Polyurea compositions from polyaspartic acid esters and 2-substituted butanedioic acid esters.

Abstract

The present invention relates to a polyurea coating composition comprising (A) a polyisocyanate, (B) a polyaspartic acid ester, and (C) a 2-substituted butanedioic acid ester prepared by reacting a fumaric acid ester in a solution of the polyaspartic acid ester with a cyanoacetate, malononitrile, or a 1,3-diketone in the presence of a base.

Description

[Technical field]

[0001] 2. Background of the Invention Polyurea coating compositions having a polyisocyanate binder component and a polyaspartic acid ester hardener for reaction with the polyisocyanate are known in the art. The compositions have been used to prepare coatings that are weather resistant, abrasion resistant, and solvent resistant. In addition, the compositions may exhibit stiffness and elasticity.

[0002] EP-A-0,403,921 describes polyaspartic esters containing secondary polyamines in combination with lacquer polyisocyanates for the preparation of solvent-free or minimally solvent-based coatings. EP-A-0,531,249 uses coating compositions of polyaspartic esters in combination with hydroxyl-containing resins, polyaldimines, or ketimines as isocyanate-reactive components.

[0003] Polyaspartic acid esters are generally prepared by the reaction of polyamines with dialkyl esters of maleic or fumaric acid. If the preparation starts with maleic acid esters, rapid isomerization to fumaric acid esters occurs, which then react with polyamines to produce polyaspartic acid esters. The reaction of polyamines with the produced fumaric acid esters is much slower than the reaction with maleic acid esters. Thus, there is always a surplus of starting material after the production of polyaspartic acid esters. In U.S. Pat. Nos. 5,236,741 and 5,623,045, the starting material was removed by distillation, which is a costly and laborious process.

[0004] In our laboratory, we found that polyaspartates prepared from diethyl maleate / fumarate and bis(4-aminocyclohexyl)methane in a 1:1 molar ratio of reactants required several weeks to achieve near quantitative conversion of the maleate / fumarate starting materials. A similar method used for the preparation of polyaspartates using (3-methyl-4-aminocyclohexyl)methane required at least three months to achieve near quantitative conversion. As a result, the use of these products in commerce is severely hindered, as customers have to wait for a very long time between the production and receipt of the products. Furthermore, it has been reported that diethyl fumarate is an irritant, which may affect the health of workers who use these substances.

[0005] US Patent 6,737,500 describes a method for removing excess maleic / fumaric esters from the production of polyaspartic esters by carrying out the reaction in two steps. After the initial reaction of a cyclic amine with the fumaric or maleic esters, an acyclic amine is added to react with the excess fumaric or maleic esters. A similar method is used in US Patent 6,590,066, where an acyclic amine is used to remove the excess fumaric / maleic esters after the initial reaction of the maleic / fumaric esters with polypropylene oxide amines. These patents describe the production of polyaspartic ester mixtures. Polyaspartic esters derived from cyclic and polypropylene oxide amines react much slower with polyisocyanates than those derived from acyclic amines. Thus, the pot life or pot life of these mixtures is significantly reduced in coating applications. This can cause premature gelation of the polyurea coating, which can result in difficulty in applying such mixtures to the substrate to be coated.

[0006] There is a need in the art for polyaspartic acid esters that are free of fumarate or maleate contaminants, that can be produced in a timely and efficient manner, and that can be used in the production of polyuric acid coatings without affecting the curing properties of the polyuric acid coating.

[0007] BRIEF SUMMARY OF THE INVETION The present invention relates to (A) polyisocyanate; (B) [ka] [wherein Z is a cycloalkyl or alkyl group, R1 and R2 are alkyl groups having 1 to 10 carbon atoms, and n is 2 to 4]; and (C) 2-substituted butanedioic acid esters prepared by reacting a fumaric acid ester in a polyaspartic acid ester solution with cyanoacetate, malononitrile, or 1,3-diketone in the presence of a base. The present invention relates to a polyurea coating composition comprising:

[0008] The present invention also provides (A) polyisocyanate; (B) [ka] [wherein Z is a cycloalkyl or alkyl group, R1 and R2 are alkyl groups having 1 to 10 carbon atoms, and n is 2 to 4]; and (C) 2-substituted butanedioic acid esters prepared by reacting a fumaric acid ester in a polyaspartic acid ester solution with cyanoacetate, malononitrile, or 1,3-diketone in the presence of a base. The present invention relates to a method for preparing a polyurea coating by using a mixture of the components of

[0009] The present invention also relates to a method for the in situ preparation of a mixture of polyaspartic acid esters and 2-substituted butanedioic acid esters by first reacting a fumaric acid ester or maleic acid ester with a polyamine and then reacting the residual fumaric acid ester or maleic acid ester with a cyanoacetate or malononitrile or a 1,3-diketone to completion in the presence of a base. This method allows the preparation of polyurea coatings without the use of maleic acid esters or fumaric acid esters, thereby providing a safer and more environmentally friendly product.

[0010] Detailed Description of the Invention The present invention relates to (A) polyisocyanate; (B) [ka] [wherein Z is a cycloalkyl or alkyl group, R1 and R2 are alkyl groups having 1 to 10 carbon atoms, and n is 2 to 4]; and (C) 2-substituted butanedioic acid esters prepared by reacting a fumaric acid ester in a polyaspartic acid ester solution with cyanoacetate, malononitrile, or 1,3-diketone in the presence of a base. The present invention relates to a polyurea coating composition comprising:

[0011] The present disclosure also relates to a method for the in situ preparation of a mixture of polyaspartic acid ester and 2-substituted butanedioic acid ester by reacting a fumaric acid ester in a polyaspartic acid ester solution with a cyanoacetate, malononitrile, or a 1,3-diketone in the presence of a base, which is then used to prepare a polyurea coating by reaction with a polyisocyanate.

[0012] Polyaspartic acid esters are [ka] [wherein Z is a cycloalkyl or alkyl group, R1 and R2 are alkyl groups containing 1 to 10 carbon atoms, and n is 2 to 4]. The polyaspartic acid ester is preferably obtained by a Michael reaction between a maleic acid ester or a fumaric acid ester and an alicyclic or acyclic diamine or triamine. Suitable examples of suitable maleic acid esters include diethyl maleate, dipropyl maleate, dibutyl maleate, methyl propyl maleate, ethyl propyl maleate, etc. Suitable examples of suitable dialkyl fumarates include diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl propyl fumarate, ethyl propyl fumarate, and mixtures thereof.

[0013] The amine component is selected from difunctional or trifunctional cycloalkyl and linear or branched alkylamines.Preferred examples of suitable amines include, but are not limited to, 2,4'- and / or 4,4'-diaminodicyclohexylmethane and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane.More preferred examples of cycloalkylamines include bis-(3-methyl-4-aminocyclohexyl)methane, 2,4-diamino-1-methylcyclohexane and 2,6-diamino-1-methylcyclohexane, 2,4- and / or 2,6-hexahydrotolylenediamine and 3-aminomethyl-3,5,5-trimethylcyclohexylamine. Furthermore, aromatic polyamines such as, for example, 2,4- and / or 2,6-diaminotoluene, and 2,4'- and / or 4,4'-diaminodiphenyl-2,4- and / or 2,6-hexahydrotolylenediamine are also suitable, but less preferred.Further preferred examples of linear and branched alkylamines include ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, and 1,12-diaminododecane.

[0014] Further preferred examples of suitable trifunctional amines include 4-aminomethyl-1,8-diaminooctane (also known as triaminononane, supplied by Ascend Corporation), tris-(2-aminoethyl)amine. Further preferred tetrafunctional amines such as N,N,N',N'-tetrakis-(2-aminoethyl)-1,2-ethanediamine are also suitable.

[0015] Z is 2,4'- and / or 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, bis-(3-methyl-4-aminocyclohexyl)methane, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-methylcyclohexane, 2,4- and / or 2,6-hexahydrotolylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 2,4- and / or 2,6-diaminotoluene, 2,4'- and / or 4,4'-diamino Preferably, the cycloalkyl or alkyl group bonded to the amino group of aminodiphenyl-2,4- and / or 2,6-hexahydrotolylenediamine, ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-dimethylhexane, 2,2,4 and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 4-aminomethyl-1,8-diaminooctane, or tris-(2-aminoethyl)amine.

[0016] The present invention also relates to a method for the in situ preparation of a mixture of polyaspartic acid esters and 2-substituted butanedioic acid esters by reacting a fumaric acid ester or maleic acid ester with a polyamine, and then reacting the residual fumaric acid ester or maleic acid ester with a cyanoacetate, or malononitrile, or a 1,3-diketone in the presence of a base until completion. This mixture is then used to prepare a polyurea coating by reaction with a polyisocyanate.

[0017] During the formation of the polyaspartic acid ester component, in the first step of the method of the present invention, a fumarate or maleate ester is reacted with a diamine or triamine. In one embodiment, the molar ratio of the diamine to the maleate or fumarate ester ranges from 1:3 to 1:2. In another embodiment, the molar ratio of the diamine to the maleate or fumarate ester ranges from 1.0:2.5 to 1.0:2.2. In another embodiment, the molar ratio of the diamine to the maleate or fumarate ester ranges from 1.0:2.0. For the reaction of the maleate or fumarate ester with a triamine, in one embodiment, the molar ratio of the triamine to the maleate or fumarate ester ranges from 1.0:4.0 to 1.0:3.0. In another embodiment, the molar ratio of the triamine to the maleate or fumarate ester ranges from 1.0:3.5. In another embodiment, the molar ratio of triamine to maleate or fumarate is in the range of 1.0:3.0. The reaction is typically carried out for about 8 hours. The reaction is preferably carried out at a temperature between 25°C and 100°C. The reaction may be carried out in the absence or presence of a suitable solvent, such as, for example, methanol, ethanol, propanol, ethyl acetate or butyl acetate, and mixtures of these solvents. The reaction is typically carried out at atmospheric pressure.

[0018] In the second step of the process of the invention, the initially formed polyaspartic acid ester and unreacted fumarate or maleate are reacted with cyanoacetate, malononitrile, or 1,3-diketone in the presence of a base (Michael reaction). In this process, the excess fumarate and maleate are consumed during the Michael reaction to produce a mixture of polyaspartic acid ester and 2-substituted butanedioic acid ester. The amount of cyanoacetate, malononitrile, or 1,3-diketone used is based on the amount of fumarate and maleate present after the first polyaspartic acid ester synthesis step. This is determined by analysis of the reaction mixture by gas chromatography or a similar analytical technique. The molar ratio of fumarate and maleate bound to the cyanoacetate, malononitrile, or 1,3-diketone used is preferably about 1.0. The amount of base used in the reaction with these compounds is preferably in the range of 0.01 to 1.0 molar equivalents relative to the cyanoacetate, malononitrile, or 1,3-diketone. The weight ratio of the polyaspartic acid ester to the 2-substituted butanedioic acid ester is preferably in the range of 98:2 to 75:25. More preferably, this ratio may be 80:20 or 92:8. An example of this method is illustrated by the reaction of ethyl cyanoacetate with diethyl fumarate in the presence of potassium carbonate as a base.

[0019] [ka]

[0020] Cyanoacetates, malononitriles, and 1,3-diketones suitable for this method are: [ka] [In the formula, R is an alkyl group having 1 to 12 carbon atoms or an aryl group, and Y is H, an alkyl group having 1 to 12 carbon atoms, or an aryl group.] [ka] [wherein X is H, an alkyl group having 1 to 12 carbon atoms, or an aryl group.] [ka] [In the formula, R' and R'' are an alkyl group having 1 to 12 carbon atoms or an aryl group, and Z is H, an alkyl group having 1 to 12 carbon atoms, or an aryl group.]

[0021] A base is used to deprotonate the hydrogen atom on a carbon bearing two electron-withdrawing groups (e.g., CN, CO). Examples of preferred bases include carbonates such as potassium carbonate, sodium carbonate, and lithium carbonate, hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and tertiary amines such as triethylamine, trimethylamine, and other trialkylamines or triarylamines. Other examples of preferred bases include cyclic amines such as tetramethylguanidine, diazabicyclononane (DBN), diazabicycloundecane (DBU), and triethylenediamine. In general, any base having sufficient strength to deprotonate the hydrogen atom on a carbon bearing two electron-withdrawing groups (CN, CO) can be used. The molar ratio of base to cyanoacetate, or malononitrile, or 1,3-diketone is preferably 0.01 to 5.0.

[0022] Preferred examples of the polyisocyanate component used in the reaction of the mixture of polyaspartic acid ester and 2-substituted butanedioic acid ester include 1,4-diisocyanatobutane, 1,6-hexamethylene diisocyanate, 2,2,4- and / or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanate, 1,4-diisocyanatobutane, 1,6-hexamethylene diisocyanate, 2,2,4- and / or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanate, 1,4-diisocyanatocyclohexane ... Examples of preferred isocyanatomethylcyclohexane (IPDI), 2,4'- and / or 4,4'-diisocyanato-dicyclohexylmethane, 2,4- and / or 4,4'-diisocyanatodiphenylmethane, and mixtures of these isomers and their higher homologues obtained in known manner by phosgenation of aniline / formaldehyde condensates, 2,4- and / or 2,6-diisocyanatotoluene, and any mixtures of these compounds. Preferred examples of cyclic isocyanates include diphenylmethane 4,4'-diisocyanate (MDI), diphenylmethane 2,4'-diisocyanate, 2,4- and / or 2,6-diisocyanatotoluene. Preferred examples of aliphatic isocyanates include hexamethylene diisocyanate, isophorone diisocyanate, 2,4'- and / or 4,4'-diisocyanatodicyclohexylmethane.

[0023] Further preferred examples of suitable polyisocyanate components include derivatives of the above-mentioned polyisocyanate monomers that are conventional in the coatings technology. Preferred examples of these derivatives include biuret group-containing polyisocyanates as described, for example, in U.S. Pat. Nos. 3,124,605, 3,201,372, and DE-A-1,101,394, the entireties of which are incorporated herein by reference; isocyanurate group-containing polyisocyanates as described, for example, in U.S. Pat. Nos. 3,001,973, DE-A-1,022,789, DE-A-1,222,067, and DE-A-1,027,394, and DE-A-1,929,034, and DE-A-2,004,048, the entireties of which are incorporated herein by reference; Polyisocyanates containing urethane groups are described in US Pat. No. 752,261, and US Pat. No. 3,394,164 and US Pat. No. 3,644,457; polyisocyanates containing carbodiimide groups are described in DE-A-1,092,007, US Pat. No. 3,152,162, and German Patent Publication No. 2,504,400, German Patent Publication No. 2,537,685 and German Patent Publication No. 2,552,350 (all of which are incorporated herein by reference); and polyisocyanates containing allophanate groups are described in, for example, GB-A-994,890, BE-A-761,626 and NL-A-7,102,524.More preferred examples of polyisocyanates also include polyisocyanates containing uretdione groups. In one embodiment, asymmetric trimers such as those described in U.S. Patent No. 5,717,091 (hereby incorporated by reference in its entirety) are also suitable. More preferably, polyisocyanate-based isocyanate group-containing prepolymers and semi-prepolymers can also be used as the polyisocyanate component. In one embodiment, these prepolymers and semi-prepolymers have an isocyanate content in the range of about 0.5% to 30% by weight.In another embodiment, the prepolymers and semi-prepolymers preferably have an isocyanate content ranging from about 1% to 20% by weight. In one embodiment, the prepolymers and semi-prepolymers are prepared by reacting starting materials, such as isocyanate-reactive compounds, such as polyols, in a known manner at an NCO / OH equivalent ratio of about 1.05:1 to 10:1. In another embodiment, the prepolymers and semi-prepolymers are prepared at an NCO / OH equivalent ratio of about 1.1:1 to 3:1.

[0024] The following invention relates to the following aspects: <1> (A) polyisocyanate; (B) [ka] [wherein Z is a cycloalkyl group or an alkyl group, R1 and R2 are alkyl groups having 1 to 10 carbon atoms, and n is 2 to 4]; and (C) 2-substituted butanedioic acid esters prepared by reacting a fumaric acid ester in a polyaspartic acid ester solution with cyanoacetate, malononitrile, or 1,3-diketone in the presence of a base. 1. A polyurea coating composition comprising: <2> Cyanoacetate, malononitrile, or 1,3-diketone, [ka] [wherein R is an alkyl group having 1 to 12 carbon atoms, or an aryl group, and Y is H, an alkyl group having 1 to 12 carbon atoms, or an aryl group]; [ka] [wherein X is H, an alkyl group containing 1 to 12 carbon atoms, or an aryl group]; and [ka] [wherein R' and R'' are alkyl groups having 1 to 12 carbon atoms or aryl groups, and Z is H, alkyl groups having 1 to 12 carbon atoms, or aryl groups] <1> The composition described. <3> Z is a cycloalkyl or alkyl group bonded to at least one of the amino groups of 2,4'- and / or 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, bis-(3-methyl-4-aminocyclohexyl)methane, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-methylcyclohexane, ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-dimethylhexane, 2,2,4 and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 4-aminomethyl-1,8-diaminooctane, or tris-(2-aminoethyl)amine. <1> The composition described. <4> The polyisocyanate is selected from the group consisting of 1,4-diisocyanatobutane, 1,6-hexamethylene diisocyanate, 2,2,4- and / or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4'- and / or 4,4'-diisocyanato-dicyclohexylmethane, 2,4- and and / or 4,4'-diisocyanatodiphenylmethane, 2,4- and / or 2,6-diisocyanatotoluene, diphenylmethane, 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, 2,4- and / or 2,6-diisocyanatotoluene, hexamethylene diisocyanate, isophorone diisocyanate, or 2,4'- and / or 4,4'-diisocyanato-dicyclohexylmethane. <1> The composition described. <5> Aspects for the preparation of polyurea coatings <1> from <4> Use of the polyurea coating composition according to any one of claims 1 to 5. <6> a) reacting a fumaric acid ester or a maleic acid ester with a polyamine; b) reacting the residual fumarate or maleate with cyanoacetate, malononitrile, or a 1,3-diketone until completion; 1. A method for preparing a mixture of a polyaspartic acid ester and a 2-substituted butanedioic acid ester, comprising: <7> The embodiment in which the polyamine of step a) is an alicyclic or acyclic diamine or triamine <6> The method described. <8> The alicyclic or acyclic diamine or triamine is selected from the group consisting of 2,4'- and / or 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, bis-(3-methyl-4-aminocyclohexyl)methane, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-methylcyclohexane, 2,4- and / or 2,6-hexahydrotolylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, and 1,12-diaminododecane. <7> The method described. <9> Cyanoacetate, malononitrile, or 1,3-diketone, [ka] [wherein R is an alkyl group having 1 to 12 carbon atoms, or an aryl group, and Y is H, an alkyl group having 1 to 12 carbon atoms, or an aryl group]; [ka] [wherein X is H, an alkyl group containing 1 to 12 carbon atoms, or an aryl group]; and [ka] [wherein R' and R'' are alkyl groups having 1 to 12 carbon atoms or aryl groups, and Z is H, alkyl groups having 1 to 12 carbon atoms, or aryl groups] <6> The method described. <10> The molar ratio of the diamine to the fumaric acid ester or maleic acid ester is in the range of 1:3 to 1:2. <7> The method described. <11> The molar ratio of triamine to fumarate or maleate is in the range of 1:4 to 1:3. <7> The method described. <12> an embodiment in which the molar ratio of residual fumarate or residual maleate to cyanoacetate, malononitrile, or 1,3-diketone is about 1.0; <6> The method described. <13> The weight ratio of the polyaspartic acid ester to the 2-substituted butanedioic acid ester is in the range of 98:2 to 75:25. <6> The method described.

[0025] Working Example Example 1. Preparation of a polyaspartate mixture from the Michael reaction of diethyl maleate, 4,4'-diaminodicyclohexylmethane (PACM), and residual diethyl fumarate with ethyl cyanoacetate / K2CO3 (equivalent molar amounts of ethyl cyanoacetate and K2CO3) A 2 L glass reactor equipped with a N2 inlet tube, thermocouple, and addition funnel was charged with 4,4'-diaminodicyclohexylmethane (PACM) (470.72 g, 2.0 mol) and heated to 80° C. Diethyl maleate (688.8 g, 4 mol) was added slowly while maintaining the temperature between 80° C. and 85° C. A mixture of polyaspartic acid ester and diethyl fumarate was obtained.

[0026] A mature sample (100 g) with a diethyl fumarate concentration of 2.31 wt% (0.013 molar) as indicated by gas chromatography was treated with ethyl cyanoacetate (0.013 molar, 1.47 g), and potassium carbonate (0.013 molar, 1.80 g) at 85°C for 3 hours under a N2 atmosphere and then at ambient temperature. The diethyl fumarate concentration was reduced to 0.26 wt%.

[0027] Example 2. Preparation of polyaspartate mixtures from the Michael reaction of diethyl maleate, 4,4'-diaminodicyclohexylmethane (PACM), and residual diethyl fumarate with ethyl cyanoacetate / tetramethylguanidine (catalytic amount) A mature sample (100 g) prepared as above and having a diethyl fumarate concentration of 2.31 wt% (0.013 moles) as indicated by gas chromatography was treated with ethyl cyanoacetate (0.013 moles, 1.47 g) and tetramethylguanidine (0.0013 moles, 0.15 g) at 40°C for 2 hours and at ambient temperature for 7 days under a N2 atmosphere. No diethyl fumarate concentration was detected.

[0028] Example 3. Preparation of polyaspartate mixtures from the Michael reaction of diethyl maleate, 4,4'-diaminodicyclohexylmethane (PACM), and residual diethyl fumarate with ethyl cyanoacetate / DBU (catalytic amount) A mature sample (100 g) prepared as above and having a diethyl fumarate concentration of 2.31 wt% (0.013 molar) as shown by gas chromatography was treated with ethyl cyanoacetate (0.013 molar, 1.47 g) and DBU (0.0013 molar, 0.20 g) at ambient temperature for 7 days under a N2 atmosphere. No diethyl fumarate concentration was detected.

[0029] Example 4. Preparation of polyaspartic acid ester mixtures from the Michael reaction of diethyl maleate, 4,4'-diaminodicyclohexylmethane (PACM), and residual diethyl fumarate with malononitrile / K2CO3 A mature sample (100 g) prepared as described above and having a diethyl fumarate concentration of 2.31 wt% (0.013 moles) as indicated by gas chromatography was treated with malononitrile (0.013 moles, g) and K2CO3 (0.0013 moles, 1.80 g) at 85°C and then cooled to ambient temperature. The concentration of diethyl fumarate was 0.47 wt%.

[0030] Example 5. Preparation of polyaspartic acid ester mixtures from the Michael reaction of diethyl maleate, 4,4'-diaminodicyclohexylmethane (PACM), and residual diethyl fumarate with acetylacetone / K2CO3 A mature sample (100 g) prepared as above and having a diethyl fumarate concentration of 2.31 wt% (0.013 moles) as indicated by gas chromatography was treated with acetylacetone (0.013 moles, g) and K2CO3 (0.0013 moles, 1.80 g) at 85°C and then cooled to ambient temperature. The concentration of diethyl fumarate was 1.18 wt%.

[0031] Example 6. Preparation of polyaspartate mixtures from the Michael reaction of diethyl maleate, 4,4'-diaminodicyclohexylmethane (PACM), and residual diethyl fumarate with ethyl acetoacetate / K2CO3 A mature sample (100 g) prepared as above and having a diethyl fumarate concentration of 2.31 wt% (0.013 moles) as indicated by gas chromatography was treated with ethyl acetoacetate (0.013 moles, g) and K2CO3 (0.0013 moles, 1.80 g) at 85°C and then cooled to ambient temperature. The concentration of diethyl fumarate was 1.82 wt%.

[0032] Example 7. Coating mixtures were prepared by mixing the products obtained in Examples 1-6 separately with polyisocyanate, hexamethylene diisocyanate trimer, at a stoichiometric ratio of NCO to amine of 1.05. 138 g of amine was added to the vessel, followed by 100 g of hexamethylene diisocyanate trimer Vestanat HT2500 / 100 (21.8% NCO). The materials in the vessel were mixed manually with a spatula for approximately 1-2 minutes to form a homogenous mixture. The mixture was then used for various tests including viscosity measurements, drying time, and Shore D hardness. A control mixture, which was a mixture of diethyl maleate, 4,4'-diaminodicyclohexylmethane (PACM) and polyaspartate and aspartate esters from the same polyisocyanate, was also prepared for sequential comparison.

[0033] Example 8. The viscosity of the amine compositions prepared in Examples 1-6 and the control were measured using ASTM D2196-10 Test Method A. The mixed viscosity and cure profile of the sample prepared in Example 7 were also measured. The cure profile recorded was the time it took for the sample to reach a viscosity of 12,000 cP. All viscosity data are shown in Tables 1a and 1b. Viscosity tests were performed on a Brookfield RV-DVIII viscometer equipped with a thermoset accessory and a small sample adapter. A chamber capable of handling 12 mL of sample and a #27 spindle were used for the measurements. All viscosity tests were performed at 25°C.

[0034] Example 9. Dry time was also measured for the mixture prepared in Example 7. A thin coating of approximately 150 microns was applied with a drawdown bar onto a 12" x 1" glass slide and placed in a BK dry time recorder. Fine needle recorder time was set at 2 hours. Touch-free (stage 1) and tack-free (stage 2) times were measured for the dried films per ASTM D5895. Dry time data are shown in Tables 1a and 1b. All dry time measurements were performed at 22°C and 50% relative humidity.

[0035] Example 10. The Shore D hardness was measured for the mixed composition prepared in Example 7. The wet mixture was poured into a small circular mold and cured to form a 1 / 8 inch coating. The hardness of the coating was measured at 4 hours, 6 hours, and 24 hours using a PTC instruments Shore D durometer (Model 307L) according to ASTM D2240. The Shore D hardness data is shown in Table 1. All Shore D measurements were performed at 22°C and 50% relative humidity.

[0036] [Table 1]

[0037] [Table 2]

Claims

1. (A) a polyisocyanate; (B) 【Chemical 1】 [In the formula, Z is a cycloalkyl group or an alkyl group, and R １ , R ２ is an alkyl group containing 1 to 10 carbon atoms, and n is 2 to 4], a polyaspartic acid ester represented by the structure; and (C) a 2-substituted butanedioate ester prepared by reacting a fumarate ester in a polyaspartic acid ester solution with cyanoacetate, malononitrile, or 1,3-diketone in the presence of a base A polyurethane coating composition comprising the same.

2. The cyanoacetate, the malononitrile, or the 1,3-diketone is [Chemical 2] [wherein, R is an alkyl group containing 1 to 12 carbon atoms or an aryl group, and Y is H, an alkyl group containing 1 to 12 carbon atoms, or an aryl group]; [Chemical Formula 3] [wherein, X is H, an alkyl group containing 1 to 12 carbon atoms, or an aryl group]; and 【Chemical Formula 4】 [wherein, R', R'' are an alkyl group containing 1 to 12 carbon atoms or an aryl group, and Z is H, an alkyl group containing 1 to 12 carbon atoms, or an aryl group], the composition according to Claim 1, which is selected from the group consisting of.

3. Z is 2,4'- and / or 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, bis-(3-methyl-4-aminocyclohexyl)methane, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-methylcyclohexane, ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-dimethylhexane, 2,2,4 and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 4-aminomethyl-1,8-diaminooctane, or the cycloalkyl group or alkyl group bonded to at least one of the amino groups of tris-(2-aminoethyl)amine, the composition according to Claim 1.

4. The composition according to claim 1, wherein the polyisocyanate is selected from the group consisting of 1,4-diisocyanatobutane, 1,6-hexamethylene diisocyanate, 2,2,4- and / or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4'- and / or 4,4'-diisocyanato-dicyclohexylmethane, 2,4- and / or 4,4'-diisocyanatodiphenylmethane, 2,4- and / or 2,6-diisocyanatotoluene, diphenylmethane, 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, 2,4- and / or 2,6-diisocyanatotoluene, hexamethylene diisocyanate, isophorone diisocyanate, or 2,4'- and / or 4,4'-diisocyanato-dicyclohexylmethane.

5. Use of the polyurea coating composition according to any one of claims 1 to 4 for the preparation of a polyurea coating.

6. a) reacting a fumaric acid ester or a maleic acid ester with a polyamine; b) reacting the residual fumaric acid ester or residual maleic acid ester with cyanoacetate, malononitrile, or 1,3-diketone until completion; A method for preparing a mixture of polyaspartic acid ester and 2-substituted butanedioic acid ester, comprising:

7. The method according to claim 6, wherein the polyamine in step a) is an alicyclic or acyclic diamine or triamine.

8. The method according to claim 7, wherein the alicyclic or acyclic diamine or triamine is selected from the group consisting of 2,4'- and / or 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, bis-(3-methyl-4-aminocyclohexyl)methane, 2,4-diamino-1-methylcyclohexane, 2,6-diamino-1-methylcyclohexane, 2,4- and / or 2,6-hexahydrotolylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminoundecane, and 1,12-diaminododecane.

9. The method according to claim 6, wherein the cyanoacetate, the malononitrile, or the 1,3-diketone is 【Chemical Formula 5】 [wherein, R is an alkyl group containing 1 to 12 carbon atoms or an aryl group, and Y is H, an alkyl group containing 1 to 12 carbon atoms, or an aryl group]; 【Chemical Formula 6】 [wherein, X is H, an alkyl group containing 1 to 12 carbon atoms, or an aryl group]; and [Chemical Formula 7] [wherein, R', R'' are an alkyl group containing 1 to 12 carbon atoms or an aryl group, and Z is H, an alkyl group containing 1 to 12 carbon atoms, or an aryl group], selected from the group consisting of.

10. The method according to claim 7, wherein the molar ratio of the diamine to the fumaric acid ester or maleic acid ester is in the range of 1:3 to 1:

2.

11. The method according to claim 7, wherein the molar ratio of the triamine to the fumaric acid ester or maleic acid ester is in the range of 1:4 to 1:

3.

12. The method according to claim 6, wherein the molar ratio of the residual fumaric acid ester or residual maleic acid ester to the cyanoacetate, the malononitrile, or the 1,3-diketone is 1.

0.

13. The method according to claim 6, wherein the weight ratio of the polyaspartic acid ester to the 2-substituted butanedioic acid ester is in the range of 98:2 to 75:25.

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