Polyurethane structural units including amide bonds and urethane bonds

Abstract

This disclosure relates to a polyurethane polymer produced by using a hydroxyl-functionalized amide / urethane-containing polyol of formula 1, wherein R is an alkyl chain of 4 to 44 carbon atoms, R1 is an alkyl chain of 2 to 44 carbon atoms, R2 is an alkyl chain of 1 to 10 carbon atoms, and n has a value of 1 to 10, more specifically 1 to 7, and more specifically 1 to 4. [Formula 1] JPEG2026513176000010.jpg22128

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 492,658, filed on March 28, 2023, which is hereby incorporated by reference in its entirety.

[0002] The present invention relates to polyols, polyurethanes containing polyols, the use of polyols, and methods for manufacturing polyurethanes. The present invention aims to provide improved polyols that can be used in manufacturing polyurethanes such that one or more properties (e.g., physical properties) of the polyurethanes are improved. The improved properties are induced through the cooperation of hydrolytically stable bonds such as urethane and amide bonds. These improved properties can include hardness, tensile strength, elongation, adhesion, chemical resistance, and hydrolysis resistance, or one or more of their improvements or combinations.

Background Art

[0003] The polyols of the present invention can be used in the manufacture of polyurethanes. Polyurethanes are extremely versatile materials and are used in a wide variety of applications such as foam insulation, automotive seats, paint coatings, adhesives, sealants, elastomers, and wear - resistant coatings.

[0004] Polyurethanes are also used in a wide variety of forms, such as non - porous materials like elastomers, and porous materials such as low - density flexible foams, high - density flexible foams, and microcellular foams. Polyurethanes are also known to find use in adhesives, for example in applications in the furniture and automotive industries, in both dispersed and non - dispersed forms.

[0005] Polyurethane dispersions are used in coating compositions. Such coating compositions provide a surface protection and / or surface decoration coating that can be applied to a substrate and dried or cured to form a continuous protective and decorative film. Such coatings can be applied to a wide range of substrates, including metals, wood, plastics, and plaster. Important properties of the formed film include hardness and water resistance.

[0006] Polyurethane dispersion polymers are an important type of binder for aqueous coating compositions because they provide excellent properties such as chemical resistance, stain resistance, hardness, and toughness in solid coating agents.

[0007] Polyurethane elastomers are used in cables, tubes, belts, sportswear (e.g., sports shoes, goggles, ski boots), films / sheets, and automotive interiors (e.g., grips, armrests, consoles).

[0008] Polyurethane is also known to be used in adhesives, such as hot melt, moisture-curing, and two-component adhesives, in both dispersed and non-dispersed forms. Hot melt adhesives are solid at room temperature and can be applied in molten form at temperatures typically ranging from 80 to 250°C. Moisture-curing two-component adhesives can also be used. Polyurethane adhesives can be used to bond a wide range of materials, including polar substrates such as paper, wood, and metal, as well as less polar substrates such as polymers and plastics.

[0009] Polyurethane is always required to have improved and / or specialized properties such as enhanced strength, hardness, rigidity, crystallinity, UV stability, color stability, chemical resistance, and / or moisture resistance.

[0010] Polyurethanes can be produced by reacting isocyanates with polyols. The polyol may contain one or more ester bonds (e.g., oligoesters or polyesters), one or more ether bonds (e.g., oligoethers or polyethers), or the polyol may contain both ester and ether bonds. [Overview of the project]

[0011] This invention is partly based on the recognition that the use of linear or branched diacid or diamine residues having 6 to 44 carbon atoms in combination with dimer fatty acid residues in polyols can provide polyols with improved properties that balance flexibility and chemical / hydrolysis resistance with increased hardness or tensile strength. Although not bound by theory, it is thought that dimer fatty acid residues can provide flexibility and chemical / hydrolysis resistance due to their amorphous and hydrophobic properties, and linear or branched diacid or diamine residues containing 6 to 44 carbon atoms can provide improved hydrolysis stability and chemical resistance through chemical amide and urethane bonds. [Modes for carrying out the invention]

[0012] As used herein, the term "dimer fatty acid residue" refers, unless otherwise defined, to a residue of a dimer fatty acid (also called a dimer fatty acid), or a residue of a dimer fatty acid derivative such as a dimer fatty diol or dimer fatty diamine.

[0013] Unless otherwise specified, all percentages reported herein are intended to be weight percentages (i.e., wt%) of the referenced final composition.

[0014] As used herein with respect to a molecule or part of a molecule, the term “functional value” refers to the number of functional groups in that molecule or part of a molecule. A “functional group” is a group in a molecule that can participate in a chemical reaction; for example, carboxylic acid groups, hydroxyl groups, and amine groups are all examples of functional groups. For example, diacids (having two carboxylic acid groups) and diols (having two hydroxyl groups) both have a functional value of 2, while triacids and triols both have a functional value of 3.

[0015] The polyols of this disclosure are derived from the condensation of a diacid with a diamine, followed by the reaction of the resulting product with a cyclic carbonate to produce a polyol.

[0016] The term "dimer fatty acid" (also called dimer fatty acid) is well known in the art and refers to the dimerization products of monounsaturated or polyunsaturated fatty acids and / or their esters. The related term trimer fatty acid similarly refers to the trimmerization products of monounsaturated or polyunsaturated fatty acids and / or their esters.

[0017] Dimer fatty acids are described in TEBreuer, "Dimer Acids," JIKroschwitz (ed.), Kirk-Othmer Encyclopaedia of Chemical Technology, 4th Ed., Wily, New York, 1993, Vol. 8, pp. 223-237. Dimer fatty acids are prepared by polymerizing fatty acids under pressure, followed by distillation to remove most of the unreacted fatty acid starting material. The final product usually contains some small amounts of mono-fatty acids and trimer fatty acids, but is mostly composed of dimer fatty acids. The resulting product can be prepared using different proportions of fatty acids, if desired.

[0018] The ratio of dimer fatty acids to trimer fatty acids can be varied by changing the processing conditions and / or the unsaturated fatty acid raw materials. Dimer fatty acids can be isolated in a substantially pure form from the product mixture using purification techniques known in the art, or a mixture of dimer and trimer fatty acids can be used.

[0019] In some embodiments, the dimer fatty acids or dimer fat residues used in the present invention are preferably derived from dimerization products of C10-C30 fatty acids, C12-C24 fatty acids, C14-C22 fatty acids, C16-C20 fatty acids, or C18 fatty acids. Thus, the resulting dimer fatty acids may contain 20-60 carbon atoms, 24-48 carbon atoms, 28-44 carbon atoms, 32-40 carbon atoms, or 36 carbon atoms.

[0020] The fatty acids from which the dimer fatty acids are derived may be selected from straight-chain or branched-chain unsaturated fatty acids. The unsaturated fatty acids may be selected from fatty acids having either a cis or trans conformation and may have one or more unsaturated double bonds.

[0021] In some embodiments, the fatty acids used are straight-chain monounsaturated fatty acids.

[0022] Dimer fatty acids may be hydrogenated. Dimer fatty acids may not be hydrogenated. Hydrogenated dimer fatty acid residues (from diacids, diols, or diamines) may have better oxidation or thermal stability, which is desirable in polyurethanes formed from copolymer polyols.

[0023] As used herein, the terms “hydrogenation” or “hydrogenated dimer acid” refer to the partial, complete, or substantially complete hydrogenation of dimer acids. The partial or substantially complete hydrogenation of natural oils and fatty acids is well known in the art. Those skilled in the art will understand that it is difficult and impractical to completely hydrogenate natural oils or fatty acids, as it is most likely that some unsaturation will remain in any hydrogenated oil, regardless of the length of time taken during hydrogenation. Attempts to completely hydrogenate oils or fatty acids lead to economic inefficiencies and degradation of the product. The degree of hydrogenation is typically reflected by referring to the residual iodine value of the product. Thus, many oils that are sold or said to be “completely” hydrogenated have been processed to this point of diminishing returns and still have a low residual iodine value. Similarly, the hydrogenation of dimer fatty acids may, in some cases, produce products with a residual iodine value.

[0024] Preferred dimer fatty acids are derived from the dimerization products (i.e., dimer equivalents) of oleic acid, linoleic acid, linolenic acid, palmitoleic acid, or elaidic acid. In some embodiments, the preferred dimer fatty acid is derived from oleic acid.

[0025] Dimer fatty acids may also be dimerization products of unsaturated fatty acid mixtures obtained from the hydrolysis of natural fats and oils, such as sunflower oil, soybean oil, olive oil, rapeseed oil, cottonseed oil, or tall oil.

[0026] The molecular weight (weight average) of the dimer fatty acid may be in the range of 450 to 690, 500 to 640 in some embodiments, 530 to 610 in some embodiments in particular, and 550 to 590 in some embodiments. The average molecular weight may be determined by methods known in the art.

[0027] In addition to dimer fatty acids, residues of various amounts of trimer fatty acids (so-called "trimers"), oligomer fatty acids, and monomer fatty acids (so-called "monomers"), or esters thereof, are usually present due to dimerization. The amount of monomers can be reduced, for example, by distillation.

[0028] Similarly, any trimer fatty acids may be derived from the trimerization products of the materials mentioned with respect to dimer fatty acids. In some embodiments, they are trimers having from C10 to C30, in some embodiments the trimers are C12 to C24, in some embodiments the trimers are C14 to C22, and in still some embodiments the trimers are C16 to C20 fatty acids, and in some embodiments they are C18 fatty acids. Thus, the trimer fatty acids can contain from 30 to 90 carbons, in some embodiments from 36 to 72 carbons, in some embodiments from 42 to 66 carbons, in some embodiments from 48 to 60 carbons, and in some embodiments 54 carbon atoms.

[0029] The molecular weight (weight average) of the trimer fatty acids can be in the range of 750 to 950 in some embodiments, 790 to 910 in some embodiments, 810 to 890 in some embodiments, and 830 to 870 in some embodiments.

[0030] The dimer fatty acids used in the present invention can have a dimer fatty acid (or dimer) content of more than 60% by weight, more than 70% by weight in some embodiments, more than 80% by weight in some embodiments, and more than 85% by weight in some embodiments. In some embodiments, the dimer content of the dimer fatty acids is in the range of 90% to 99% by weight. In some embodiments, the dimer fatty acids preferably have a dimer fatty acid (or dimer) content in the range of 70% to 96% by weight.

[0031] In addition, particularly preferred dimer fatty acids may have a trimer fatty acid (or trimer) content of less than 40% by weight, less than 30% by weight in some embodiments, less than 20% by weight in some embodiments, and less than 15% by weight in some embodiments. In some embodiments, the trimer fatty acid content may be less than 1% by weight.

[0032] Furthermore, the dimer fatty acid preferably comprises less than 10% by weight, less than 6% by weight in some embodiments, less than 4% by weight in some embodiments, and less than 3.5% by weight of monofatty monoacids (or monomers).

[0033] All of the above weight percentage values ​​are based on the total weight of polymerized and monofatty acids present.

[0034] Dimer fatty acids (or dimer fatty acids) may be converted to dimer fatty diamines, as is known in the art. Dimer fatty diamines may have the same structural properties as those described herein with respect to dimer fatty acids (or dimer fatty acids), except that the acid group in the dimer fatty acid is replaced by an amine group in the dimer fatty diamine. Similarly, trimer fatty triacids may be converted to trimer fatty triamines, which may have the same properties as those described herein with respect to trimer fatty triacids.

[0035] The dimer fatty acid diamine may be hydrogenated. The dimer fatty acid diamine does not need to be hydrogenated.

[0036] Hydroxyl-functionalized amide / urethane-containing polyol A hydroxyl-functionalized amide / urethane-containing polyol is shown in Formula 1.

[0037] [ka] During the ceremony, R is an alkyl chain of 4 to 44 carbon atoms. R1 is an alkyl chain of 2 to 44 carbon atoms. R2 is an alkyl chain of 1 to 10 carbon atoms. n has values ​​between 1 and 10, more specifically between 1 and 7, and more specifically between 1 and 4.

[0038] The polyols of this disclosure are prepared by a two-step process. In the first step, a mixture of diacid and diamine (or a mixture of diacid and diamine) is combined and reacted to form a mixture of amide or polyamide described in Formula 2 below.

[0039] [ka] During the ceremony, R is an alkyl chain of 4 to 44 carbon atoms. R1 is an alkyl chain of 2 to 44 carbon atoms. n has values ​​between 1 and 10, more specifically between 1 and 7, and more specifically between 1 and 4.

[0040] As used herein, the term "alkyl" means a saturated or unsaturated, branched or linear divalent hydrocarbon group derived by removing two hydrogen atoms from the carbon atoms of a parent alkane, alkene, or alkyne. In some embodiments, one or more alkyl groups are substantially saturated. In some embodiments, one or more alkyl groups are completely or partially saturated.

[0041] In some embodiments, the alkyl group may be branched. In other embodiments, the alkyl group may be unbranched and may be alternatively referred to as a linear alkyl group.

[0042] Techniques for forming amides and polyamides of formula 2 are well known to those skilled in the art. Typically, the acid and amine reactants are heated to a high temperature. During the reaction, water byproducts are removed by the high temperature. For example, diacids and diamines (or mixtures of diacids and / or diamines) may be heated to a temperature of 200°C to 230°C under atmospheric pressure and a nitrogen atmosphere. The reaction is allowed to proceed until the desired acid value is obtained. Typically, an acid value of less than 2 or less than 1 is used as the endpoint. Alternatively, the condensation reaction may be carried out with the assistance of a catalyst or under reduced pressure, but it is not necessarily required to be carried out in this manner.

[0043] The diacitor contains an R group comprising an alkyl chain of 6 to 44 carbon atoms. The diacitor may be a dimer diacitor or a commercially available diacitor. The alkyl chain of the R group may be linear or branched. In some embodiments, R is a linear alkyl chain of 6 to 40 carbon atoms. The R group may be a mixture of alkyl chains. In some embodiments, the R group is a mixture of a linear alkyl chain of 7 carbon atoms and a linear alkyl chain of 34 carbon atoms. The R group may be derived from a mixture of diacitors.

[0044] The diamine contains an R1 group. The diacid contains an R1 group comprising an alkyl chain of 6 to 44 carbon atoms. The diamine may be a dimer amine or a commercially available diamine. The alkyl chain of the R1 group may be linear or branched. In some embodiments, R1 is a linear alkyl chain of 6 to 40 carbon atoms. The R1 group may be a mixture of alkyl chains. In some embodiments, the R1 group is a mixed alkyl chain comprising a linear alkyl chain of 34 carbon atoms.

[0045] Next, the compound of formula 2 is reacted to form the compound of formula 1. For example, the terminal amine group of formula 2 can be reacted with a cyclic carbonate such as ethylene carbonate or propylene carbonate. This type of ring-opening reaction is well known in the art. For example, immediately after the above condensation, the reaction temperature can be lowered to about 100°C, a cyclic carbonate can be added, and the reaction can proceed to an amine value of less than 10.

[0046] In some embodiments, the compound of formula 1 is an alkyl chain having 2 to 4 carbon atoms where R2 is located.

[0047] The compounds of formula 1 can then be isolated from the reactor after cooling. They can be used directly or purified by methods known in the art.

[0048] The weight ratio of diamine-resistant compounds in the polyol may be in the range of 90:10 to 30:70, preferably in the range of 85:15 to 45:55.

[0049] The weight percentage of the diamine in the polyol may be greater than the weight percentage of the diacid.

[0050] These relative amounts of diacids and diamines in polyols can provide a favorable balance of flexibility, tensile strength, hardness, and hydrolysis resistance in polyurethanes formed from polyols, as will be discussed in more detail herein.

[0051] In some embodiments, the polyol may have a molecular weight (weight average) of at least 500, at least 800, or at least 1000, or at least 1500, or at least 1800.

[0052] Polyurethane Another aspect of this disclosure is a polyurethane comprising a polyol as described herein.

[0053] A composition comprising a mixture of a polyol and an isocyanate can be considered a “prepolymer,” and for convenience, will be referred to as such herein. Such a prepolymer can be produced by efficiently mixing the polyol and the isocyanate. The prepolymer may then be reacted to form a polyurethane, which may be induced by any preferred means, for example, by curing at high temperatures or by introducing an initiator catalyst. In some embodiments, the polyol and isocyanate may be reacted (cured) at high temperatures, which may be in the range of 50°C to 80°C, and in other embodiments, in the range of 60°C to 75°C. In the reacted polyurethane polymer composition, the isocyanate to polyol (NCO / OH) ratio used is preferably in the range of 1 to 1.2:1, more preferably 1 to 1.1:1, and particularly 1 to 1.03:1.

[0054] In some embodiments, the polymer composition may have an isocyanate content (measured in accordance with ASTM2572) in the range of NCOs of 5% to 30% by weight, 10% to 23% by weight, 15% to 20% by weight, or 18% to 19% by weight.

[0055] In some embodiments, the isocyanate comprises at least one isocyanate having at least two functional values.

[0056] The isocyanate may be an aliphatic isocyanate, an alicyclic isocyanate, or an aromatic isocyanate. In some embodiments, the isocyanate is preferably an aliphatic isocyanate. However, in some alternative embodiments, the isocyanate may preferably be an aromatic isocyanate. Aliphatic isocyanates are often used when the polymer composition is intended to be a polymer substrate in the form of a coating composition, while aromatic isocyanates are often used when the polymer composition is intended to be used in the production of a polymer substrate in the form of a polyurethane elastomer. This is because aromatic isocyanates, compared to aliphatic isocyanates, can provide improved stiffness or strength to the elastomer due to their aromatic structure.

[0057] Preferably, the prepolymer composition may contain an isocyanate selected from one or more isocyanates, polyisocyanates, diisocyanates, or triisocyanates. The polyisocyanate may be selected from aliphatic polyisocyanates and hydrophilic polyisocyanates. The isocyanate monomer may be used alone or in mixtures thereof. In some embodiments, the isocyanate is a diisocyanate.

[0058] Ideally, polyisocyanates should be one or more of the following: hexamethylene 1,6-diisocyanate, isophorone diisocyanate (IPDI), ethylene diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 1,6-diisocyanatohexane, 1,4-butylene diisocyanate, lysine diisocyanate, hexamethylene diisocyanate (HDI), 1,4-methylenebis-(cyclohexyl isocyanate), and isophorone diisocyanate, with toluene diisocyanate being the most appropriate. The polyisocyanates may be selected from one or more of the following: cyanates, m-phenylenediisocyanates, p-phenylenediisocyanates, xylylenediisocyanates, 4,4'-diphenylmethanediisocyanates, polymethylene polyphenyl diisocyanates, 3,3'-dimethyl-4,4'-diphenylenediisocyanates, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanates, 3,3-dichloro-4,4'-diphenylenediisocyanates, 1,5-naphthalenediisocyanates, or modified compounds thereof. Examples of commercially available suitable polyisocyanates include Desmodur® N7300, N3300, N3900, N3600, N3390, and Tolonate® HDB, HDT-LV.

[0059] Therefore, suitable aromatic isocyanates may be selected from one or more of the following: toluene diisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylenediisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3-dichloro-4,4'-diphenylenediisocyanate, 1,5-naphthalene diisocyanate, or modified compounds thereof, with uretonimine-modified compounds of these being particularly preferred.

[0060] Aliphatic polyisocyanates, particularly hexamethylene diisocyanate and / or isophorone diisocyanate, may be preferred, and this embodiment is especially preferred when the polymer composition is used to yield a coating composition.

[0061] Additionally or alternatively, 4,4'-diphenylmethane diisocyanate (MDI) is used in one embodiment of the present invention. In another embodiment, (MDI) is used alone, and in a further embodiment, a mixture of MDI, such as its uretonimine-modified compound, and uretonimine-modified 4,4'-diphenyl metadiisocyanate (modified MDI) is preferably used. This embodiment can be used when providing a polymer substrate in the form of an elastomer or adhesive using a polymer composition.

[0062] Biuret, alophonate, and / or isocyanurate of such aliphatic polyisocyanates or aromatic polyisocyanates are also suitable for use. In some embodiments, biuret and isocyanurate of polyisocyanates, particularly aliphatic polyisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, are used. In some embodiments, biuret and isocyanurate of hexamethylene diisocyanate are used. This embodiment is used when the polymer composition is intended to be provided as a polymer substrate in the form of a coating, and more specifically, special coating agents can utilize biuret and isocyanurate.

[0063] A further aspect of this disclosure provides a prepolymer composition comprising the polyol of Formula 1 described above.

[0064] The prepolymer composition containing polyamide urethane diol may preferably be blended into a more complex resin or binder system. In this case, the prepolymer composition of the present invention may be further mixed and / or reacted with one or more additional polymer components, which may constitute the majority of the resin or binder system. In this aspect of the present invention, it is convenient to refer to the additional polymer components as binder polymer components. Therefore, the prepolymer composition may contain binder polymer components, which are preferably the main components of the prepolymer composition. That is, the prepolymer composition contains a greater amount of binder polymer components than any other individual components of the prepolymer composition.

[0065] In other embodiments, the prepolymer composition may further contain a chain extender, which is particularly desirable when the polymer composition is polyurethane. The chain extender may be in the form of a chain extender composition. The chain extender composition may be prepared, for example, by a simple premixing of a chain extender and other additives (such as a blowing agent, and / or a urethane catalyst, and / or a pigment, and / or a filler, and / or a blowing agent).

[0066] Chain extenders or chain extender compositions used to form polyurethanes may include low molecular weight compounds having two or more active hydroxyl groups, such as polyols including ethylene glycol, diethylene glycol, propylene glycol, 1,4-butylene glycol, 1,5-pentylene glycol, methylpentanediol, isosorbide (and other isohexides), 1,6-hexylene glycol, neopentyl glycol, trimethylolpropane, hydroquinone ether alkoxylate, resorcinol ether alkoxylate, glycerol, pentaerythritol, diglycerol, dextrose, and dimer fatty diols. The chain extenders may also include aliphatic polyhydric amines such as ethylenediamine, hexamethylenediamine, and isophoronediamine; aromatic polyhydric amines such as methylene-bis(2-chloroaniline), methylenebis(dipropylaniline), diethyltoluenediamine, and trimethylene glycol di-p-aminobenzoate; and alkanolamines such as diethanolamine, triethanolamine, and diisopropanolamine.

[0067] In one aspect of the present invention, the chain extender is a polyol, in some aspects a diol, having an aliphatic straight carbon chain containing in particular 1 to 10 or 3 to 5 carbon atoms. In some aspects, the diol is ethylene glycol, propylene glycol, 1,4-butylene glycol, and 1,5-pentylene glycol.

[0068] The molar ratio of the chain extender to the total amount of other polyols present in the polymer composition may be in the range of 1 to 10:1, or 1.5 to 8:1, or 2 to 5:1, or 2.5 to 4:1.

[0069] In some embodiments, the polymer composition may contain one or more optional additives. These additives may be selected from pigments, dyes, rheological modifiers, foaming agents, fillers, catalysts, stabilizers, emulsifiers, dispersants, and other surfactants, as well as mixtures thereof. In addition to the binder polymer components described above, optional additives may be present and may be selected by those skilled in the art depending on the intended end use or the product produced by the polymer composition.

[0070] Pigment additives may be organic or inorganic. Examples of organic pigments include, but are not limited to, azo pigments, phthalocyanines, and quinacridone. Examples of inorganic pigments include iron oxide pigments, titanium dioxide, and carbon black.

[0071] Examples of dyes include, but are not limited to, azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine, thiazine, and triarylmethane dyes. These dyes can be used as basic or cationic dyes, metal complexes, reactive, acidic, sulfur, binding dyes, or direct dyes.

[0072] Suitable blowing agents include water, as well as fluorocarbons such as trichlorofluoromethane, dichlorodifluoromethane, and trichlorodifluoroethane. The blowing agents may be used alone or in mixtures thereof. Blowing agents are often used when the polymer composition is intended to be an elastomer.

[0073] Suitable catalysts for polymerization include known polyurethane catalysts that promote the reaction between isocyanates and polyols to form polyurethanes. Examples include divalent and tetravalent tin compounds, more specifically divalent tin dicarboxylates, and dialkyltin and dialkyltin dialkoxylates. Specific examples include, but are not limited to, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin diacetate, dibutyltin maleate, tin(II) octolate, tin(II) phenolates, and divalent and tetravalent tin acetylacetonates. Furthermore, tertiary amines or amidines may also be used alone or in combination with the aforementioned tin compounds. Suitable amines include, but are not limited to, tetramethylbutanediamine, bis-(dimethylaminoethyl)-ether, 1,4-diazabicyclooctane (DABCO), 1,8-diazabicyclo-(5.4.0)-undecane, 2,2'-dimorpholinodiethyl ether, dimethylpiperazine, and mixtures thereof.

[0074] Suitable stabilizers include, but are not limited to, monofunctional carboxylate chlorides, monofunctional highly reactive isocyanates, and noncorrosive inorganic acids, which stabilize the viscosity of polyurethane during its manufacture, storage, and application. Examples of such stabilizers include benzoyl chloride, toluenesulfonyl isocyanate, phosphoric acid, or phosphorous acid. Furthermore, suitable hydrolysis stabilizers include, for example, carbodiimide-type stabilizers. Stabilizers that are antioxidants or UV absorbers may also be used. Examples of such stabilizers include HALS sterically hindered amine light stabilizers, hydrogen-donating antioxidants (such as sterically hindered phenols and secondary aromatic amines), benzofuranones, oxanilides, benzophenones, benzotriazoles, and UV-absorbing pigments.

[0075] Suitable surfactants include silicone surfactants such as dimethylpolysiloxane, polyoxyalkylene polyol-modified dimethylpolysiloxane, and alkylene glycol-modified dimethylpolysiloxane, as well as anionic surfactants such as fatty acid salts, sulfate esters, phosphate esters, and sulfonates.

[0076] In some embodiments, the polymer composition is provided as a two-component (2K) polyurethane resin system. This is particularly preferred when the polymer composition is used to produce a coating composition. In the 2K polyurethane system, the polyamide urethane diol and binder polymer of the present invention may provide a first component of the resin system, and the polyisocyanate may provide a second component of the resin system. In this embodiment, one or more optional additives may be provided in either the first or second component. Such a 2K system is particularly preferred for the preparation of coating agents comprising or consisting of the polymer composition. Accordingly, the present invention can preferably provide a coating composition comprising the polymer composition described herein and, therefore, the polyamide urethane diol and polyisocyanate described above.

[0077] One aspect of the present disclosure also provides a polymer substrate which is a coating agent, adhesive, sealant, or elastomer comprising a polyol of Formula 1.

[0078] Accordingly, according to one aspect of the present disclosure, a coating agent comprising the above-mentioned polyamide urethane diol or the above-mentioned polymer composition is provided. The coating agent may comprise one or more polyisocyanates, in some aspects two or three, and in other aspects two, as described above with respect to the polymer composition. A suitable polyisocyanate can be selected from those described above with respect to the polymer composition.

[0079] All coating agents may contain at least 1% by weight, preferably at least 2% by weight, particularly at least 5% by weight, and preferably at least 10% by weight of polyisocyanate, based on the total weight of the coating composition. All coating agents may also contain at most 50% by weight, preferably at most 40% by weight, and particularly at most 30% by weight of polyisocyanate, based on the total weight of the coating agent.

[0080] The molar ratio of free isocyanate groups to free hydroxyl groups (NCO / OH ratio) in the solid portion of the coating composition before curing may be at least 0.7, preferably at least 0.8, more preferably at least 0.9, and particularly at least 1. The NCO / OH ratio may be at most 3, preferably at most 2.5, more preferably at most 2, and particularly at most 1.8. A higher NCO / OH ratio may provide improved hardness and / or chemical resistance to the cured coating.

[0081] The coating agent may have a total solid content of at least 25% by weight, preferably at least 30% by weight, more preferably at least 35% by weight, and particularly at least 40% by weight, based on the total weight of the coating composition, in accordance with DIN EN ISO 3251. The coating agent may have a total solid content of at most 80% by weight, preferably at most 70% by weight, more preferably at most 65% by weight, and particularly at most 60% by weight, based on the total weight of the coating agent.

[0082] All coating agents may contain at least 10% by weight of water, preferably at least 20% by weight, and particularly at least 30% by weight, based on the total weight of the coating agent. All coating agents may contain at most 90% by weight of water, preferably at most 80% by weight, and particularly at most 70% by weight, based on the total weight of the coating composition.

[0083] The coating agent may preferably contain one or more additional components, in particular coloring additives, such as pigments and / or dyes.

[0084] The coating agent may be a clear coat. The coating agent may be transparent or substantially transparent, and in one embodiment, the coating composition is transparent. The coating agent may not contain coloring additives, for example, pigments and / or dyes.

[0085] The coating agent according to the present invention may be applied to a substrate (i.e., a substrate different from the polymer substrate of the present invention). Application of the coating agent to the substrate may be provided by any number of techniques, including spraying, brushing, rolling, painting mitts, and others known in the art. Numerous substrates are suitable for application of the coating composition. The substrate may be selected from metals, particularly steel and aluminum, wood, brick, concrete, and plastic. The substrate may be an exterior wall, an interior wall, or a floor.

[0086] Preferably, the coating agent may be applied to a substrate as a primer coating. A further coating layer, such as an overcoat or topcoat, may be applied on top of the primer coating. Alternatively, the coating composition of the present invention may be applied as a topcoat. The coating agent may be provided as a paint or lacquer.

[0087] Additionally or alternatively, according to one aspect of the present disclosure, elastomers comprising the above-described polyamide urethane diol or the above-described polymer composition are provided. Elastomers are polymers that exhibit elasticity, i.e., a tendency to return to their original shape after being deformed. Polyurethane elastomers are used in many applications, including cables, tubes, belts, films / sheets (e.g., as flooring materials) and automotive interiors (e.g., grips, armrests, consoles). Elastomers may be provided as sheets (e.g., for flooring materials or other surface coatings) or automotive interiors.

[0088] The polyurethane elastomer may be a solid elastomer or a microporous elastomer. The elastomer may be a reinforced elastomer. The reinforced elastomer may contain reinforcing fibers or fiber mats. The reinforcing fibers may contain glass fibers, carbon fibers, or polyester fibers.

[0089] Polyurethane elastomers may have a tensile strength at break measured according to ISO 37 standards, at least 1 MPa, preferably at least 5 MPa, and more preferably at least 10 MPa. Tensile strength measured according to ISO 37 standards is a standard measurement for standard elastomer samples.

[0090] Polyurethane elastomers may have a (maximum) elongation of at least 50%, preferably at least 150%, and more preferably at least 450%, according to ISO 37-2. Elastomers may have a (maximum) elongation of up to 500%.

[0091] All of the features described herein may be combined in any combination with any of the embodiments described above. [Examples]

[0092] The present invention is illustrated by the following non-limiting examples.

[0093] It should be understood that all test procedures and physical parameters described herein were determined at atmospheric pressure, room temperature (i.e., approximately 20°C) and 50% relative humidity, unless otherwise specified herein or in the referenced test methods and procedures. All parts and percentages are by weight unless otherwise indicated.

[0094] The substances used in the examples are identified as follows:

[0095] [Table 1]

[0096] Test method In this specification, the following test methods were used.

[0097] The hydroxyl value was defined as the number of mg of potassium hydroxide equivalent to the hydroxyl content in 1 g of sample, and was measured by acetylation followed by hydrolysis of excess acetic anhydride. The resulting acetic acid was then titrated with an ethanolic potassium hydroxide solution. The hydroxyl value may also be determined by the AOCS standard method Cd13-60.

[0098] The acid value was defined as the number of mg of potassium hydroxide required to neutralize the free fatty acids in 1 g of sample, and was measured by direct titration with a standard potassium hydroxide solution. The AV (Abdominal Value) can be determined by AOCS Official Method Ca 5a-40.

[0099] The amine value was defined as the number of milligrams of potassium hydroxide required to neutralize the free fatty acids in 1 g of sample, and was measured by direct titration with standard hydrochloric acid. AmV can be determined by AOCS Official Method Cd 5a-40.

[0100] Unless otherwise specified, elongation was measured using a Type 2 dumbbell specimen and an Instron tensile testing machine in accordance with ISO 37.

[0101] Unless otherwise specified, tensile strength was measured using a Type 2 dumbbell test specimen and an Instron tensile testing machine in accordance with ISO 37.

[0102] The König hardness was tested according to DIN ISO 2815.

[0103] Chemical resistance was evaluated according to DIN 12720, with coated samples spot-tested for a predetermined time and given a score from 5 = no damage to 0 = complete damage.

[0104] The overlapping shear test was evaluated using ASTM 1002.

[0105] Polyols containing the hydroxy-functional polyamide urethane diol compounds of Examples 1 to 8 were synthesized as follows.

[0106] Example 1 A reactor equipped with a stirrer, thermometer, gas inlet, and condenser was filled with 100 parts by weight of PRIPOL 1006 and 200 parts by weight of Priamine. Subsequently, the reactor temperature was raised to 200-230°C above ambient temperature under atmospheric pressure and in a nitrogen atmosphere. Under these conditions, the condensation reaction was carried out until the desired acid / amine value was observed. In this example, the resulting polyol had an acid value of less than 1 mg KOH / g and an amine value of 75 mg KOH / g.

[0107] The temperature was lowered to 100°C, and then 38.3 parts of propylene carbonate (BASF Propylene Carbonate S) were added. The ring-opening reaction was carried out until the acid / amine / hydroxyl values ​​were obtained. The resulting polyol showed an acid value of <1 mg KOH / g, an amine value of <10 mg KOH / g, and a hydroxyl value of 59 mg KOH / g.

[0108] Example 2 A reactor equipped with a stirrer, thermometer, gas inlet, and condenser was filled with 100 parts by weight of Crodacid 1195D and 600 parts of Priamine 1075. Subsequently, the reactor temperature was raised to 200-230°C above ambient temperature under atmospheric pressure and in a nitrogen atmosphere. Under these conditions, the condensation reaction was carried out until the desired acid / amine value was observed. In this example, the resulting polyol had an acid value of less than 1 mg KOH / g and an amine value of 88 mg KOH / g.

[0109] The temperature was lowered to 100°C, and then 107 parts of propylene carbonate (BASF Propylene Carbonate S) were added. The ring-opening reaction was carried out until the acid / amine / hydroxyl values ​​were obtained. The resulting polyol showed an acid value of <1 mg KOH / g, an amine value of <10 mg KOH / g, and a hydroxyl value of 75 mg KOH / g.

[0110] Example 3 A reactor equipped with a stirrer, thermometer, gas inlet, and condenser was filled with 100 parts by weight of PRIPOL 1006, 25.4 parts by weight of adipic acid, and 400 parts of Priamine 1075. Subsequently, the reactor temperature was raised to 200-230°C above ambient temperature under atmospheric pressure and in a nitrogen atmosphere. Under these conditions, the condensation reaction was carried out until the desired acid / amine value was observed. In this example, the resulting polyol had an acid value of less than 1 mg KOH / g and an amine value of 83 mg KOH / g.

[0111] The temperature was lowered to 100°C, and then 76 parts of propylene carbonate (BASF Propylene Carbonate S) were added. The ring-opening reaction was carried out until the acid / amine / hydroxyl values ​​were obtained. The resulting polyol showed an acid value of <1 mg KOH / g, an amine value of <10 mg KOH / g, and a hydroxyl value of 75 mg KOH / g.

[0112] Example 4 A reactor equipped with a stirrer, thermometer, gas inlet, and condenser was filled with 100 parts by weight of C18 diacid and 339 parts of Priamine 1075. Subsequently, the reactor temperature was raised to 200-230°C above ambient temperature under atmospheric pressure and in a nitrogen atmosphere. Under these conditions, the condensation reaction was carried out until the desired acid / amine value was observed. In this example, the resulting polyol had an acid value of less than 1 mg KOH / g and an amine value of 81 mg KOH / g.

[0113] The temperature was lowered to 100°C, and then 60.2 parts of propylene carbonate (BASF Propylene Carbonate S) were added. The ring-opening reaction was carried out until the acid / amine / hydroxyl values ​​were obtained. The resulting polyol showed an acid value of <1 mg KOH / g, an amine value of <10 mg KOH / g, and a hydroxyl value of 65 mg KOH / g.

[0114] Example 5 A reactor equipped with a stirrer, thermometer, gas inlet, and condenser was filled with 100 parts by weight of FDCA and 339 parts of Priamine 1075. Subsequently, the reactor temperature was raised to 200-230°C above ambient temperature under atmospheric pressure and in a nitrogen atmosphere. Under these conditions, the condensation reaction was carried out until the desired acid / amine value was observed. In this example, the resulting polyol had an acid value of less than 1 mg KOH / g and an amine value of 81 mg KOH / g.

[0115] The temperature was lowered to 100°C, and then 60.2 parts of propylene carbonate (BASF Propylene Carbonate S) were added. The ring-opening reaction was carried out until the acid / amine / hydroxyl values ​​were obtained. The resulting polyol showed an acid value of <1 mg KOH / g, an amine value of <10 mg KOH / g, and a hydroxyl value of 65 mg KOH / g.

[0116] Example 6 A reactor equipped with a stirrer, thermometer, gas inlet, and condenser was filled with 100 parts by weight of Pripol 1004 and 167 parts of Priamine 1075. Subsequently, the reactor temperature was raised to 200-230°C above ambient temperature under atmospheric pressure and in a nitrogen atmosphere. Under these conditions, the condensation reaction was carried out until the desired acid / amine value was observed. In this example, the resulting polyol had an acid value of less than 1 mg KOH / g and an amine value of 68 mg KOH / g.

[0117] The temperature was lowered to 100°C, and then 29.2 parts of propylene carbonate (BASF Propylene Carbonate S) were added. The ring-opening reaction was carried out until the acid / amine / hydroxyl values ​​were obtained. The resulting polyol showed an acid value of <1 mg KOH / g, an amine value of <10 mg KOH / g, and a hydroxyl value of 53 mg KOH / g.

[0118] Example 7 A reactor equipped with a stirrer, thermometer, gas inlet, and condenser was filled with 100 parts by weight of Pripol 1004 and 200 parts of dimer amine. Subsequently, the reactor temperature was raised to 200-230°C above ambient temperature under atmospheric pressure and in a nitrogen atmosphere. Under these conditions, the condensation reaction was carried out until the desired acid / amine value was observed. In this example, the resulting polyol had an acid value of less than 1 mg KOH / g and an amine value of 57 mg KOH / g.

[0119] The temperature was lowered to 100°C, and then 30.6 parts of propylene carbonate (BASF Propylene Carbonate S) were added. The ring-opening reaction was carried out until the acid / amine / hydroxyl values ​​were obtained. The resulting polyol showed an acid value of <1 mg KOH / g, an amine value of <10 mg KOH / g, and a hydroxyl value of 49 mg KOH / g.

[0120] Example 8 A reactor equipped with a stirrer, thermometer, gas inlet, and condenser was filled with 27 parts by weight of adipic acid and 200 parts of Priamine 1075. Subsequently, the reactor temperature was raised to 200-230°C above ambient temperature under atmospheric pressure and in a nitrogen atmosphere. Under these conditions, the condensation reaction was carried out until the desired acid / amine value was observed. In this example, the resulting polyol had an acid value of less than 1 mg KOH / g and an amine value of 93 mg KOH / g.

[0121] The temperature was lowered to 100°C, and then 38.5 parts of propylene carbonate (BASF Propylene Carbonate S) were added. The ring-opening reaction was carried out until the acid / amine / hydroxyl values ​​were obtained. The resulting polyol showed an acid value of <1 mg KOH / g, an amine value of <10 mg KOH / g, and a hydroxyl value of 80 mg KOH / g.

[0122] Example 9 - Polyurethane elastomer formed using the polyols of Examples 1, 2, 3, 5, 6 and 7 As detailed in Table 2, the polyurethane elastomers of the examples (indicated as E1, E2, E3, E5, E6, and E7) were prepared using a one-shot method with 1 part by weight of each polyol, 2 parts of 1,4-butanediol (BDO) as a chain extender, and 3.1 parts of 4,4'-5-diphenylmethane diisocyanate (MDI). To form the elastomer from Example 1 or 2, the 1,4-butanediol (BDO) chain extender was blended, preheated to 50°C, and degassed in a degassing chamber. The BDO was thoroughly mixed, and then the molten 4,4'-diphenylmethane diisocyanate (MDI) was added. The reaction mixture was efficiently stirred and transferred to the degassing chamber for several minutes until a significant increase in viscosity occurred. The mixture was then poured into a preheated 100°C steel mold. The mold was closed and transferred to a 100°C oven. After 2 hours, the elastomer was demolded and further cured at 100°C for 18 hours. For benchmark comparison, similar reference elastomers were prepared using commercially available polyols Priplast 3192 and PCD, following the same procedure as above.

[0123] The physical properties of each elastomer produced using the polyols of Examples 1, 2, 3, 6, and 7 were measured and are shown in Table 2 below. The samples possessed properties suitable for use as elastomers or sealants.

[0124] [Table 2]

[0125] Considering the mechanical data detailed in Table 2 above, when polyamide urethane diols are included in the polyurethane elastomer matrix, they form polyurethane elastomers with higher strength and overall elongation comparable to the comparative reference polyurethane (PCD) elastomer material, for example in Examples 2, 3, and 6. Additionally, the retention of tensile strength is found to be improved above the baseline while maintaining elongation.

[0126] Example 10 - Two-component polyurethane adhesive formed using the polyols of Examples 1, 2, 3, 6, and 8. The polyols of Examples 1, 2, 3, 4, 6, and 8 were mixed with Desmodur VK10L and then coated onto steel substrates according to ASTM D1002. For benchmark comparison, a similar comparative reference adhesive was prepared using the commercially available polyol Priplast 3192.

[0127] [Table 3]

[0128] Considering the mechanical data detailed in Table 3 above, the polyamide urethane diol contained in the polyurethane adhesive system improves adhesion to steel compared to the commercially available polyester polyol, Priplast 3192. These steel substrates are polished and degreased according to the ASTM protocol.

[0129] Polyurethane two-component adhesive on an oily substrate using the polyols of Examples 11-3 and commercially available polyols. In the table below, the comparison was performed in the same manner as in Example 11, but the adhesive strength was investigated by comparing the preparation of the metal surface and the adhesive properties after the metal substrate was exposed to metalworking without subsequent degreasing. The metal surface was exposed to metalworking oil, and excess oil was lightly wiped off with a towel.

[0130] [Table 4]

[0131] Considering the mechanical data detailed in Table 4 above when the polyamide urethane diol from Example 3 is included, the polyurethane adhesive system performs far better on oil-coated steel than the commercially available Priplast 3192 containing the reference. The adhesive strength of the adhesive prepared from the diol of Example 3 was already high, but it maintained 80% of the adhesive strength on oil-coated steel, compared to only 60% of the benchmark adhesive strength using the commercially available polyester polyol Priplast 3192.

[0132] Example 12 - Polyurethane coating agent formed using Examples 1, 2, and 3 and a commercially available PCD polyol. The polyols from Examples 1, 2, and 3, along with commercially available PCD diols, were incorporated into coating compositions. Immediately before applying the coating composition to the substrate, isocyanate Desmodur N3900 was added to the mixture and mixed. Each coating composition was prepared by mixing in an OH:NCO ratio of 1:1.1. To evaluate hardness and chemical resistance, the coating compositions were applied to glass substrates coated with a 120 μm film of the coating composition using an applicator frame (BYK PA-2030).

[0133] The cured coating properties were evaluated, and the results are shown in Table 5 below.

[0134] [Table 5]

[0135] The table shows that the polyamide urethane diols of this disclosure have slightly lower hardness compared to commercially available polycarbonate diols (PCDs). However, advantageously, coatings containing polyamide urethane diols have improved chemical resistance. This is particularly evident in their resistance to acetic acid and water.

Claims

1. A hydroxyl-functionalized amide / urethane-containing polyol of formula 1, 【Chemistry 1】 During the ceremony, R is an alkyl chain of 4 to 44 carbon atoms. R １ However, it is an alkyl chain of 2 to 44 carbon atoms, R ２ However, it is an alkyl chain of 1 to 10 carbon atoms, A hydroxyl-functionalized amide / urethane-containing polyol in which n has a value of 1 to 10, more specifically 1 to 7, and more specifically 1 to 4.

2. R １ The polyol according to claim 1, wherein the chain is an alkyl chain of 36 to 44 carbon atoms.

3. The polyol according to claim 2, wherein n is 1 to 4.

4. The polyol according to claim 1, wherein the R group is derived from a mixture of diacids.

5. R ２ The polyol according to any one of claims 1 to 4, wherein the chain is an alkyl chain of 2 to 4 carbon atoms.

6. A polyurethane polymer comprising a hydroxyl-functionalized amide / urethane-containing polyol according to any one of claims 1 to 5.

7. The polyurethane polymer according to claim 6, which is an adhesive, coating agent, or sealant.

8. A method for adhering a polyurethane polymer to an oily surface, comprising exposing the surface to the polyurethane polymer described in claim 6.

9. A method for bonding two surfaces together, comprising bringing both surfaces into contact with the polyurethane polymer described in claim 6.

10. The method according to claim 9, wherein the surface is substantially oil-free, oily, or a mixture thereof.

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