CN112105665A

CN112105665A - Extended pot life polyuretdione resins for low temperature cure

Info

Publication number: CN112105665A
Application number: CN201980034098.3A
Authority: CN
Inventors: A·埃金; D·P·齐林斯基
Original assignee: Covestro Deutschland AG; Covestro LLC
Current assignee: Covestro Deutschland AG; Covestro LLC
Priority date: 2018-03-23
Filing date: 2019-03-21
Publication date: 2020-12-18
Also published as: WO2019180128A1; WO2019183307A1; EP3768756A1; WO2019183315A1; WO2019183323A1; EP3768747A1; WO2019183300A1; WO2019183319A1; CN112105666A; CN111886272A; EP3768749A1; WO2019183313A1; CN112041367A; CN111868135A; CN112004853A; CN111886273A; EP3768750A1; EP3768752A1; WO2019183330A1; EP3768751A1

Abstract

The present invention provides a reaction mixture comprising a polyuretdione resin, a neutralized polyol, an acid blocked tertiary amine catalyst; and optionally, an additive package selected from a flow control additive, and a wetting agent, and a solvent, wherein the acid has a pKa greater than 4.82. The compositions prepared from the reaction mixtures of the present invention can be catalyzed at temperatures from room temperature to 130 ℃ and are particularly suitable for or as coatings, adhesives, castings, composites and sealants, with good properties and extended pot life.

Description

Extended pot life polyuretdione resins for low temperature cure

Technical Field

The present invention relates generally to polymers and more particularly to compositions made with polyuretdione and polyols in the presence of acid blocked tertiary amine catalysts for use as coatings, adhesives, castings, composites and sealants to extend the pot life of the resulting coatings, adhesives, castings, composites and sealants without degrading performance.

Background

Polyurethane-forming compositions are widely used in a variety of commercial, industrial, and domestic applications, such as in automotive clear coat and seating applications. Polyurethane systems which use isocyanate pre-reaction with monofunctional reagents to form relatively thermally unstable compounds are known as blocked isocyanates. Urea diketones are blocked isocyanates. Uretdione compounds are typically prepared by dimerizing isocyanates to form uretdiones having unreacted isocyanate groups, which can then be extended with a polyol to form a polymeric material containing two or more uretdione groups in the polymer chain. In some literature, uretdiones are referred to as "1, 3-diaza 2, 4-cyclobutanone compounds", "1, 3-diazetidine-2, 4-diones", "2, 4-dioxo-1, 3-diazetidine compounds", "uretdiones" or "uretidiones". Generally, the polymer has few, if any, free isocyanate groups, which is achieved by controlling the stoichiometry of the polyisocyanate, polyol, and by using a blocking agent.

In the presence of tertiary amine catalysts, polyurea diketones and polyols can react in a very fast manner and thus have a short pot life. To the best of the inventors' knowledge, no one has developed a crosslinking process using an acid blocked tertiary amine catalyst in combination with a uretdione and a polyol.

To reduce or eliminate pot life problems, there is a need in the art for alternative crosslinking processes to obtain compositions having physical properties similar to polyurethane compositions.

Disclosure of Invention

Accordingly, the present invention attempts to alleviate the problems inherent in the art by providing such an alternative crosslinking process to obtain a composition having similar physical properties as the polyurethane composition. Various embodiments of the present methods involve crosslinking a polyuretdione resin with a polyol in the presence of an acid blocked tertiary amine catalyst, wherein the acid has a pKa greater than 4.82. The tertiary amine catalyst may be activated at room temperature (20-25 ℃) or at any temperature up to 130 ℃. The compositions of the present invention can extend the pot life of the resulting coatings, adhesives, castings, composites and sealants.

It is to be understood that the invention disclosed and described in this specification is not limited to the embodiments summarized in the summary of the invention section.

These and other advantages and benefits of the present invention will be apparent from the detailed description of the invention below.

Detailed Description

The present invention will now be described for purposes of illustration and not limitation. Except in the operating examples, or where otherwise indicated, all numbers expressing quantities, percentages, and so forth, in the specification are to be understood as being modified in all instances by the term "about".

Any numerical range recited in this specification is intended to include all sub-ranges within the recited range with the same numerical precision. For example, a range of "1.0 to 10.0" is intended to include all sub-ranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, i.e., all sub-ranges having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, e.g., 2.4 to 7.6. Any maximum numerical limitation recited in this specification is intended to include all lower numerical limitations subsumed therein, and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, applicants reserve the right to modify the specification (including the claims) to specifically recite any sub-ranges subsumed within the ranges specifically recited herein. All such ranges are intended to be inherently described in this specification such that modifications to explicitly recite any such sub-ranges would comply with the requirements of 35 u.s.c. § 112(a) and 35 u.s.c. § 132 (a).

Unless otherwise indicated, the entire contents of any patent, publication, or other disclosure material identified herein are incorporated by reference into this specification, but only to the extent that the incorporated material does not conflict with existing definitions, statements, or other disclosure material set forth in this specification. As such, and to the extent necessary, the explicit disclosure set forth in this specification supersedes any conflicting material incorporated herein by reference. That is, any material, or portion thereof, that is incorporated by reference into this specification, but which conflicts with existing definitions, statements, or other disclosure material set forth herein is only incorporated to the extent that no conflict arises between that incorporated material and the existing disclosure material. Applicants reserve the right to modify the specification to specifically list any subject matter or portion thereof incorporated by reference herein.

Throughout the specification, references to "various non-limiting embodiments," "certain embodiments," and the like, mean that a particular feature or characteristic may be included in an embodiment. Thus, use of the phrases "in various non-limiting embodiments," "in certain embodiments," and the like in this specification does not necessarily refer to a common embodiment, and may refer to different embodiments. Furthermore, the particular features or characteristics may be combined in any suitable manner in one or more embodiments. Thus, particular features or characteristics illustrated or described in connection with various or certain embodiments may be combined, in whole or in part, with features or characteristics of one or more other embodiments without limitation. Such modifications and variations are intended to be included within the scope of this description.

As used herein, the grammatical articles "a", "an" and "the" are intended to include "at least one" or "one or more", even if "at least one" or "one or more" is used in some instances, unless otherwise indicated. Thus, an item as used in this specification refers to one or more of the grammatical object of the item (i.e., "at least one"). For example, but not limited to, "a component" refers to one or more components, thus, more than one component is contemplated and may be employed or used in the implementation of the described embodiments. Furthermore, the use of a singular noun includes the plural, and the use of a plural noun includes the singular, unless the context of use requires otherwise.

While compositions and methods have been described in terms of "comprising" various compositions or steps, the compositions and methods can also "consist essentially of" or "consist of" the various compositions or steps.

In various embodiments, the instant invention provides a reaction mixture comprising a polyuretdione resin; a polyol; and an acid blocked tertiary amine catalyst; and optionally, an additive package (e.g., flow control agent, wetting agent) and a solvent, wherein the acid has a pKa greater than 4.82. In certain embodiments, the instant invention further provides a process comprising reacting a polyuretdione resin with a polyol in the presence of an acid blocked tertiary amine catalyst, wherein the reaction mixture optionally comprises an additive package (e.g., flow control agent, wetting agent) and a solvent, and wherein the acid has a pKa greater than 4.82. The acid blocked tertiary amine catalyst can be activated at any temperature from room temperature (20 ℃) to 130 ℃.

The allophanate polymers of the invention are particularly useful in coatings, adhesives, castings, composites and sealants.

As used herein, the term "polymer" includes prepolymers, oligomers, and both homopolymers and copolymers; herein, the prefix "poly" refers to two or more. As used herein, unless otherwise specified, the term "molecular weight" when used in reference to a polymer refers to number average molecular weight.

As used herein, the term "coating composition" refers to a mixture of chemical components that, when applied to a substrate, will cure and form a coating.

The term "adhesive" or "adhesive compound" refers to any substance that can adhere or bond two items together. Implicit in the definition of "adhesive composition" or "adhesive formulation" is the concept that the composition or formulation is a combination or mixture of more than one substance, component or compound, which may include adhesive monomers, oligomers, and polymers, as well as other materials.

"sealant composition" refers to a composition that can be applied to one or more surfaces to form a protective barrier, for example, to prevent ingress or egress of solid, liquid, or gaseous materials, or alternatively to allow selective permeation through gas and liquid barriers. In particular, it may provide a seal between surfaces.

"casting composition" refers to a mixture of liquid chemical components, which is typically poured into a mold containing a hollow cavity of the desired shape and then allowed to cure.

"composite" refers to a material made of two or more polymers, optionally including other kinds of materials. The properties of the composite material are different from the properties of the individual polymers/materials that make up it.

"cured", "cured composition" or "cured compound" refers to components and mixtures obtained from a reactive curable starting compound or mixture thereof that has undergone a chemical and/or physical change such that the starting compound or mixture is converted into a solid, substantially non-flowing material. A typical curing process may involve crosslinking.

The term "curable" refers to a material that can be converted from a starting compound or composition material into a solid, substantially non-flowing material by chemical reaction, crosslinking, radiation crosslinking, and the like. Thus, the compositions of the present invention are curable, but the starting compound or composition material is not cured unless otherwise specified.

The compositions useful in the present invention comprise a polyisocyanate. As used herein, the term "polyisocyanate" refers to a compound that contains at least two unreacted isocyanate groups, for example three or more unreacted isocyanate groups. The polyisocyanate may include diisocyanates such as linear aliphatic polyisocyanates, aromatic polyisocyanates, cycloaliphatic polyisocyanates, and aralkyl polyisocyanates.

Particularly preferred in the context of the present invention are those blocked isocyanates which are referred to as uretdiones. The uretdione compounds which can be used in the present invention can be obtained by catalytic dimerization of polyisocyanates by methods known to the person skilled in the art. Examples of dimerization catalysts include, but are not limited to, trialkylphosphines, aminophosphines and aminopyridines, such as dimethylaminopyridines, and tris (dimethylamino) phosphine, as well as any other dimerization catalyst. The result of the dimerization reaction depends, in a manner known to the person skilled in the art, on the catalyst used, on the process conditions and on the polyisocyanate employed. In particular, products may be formed which contain on average more than one uretdione group per molecule, the number of uretdione groups being subject to distribution. In addition to the uretdione groups, the (poly) uretdiones may optionally contain isocyanurate, biuret, allophanate and iminooxadiazinedione groups.

Uretdione compounds are NCO-functional compounds and may be subjected to further reactions, such as blocking of free NCO groups, or further reaction of NCO groups with NCO-reactive compounds having a functionality of 2 or more to extend uretdione to form polyuretdione prepolymers. This results in compounds which contain uretdione groups and have a higher molecular weight, which, depending on the ratio selected, may also contain NCO groups, contain no NCO groups or may contain blocked isocyanate groups.

Suitable blocking agents include, but are not limited to, alcohols, lactams, oximes, malonates, alkyl acetoacetates, triazoles, phenols, imidazoles, pyrazoles and amines, such as butanone oxime, diisopropylamine, 1,2, 4-triazole, dimethyl-1, 2, 4-triazole, imidazole, diethyl malonate, ethyl acetoacetate, acetoxime, 3, 5-dimethylpyrazole, caprolactam, N-t-butylbenzylamine and cyclopentanone, including mixtures of these blocking agents.

Examples of NCO-reactive compounds having a functionality of 2 or greater include polyols. In some embodiments, the NCO-reactive compound is used in an amount sufficient to react with all free NCO groups in the uretdione. By "free NCO groups" is meant all NCO groups that are not present as part of uretdione, isocyanurate, biuret, allophanate, and iminooxadiazinedione groups.

The polyuretdione produced comprises at least 2, for example 2 to 10, uretdione groups. More preferably, the polyuretdione comprises 5% to 45% uretdione, 10% to 55% urethane and less than 2% isocyanate groups. The percentages are weight percentages based on the total weight of the resin comprising uretdione, urethane, and isocyanate.

Suitable polyisocyanates for use in producing the uretdione compounds useful in embodiments of the present invention include organic diisocyanates represented by the following formula:

R(NCO)₂

wherein R represents an organic group obtained by removing an isocyanate group from an organic diisocyanate having a (cyclo) aliphatically bonded isocyanate group and having a molecular weight of 112 to 1000, preferably 140 to 400. Preferred diisocyanates for the purposes of the present invention are those represented by the formula, wherein R represents a divalent aliphatic hydrocarbon radical having from 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon radical having from 5 to 15 carbon atoms or a divalent araliphatic hydrocarbon radical having from 7 to 15 carbon atoms.

Examples of organic diisocyanates particularly suitable for use in the present invention include 1, 4-tetramethylene diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), 2,2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, cyclohexane-1, 3-and 1, 4-diisocyanate, 1-isocyanato-2-isocyanato-methylcyclopentane, 1-isocyanato-3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane (isophorone diisocyanate or IPDI), bis- (4-isocyanatocyclohexyl) methane, 1, 3-and 1, 4-bis (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methyl-cyclohexyl) -methane, α, α, α ', α' -tetramethyl-1, 3-and 1, 4-xylene diisocyanate, 1-isocyanato-1-methyl-4 (3) -isocyanato-methylcyclohexane, and 2, 4-and 2, 6-hexahydrotoluene diisocyanate, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Pentane Diisocyanate (PDI) -biobased, and, isomers of any of these; or a combination of any of these. Mixtures of diisocyanates may also be used. Preferred diisocyanates include 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, and bis (4-isocyanatocyclohexyl) -methane because they are readily available and produce a relatively low viscosity polyuretdione polyurethane oligomer.

In some embodiments, the uretdione compounds may comprise 35% to 85% resin solids in the compositions of the invention excluding solvents, additives, or pigments. From 50% to 85% in other embodiments, and from 60% to 85% in still other embodiments. The uretidiones may comprise any amount of resin solids between any combination of these values, inclusive of the recited values.

As is known to those skilled in the art, some acid-blocked tertiary amine catalysts are susceptible to reversible dissociation upon heating. CO used as blowing agent is produced due to the heating necessary to activate the catalyst₂Such catalysts are therefore often included in formulations used to produce polyurethane foams.

In various embodiments, the tertiary amine of the tertiary amine catalyst includes, but is not limited to, triethylenediamine; substituted imidazoles, such as 1-2 dimethyl imidazole, 1-methyl-2-hydroxyethyl imidazole; n, N '-dimethylpiperazine or substituted piperazines, such as aminoethylpiperazine or bis (N-methylpiperazine) ethylurea or N, N' -trimethylaminoethylpiperazine; n-methylpyrrolidines and substituted methylpyrrolidines, such as 2-aminoethyl-N, methylpyrrolidines or bis (N-methylpyrrolidine) ethylurea; or other tertiary aminoalkyl ureas or bis (tertiary aminoalkyl) ureas, such as N, N- (3-dimethylaminopropyl) urea; 3-dimethylaminopropylamine; n, N "-tetramethyldipropylenetriamine; n, N-bis (3-dimethylaminopropyl) 1-3 propanediamine; n, N-dimethylamino-N ', N' -bis (hydroxy- (2) -propylidene (1,3) diamine; tetramethylguanidine; dimethylaminopropylamine, 1, 2-bis-diisopropylalcohol (3-dimethyl-aminopropylamine), substituted piperidines and aminotriazines such as N, N-dimethylamino-N ', N' -bis (hydroxy- (2) -propylidene (1,3) diamine), N-dimethylamino-N '-diisopropylamine, N' -bis-diisopropylamine, N-dimethylaminopropyl₅N-dimethylaminopropyl-S-triazine.

In certain embodiments, the tertiary amine catalyst is an acid blocked form of: 1, 8-diazabicyclo [5.4.0] undec-7-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1,4,5, 6-tetrahydro-1, 2-dimethylpyrimidine, 1,2, 4-triazole, sodium derivatives, and 2-tert-butyl-1, 1,3, 3-tetramethylguanidine and combinations thereof.

In various embodiments of the present invention, suitable acids for blocking tertiary amines includeOrganic carboxylic acids, including C₁-C₂₀Mono-or dicarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, carbolic acid, 2-ethylhexanoic acid, caprylic acid, cyanoacetic acid, pyruvic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, salicylic acid and maleic acid.

Examples of such acid blocked tertiary amine catalysts that may be used in embodiments of the present invention include, but are not limited to, those available from Air Products under the tradenames POLYCAT, DABCO, LK and VERSALINK, those available from Momentive Performance Materials under the tradename NIAX; and JEFFCAT catalyst from Huntsman.

In some embodiments of the invention, the acid-blocked tertiary amine catalyst may be heated to a temperature of 100 ℃. In other embodiments, a broader temperature range from room temperature (-20 ℃) to 130 ℃ may be used.

The inventors have surprisingly found that the pKa of the acid component of the acid-blocked tertiary amine catalyst has an effect on the pot life and physical properties of the resulting material. Those acids having pKa of 4.82 or less appear to be less effective in extending pot life and maintaining physical properties. Those acids with pKa greater than 5.0 gave better results, while those with pKa greater than 5.5 gave even better results. The inventors believe that those acids having a pKa of greater than 4.82 to 10 provide the best combination of pot life and physical properties in the resulting coatings, adhesives, castings, composites and sealants made from the compositions of the present invention.

The polyols useful in the present invention may be low molecular weight (62-399 Da, as determined by gel permeation chromatography) or high molecular weight (400 to 10,000 Da, as determined by gel permeation chromatography) materials and in various embodiments will have an average hydroxyl number of 1000 to 10, preferably 500 to 50, as determined by ASTM E222-10, method B.

The polyols in the present invention include low molecular weight diols, triols and higher alcohols as well as polymer polyols such as polyester polyols, polyether polyols, polyurethane polyols and hydroxyl group-containing (meth) acrylic polymers.

Low molecular weight diols, triols and higher alcohols useful in the present invention are known to those skilled in the art. In many embodiments, they are monomeric and have hydroxyl numbers above 200, typically in the range of 1500 to 200. Such materials include aliphatic polyols, particularly alkylene polyols containing from 2 to 18 carbon atoms. Examples include ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol; alicyclic polyols such as cyclohexanedimethanol. Examples of triols and higher alcohols include trimethylolpropane and pentaerythritol. Polyols containing ether linkages such as diethylene glycol and triethylene glycol may also be used.

In various embodiments, suitable polyols are polymer polyols having a hydroxyl number of less than 200, for example, from 10 to 180. Examples of the polymer polyol include polyalkylene ether polyols, polyester polyols, including polycaprolactone containing a hydroxyl group, a (meth) acrylic polymer containing a hydroxyl group, polycarbonate polyols, and polyurethane polymers.

Examples of polyether polyols include poly (oxytetramethylene) glycol, poly (oxyethylene) glycol, and the reaction products of ethylene glycol with mixtures of propylene oxide and ethylene oxide.

Polyether polyols formed by the alkoxylation of various polyols, such as diols, e.g., ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, and the like, or higher polyols, e.g., trimethylolpropane, pentaerythritol, and the like, may also be used. One commonly used alkoxylation process is to react a polyol with an alkylene oxide, such as ethylene oxide, in the presence of an acidic or basic catalyst.

In certain embodiments of the present invention, polyester polyols may also be used as the polymer polyol component. The polyester polyol can be prepared by polyesterification of an organic polycarboxylic acid or anhydride thereof with an organic polyol. Preferably, the polycarboxylic acids and polyols are aliphatic or aromatic diacids and diols.

Diols useful in the preparation of the polyesters include alkylene glycols, such as ethylene glycol and butylene glycol, neopentyl glycol and other glycols, such as cyclohexanedimethanol, caprolactone glycols (e.g., the reaction product of caprolactone and ethylene glycol), polyether glycols, such as poly (oxytetramethylene) glycol, and the like. However, various types of other diols, as well as higher functionality polyols as noted, may also be used in various embodiments of the present invention. Such higher polyols may include, for example, trimethylolpropane, trimethylolethane, pentaerythritol, and the like, as well as higher molecular weight polyols such as those prepared by alkoxylating low molecular weight polyols. An example of such a high molecular weight polyol is the reaction product of 20 moles of ethylene oxide per mole of trimethylolpropane.

The acid component of the polyester consists essentially of monomeric carboxylic acids or anhydrides having from 2 to 18 carbon atoms per molecule. Acids which may be used include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid, chlorendic acid, tetrachlorophthalic acid and various types of other dicarboxylic acids. Also, higher polycarboxylic acids such as trimellitic acid and tricarballylic acid may be used (where the acids mentioned above, it being understood that anhydrides of those acids which form anhydrides may be used in place of the acids). Likewise, lower alkyl esters of acids, such as dimethyl glutamate, may be used.

In addition to polyester polyols formed from polybasic acids and polyols, polycaprolactone-type polyesters may also be used. These products are formed from the reaction of a cyclic lactone such as caprolactone with a polyol having primary hydroxyl groups as described above. Such a product is described in U.S. patent No. 3,169,949.

In addition to polyether and polyester polyols, (meth) acrylic polymers or (meth) acrylic polyols containing hydroxyl groups may be used as the polyol component.

2 to 20% by weight of the polymer in the (meth) acrylic polymer is a vinyl monomer containing a primary hydroxyl group, such as hydroxyalkyl acrylates and hydroxyalkyl methacrylates having 2 to 6 carbon atoms in the alkyl group, and 80 to 98% by weight is other ethylenically unsaturated copolymerizable material such as alkyl (meth) acrylate; the weight percentages are based on the total weight of the monomer charge (charge).

Examples of suitable hydroxyalkyl (meth) acrylates are hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate. Examples of suitable alkyl acrylates and alkyl (meth) acrylates are lauryl methacrylate, 2-ethylhexyl methacrylate and n-butyl acrylate.

In addition to the acrylic and methacrylic esters, other copolymerizable monomers which can be copolymerized with the hydroxyalkyl (meth) acrylates include ethylenically unsaturated materials such as monoolefins and diolefins, halogenated monoolefins and diolefins, unsaturated esters of organic and inorganic acids, amides and esters of unsaturated acids, nitriles and unsaturated acids, and the like. Examples of such monomers include styrene, 1, 3-butadiene, acrylamide, acrylonitrile, alpha-methylstyrene, alpha-methylchlorostyrene, vinyl butyrate, vinyl acetate, alkyl chlorides, divinylbenzene, diallyl itaconate, triallyl cyanurate and mixtures thereof. Preferably, these other ethylenically unsaturated materials are used in admixture with the above-mentioned acrylates and methacrylates.

Suitable hydroxy-functional polycarbonate polyols may be those prepared by reacting a monomeric diol (e.g., 1, 4-butanediol, 1, 6-hexanediol, di-, tri-, or tetraethylene glycol, di-, tri-, or tetrapropylene glycol, 3-methyl-1, 5-pentanediol, 4,4' -dimethylolcyclohexane, and mixtures thereof) with a diaryl carbonate (e.g., diphenyl carbonate, dialkyl carbonates (e.g., dimethyl carbonate and diethyl carbonate), alkylene carbonates (e.g., ethylene carbonate or propylene carbonate), or phosgene.

In various embodiments of the invention, the polyol is neutralized, for example, by the addition of an acid scavenger. The acid scavenger should be covalently bonded to the acidic groups in the polyol. The acid scavenger may be from the family of carboxylic or acrylic group reactants, such as carbodiimide-based compounds, anhydrides, epoxides, trialkyl orthoformates, amine compounds or oxazoline-based compounds. The inventors believe, without wishing to be bound by any particular theory, that these acid scavengers are covalently bound to carboxylic acid groups and acrylic acid groups in the polyol. Such compounds are commercially available from a number of suppliers, for example monomeric carbodiimide sold under the trade name STABAXOL by Rhein Chemie and bis (2, 6-diisopropylphenyl) carbodiimide sold as EUSTAB HS-700 by Eutec Chemical co.

In certain embodiments of the present invention, the polyol may be a polyurethane polyol. These polyols can be prepared by reacting any of the above polyols with a small amount of polyisocyanate (OH: NCO equivalent ratio greater than 1: 1) such that free primary hydroxyl groups are present in the product. In addition to the high molecular weight polyols described above, mixtures of both high and low molecular weight polyols (such as those described above) may also be used.

The compositions of the present invention may further comprise any of a variety of additives, such as defoamers, devolatilizers, surfactants, thickeners, flow control additives, colorants (including pigments and dyes) or surface additives.

Examples of suitable solvents include, but are not limited to, aliphatic and aromatic hydrocarbons, such as toluene, xylene, isooctane, acetone, butanone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, amyl acetate, tetrahydrofuran, ethyl ethoxypropionate, N-methylpyrrolidone, dimethylacetamide and dimethylformamide solvents naphtha, solvasso 100 or hydro sol (ara), ethers or mixtures thereof.

The compositions of the present invention may be contacted with the substrate by any method known to those skilled in the art, including but not limited to spraying, dipping, flow coating, roll coating, brushing, pouring, and the like. In some embodiments, the compositions of the present invention may be applied in the form of paints or varnishes to any compatible substrate, such as metals, plastics, ceramics, glass and natural materials. In certain embodiments, the composition is applied as a monolayer. In other embodiments, the compositions of the present invention may be applied as multiple layers as desired.

Examples

The following non-limiting and non-exhaustive examples are intended to further describe various non-limiting and non-exhaustive embodiments, but not to limit the scope of the embodiments described in this specification. Unless otherwise indicated, all amounts given in "parts" and "percentages" are to be understood as being by weight. Although the invention is described in the examples in the context of coatings, it will be understood by those skilled in the art that the invention is equally applicable to adhesives, castings, composites and sealants. The pKa values reported below are provided by the manufacturer.

The following materials were used to prepare the compositions of the examples:

polyol a an aromatic-free, hydroxyl-containing, branched polyester polyol commercially available from Covestro as DESMOPHEN 775 XP;

additive a an active hydrolysis resistant agent for polyester polyurethane, useful as an acid scavenger for acid groups in polyols, commercially available as STABAXOL I from Rhein Chemie;

additive B a polyacrylate based surface additive for solvent borne coating systems and printing inks, commercially available from BYK Chemie as BYK 358N;

catalyst A1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), a tertiary amine catalyst, commercially available as POLYCAT DBU from Air Products;

catalyst B a low-emissive, acid-blocked (pK)_a2.89 and 5.51) DBU-based tertiary amine catalyst, an-50% DBU content, commercially available from Air Products as POLYCAT SA2 LE;

catalyst C an acid blocked (pKa of 10.0) tertiary amine catalyst, based on DBU, -60% DBU content, commercially available from Air Products as POLYCAT SA-1;

catalyst D an acid-blocked (pKa of 4.82) thermally activated tertiary amine catalyst, based on the DBU, -40% DBU content, commercially available from Air Products as POLYCAT SA-102;

catalyst E an acid-blocked (pKa of 2.97) thermally activated tertiary amine catalyst, based on DBU, -30% DBU content, commercially available as NIAX a-575 from Momentive Performance Materials;

catalyst F an acid blocked (pKa of 2.89 and 5.51) thermally activated tertiary amine catalyst, based on DBU, 30% DBU content, commercially available from Air Products as POLYCAT SA 8;

uretdione A uretdione based on 1-isocyanato-3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane (isophorone diisocyanate or IPDI) is commercially available from Covestro as CRELAN EF 403.

Coating formulation 1 was prepared as follows: prior to formulation, 11.69 parts of polyol a and 0.12 parts of additive a were mixed and stored at 80 ℃ for one week. In a 200mL plastic container, 11.81 parts of a mixture of additive A and polyol A, 0.47 parts of additive B, 6.60 parts of n-Butyl Acetate (BA), 0.25 parts of catalyst A were added. The resulting mixture was mixed for one minute using a FLACKTEK speed mixer. Then, 80.51 parts of uretdione A solution (50% in n-butyl acetate) are added to the mixture. The resulting mixture was mixed for a further minute and then applied to a test panel using a drawdown bar. The formulations of the other examples were prepared in a similar manner according to the amounts and ingredients listed in table I.

To evaluate microhardness and MEK double rubs, test samples were prepared by applying the formulation at a thickness of 4 mils (100 μm) of wet film (2 mils (50 μm) after drying) on a 4 "x 12" (10.2 cm x 30.5 cm) steel test panel (ACT B1000) pretreated with iron phosphate.

The "room temperature" films were cured at 20-25 ℃ for 24 hours prior to testing. Before testing, the "100 ℃ film was cured in an electric oven at 100 ℃ for 30 minutes and left at room temperature for 24 hours.

Measurement of the microhardness ("mahalanobis hardness") was carried out according to the method described in DIN EN ISO 14577, using a FISCHERSCOPE H100C instrument. Microhardness readings were taken at 20 mN test load developed to a maximum of 5 μm indentation depth during an application time of 20 seconds. The results reported are the average of three readings for each formulation.

MEK double rubs were measured according to ASTM D4752-10 (2015). The results reported are the average of three readings for each formulation.

The viscosity of the formulation was measured using a BROOKFIELD RST rheometer at 25 ℃, 100s-1 shear rate, with a RST-50-1 spindle, for two minutes, according to ASTM D7395-07 (2012). "initial viscosity" refers to the viscosity of the composition at the time of manufacture, and "1 hour viscosity" refers to the viscosity of the composition one hour after manufacture.

Table I includes data comparing various forms of catalysts comprising acid blocked and unblocked DBUs. Including hardness testing, chemical resistance by MEK double rub, and pot life results from viscosity over time. The formulations of examples 1,3, 5,7, 9 and 11 are in comparison to the formulations of examples 2,4, 5,6, 10 and 12 using 1% DBU catalyst (based on solids) in terms of DBU amount (0.5% DBU loading (based on solids)). The catalyst levels included in table I illustrate DBU catalyst and acid blocking agent. Examples 3, 4,5 and 6 show improvements in pot life without sacrificing physical properties compared to the unblocked catalysts of examples 1 and 2.

As demonstrated in the examples, the pKa of the acid blocking agent has an effect on pot life and physical properties. The acid blocking agent used in examples 5 and 6 had a pKa of 10 (catalyst C), which showed an improvement in pot life without sacrificing physical properties. The pKa of the acid blocking agent used in examples 7 and 8 was 4.82 (catalyst D), which showed an improvement in pot life; however, the physical properties are insufficient. The acid blocking agent used in examples 9 and 10 had a pKa of 2.97 (catalyst E), which in turn showed an improvement in pot life; however, the physical properties are insufficient. The acid blocking agents used in examples 3, 4, 11 and 12 had two pKa values and were the same (catalyst B and catalyst F). Catalyst B and catalyst F have the same acid blocking agent. Examples 3 and 4 (using catalyst B) show improvements in pot life without sacrificing physical properties. Examples 11 and 12 (using catalyst F) show an improvement in pot life; however, the physical properties are insufficient. The reason for this difference is the amount of DBU present compared to the acidic groups. Catalyst B has 50% DBU, where two acid groups with pKa 2.89 and 5.51 were used during blocking. Catalyst F has 30% DBU, with most of the DBU being blocked with a stronger acid with a pKa of 2.89 rather than a pKa of 5.51. The effect of the pKa of the acid blocking agent is well demonstrated by a comparison of the properties of the formulations using catalysts B and F (examples 3, 4, 11 and 12), where a pKa higher than 4.82 is required in order to improve pot life without sacrificing physical properties.

The compositions of the present invention are particularly suitable for or as coatings, adhesives, castings, composites and sealants, with good properties and extended pot life.

This description has been written with reference to various non-limiting and non-exhaustive embodiments. However, one of ordinary skill in the art will recognize that various substitutions, modifications, or combinations of any of the embodiments (or portions thereof) disclosed may be made within the scope of the present description. Accordingly, it is contemplated and understood that this specification supports other embodiments not explicitly set forth herein. Such embodiments may be obtained, for example, by combining, modifying or reorganizing any of the disclosed steps, components, elements, features, aspects, characteristics, limitations, etc. of the various non-limiting embodiments described in this specification. In this manner, applicants reserve the right to modify the claims during the application to add various features described in this specification, and such modifications are in compliance with the requirements of 35 u.s.c. § 112(a) and 35 u.s.c. § 132 (a).

Various aspects of the subject matter described herein are set forth in the following numbered clauses:

1. a reaction mixture comprising: a polyuretdione resin; a neutralized polyol; an acid blocked tertiary amine catalyst; and optionally, an additive package selected from the group consisting of flow control additives, wetting agents, and solvents, wherein the acid has a pKa greater than 4.82.

2. The reaction mixture according to clause 1, wherein the polyuretdione resin comprises the reaction product of the catalytic dimerization of isocyanates.

3. The reaction mixture according to clause 2, wherein the isocyanate is selected from the group consisting of 1, 4-tetramethylene diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), 2,2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, cyclohexane-1, 3-and 1, 4-diisocyanate, 1-isocyanato-2-isocyanato-methylcyclopentane, 1-isocyanato-3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane (isophorone diisocyanate or IPDI), bis- (4-isocyanatocyclohexyl) methane, 1, 3-and 1, 4-bis (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methyl-cyclohexyl) -methane, α, α, α ', α' -tetramethyl-1, 3-and 1, 4-xylene diisocyanate, 1-isocyanato-1-methyl-4 (3) -isocyanato-methylcyclohexane, and 2, 4-and 2, 6-hexahydrotoluene diisocyanate, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Pentane Diisocyanate (PDI) -biobased, and, isomers of any of these.

4. The reaction mixture according to one of clauses 1 to 3, wherein the acid has a pKa greater than 5.0

5. The reaction mixture according to one of clauses 1 to 4, wherein the acid has a pKa greater than 5.5.

6. The reaction mixture according to one of clauses 1 to 3, wherein the acid has a pKa in the range of greater than 4.82 to 10.

7. The reaction mixture according to one of clauses 1 to 6, wherein the acid-blocked tertiary amine catalyst comprises an amidine.

8. The reaction mixture according to one of clauses 1 to 7, wherein the acid-blocked tertiary amine catalyst comprises one selected from the group consisting of: 1, 8-diazabicyclo [5.4.0] undec-7-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1,4,5, 6-tetrahydro-1, 2-dimethylpyrimidine, 1,2, 4-triazole, sodium derivatives, and 2-tert-butyl-1, 1,3, 3-tetramethylguanidine and combinations thereof.

9. The reaction mixture according to one of clauses 1 to 8, wherein the acid comprises a mono-or dicarboxylic acid having 1 to 20 carbon atoms.

10. The reaction mixture according to one of clauses 1 to 9, wherein the acid is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, caproic acid, carbolic acid, 2-ethylhexanoic acid, caprylic acid, cyanoacetic acid, pyruvic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, salicylic acid, and maleic acid, and combinations thereof.

11. The reaction mixture according to one of clauses 1 to 10, wherein the polyol is selected from one or more of the following: polyether polyols, polyester polyols, (meth) acrylic polymers and (meth) acrylic polyols containing hydroxyl groups, polyurethane polyols, polycaprolactone polyols and combinations thereof.

12. The reaction mixture according to one of clauses 1 to 11, wherein the neutralized polyol comprises the reaction product of a polyol and an acid scavenger.

13. The reaction mixture according to clause 12, wherein the acid scavenger is covalently bonded to the acidic groups in the polyol and is selected from the group consisting of carbodiimide-based compounds, anhydrides, epoxides, trialkyl orthoformates, amine compounds and oxazoline-based compounds, and combinations thereof.

14. The reaction mixture according to one of clauses 1 to 13, wherein the solvent is selected from the group consisting of toluene, xylene, isooctane, acetone, butanone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, amyl acetate, tetrahydrofuran, ethyl ethoxypropionate, N-methylpyrrolidone, dimethylacetamide, dimethylformamide solvent naphtha, ethers and mixtures thereof.

15. A method of applying a reaction mixture prepared according to one of clauses 1 to 14, wherein the method comprises at least one of spraying, dipping, flow coating, roll coating, brushing, and pouring.

16. One of a coating, an adhesive, a casting, a composite, and a sealant comprising the reaction mixture according to one of clauses 1 to 15.

17. A method of making a composition, the method comprising: reacting a polyuretdione resin with a neutralized polyol in the presence of an acid blocked tertiary amine catalyst, wherein the acid has a pKa greater than 4.82.

18. The method according to clause 17, wherein the composition further comprises an additive package selected from the group consisting of flow control additives, wetting agents, and solvents.

19. The method of one of clauses 17 and 18, wherein the polyuretdione resin comprises the reaction product of the catalytic dimerization of isocyanates.

20. The process according to clause 19, wherein the isocyanate is selected from the group consisting of 1, 4-tetramethylene diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), 2,2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, cyclohexane-1, 3-and 1, 4-diisocyanate, 1-isocyanato-2-isocyanato-methylcyclopentane, 1-isocyanato-3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane (isophorone diisocyanate or IPDI), bis- (4-isocyanatocyclohexyl) methane, 1, 3-and 1, 4-bis (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methyl-cyclohexyl) -methane, α, α, α ', α' -tetramethyl-1, 3-and 1, 4-xylene diisocyanate, 1-isocyanato-1-methyl-4 (3) -isocyanato-methylcyclohexane, and 2, 4-and 2, 6-hexahydrotoluene diisocyanate, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Pentane Diisocyanate (PDI) -biobased, and, isomers of any of these.

21. The method according to one of clauses 17 to 20, wherein the acid has a pKa greater than 5.0.

22. The method according to one of clauses 17 to 21, wherein the acid has a pKa greater than 5.5.

23. The method according to one of clauses 17 to 22, wherein the acid has a pKa of greater than 4.82 to 10.

24. The method according to one of clauses 17 to 23, wherein the acid-blocked tertiary amine catalyst comprises an amidine.

25. The method according to one of clauses 17 to 24, wherein the acid-blocked tertiary amine catalyst comprises one selected from the group consisting of: 1, 8-diazabicyclo [5.4.0] undec-7-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1,4,5, 6-tetrahydro-1, 2-dimethylpyrimidine, 1,2, 4-triazole, sodium derivatives, and 2-tert-butyl-1, 1,3, 3-tetramethylguanidine and combinations thereof.

26. The method according to one of clauses 17 to 25, wherein the acid comprises a mono-or dicarboxylic acid having 1-20 carbon atoms.

27. The method according to any one of clauses 17 to 26, wherein the acid is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, caproic acid, carbolic acid, 2-ethylhexanoic acid, caprylic acid, cyanoacetic acid, pyruvic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, salicylic acid, and maleic acid, and combinations thereof.

28. The method according to one of clauses 17 to 27, wherein the polyol is selected from one or more of the following: polyether polyols, polyester polyols, (meth) acrylic polymers and (meth) acrylic polyols containing hydroxyl groups, polyurethane polyols, polycaprolactone polyols and combinations thereof.

29. The method according to one of clauses 17 to 28, wherein the neutralized polyol comprises the reaction product of a polyol and an acid scavenger.

30. The method according to clause 29, wherein the acid scavenger is covalently bonded to the acidic group in the polyol and is selected from the group consisting of carbodiimide-based compounds, anhydrides, epoxides, trialkyl orthoformates, amine compounds and oxazoline-based compounds, and combinations thereof.

31. The method according to one of clauses 17 to 30, wherein the solvent is selected from the group consisting of toluene, xylene, isooctane, acetone, butanone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, amyl acetate, tetrahydrofuran, ethyl ethoxypropionate, N-methylpyrrolidone, dimethylacetamide, dimethylformamide solvent naphtha, ethers and mixtures thereof.

32. The method according to one of clauses 17 to 31, wherein the reacting step occurs at 20 ℃ to 25 ℃.

33. The method according to one of clauses 17 to 32, wherein the reaction of the polyuretdione resin with the polyol occurs in the presence of the acid-blocked tertiary amine catalyst at a temperature of 20 ℃ to 130 ℃.

34. The method according to clause 33, wherein the temperature is 100 ℃.

35. A method of applying a reaction mixture made according to one of clauses 17 to 34, wherein the method comprises at least one of spraying, dipping, flow coating, roll coating, brushing, and pouring.

36. One of a coating, an adhesive, a casting, a composite, and a sealant comprising the composition prepared according to the method of one of clauses 17 to 35.

Claims

1. A reaction mixture comprising:

a polyuretdione resin;

a neutralized polyol; and

an acid blocked tertiary amine catalyst; and

optionally, the step of (a) is carried out,

an additive package selected from the group consisting of flow control additives, wetting agents, and solvents,

wherein the acid has a pKa greater than 4.82.

2. The reaction mixture of claim 1, wherein the polyuretdione resin comprises the reaction product of the catalytic dimerization of isocyanates.

3. The reaction mixture according to claim 2, wherein the isocyanate is selected from the group consisting of 1, 4-tetramethylene diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), 2,2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, cyclohexane-1, 3-and 1, 4-diisocyanate, 1-isocyanato-2-isocyanato-methylcyclopentane, 1-isocyanato-3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane (isophorone diisocyanate or IPDI), bis- (4-isocyanatocyclohexyl) methane, 1, 3-and 1, 4-bis (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methyl-cyclohexyl) -methane, α, α, α ', α' -tetramethyl-1, 3-and 1, 4-xylene diisocyanate, 1-isocyanato-1-methyl-4 (3) -isocyanato-methylcyclohexane, and 2, 4-and 2, 6-hexahydrotoluene diisocyanate, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Pentane Diisocyanate (PDI) -biobased, and, isomers of any of these.

4. The reaction mixture of claim 1, wherein the acid-blocked tertiary amine catalyst comprises an amidine.

5. The reaction mixture of claim 1, wherein the acid-blocked tertiary amine comprises one selected from the group consisting of: 1, 8-diazabicyclo [5.4.0] undec-7-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1,4,5, 6-tetrahydro-1, 2-dimethylpyrimidine, 1,2, 4-triazole, sodium derivatives, and 2-tert-butyl-1, 1,3, 3-tetramethylguanidine and combinations thereof.

6. The reaction mixture of claim 1, wherein the acid is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, caproic acid, carbolic acid, 2-ethylhexanoic acid, caprylic acid, cyanoacetic acid, pyruvic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, salicylic acid, and maleic acid, and combinations thereof.

7. The reaction mixture of claim 1, wherein the acid has a pKa greater than 5.0.

8. The reaction mixture of claim 1, wherein the acid has a pKa greater than 5.5.

9. The reaction mixture of claim 1, wherein the acid has a pKa of greater than 4.82 to 10.

10. The reaction mixture of claim 1, wherein the neutralized polyol comprises a reaction product of a polyol and an acid scavenger.

11. The reaction mixture of claim 10, wherein the acid scavenger is covalently bonded to an acidic group in the polyol and is selected from the group consisting of carbodiimide-based compounds, anhydrides, epoxides, trialkyl orthoformates, amine compounds, and oxazoline-based compounds, and combinations thereof.

12. The reaction mixture of claim 1, wherein the acid comprises a mono-or dicarboxylic acid having 1-20 carbon atoms.

13. The reaction mixture of claim 1, wherein the polyol is selected from the group consisting of: polyether polyols, polyester polyols, (meth) acrylic polymers and (meth) acrylic polyols containing hydroxyl groups, polyurethane polyols, polycarbonate polyols and polycaprolactone polyols and combinations thereof.

14. One of a coating, an adhesive, a casting, a composite, and a sealant comprising the reaction mixture of claim 1.

15. A method of making a composition, the method comprising:

the polyuretdione resin is reacted with a neutralized polyol and optionally an additive package selected from the group consisting of flow control additives, wetting agents and solvents in the presence of an acid blocked tertiary amine catalyst, wherein the acid has a pKa greater than 4.82.

16. The method of claim 15, wherein the polyuretdione resin comprises the reaction product of the catalytic dimerization of isocyanates.

17. The process of claim 16, wherein the isocyanate is selected from the group consisting of 1, 4-tetramethylene diisocyanate, 1, 6-Hexamethylene Diisocyanate (HDI), 2,2, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 12-dodecamethylene diisocyanate, cyclohexane-1, 3-and 1, 4-diisocyanate, 1-isocyanato-2-isocyanato-methylcyclopentane, 1-isocyanato-3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane (isophorone diisocyanate or IPDI), bis- (4-isocyanatocyclohexyl) methane, 1, 3-and 1, 4-bis (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methyl-cyclohexyl) -methane, α, α, α ', α' -tetramethyl-1, 3-and 1, 4-xylene diisocyanate, 1-isocyanato-1-methyl-4 (3) -isocyanato-methylcyclohexane, and 2, 4-and 2, 6-hexahydrotoluene diisocyanate, Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Pentane Diisocyanate (PDI) -biobased, and, isomers of any of these.

18. The method of claim 15, wherein the acid-blocked tertiary amine catalyst comprises an amidine.

19. The method of claim 15, where the acid-blocked tertiary amine catalyst comprises one selected from the group consisting of: 1, 8-diazabicyclo [5.4.0] undec-7-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1,4,5, 6-tetrahydro-1, 2-dimethylpyrimidine, 1,2, 4-triazole, sodium derivatives, and 2-tert-butyl-1, 1,3, 3-tetramethylguanidine and combinations thereof.

20. The method of claim 15, wherein the acid is selected from the group consisting of: formic acid, acetic acid, propionic acid, butyric acid, caproic acid, carbolic acid, 2-ethylhexanoic acid, caprylic acid, cyanoacetic acid, pyruvic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, salicylic acid, and maleic acid, and combinations thereof.

21. The method of claim 15, wherein the acid has a pKa greater than 5.0.

22. The method of claim 15, wherein the acid has a pKa greater than 5.5.

23. The method of claim 15, wherein the acid has a pKa of greater than 4.82 to 10.

24. The method of claim 15, wherein the neutralized polyol comprises a reaction product of a polyol and an acid scavenger.

25. The method of claim 24, wherein the acid scavenger is covalently bonded to an acidic group in the polyol and is selected from the group consisting of carbodiimide-based compounds, anhydrides, epoxides, trialkyl orthoformates, amine compounds, and oxazoline-based compounds, and combinations thereof.

26. The method of claim 15, wherein the acid comprises a mono-or dicarboxylic acid having 1-20 carbon atoms.

27. The method of claim 15, wherein the polyol is selected from the group consisting of: polyether polyols, polyester polyols, (meth) acrylic polymers and (meth) acrylic polyols containing hydroxyl groups, polyurethane polyols, polycarbonate polyols and polycaprolactone polyols and combinations thereof.

28. The method of claim 16, wherein the reaction of the polyuretdione resin with the polyol occurs in the presence of the acid-blocked tertiary amine catalyst at a temperature of 20 ℃ to 130 ℃.

29. One of a coating, an adhesive, a casting, a composite, and a sealant comprising the composition prepared according to the method of claim 15.