pressure of 0 to 1000 psi. In some embodiments, the effective conditions include a batch process with a residence time in the reaction vessel of about 1 hour to about 10 hours. In some embodiments, the effective conditions include a continuous process. The dicarboxylic acid and nitro dicarboxylic acid are then separated, such as by filtering the mixture and evaporating the nitric acid, such as under reduced pressure. The dicarboxylic acid and nitro dicarboxylic acid can then be esterified, such as in the presence of an acid catalyst, such as hydrochloric acid or sulfuric acid, in the presence of an alcohol, such as a C1-C6 alcohol, to form the corresponding dicarboxylic acid C 1-4 ester and nitro dicarboxylic acid C 1-4 ester. In some embodiments, the dicarboxylic acid C 1-4 ester is a methyl ester, an ethyl ester, a propyl ester, a butyl ester, or a pentyl ester. 1-4 ester is a methyl ester, an ethyl ester, a propyl ester, a butyl ester, or a pentyl ester.

[0099] In some embodiments, succinic acid is present in an amount of about 10 to about 25 wt.%, glutaric acid is present in an amount of about 11 to about 25 wt.%, adipic acid is present in an amount of about 14 to about 22 wt.%, pimelic acid is present in an amount of about 10 to about 20 wt.%, and azelaic acid is present in an amount of about 3 to about 10 wt.%, or esters thereof in equivalent amounts, and, if present, oxalic acid is present in an amount up to 10 wt.%, if present, suberic acid is present in an amount of about 5 to about 16 wt.%, if present, sebacic acid is present in an amount of about 1 to about 15 wt.%, if present, undecanedioic acid is present in an amount of about 1 to about 8 wt.%, if present, dodecanedioic acid is present in an amount up to about 5 wt.%, if present, tridecanedioic acid is present in an amount up to about 4 wt.%, if present, tetradecanedioic acid is present in an amount up to about 2 wt.%, if present, pentadecanedioic acid is present in an amount up to about 1 wt.%, if present, hexadecanedioic acid is present in an amount up to about 1 wt.%, if present, heptadecanedioic acid is present in an amount up to about 1 wt.%, and, if present, octadecanedioic acid is present in an amount up to about 1 wt.%, or esters thereof in equivalent amounts.

[0100] In some embodiments, succinic acid is present in an amount of about 15 to about 19 wt%, glutaric acid is present in an amount of about 17 to about 21 wt%, adipic acid is present in an amount of about 16 to about 20 wt%, pimelic acid is present in an amount of about 13 to about 17 wt%, and azelaic acid is present in an amount of about 4 to about 8 wt%, or esters of the equivalent thereof, and, if present, oxalic acid is present in an amount up to 10 wt%, if present, suberic acid is present in an amount of about 9 to about 13 wt%, if present, sebacic acid is present in an amount of about 5 to about 9 wt%, if present, undecanedioic acid is present in an amount of about 2 to about 4 wt%, if present, dodecanedioic acid is present in an amount of about 1 to about 3 wt%, if present, tridecanedioic acid is present in an amount of about 0.5 to about 1.5 wt%, if present, tetradecanedioic acid is present in an amount up to about 0.2 wt%, if present, pentadecanedioic acid is present in an amount up to about 0.2 wt%, if present, hexadecanedioic acid is present in an amount up to about 0.2 wt%, if present, heptadecanedioic acid is present in an amount up to about 0.2 wt%, and if present, octadecanedioic acid is present in an amount up to about 0.2 wt%, or esters of the equivalent thereof.

[0101] In some embodiments, succinic acid is present in an amount of about 5 to about 40 wt%, glutaric acid is present in an amount of about 8 to about 27 wt%, adipic acid is present in an amount of about 10 to about 29 wt%, pimelic acid is present in an amount of about 10 to about 20 wt%, and azelaic acid is present in an amount of about 1 to about 13 wt%, or esters of the equivalent thereof, and, if present, oxalic acid is present in an amount up to 10 wt%, if present, suberic acid is present in an amount of about 4 to about 20 wt%, if present, sebacic acid is present in an amount up to about 12 wt%, if present, undecanedioic acid is present in an amount up to about 8 wt%, if present, dodecanedioic acid is present in an amount up to about 5 wt%, if present, tridecanedioic acid is present in an amount up to about 4 wt%, if present, tetradecanedioic acid is present in an amount up to about 2 wt%, if present, pentadecanedioic acid is present in an amount up to about 0.4 wt%, if present, hexadecanedioic acid is present in an amount up to about 0.4 wt%, if present, heptadecanedioic acid is present in an amount up to about 0.4 wt%, and if present, octadecanedioic acid is present in an amount up to about 0.4 wt%, or esters of the equivalent thereof.

[0102] In some embodiments, the dicarboxylic acid further comprises at least one C8-C 20 dicarboxylic acid or ester thereof. The nitro-substituted C8-C 20 The dicarboxylic acid can be substituted at the 2-, 3-, 4-, 5-, 6-, 7-, or 8- position of the dicarboxylic acid.

[0103] In some embodiments, the at least one nitro-substituted dicarboxylic acid is 2-nitrooctanedioic acid, 2-nitrononanedioic acid, 2-nitrodecanedioic acid, 2-nitro-undecanedioic acid, 2-nitrododecanedioic acid, 2-nitrotridecanedioic acid, 2-nitrotetradecanedioic acid, 2-nitropentadecanedioic acid, 2-nitrohexadecanedioic acid, 2-nitroheptadecanedioic acid, 2-nitrooctadecanedioic acid, 2-nitrononadecanedioic acid, or 2-nitroicosanedioic acid or esters thereof.

[0104] In some embodiments, the dicarboxylic acid comprises:

[0105] 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

[0106] b. at least one C8-C20 dicarboxylic acid substituted with a single nitro group. 20 dicarboxylic acid or ester thereof.

[0107] In some embodiments, the at least one C8-C20 dicarboxylic acid substituted with a single nitro group is nitrooctanedioic acid, nitrononanedioic acid, nitrodecanedioic acid, nitro-undecanedioic acid, nitrododecanedioic acid, nitrotridecanedioic acid, nitrotetradecanedioic acid, nitropentadecanedioic acid, nitrohexadecanedioic acid, nitroheptadecanedioic acid, nitrooctadecanedioic acid, nitrononadecanedioic acid, or nitroicosanedioic acid or esters thereof. 20 dicarboxylic acid is nitrooctanedioic acid, nitrononanedioic acid, nitrodecanedioic acid, nitro-undecanedioic acid, nitrododecanedioic acid, nitrotridecanedioic acid, nitrotetradecanedioic acid, nitropentadecanedioic acid, nitrohexadecanedioic acid, nitroheptadecanedioic acid, nitrooctadecanedioic acid, nitrononadecanedioic acid, or nitroicosanedioic acid or esters thereof. In some embodiments, the C8-C20 dicarboxylic acid is a 2-nitro-substituted dicarboxylic acid. 20 dicarboxylic acid is nitrooctanedioic acid, nitrononanedioic acid, nitrodecanedioic acid, nitro-undecanedioic acid, nitrododecanedioic acid, nitrotridecanedioic acid, nitrotetradecanedioic acid, nitropentadecanedioic acid, nitrohexadecanedioic acid, nitroheptadecanedioic acid, nitrooctadecanedioic acid, nitrononadecanedioic acid, or nitroicosanedioic acid or esters thereof. In some embodiments, the C8-C20 dicarboxylic acid is a 2-nitro-substituted dicarboxylic acid. 20 dicarboxylic acid is nitrooctanedioic acid, nitrononanedioic acid, nitrodecanedioic acid, nitro-undecanedioic acid, nitrododecanedioic acid, nitrotridecanedioic acid, nitrotetradecanedioic acid, nitropentadecanedioic acid, nitrohexadecanedioic acid, nitroheptadecanedioic acid, nitrooctadecanedioic acid, nitrononadecanedioic acid, or nitroicosanedioic acid or esters thereof. In some embodiments, the C8-C20 dicarboxylic acid is a 2-nitro-substituted dicarboxylic acid. 20The dicarboxylic acid is 4-nitrooctanedioic acid, 4-nitrononanedioic acid, 4- nitrodecanedioic acid, 4-nitrioundecanedioic acid, 4-nitrododecanedioic acid, 4- nitrotetradecanedioic acid, 4-nitripentadecanedioic acid, 4-nitrohexadecanedioic acid, 4- nitroheptadecanedioic acid, 4-nitrooctadecanedioic acid, 4-nitrononadecanedioic acid, or 4-nitroicosanedioic acid, or an ester thereof. In some embodiments, the C8-C 20 The dicarboxylic acid is 5-nitrooctanedioic acid, 5-nitrononanedioic acid, 5- nitrodecanedioic acid, 5-nitrioundecanedioic acid, 5-nitrododecanedioic acid, 5- nitrotetradecanedioic acid, 5-nitripentadecanedioic acid, 5-nitrohexadecanedioic acid, 5- nitroheptadecanedioic acid, 5-nitrooctadecanedioic acid, 5-nitrononadecanedioic acid, or 5-nitroicosanedioic acid, or an ester thereof. In some embodiments, the C8-C 20 The dicarboxylic acid is present in the decomposition mixture up to about 70% by weight.

[0108] In some embodiments, the nitro dicarboxylic acid composition comprises the dicarboxylic acid in an amount of Figure 1 as shown.

[0109] The ester of the dicarboxylic acid composition

[0110] In some embodiments, the dicarboxylic acid and the nitro dicarboxylic acid are in ester form. These esters are prepared under esterification conditions. In some embodiments, the dicarboxylic acid is at least partially in ester form.

[0111] In some embodiments, the ester is a methyl ester, an ethyl ester, a propyl ester, an isopropyl ester, a butyl ester, an isobutyl ester, a sec-butyl ester, a t-butyl ester, a pentyl ester, or a hexyl ester, or a combination thereof. In some embodiments, the ester is a methyl ester. In some embodiments, the conversion is by an esterification reaction or esterification.

[0112] Any suitable esterification conditions known in the art can be used to form the ester. For example, the dicarboxylic acid and the nitro dicarboxylic acid can be mixed with at least one alcohol, and the mixture is heated to cause esterification. An inorganic acid or an organic acid can be added as a catalyst. In some embodiments, the at least one alcohol is at least one selected from the group consisting of a linear alcohol, a branched alcohol, a cyclic alcohol, and combinations thereof. In some embodiments, the at least one alcohol is at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, and combinations thereof. In some embodiments, the at least one alcohol is a C1-C10 alcohol. In some embodiments, the at least one alcohol is a C1-C4 alcohol. In some embodiments, the at least one alcohol is methanol.

[0113] In some embodiments, the succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid are each independently in ester form.

[0114] In some embodiments, oxalic acid, suberic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, 2-octenedioic acid, 2-nonenedioic acid, 2-decenedioic acid, and 2-undecenedioic acid are independently in ester form.

[0115] In some embodiments, 2-nitrooxalic acid, 2-nitrosuberic acid, 2-nitro sebacic acid, 2-nitro undecanedioic acid, 2-nitrododecanedioic acid, 2-nitrotridecanedioic acid, 2-nitrotetradecanedioic acid, 2-nitropentadecanedioic acid, 2-nitrohexadecanedioic acid, 2-nitroheptadecanedioic acid, 2-nitrooctadecanedioic acid, 2-nitrononadecanedioic acid, and 2-nitroicosanedioic acid are independently in ester form.

[0116] In some embodiments, C8-C20carboxylic acids substituted with a single nitro group are independently in ester form. 20 In some embodiments, C8-C20carboxylic acids substituted with a single nitro group are independently in ester form. 20 In some embodiments, C8-C20carboxylic acids substituted with a single nitro group are independently in ester form. 20 In some embodiments, C8-C20carboxylic acids substituted with a single nitro group are independently in ester form.

[0117] As used herein, the term "diester" refers to an ester formed by converting two carboxyl groups from a dicarboxylic acid form to an ester form under esterification conditions.

[0118] In some embodiments, the at least one ester comprises: dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl undecanedioate, dimethyl dodecanedioate, dimethyl oxalate, dimethyl brassylic acid, dimethyl tridecanedioate, dimethyl myristoleate, dimethyl pentadecanedioate, dimethyl 2-octene dioate, dimethyl 2-nonene dioate, 2-dimethyl 2-decene dioate, and dimethyl undecene-2-dioate.

[0119] 2-nitrooctanedioate, 2-nitrononanedioate, 2-nitrodecanedioate, 2-nitro- undecanedioate, 2-nitrododecanedioate, 2-nitrotetradecanedioate, 2-nitro- pentadecanedioate, 2-nitrohexadecanedioate, 2-nitroheptadecanedioate, 2- nitrooctadecanedioate, 2-nitrotetradecanedioate, 3-nitrooctanedioate, 3- nitrononanedioate, 3-nitrodecanedioate, 3-nitro-undecanedioate, 3-nitrodode- canedioate, 3-nitrotetradecanedioate, 3-nitro-pentadecanedioate, 3-nitrohexa- decanedioate, 3-nitroheptadecanedioate, 3-nitrooctadecanedioate, 3-nitro- tetradecanedioate, 4-nitrooctanedioate, 4-nitrononanedioate, 4-nitrodecanedi- oate, 4-nitro-undecanedioate, 4-nitrododecanedioate, 4-nitrotetradecanedio- ate, 4-nitro-pentadecanedioate, 4-nitrohexadecanedioate, 4-nitroheptadecan- dioate, 4-nitrooctadecanedioate, 5-nitrooctanedioate, 5-nitrononanedioate, 5- nitrodecanedioate, 5-nitro-undecanedioate, 5-nitrododecanedioate, 5-nitro- tetradecanedioate, 5-nitro-pentadecanedioate, 5-nitrohexadecanedioate, 5- nitroheptadecanedioate, 5-nitrooctadecanedioate, 5-nitrotetradecanedioate, and 5-nitro-pentadecanedioate, and combinations thereof.

[0120] In some embodiments, the at least one corresponding ester comprises: dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl undecanedioate, dimethyl dodecanedioate, and combinations thereof.

[0121] In some embodiments, the at least one ester comprises 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 undecanedioate, 0-10% dimethyl dodecanedioate, and combinations thereof.

[0122] In some embodiments, the at least one corresponding ester comprises 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 undecanedioate, 0-10% dimethyl dodecanedioate, and combinations thereof.

[0123] In some embodiments, the esterification mixture comprises a composition comprising at least one of: dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl undecanedioate, dimethyl dodecanedioate, and combinations thereof.

[0124] In some embodiments, the esterification mixture comprises a composition comprising at least one of: 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 undecanedioate, 0-10% dimethyl dodecanedioate, and combinations thereof.

[0125] In some embodiments, the esterification mixture comprises at least one of: dimethyl succinate in an amount of about 5 to about 18 weight percent, dimethyl glutarate in an amount of about 8 to about 28 weight percent, dimethyl adipate in an amount of about 10 to about 29 weight percent, dimethyl pimelate in an amount of about 10 to about 20 weight percent, and dimethyl azelate in an amount of about 8 to about 13 weight percent, and combinations thereof.

[0126] In some embodiments, the esterified mixture contains at least one of: dimethyl oxalate in an amount up to 10 wt%, dimethyl suberate in an amount of about 9 to about 20 wt%, dimethyl sebacate in an amount of about 1 to about 10 wt%, dimethyl undecanedioate in an amount of about 1 to about 8 wt%, dimethyl dodecanedioate in an amount up to about 5 wt%, dimethyl tridecanedioate in an amount up to about 4 wt%, dimethyl tetradecanedioate in an amount up to about 2 wt%, and dimethyl pentadecanedioate in an amount up to about 0.4 wt%, and combinations thereof.

[0127] In some embodiments, the esterified mixture contains at least one of: dimethyl oxalate in an amount up to 10 wt%, dimethyl suberate in an amount of about 9 to about 20 wt%, dimethyl sebacate in an amount of about 1 to about 10 wt%, dimethyl undecanedioate in an amount of about 1 to about 8 wt%, dimethyl dodecanedioate in an amount up to about 5 wt%, dimethyl tridecanedioate in an amount up to about 4 wt%, dimethyl tetradecanedioate in an amount up to about 2 wt%, and dimethyl pentadecanedioate in an amount up to about 0.4 wt%, and combinations thereof.

[0128] In some embodiments, the esterified mixture contains at least one of: dimethyl oxalate in an amount up to 10 wt%, dimethyl suberate in an amount of about 9 to about 20 wt%, dimethyl sebacate in an amount of about 1 to about 10 wt%, dimethyl undecanedioate in an amount of about 1 to about 8 wt%, dimethyl dodecanedioate in an amount up to about 5 wt%, dimethyl tridecanedioate in an amount up to about 4 wt%, dimethyl tetradecanedioate in an amount up to about 2 wt%, and dimethyl pentadecanedioate in an amount up to about 0.4 wt%, and combinations thereof.

[0129] In some embodiments, the ester is:

[0130] 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

[0131] b. at least one C8-C14 dicarboxylic acid substituted with a single nitro group; 20 dicarboxylic acid;

[0132] and at least one polyol.

[0133] In some embodiments, the method further comprises isolating at least one corresponding ester. In some embodiments, isolation is by distillation. In some embodiments, distillation is at least one selected from simple distillation, fractional distillation, vacuum distillation, azeotropic distillation, co-distillation, and combinations thereof.

[0134] In some embodiments, the method further comprises converting at least one compound containing at least one carboxyl group from an ester form to an acid form (e.g., converting the ester form back to the acid form). In some embodiments, the conversion of the ester form to the acid form is conducted under ester hydrolysis conditions.

[0135] Nitro-functionalized polyester diol (N02-PED) compositions

[0136] The present invention also provides a nitro-functionalized polyester diol (N02-PED) by reacting a dicarboxylic acid and a nitro dicarboxylic acid or ester thereof with a diol.

[0137] The polyester diol has the following formula:

[0138]

[0139] wherein n is 0-14, y is 1-100, X is H or N02, and R is an alkylene group, an alkylene group in which one or more CH2groups are replaced by -0-, a cycloalkylene group, or an arylene group, wherein at least one X is N02.

[0140] In some embodiments, R is an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, or an octylene group. In some embodiments, R is an alkylene group in which one or more CH2groups are replaced by -0-. In some embodiments, R is -(CH2)0-4-, o -O-(CH2) o -CH3-O-(CH2) o -O-(CH2) o -CH3, (CH3CH(OH)CH2)20, wherein o is 2 to 4. In some embodiments, the polyester diol has a molecular weight of 300 g / mol to 10,000 g / mol prior to reaction with isocyanate.

[0141] 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, trimethylol ethane, trimethylol propane, neopentyl glycol, pentaerythritol, dipentaerythritol, sorbitol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 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), hydroxypivalyl 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 a C1-8 Diols, for example, or C 1-4 Diols, such as diethylene glycol, 1,2-propanediol and 1,3-propanediol.

[0142] NO2-PED is prepared by reacting a dicarboxylic acid with a nitrocarboxylic acid or its ester under suitable reaction conditions. In some embodiments, NO2-PED is synthesized according to the following general steps, as shown in Scheme 1: a mixture of dicarboxylic acids is mixed with a diol (e.g., 1,6-hexanediol) and a catalytic amount of concentrated sulfuric acid or other suitable catalyst; the catalyst loading can vary between 0.2 mol% and 4 mol%. The mixture is heated in a preheated oil bath at 100-110°C under atmospheric pressure with stirring for 2-4 hours, followed by a 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 according to a slightly modified ASTM D-4274-99 using Test Method A, and the results are used to calculate the approximate molecular weight of the polyester diol. Polyester glycols stored outside the desiccator for extended periods are dried before use by incubating overnight in a vacuum oven at 80°C, or by bubbling a dry inert gas (e.g., argon) through the polyol at ≥100°C while applying a vacuum for 1 hour, and then stored in an ambient pressure desiccator. The reaction is typically carried out at atmospheric pressure, but other pressures can also be used.

[0143]

[0144] Option 1

[0145] In scheme 1, n is 0-20 and y is 1-100. In some implementations, y is 1-30.

[0146] In another embodiment, NO2-PED is prepared by reacting dicarboxylic acids and nitrodicarboxylic acids with polyols in the presence of a suitable catalyst such as sulfuric acid or other inorganic acid, according to Scheme 2.

[0147]

[0148] Option 2

[0149] In scheme 2, n is 0-20 and y is 1-100. In some implementations, y is 1-30.

[0150] The catalyst can be hydrochloric acid, sulfuric acid, or other inorganic acid. In the alternative, the catalyst can be dibutyltin dilaurate (IV) in an organic solvent such as heptane. The mixture can be heated at atmospheric pressure for 1-20 hours while stirring at 100-130 °C, and the alcohol byproduct (e.g., methanol) and organic solvent (if used) (e.g., heptane) are evaporated and removed from the reactor. In some embodiments, reduced pressure (< 19 mbar) is then applied for 1-20 hours. Removal of the alcohol byproduct and organic solvent can also be removed by bubbling an inert gas through the mixture while applying a 1 hour vacuum.

[0151] The number average molecular weight of the NO2-PED is 300 to 10,000 g / mol. In some embodiments, the number average molecular weight is about 500 to about 4,000 g / mol.

[0152] Thermoplastic polyurethane (TPU)

[0153] The TPU can be prepared by a one-step or two-step process. In the one-step process, the NO2-PED and chain extender are blended in a reaction vessel. The polyisocyanate is slowly added to the vessel while stirring vigorously. The reaction is carried out at a temperature of 60-120 °C for 2.5 hours. The resulting TPU is then cast into a preheated silicone mold and cured at a temperature of 80 to 120 °C, for example, 20 to 48 hours. The two-step process involves reacting the NO2-PED with a polyisocyanate to provide a TPU prepolymer, followed by chain extension to give the final TPU elastomer. The NO2-PED is reacted with the polyisocyanate at a temperature of up to 80 °C. The catalyst and chain extender are then added while stirring rapidly and allowed to react at a temperature of up to 120 °C. The catalyst can be any tin laurate or amine catalyst such as DABCO or triethylamine at a weight % of 0.05 to 1.0 compared to the NO2-PED. The NO2-PED can be 20-80 weight % of the chain-extended TPU. The polyisocyanate can be 20-80 weight % of the chain-extended TPU. The chain extender can be 1-20 weight % of the chain-extended TPU.

[0154] The chain-extended TPU is then poured into a mold and cured at a temperature of 80 to 120 °C, for example, 20 to 48 hours.

[0155] 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'- dimethylphenyl diisocyanate, 4,4'-biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis(2-isocyanatoethyl)fumarate, 6-isopropyl-l,3-phenyl diisocyanate, 4- diphenylpropane diisocyanate, lysine diisocyanate, and mixtures thereof. In one embodiment, the polyisocyanate comprises an aromatic ring.

[0156] In some embodiments, the polyisocyanate is 4,4'-diisocyanatodiphenylmethane (4,4'-MDI), 2,4'-diisocyanatodiphenylmethane (2,4'-MDI), p-phenylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-diisocyanatocyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, and mixtures thereof.

[0157] In some embodiments, the ratio of polyisocyanate to active hydrogen containing groups (NCO index) is 0.9-1.5. As known in the art, the NCO index is defined as the number of equivalents of isocyanate divided by the total number of equivalents of active hydrogens multiplied by 100. The NCO index is expressed by the following formula:

[0158]

[0159] The TPU prepolymer is then reacted with a chain extender. Examples of chain extenders include diols, 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, trimethylol ethane, trimethylol propane, neopentyl glycol, pentaerythritol, dipentaerythritol, sorbitol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 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), hydroxypivalyl 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 a C 1-8 polyol, for example, a C 1-8 diol, or a C 1-4 diol, for example, diethylene glycol, 1,2-propanediol, and 1,3-propanediol.

[0160] In some embodiments, the chain extender is a dihydroxyalkane or a dihydroxycycloalkane. In another embodiment, 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. In some embodiments, the chain extender is an alkylene or arylene diamine. In some embodiments, the chain extender is ethylenediamine, hexamethylenediamine, 1,4-cyclohexanediamine, 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 a hydrazine. In some embodiments, the chain extender is an amino alcohol. In some embodiments, the chain extender is ethanolamine, N-methylethanolamine, N-butylethanolamine, N-oleylethanolamine, 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'-methylenebis(o-chloroaniline), 4,4'-methylenebis(3-chloro-2-6-diethylaniline), or a mixture thereof.

[0161]

[0162] Scheme 3

[0163] Optional Additives

[0164] The TPU compositions of the present application have a number of optional additives. Optional additives include: other crosslinking agents, oligomers, light stabilizers, UV stabilizers, inorganic fillers and organic fillers, flame retardants, dispersants, blowing agents, reactive diluents, free radical photoinitiators, cationic photoinitiators, and other additives.

[0165] In some embodiments, the crosslinking agent is glycerol, trimethylolpropane, diethanolamine, triethanolamine, or mixtures thereof.

[0166] In some embodiments, the other oligomers include, for example, polyethers, polyesters, polycarbonates, polyacrylates, and copolymers thereof. The other oligomers can contain one or more (e.g., two or more) hydroxyl groups, contain one or more (e.g., two or more) ethylenically unsaturated groups, and / or contain one or more (e.g., two or more) epoxy groups. In one embodiment, the present composition contains 0 to 60 wt.%, e.g., 5 to 40 wt.%, of the other oligomers, relative to the total weight of the composition.

[0167] In some embodiments, the light stabilizers 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(a,a-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2'-methylenebis(4-cumyl-6- benzotriazylphenyl), 2,2'-p-phenylenbis(l,3-benzoxazin-4-ketone), and mixtures thereof.

[0168] In some embodiments, the inorganic fillers include silicate minerals, metal oxides, metal salts, clays, metal silicates, glass fibers, natural fibrous materials, synthetic fibrous minerals, or mixtures thereof.

[0169] In some embodiments, the organic fillers include carbon black, fullerenes, carbon nanotubes, biochar, melamine resins, cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and / or aliphatic dicarboxylic esters, carbon fibers, or mixtures thereof.

[0170] In some embodiments, the fillers comprise 0.5 to 30 wt.% of the composition.

[0171] In some embodiments, the flame retardants are organophosphates, metal polyphosphates, metal oxides, metal salts, cyanuric acid derivatives, or mixtures thereof.

[0172] In some embodiments, the flame retardant comprises 10 to 35 weight percent of the composition.

[0173] In some embodiments, the dispersant comprises styrene, acrylate, di- and tri-acrylate / methacrylate, ester acrylate / methacrylate, urethane or urea acrylate / methacrylate, or mixtures thereof.

[0174] In some embodiments, the blowing agent is at least one of water, pentane, cyclopentane, hydrofluorocarbon, or mixtures thereof.

[0175] Examples of the reactive diluent include monofunctional monomers and polyfunctional monomers. Examples of the monofunctional monomers include monomers having a vinyl group, such as N-vinylpyrrolidone, N-vinylcaprolactam, vinyl imidazole, vinyl pyridine; isobornyl (meth)acrylate, bornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloyl morpholine, 2-hydroxyethyl (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, hexylactone (meth)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, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiglycol (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, isobutoxy methyl (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; and a compound represented by the following formula (2): CH2C(R 6 )-COO(R 7 O) m -R 8 (2), wherein R 6 is a hydrogen atom or a methyl group; and R 7alkylene group containing 2 to 8, preferably 2 to 5 carbon atoms; and m is an integer from 0 to 12, preferably 1 to 8; R 8 is a hydrogen atom or an alkyl group containing 1 to 12, preferably 1 to 9 carbon atoms; or R 8 is a tetrahydrofuran group containing an alkyl group having 4-20 carbon atoms, optionally substituted with an alkyl group having 1-2 carbon atoms; or R 8 is a dioxane group containing an alkyl group having 4-20 carbon atoms, optionally substituted with a methyl group; or R 8 is an aromatic group, optionally substituted with C1-C 12 alkyl (preferably C8-C9 alkyl) groups; and alkoxylated fatty monofunctional monomers, such as, for example, ethoxylated isodecyl (meth)acrylate, ethoxylated lauryl (meth)acrylate, and the like.

[0176] Examples of multifunctional monomers include monomers containing two or more (meth)acrylate groups, such as, for example, 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 trioxaethyl (meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate, tricyclodecane diyl dimethyl di(meth)acrylate, di(meth)acrylates of diols which are ethylene or propylene oxide adducts of bisphenol A, di(meth)acrylates of diols which are ethylene or propylene oxide adducts of hydrogenated bisphenol A, (meth)acrylate ester of a diglycidyl ether which is a (meth)acrylate adduct of bisphenol A, diacrylate of a polyoxyalkylated bisphenol A, and triethylene glycol divinyl ether, adduct of isophorone diisocyanate and hydroxyethyl acrylate (HIH), adduct of toluene diisocyanate and hydroxyethyl acrylate (HTH), and amido ester acrylate.

[0177] In one embodiment, the composition comprises at least 10 wt% of one or more reactive diluents, for example at least 20 wt% or at least 30 wt%, relative to the total weight of the composition. The composition typically comprises less than 90 wt% of one or more reactive diluents, for example, less than 75 wt% or less than 50 wt%.

[0178] Examples of free radical photoinitiators include: benzophenones (e.g., benzophenone, alkyl-substituted benzophenones, or alkoxy-substituted benzophenones); benzoin and benzoin ethers, such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, benzoin phenyl ether, and benzoin acetate; acetophenones, such as acetophenone, 2,2-dimethoxyacetophenone, 4-(phenylthio)acetophenone, and 1,1-dichloroacetophenone; benzil and benzil ketals, such as benzil dimethyl ketal and benzil diethyl ketal; anthraquinones, such as 2-methylanthraquinone, 2-ethylanthraquinone, and 2-tert-butylanthraquinone, 1-chloroanthraquinone, and 2-amylanthraquinone; triphenylphosphine; benzoylphosphine oxides, such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; thioxanthone and xanthone, acridine derivatives, phenazene derivatives, quinoxaline derivatives, or 1-phenyl-1,2-propanedione-2-O-benzoyl oxime, 1-aminophenyl ketone or 1-hydroxyphenyl ketone, such as 1-hydroxycyclohexyl phenyl ketone, phenyl(1-hydroxyisopropyl)ketone, and 4-isopropylphenyl(1-hydroxyisopropyl)ketone, or triazine compounds, such as 4'-methylthiophene-1-di(trichloromethyl)-3,5-S-triazine, S-triazine-2-(diphenylstilbene)-4,6-bis(trichloromethyl), and p-methoxystyryltriazine. Free radical photoinitiators are particularly useful if the composition comprises an ethylenically unsaturated component, such as an acrylate or methacrylate. In one embodiment, the composition comprises from 0 to 10 wt% of one or more free radical photoinitiators, such as from 0.5 to 7.5 wt%, relative to the total weight of the composition.

[0179] Examples of cationic photoinitiators include, for example, onium salts with weakly nucleophilic anions. Examples include halonium salts, iodosyl salts, or sulfonium salts, such as those described in published European Patent Applications EP 153904 and WO 98 / 28663; sulfonium oxide salts, such as those described in published European Patent Applications EP 35969, 44274, 54509, and 164314; or diazonium salts, such as those described in U.S. Patents 3708296 and 5002856.

[0180] Other examples of additives include antioxidants, dyes, wetting agents, antifoams, thickeners, photosensitizers, solvents (preferably, in an amount less than 20 wt%, such as less than 10 wt%, less than 5 wt%, or about 0 wt%), and metallic, organic, inorganic, or organic / inorganic hybrid fillers (e.g., silica particles, glass beads, or talc). The size of the fillers can vary, and can be, for example, in the nanometer range or in the micrometer range. In one embodiment, the present composition comprises less than 20 wt% of fillers, such as less than 10 wt%, less than 5 wt%, or about 0 wt%, relative to the total weight of the composition.

[0181] Other additives include colorants, such as titanium dioxide and carbon black.

[0182] Method of manufacture

[0183] In some embodiments, the TPU is prepared by a method comprising reacting under the following conditions:

[0184] (a) a polyester containing at least one nitro-substituted polyester diol, and

[0185] (b) at least one polyisocyanate, and condensing with,

[0186] (c) at least one chain extender.

[0187] In some embodiments, the reaction conditions include a temperature of 25 °C to 120 °C.

[0188] In some embodiments, the polyester containing at least one nitro-substituted polyester diol further comprises at least one polyester diol that does not contain a nitro group.

[0189] In some embodiments, the TPU foam is prepared by a method comprising reacting under the following reaction conditions:

[0190] (a) a polyester containing at least one nitro-substituted polyester diol,

[0191] (b) at least one polyisocyanate,

[0192] (c) at least one chain extender,

[0193] (d) at least one flame retardant,

[0194] (e) at least one surfactant,

[0195] (f) at least one blowing agent, and

[0196] (g) at least one urethane catalyst.

[0197] Applications

[0198] The TPU can be used in a wide variety of applications. In some embodiments, the compositions can be used to make molded articles, such as shoe soles for footwear, hard solid plastics (such as electronic instrument bezels and structural parts), flexible plastics (such as straps and belts), and for seals, gaskets, durable elastomeric wheels and tires, automotive suspension bushings, and electrical insulation parts. In some embodiments, the compositions can be used for 3D printing when the compositions are extruded into filaments. In some embodiments, the compositions can be pelletized and expanded to produce expanded TPU foams for footwear applications.

[0199] It is to be understood that this application is not limited to the particular methodology, protocols, reagents, etc. described herein as such can vary. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present application which is limited only by the claims. Examples

[0200] The present application is further illustrated by the following examples which are intended to be merely exemplary of the present application and are not to be interpreted in any manner as limiting the application. The following examples are provided for illustrative purposes only and are not intended to limit any aspect of this application in any way. The following examples are provided to better illustrate the claimed application and are not to be interpreted as limiting the scope of the application. To the extent that specific materials are mentioned, it is merely for purposes of illustration and is not intended to limit the scope of the application. One skilled in the art can develop equivalent means or reagents without departing from the scope of the application and without the use of inventive faculty.

[0201] General Materials and Methods

[0202] Dicarboxylic acids (DCAs) used in the synthesis of polyester diols were obtained from accelerated thermal oxidative decomposition (ATOD) of polyethylene plastics and consisted of a mixture of linear aliphatic DCAs with carbon numbers ranging from 4 to 24 carbons. The mixture also contained DCAs bearing one or more nitro functional groups along the aliphatic linkage. The average DCA molecular weight for chemical synthesis purposes was determined by titration with aqueous sodium hydroxide using phenothalin as an indicator (acid value determination). Unless otherwise stated, other reagents and equipment were obtained from commercial sources and used as received. The materials used in the examples were as follows:

[0203] The following methods and standards were used for the evaluation and determination of various TPU parameters.

[0204] Glass transition temperature:

[0205] Glass transition temperature (T g ) was determined by differential scanning calorimetry (DSC).

[0206] Shore A hardness:

[0207] Shore A hardness was measured according to DIN 53 350 5, wherein the hardness decreases 3 seconds after the foot comes into contact with the test specimen. The hardness is indicated hereinafter as Shore A hardness.

[0208] Tensile strength:

[0209] Tensile strength was measured by an Instron universal tester using ASTM type 4 test bars.

[0210] Elongation:

[0211] Elongation was measured by an Instron universal tester using ASTM type 4 test bars.

[0212] The materials used in the examples are as follows:

[0213] PED = polyester diol (synthetic mixture of dicarboxylic acid and 1,6-hexanediol)

[0214] NO2-PED = nitro-functionalized polyester diol (synthesized from ATOD DCA)

[0215] Emerox 14801 = bio-based polyester diol (commercially available)

[0216] MDI = 4,4'-diphenylmethane diisocyanate (commercially available)

[0217] HDI = hexamethylene diisocyanate (commercially available)

[0218] HD = 1,6-hexanediol (commercially available)

[0219] MPD = 2-methylpropanediol (commercially available)

[0220] 1,4-BD = 1,4-butanediol (commercially available)

[0221] DTBL = dibutyltin dilaurate (commercially available)

[0222] Irganox 1076 = phenolic antioxidant (commercially available)

[0223] Irgafos 168 = phosphite antioxidant (commercially available)

[0224] Tinuvin 234 = benzotriazole UV absorber (commercially available)

[0225] Nitro polyester diol synthesis

[0226] Nitro-substituted polyester diols were synthesized according to the following general procedure, as shown in Scheme 1 : a mixture of dicarboxylic acids was mixed with a diol (e.g., 1,6-hexanediol) and a catalytic amount of concentrated sulfuric acid or other suitable catalyst; the catalyst loading varied between 0.2 mole percent (mol%) and 4 mol%. The mixture was heated in an air open and stirred for 2-4 hours in a preheated oil bath at 100-110 °C, followed by applying 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 number and hydroxyl number). Titration was performed according to ASTM D-4274-99 using test method A with slight modifications, and the results were used to calculate the approximate polyester diol molecular weight. Polyester diols that had been stored outside of a desiccator for long periods of time were dried prior to use by incubation in a vacuum oven at 80 °C overnight, or by bubbling dry inert gas (e.g., argon) through the polyol at > 100 °C while applying vacuum for 1 hour, and then stored in an ambient pressure desiccator. Specific non-limiting examples of synthetic polyester diols containing recycle components are listed in Examples 1-4.

[0227] Example 1

[0228] A mixture of dicarboxylic acids (DCAs) obtained from polyethylene scrap ATOD having an average molecular weight of 178.14 g / mol (23.517 g, 0.5869 mole equivalents) and 1,6-hexanediol (26.581 g, 1 mole equivalent) and sulfuric acid catalyst (0.131 g, 1 mole % relative to the DCA mixture) were mixed at room temperature in a round bottom flask containing a Teflon-coated magnetic stir bar. The mixture was heated to 105 °C with air open and stirring for 4 hours, at which time the reaction melt was continued to heat and stir under applied vacuum (< 19 mbar) for 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), hydrogen nuclear magnetic resonance (HNMR), gel permeation chromatography (GPC), and end group titration (total acid number and hydroxyl number determined by acetylation method (test method A according to ASTM D-4274-99)). The acid number was measured to be 4.6 ± 0.3 mg KOH / g sample, and the hydroxyl number was 183 ± 9 mg KOH / g sample, as determined by titration, and the number average molecular weight was determined to be 614 ± 30 g / mol. 1 HNMR, gel permeation chromatography (GPC), and end group titration (total acid number and hydroxyl number determined by acetylation method (test method A according to ASTM D-4274-99)). The acid number was measured to be 4.6 ± 0.3 mg KOH / g sample, and the hydroxyl number was 183 ± 9 mg KOH / g sample, as determined by titration, and the number average molecular weight was determined to be 614 ± 30 g / mol.

[0229] Example 2

[0230] An ATOD DCA mixture (42.803 g, 0.901 mole equivalents) was mixed with 1,6- hexanediol (31.513 g, 1 mole equivalent) and concentrated sulfuric acid (98%, 0.229 g, 1 mole % relative to DCA mixture) in a round bottom flask with a Teflon coated magnetic stir bar. The mixture was heated at 105 °C for 4 hours with open air to obtain a homogenous melt, then vacuum was applied (< 19 mbar) and heating was continued for another 2 hours. The product was cooled under vacuum and stored in a desiccator at ambient pressure. The nitro group containing polyester diol product PE-2 was characterized by ATR FTIR, GPC and end group titration as in Example 1. The acid value was 6.3 ± 0.6 mg KOH / g, the hydroxyl value was 37.4 ± 8.1 mg KOH / g, determined by titration, and the number average molecular weight was 2615 g / mol.

[0231] Other non-limiting examples of nitro-substituted polyester diols (NO2-PE) prepared by the above method are shown in Table 1.

[0232]

[0233]

[0234] * relative to DCA

[0235] Table 1

[0236] The nitro-substituted polyester diols can optionally be synthesized from the corresponding dimethyl esters of DCA obtained from polyethylene plastic waste ATOD as shown in Scheme 2 and described in Examples 3 and 4.

[0237] Example 3 (Reference: RP1-139A)

[0238] The average molecular weight of the starting diester mixture was estimated to be 177 g / mol. 100 parts by mass of the diester mixture and 107 parts by mass of 1,6-hexanediol were added to a reactor and heated to 120 °C. To this mixture, 6 parts of a 10 wt% solution of dibutyltin dilaurate (IV) in heptane was added. The solution was stirred and allowed to react at 120 °C for 17 hours, allowing heptane and released methanol to evaporate away from the reactor. The reaction was then allowed to cool, resulting in 146 parts by weight of isolated product as a clear yellow liquid. GPC analysis with THF and polystyrene standards indicated Mn 600, PDI 3.49.

[0239] Example 4 (Reference: RP1-139D)

[0240] The average molecular weight of the starting diester mixture was estimated to be 177 g / mol. To a reactor was added 100 parts by mass of the diester mixture and 72 parts by mass of 1,6-hexanediol and heated to 120 °C. To this mixture was added 5.5 parts of a 10 wt% solution of dibutyltin dilaurate (IV) in heptane. The solution was stirred and allowed to react at 120 °C for 17 hours, allowing heptane and released methanol to evaporate away from the reactor. The reaction was then allowed to cool, resulting in 119 parts by weight of isolated product as a clear yellow liquid. GPC analysis with THF and polystyrene standards indicated Mn 3200, PDI 2.13.

[0241] Example 5 (Reference: KK1-153B)

[0242] Parts and percentages mentioned in the examples are by weight (pbw) or in high percentages. All samples were prepared in the same manner. The diisocyanate 4,4’-MDI was dried and directly fed to the reaction vessel in excess. The PED (composition as shown in Table 2) was added to the excess diisocyanate and allowed to react fully at temperatures up to 60 °C, resulting in a TPU prepolymer. While stirring rapidly, the DTBL catalyst and 2-methylpropanediol (MPD) chain extender were added to the prepolymer and allowed to react fully at temperatures up to 100 °C. The chain-extended TPU was poured into a mold heated to a temperature up to 125 °C. The mold was placed in an oven at 100 °C for 24 hours, or until the TPU was fully cured. The cast elastomer was compression molded into test specimens. The post-cured TPU was characterized using FTIR, DSC, TGA, Instron mechanical testing, and Shore A hardness.

[0243]

[0244]

[0245] * relative to DCA

[0246] Table 2

[0247] Properties Example 5 Comparative Sample A NO2-PED (wt. %) 64.0 -- PED (% by weight) -- 64.0 MDI (% by weight) 31.0 31.0 MPD (% by weight) 5.0 5.0 % Recovery Ingredient (nitro component) 36.3 -- [C=O H键 / C=O 游离 (FTIR) 0.92 0.92 T g (°C) 0.02 -9.29 T d (°C) 364 389 Shore A hardness 70.0 60 Tensile strength (MPa) 9.6 1.6 Elongation (%) 367.0 730.0

[0248] Table 3

[0249] TPU elastomer Example 5 and Comparative Sample A were prepared from the formulations shown in Table 2. The results in Table 3 show that the presence of nitro groups on the PED backbone resulted in a TPU with a higher glass transition temperature, higher Shore A hardness, higher tensile strength, and lower elongation compared to Sample A.

[0250] Example 6 (Reference: KK2-53)

[0251] Example 6 and Comparative Sample B were prepared using the PEDs shown in Table 4. For Example 6, a number average molar mass of 1.0 x 10 3 g / mol of NO2-PED and 1,4-BD derived from an ester exchange NO2-diester mixture was dried and charged into the reaction vessel. While stirring vigorously, HDI was added slowly. The reaction was carried out at 80 °C for 2.5 hours. The reaction mixture was poured into a preheated silicone mold and cured at 100 °C for 24 hours. The cast elastomer was subsequently compression molded into test specimens. 3 Comparative Sample B was prepared following the same procedure using Emerox 14801, a nitro-free polyester diol with a number average molar mass of 1.1 x 10

[0252] Example 7 (Reference: KK2-082)

[0253] A number average molar mass of 1.8 x 10 3 g / mol of NO2-PED and 1,4-BD derived from an ester exchange NO2-diester mixture was dried and charged into the reaction vessel. While stirring vigorously, HDI was added slowly. The reaction was carried out at 80 °C for 2.5 hours. The reaction mixture was poured into a preheated silicone mold and cured at 100 °C for 24 hours. The cast elastomer was subsequently compression molded into test specimens.

[0254]

[0255] *diester form

[0256] Table 4

[0257] Properties Example 6 Example 7 Sample B NO2-PED (wt. %) 73.1 71.8 -- PED (% by weight) -- -- 75.3 HDI (% by weight) 21.0 22.1 20.1 1,4-BD (% by weight) 5.8 6.1 4.6 % Recovery Ingredient 34.5 33.0 -- T g (°C) -39.0 -42 -38.0 Shore A hardness 85 80 70 Tensile strength (MPa) 12.6 20.7 3.3 Elongation (%) 404.0 541.6 202.0

[0258] Table 5

[0259] Example 8 (Reference: KK2-017)

[0260] HDI was dried and fed to the reaction vessel in excess. A number average molar mass of 1.3 x 10 3NO2-PED having a number average molecular weight of 500 g / mol was blended with 2.0 wt% carbon black alone. The configured NO2-PED was then added to an excess of diisocyanate and allowed to react fully at temperatures up to 60 °C to yield a TPU prepolymer. The DTBL catalyst and MPD were added to the prepolymer while under rapid stirring and allowed to react fully at temperatures up to 100 °C. The chain extended TPU was poured into a preheated silicone mold. The mold was placed in a 100 °C oven for 24 hours or until the TPU was fully cured. The cast elastomer was compression molded into test specimens.

[0261] Example 9 (Reference: KK2-29)

[0262] 4,4’-MDI was dried and fed into the reaction vessel in excess. The number average molecular weight of the NO2-PED was 1.3 x 10 3 NO2-PED having a number average molecular weight of 500 g / mol was blended with 0.5 wt% Tinuvin 234, 0.17 wt% Irgafos 168, and 0.33 wt% Irganox 1076 alone. The configured NO2-PED was then added to an excess of diisocyanate and allowed to react fully at temperatures up to 60 °C to yield a TPU prepolymer. The DTBL catalyst and 1,4-BD were added to the prepolymer while under rapid stirring and allowed to react fully at temperatures up to 100 °C. The chain extended TPU was poured into a preheated silicone mold. The mold was placed in a 100 °C oven for 24 hours or until the TPU was fully cured. The cast elastomer was compression molded into test specimens.

[0263] Example 10 (Reference: KK1-97)

[0264] NO2-PED having a number average molecular weight of 500 g / mol was blended with 3.0 wt% distilled water, 2 wt% silicone oil, and 1.0 wt% DTBL catalyst in a flat bottomed polyethylene beaker and mixed. MDI was added directly to the formulated polyol and mixed vigorously for 15 seconds. The resulting foam was allowed to stabilize at room temperature for 24 hours prior to characterization.

[0265] Properties Example 8 Example 9 Example 10 NO2-PED (wt. %) 74.9 67.1 70.0 MDI (% by weight) -- 27.8 30.0 HDI (% by weight) 19.3 -- -- 1,4-BD (% by weight) -- 5.1 -- MPD (% by weight) 5.7 -- -- % Recovery Ingredient 34.8 34.5 37.1 T g (°C) -46.4 -12.5 -0.50 Shore A hardness 85 60 --*

[0266] *Foam

[0267] Table 6

[0268] The various methods and techniques described above provide many ways to carry out applications. Of course, it should be understood that every embodiment need not achieve all of the objects or advantages set forth, nor do they necessarily achieve all of the benefits provided by one or more of the embodiments described herein. Thus, for instance, one could implement the methods in ways other than those specifically set forth herein without necessarily deviating from the spirit of the teachings presented herein. Various alternatives to the embodiments described herein are encompassed by the claims and the full scope of equivalents thereof. Various alternatives to the embodiments described herein are encompassed by the claims and the full scope of equivalents thereof. For instance, elements from one alternative are combinable with elements from a different alternative. It is therefore anticipated that each of the claims is embraced by the others as if every combination of one or more elements from each alternative were specifically claimed. It will be apparent to one of ordinary skill in the art that aspects of the application, as described herein, can be implemented in various forms of hardware, software, or combinations thereof; specifically claimed; and that the preferred claims have as their pendency the full scope of equivalents thereof. All such possibilities will be evident to one of ordinary skill in the art having the benefit of this disclosure. Many of the above-described steps can be performed by machine code, firmware, software, or combinations thereof. The terms "machine code" and "software" are used interchangeably herein. The machine code or software can be stored on a machine-readable medium and loaded into a machine's memory for execution by the machine. The machine-readable medium, which can also be a machine-readable storage medium, is a medium that provides (i.e., stores) data which can be read by a machine. The machine-readable medium, which can also be a machine-readable storage medium, is a medium that provides (i.e., stores) data which can be read by a machine. The machine-readable medium can include, without limitation, floppy diskettes, DVDs, CD-ROMs, DVDs, Blu-ray discs, ROMs, RAMs, EPROMs, EEPROMs, flash memory devices, magnetic tapes, hard disk drives, or any other medium that can be used to provide (i.e., store and / or transfer) data in a form that can be read by a machine.

[0269] Further, those skilled in the art will recognize the applicability of various features from different embodiments. Similarly, the various elements, features and steps described above can be employed in various combinations within the scope of the disclosure, either literally or equivalently in terms of their performance. In various elements, features and steps, some will be specifically included while others will be specifically excluded, in different embodiments.

[0270] While the present application has been disclosed by context of certain embodiments and examples, those skilled in the art will appreciate that the embodiments of the application extend beyond the specifically disclosed embodiments and to other alternative embodiments and / or uses of the application and modifications and equivalents thereof.

[0271] Various embodiments of the application are described herein, including the best mode known to the inventors. Variations of those embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the application to be practiced with variations of those described herein using the appropriate apparatus and methods. Accordingly, the actual scope of the application is not limited to the specific embodiments described herein, but is only limited by the claims that follow, that full scope being understood to include all variations equivalent to those recited.

[0272] All patents, patent applications, publications, and other documents (such as articles, books, treatises, reports, publications, documents, things, etc.) cited, referenced or otherwise referred to in this document are incorporated by reference in their entirety for all purposes and to the same extent as if each were incorporated by reference individually. For any document consisting of more than one part, the entirety of all the parts is incorporated by reference. For any document incorporated by reference, the version of the document incorporated by reference is the version of the document that was available on or before the priority date of the present document. If the document incorporated by reference changes after the priority date of the present document, then the version of the document incorporated by reference is the version that was available on or before the priority date of the present document. For any document incorporated by reference, the reference in this document to the document's disclosure or teaching is not to be construed as an admission that the document is prior art with respect to the present document, that the document is commonly owned, or that the document is otherwise common source.

[0273] It is to be understood that the embodiments disclosed herein are merely meant to illustrate the principles of the embodiments of the application. Other modifications can be employed which fall within the scope of the application. Accordingly, the embodiments of the application can be employed with alternative configurations according to the teachings herein, without departing from the scope of the embodiments of the application. Therefore, the embodiments of the application are not limited to be exact as shown and described.

[0274] Various embodiments of the application are described in the detailed description above. While these descriptions directly describe the above embodiments, it is understood that those skilled in the art can conceive modifications and / or variations to the specific embodiments shown and described herein. Any such modifications or variations falling within the scope of the specification are to be included therein. Unless specifically indicated, it is the applicant's intention that the words and phrases in the specification and claims be given their ordinary and accustomed meaning to those of ordinary skill in the applicable arts.

[0275] The foregoing description of various embodiments of the application known to the Applicant at the time of filing has been presented for purposes of illustration and description. The specification is not intended to be exhaustive or to be limited to the precise form disclosed, and many modifications and variations are possible in light of the above teachings. The described embodiments are intended to explain the principles of the application and its practical application and to enable others skilled in the art to utilize the application in various embodiments and with various modifications as are suited to the particular use contemplated. Accordingly, it is intended to be covered within the scope of the application the specific embodiments disclosed.

[0276] While particular embodiments of the application have been shown and described, it will be obvious to those skilled in the art that, based upon the teachings herein, changes and modifications can be made without departing from this application and its broader aspects. The appended claims are to encompass within their scope all such changes and modifications as fall within the true spirit and scope of the application.

Claims

1. A thermoplastic polyurethane elastomer composition comprising the reaction product of: (a) a composition comprising: (i) at least one nitro-substituted polyester diol represented by the following general formula, wherein, the polyester diol is substituted with a nitro group between two carboxyl groups, and (ii) at least one polyester diol that is not substituted with a nitro group, wherein n is 0-14, y is 1-100, X = H or NO2, and R is an alkylene group, an alkylene group in which one or more CH2 groups are substituted with -O-, a cycloalkylene group, or an arylene group, wherein at least one X is NO2, (b) at least one polyisocyanate, and (c) at least one chain extender.

2. The thermoplastic polyurethane elastomer composition of claim 1, wherein, R is an alkylene group.

3. The thermoplastic polyurethane elastomer composition of claim 1, wherein, R is an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, or an octylene group.

4. The thermoplastic polyurethane elastomer composition of claim 1, wherein, R is an alkylene group in which one or more CH2 groups are substituted with -O-.

5. The thermoplastic polyurethane elastomer composition of claim 1, wherein, R is -(CH2) o -O-(CH2) o - wherein o is 2 to 4.

6. The thermoplastic polyurethane elastomer composition of claim 1, wherein, R is an arylene group.

7. The thermoplastic polyurethane elastomer composition of claim 1, wherein, The molecular weight of the polyester diol substituted with a nitro group prior to reaction is 400 to 10,000 g / mol.

8. The thermoplastic polyurethane elastomer composition of claim 1, wherein, The chain extender is a dihydroxyalkane or a dihydroxycycloalkane.

9. The thermoplastic polyurethane elastomer composition of 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-cyclohexane dimethanol, 1,4-dihydroxycyclohexane, or a mixture thereof.

10. The thermoplastic polyurethane elastomer composition of claim 1, wherein, The chain extender is an alkylene or aralkylene diamine.

11. The thermoplastic polyurethane elastomer composition of claim 10, wherein, The chain extender is ethylene diamine, hexamethylene diamine, 1,4-cyclohexane diamine, or a mixture thereof.

12. The thermoplastic polyurethane elastomer composition of claim 1, wherein, The chain extender is an aromatic diamine.

13. The thermoplastic polyurethane elastomer composition of claim 12, wherein, The aromatic diamine is benzidine, dihydroxymethoxyhydroquinone, toluene diamine, diaminodiphenylmethane, phenylene diamine, or a mixture thereof.

14. The thermoplastic polyurethane elastomer composition of claim 1, wherein, The chain extender is a hydrazine.

15. The thermoplastic polyurethane elastomer composition of claim 1, wherein, The chain extender is an amino alcohol.

16. The thermoplastic polyurethane elastomer composition of claim 15, wherein, The chain extender is ethanol amine, N-methylethanolamine, N-butylethanolamine, N-oleoyl ethanolamine, N-cyclohexylisopropanolamine, or a mixture thereof.

17. The thermoplastic polyurethane elastomer composition of claim 1, wherein, The chain extender is a substituted aromatic diamine.

18. The thermoplastic polyurethane elastomer composition of claim 17, wherein, The chain extender is 4,4'-methylenebis(o-chloroaniline), 4,4'-methylenebis(3-chloro-2,6-diethylaniline), or a mixture thereof.

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

20. The thermoplastic polyurethane elastomer composition of claim 19, wherein, The at least one crosslinking agent is glycerol, trimethylolpropane, diethanol amine, triethanol amine, or a mixture thereof.

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

5.

22. The thermoplastic polyurethane elastomer composition of claim 1, wherein, The at least one polyisocyanate is 4,4'-diisocyanatodiphenylmethane (4,4'-MDI), 2,4'-diisocyanatodiphenylmethane (2,4'-MDI), p-phenylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-diisocyanatocyclohexane, hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, 4,4'-diisocyanatodicyclohexylmethane, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, or a mixture thereof.

23. The thermoplastic polyurethane elastomer composition of claim 1, further comprising at least one additive comprising: (a) a UV stabilizer; (b) an inorganic filler or an organic filler; (c) silicate minerals, metal oxides, metal salts, clays, metal silicates, glass fibers, natural fibrous materials, or synthetic fibrous minerals; (d) carbon black, fullerenes, carbon nanotubes, biochar, melamine resins, cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and / or aliphatic dicarboxylic esters, or carbon fibers; and (e) organophosphates, metal oxides, metal salts, or cyanuric acid derivatives; wherein the additive is present in 0.5 to 30 wt% of the composition.

24. The thermoplastic polyurethane elastomer composition of claim 1, further comprising at least one flame retardant, which is an organic phosphonate, a metal polyphosphate, a metal oxide, a cyanuric acid derivative, or a mixture thereof; wherein, The at least one flame retardant is present in 500 to 4000 ppm of the composition.

25. The thermoplastic polyurethane elastomer composition of claim 1, further comprising a blowing agent, which is water, pentane, cyclopentane, or hydrofluorocarbon, or a mixture thereof.

26. The thermoplastic polyurethane elastomer composition of claim 1, wherein, The at least one nitro-substituted polyester diol comprises at least one C8-C 20 dicarboxylic acid and at least one polyol.

27. The thermoplastic polyurethane elastomer composition of claim 26, wherein, The at least one polyol is C 1-8 Diols.

28. The thermoplastic polyurethane elastomer composition of claim 1, comprising 20 to 80 wt% of the nitro-substituted polyester diol.

29. The thermoplastic polyurethane elastomer composition of claim 1, wherein, At least one additive is added to the thermoplastic polyurethane elastomer composition, wherein the at least one additive is an antioxidant, a dye, a wetting agent, an antifoam agent, a thickening agent, a photosensitizer, or a solvent, and the filler is present in less than 20 wt% relative to the total weight of the composition.

30. The thermoplastic polyurethane elastomer composition of claim 1, wherein, At least one additive is added to the thermoplastic polyurethane elastomer composition, wherein the at least one additive is a metal, organic, inorganic, or organic / inorganic hybrid filler, and the filler is present in less than 20 wt% relative to the total weight of the composition.

31. A method of making the thermoplastic polyurethane elastomer composition of claim 1, comprising reacting at least one nitro-substituted polyester diol, at least one polyester diol that is not substituted with a nitro group, at least one polyisocyanate, and at least one chain extender.

32. A molded article comprising the thermoplastic polyurethane elastomer composition of claim 1.

33. A TPU foam for footwear applications comprising the thermoplastic polyurethane elastomer composition of claim 1, wherein, The thermoplastic polyurethane elastomer composition is pelletized and expanded. (c) silicate minerals, metal oxides, metal salts, clays, metal silicates, glass fibers, natural fibrous materials, or synthetic fibrous minerals; (d) carbon black, fullerenes, carbon nanotubes, biochar, melamine resins, cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and / or aliphatic dicarboxylic esters, or carbon fibers; and (e) organophosphates, metal oxides, metal salts, or cyanuric acid derivatives; wherein the additive is present in 0.5 to 30 wt% of the composition. The at least one flame retardant is present in 500 to 4000 ppm of the composition.

25. The thermoplastic polyurethane elastomer composition of claim 1, further comprising a blowing agent, which is water, pentane, cyclopentane, or hydrofluorocarbon, or a mixture thereof.

28. The thermoplastic polyurethane elastomer composition of claim 1, comprising 20 to 80 wt% of the nitro-substituted polyester diol. At least one additive is added to the thermoplastic polyurethane elastomer composition, wherein the at least one additive is an antioxidant, a dye, a wetting agent, an antifoam agent, a thickening agent, a photosensitizer, or a solvent, and the filler is present in less than 20 wt% relative to the total weight of the composition. At least one additive is added to the thermoplastic polyurethane elastomer composition, wherein the at least one additive is a metal, organic, inorganic, or organic / inorganic hybrid filler, and the filler is present in less than 20 wt% relative to the total weight of the composition.

31. A method of making the thermoplastic polyurethane elastomer composition of claim 1, comprising reacting at least one nitro-substituted polyester diol, at least one polyester diol that is not substituted with a nitro group, at least one polyisocyanate, and at least one chain extender.

32. A molded article comprising the thermoplastic polyurethane elastomer composition of claim 1. The thermoplastic polyurethane elastomer composition is pelletized and expanded.

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