Method for preparing aminosuccinic acid resin with low amine value

Abstract

The present invention relates to a method for preparing an aminosuccinic acid resin, and also to an aminosuccinic acid resin obtainable according to this method, which exhibits an amine value of less than 190 mg KOH / g. Another subject of the invention is the use of such an aminosuccinic acid resin for producing a two-component adhesive comprising at least one polyisocyanate.

Description

[0001] Subject matter of the invention

[0002] The present invention relates to a process for preparing an aminosuccinic acid resin and also to an aminosuccinic acid resin obtainable according to the process, which exhibits an amine number of less than 190 mg KOH / g. Another subject of the present invention is the use of such an aminosuccinic acid resin in the manufacture of a two-component adhesive comprising at least one polyisocyanate. Background Art

[0003] Aminosuccinic or aspartic acid resins are polymers exhibiting -OC(=O)-CH2-CH(NR)-C(=O)-O-units, R being H or an alkyl group. These units may in particular be derived from the addition of primary or secondary amines to succinic acid or derivatives of the latter, in particular succinic anhydride or dialkyl succinates. The combination of aminosuccinic acid resins with crosslinking agents such as polyisocyanates makes it possible to obtain instant formulations of two-component adhesives. These formulations can be used to prepare compositions of adhesives, paints or coatings, in particular for protecting metal surfaces from corrosion, impact or wear. These compositions are particularly useful in the motor vehicle industry, the wind turbine industry and the construction industry (floor coverings, sealing components, etc.).

[0004] Aspartic acid resins are sold by Covestro under the commercial reference Pasquick®. These aspartic acid resins are prepared from primary diamines sold under the commercial reference Desmophen® and they can react with aliphatic polyisocyanates sold under the commercial reference Desmodur® to form polyureas. Their amine value is at least 190 mg KOH / g.

[0005] Document EP 1 516 886 also describes aspartic acid resins that can be used to make adhesives. These resins are obtained according to a process comprising the following steps: a first stage of transesterification of α,β-unsaturated C1-C9 alkyl esters such as maleates or fumarates with polyols such as butanediol or sugars, and a second stage of reacting the product thus obtained with primary monoamines or polyamines such as cyclohexylamine or 1,6-hexanediamine under conditions such that primary amine groups are no longer retained. The aspartic acid resins thus obtained exhibit an amine value of at least 200 mg KOH / g.

[0006] Document U.S. Pat. No. 5,925,711 discloses a similar process for preparing aspartic acid resins, except that the oligoesters obtained in the first stage are formed by reaction of an unsaturated diacid (e.g. maleic acid or fumaric acid) with a polyol and a monool (e.g. a combination of 1,6-hexanediol and n-butanol) or by transesterification of a C1-C8 alkyl diester with a polyol (e.g. 1,6-hexanediol).

[0007] Known aspartic resins make it possible to obtain coating compositions that adhere well to the substrate and quickly acquire their mechanical properties. However, they are rich in amine functional groups, which means that large amounts of polyisocyanate resins are used to formulate the adhesive. In view of the toxicity and cost of these polyisocyanate resins, it is desirable to have available reactive diluents with a low amine value. It is also desirable to achieve this property without impairing the properties of the composition after application to the substrate, in particular its Persoz hardness. Summary of the invention

[0008] The inventors have developed a process that makes it possible to meet the above-mentioned need by employing, in the first stage of the preparation of the aminosuccinic acid resin, light diesters transesterified with one or more heavy monools and optionally one or more polyols. It has been observed that the use of heavy monools makes it possible to increase the molar mass of the diesters and therefore to reduce the amine value of the aminosuccinic acid resins subsequently prepared, without significantly increasing the polydispersity (and therefore the viscosity) of the diesters thus obtained, and maintaining a pot life of the mixture of the resin and the polyisocyanate suitable for the intended use.

[0009] The subject of the present invention is therefore a process for preparing an aminosuccinic acid resin comprising the following stages:

[0010] A) transesterifying at least one alkyl diester of formula (I) with at least one compound A selected from the group consisting of monohydric alcohols of formula (II), precursors of the latter and mixtures thereof and optionally at least one polyhydric alcohol of formula (III):

[0011] R1-OOC-CH=CH-COO-R2(I)

[0012] R3-OH(II)

[0013] R4-(OH) n (III)

[0014] wherein R1 and R2 are independently saturated, straight or branched hydrocarbon chains, each of which contains less than 5 carbon atoms; R3 represents a saturated or unsaturated, straight, branched or (mono- or poly-)cyclic hydrocarbon chain containing more than 4 carbon atoms; R4 represents a hydrocarbon chain containing at least 2 carbon atoms; and 2≤n≤6,

[0015] The molar ratio of the compound A to the diester is 0.01 to 1.99,

[0016] b) reacting the product of this reaction with at least one primary polyamine and optionally at least one primary monoamine, the molar ratio of amine functions to double bonds of the diester being from 0.8 to 1.2.

[0017] Another subject of the present invention is an aminosuccinic acid resin obtainable according to this process and exhibiting an amine number of less than 190 mg KOH / g.

[0018] A further subject matter of the present invention is the use of such aminosuccinic acid resins for the production of two-component adhesives comprising at least one polyisocyanate.

[0019] Another subject matter of the present invention is an adhesive formulation comprising the above-described aminosuccinic acid resin and a polyisocyanate component.

[0020] A further subject matter relates to the use of the binder formulation for obtaining a coating, a mastic or an adhesive, in particular for obtaining a coating, more particularly for obtaining a film, a paint, a varnish, a lacquer, a stain, an adhesive primer or an ink.

[0021] Finally, another subject of the present invention is a coating, adhesive or mastic obtained by applying and drying the above-described binder formulation. DETAILED DESCRIPTION

[0022] Method for preparing aminosuccinic acid resin

[0023] The present invention relates to a process for preparing an aminosuccinic acid resin, which essentially comprises two stages, namely a first stage of transesterification and a second stage of reaction of the product obtained thereby with an amine.

[0024] Transesterification

[0025] The first stage of the process comprises the transesterification of at least one alkyl diester using at least one compound A chosen from monoalcohols, precursors of monoalcohols and mixtures thereof and optionally at least one polyol.

[0026] The alkyl diester corresponds to formula (I):

[0027] R1-OOC-CH=CH-COO-R2(I)

[0028] wherein R1 and R2 are independently saturated, straight or branched hydrocarbon chains, each containing less than 5 carbon atoms.

[0029] Within the meaning of the present invention, the term "hydrocarbon chain" may particularly denote a chain comprising carbon and hydrogen atoms. The hydrocarbon chain may additionally comprise one or more heteroatoms (that is to say atoms other than carbon and hydrogen), in particular one or more heteroatoms selected from O, N and S. These heteroatoms may be incorporated into the chain (i.e. between two carbon atoms) and / or may be incorporated into the chain as substituents. In particular, the hydrocarbon chain may be interrupted by one or more functional groups selected from ethers, amines, thioethers, esters, amides, thioesters, carbonates, ureas and carbamates.

[0030] The hydrocarbon chains R1 and R2 are preferably chains consisting only of carbon or hydrogen atoms. Examples of such diesters (or "light diesters") are in particular alkyl maleates and alkyl fumarates, for example: dimethyl maleate, diethyl maleate, dipropyl maleate, diisopropyl maleate, dibutyl maleate, di-tert-butyl maleate, diisobutyl maleate, di-sec-butyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, diisopropyl fumarate, dibutyl fumarate, di-tert-butyl fumarate, diisobutyl fumarate, di-sec-butyl fumarate, and mixtures thereof.

[0031] As such, the monohydric alcohol corresponds to the formula (II):

[0032] R3-OH(II)

[0033] wherein R3 represents a saturated or unsaturated, linear, branched or (mono- or poly-)cyclic hydrocarbon chain containing more than 4 carbon atoms, preferably more than 9 carbon atoms and generally less than 18 carbon atoms. Preferably, the hydrocarbon chain R3 contains only carbon and hydrogen atoms and is optionally interrupted and / or substituted by one or more oxygen atoms.

[0034] The hydrocarbon chain R3 is preferably a (mono- or poly-)cyclic hydrocarbon chain, more preferably a non-aromatic mono-cyclic hydrocarbon chain. Within the meaning of the present invention, a (mono- or poly-)cyclic hydrocarbon chain is a chain comprising at least one ring, preferably a non-aromatic ring, and optionally at least one linear or branched non-cyclic chain. The hydrocarbon chain R3 is preferably interrupted by one or more ester functions. The hydrocarbon chain R3 preferably does not contain oxyethylene units; more preferably, the hydrocarbon chain R3 does not contain ether functions.

[0035] Examples of such alcohols (referred to as "heavy alcohols") are in particular: pentanol, methylbutanol, dimethylpropanol, hexanol, methylpentanol, ethylbutanol, diethylpropanol, cyclohexanol, heptanol, methylcyclohexanol, octanol, ethylhexanol, nonanol, trimethylcyclohexanol, decanol, tert-butylcyclohexanol, tridecanol, isotridecanol, dodecanol, butoxyethanol, benzyl alcohol, borneol, menthol, tricyclodecanol, methoxypolyethylene glycol, and mixtures thereof. Particularly preferred heavy alcohols are in particular: cyclohexanol, methylcyclohexanol, trimethylcyclohexanol, tert-butylcyclohexanol, benzyl alcohol, borneol, menthol, tricyclodecanol, and mixtures thereof.

[0036] In an embodiment of the present invention, compound A may comprise a precursor of a monoalcohol, that is to say a compound capable of forming a monoalcohol under the conditions of an ester exchange reaction (particularly by ring opening). Instead of a monoalcohol of formula (II), a precursor may be used, i.e. a compound capable of forming a monoalcohol of formula (II) under the conditions of an ester exchange reaction. The precursor may also be used as a mixture with a monoalcohol, in particular a heavy monoalcohol as defined above. The precursor may in particular be a lactone, such as γ-butyrolactone, δ-valerolactone or ε-caprolactone or a cyclic diester. The cyclic diester may in particular be a cyclic diester of any α-hydroxylated acid (AHA). In particular, the cyclic diester may be a cyclic dimer of a combination of two identical AHAs or two different AHAs. For example, the cyclic diester may be formed by two glycolic acid molecules to obtain glycolide, or by two lactic acid molecules to form lactide, or by one glycolic acid molecule and one lactic acid molecule. It should be understood that all isomeric forms of AHA can be used to form cyclic diesters. In particular, the cyclic diesters may correspond to the following formula (IIa):

[0037] (IIa)

[0038] wherein Ra, Rb, Rc and Rd are independently selected from H, methyl or ethyl.

[0039] Examples of cyclic diesters are lactide (Ra and Rc = H and Rb and Rd = methyl) or glycolide (Ra, Rb, Rc and Rd = H).

[0040] According to a preferred embodiment, compound A corresponds to formula (IIb):

[0041] (IIb)

[0042] in:

[0043] R' is a saturated or unsaturated, linear, branched or (mono- or poly-)cyclic hydrocarbon chain containing more than 4 carbon atoms, preferably more than 9 carbon atoms and generally less than 18 carbon atoms,

[0044] R1 and R2 are independently selected from H or alkyl, preferably H, methyl or ethyl,

[0045] y is equal to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; preferably, y is equal to 1, 2, 3, 4, 5 or 6, and z is 0 to 20; preferably, z is 1 to 20.

[0046] The hydrocarbon chain R' is preferably a (mono- or poly-)cyclic hydrocarbon chain, more preferably a non-aromatic monocyclic hydrocarbon chain. The hydrocarbon chain R' preferably does not contain oxyethylene units; more preferably, the hydrocarbon chain R' does not contain ether functional groups.

[0047] According to a particularly preferred embodiment, compound A corresponds to formula (IIb), wherein at least one of the following conditions is met:

[0048] - R' is a (mono- or poly-)cyclic hydrocarbon chain; preferably, R' is a non-aromatic monocyclic hydrocarbon chain,

[0049] - z is greater than 0; preferably, z is from 1 to 20.

[0050] When z is greater than 0, compound A may in particular be a monool resulting from the reaction between a monool, in particular a heavy monool as defined above, and a monool precursor chosen from lactones and cyclic diesters.

[0051] A polyol may optionally be present in the reaction mixture in order to adjust the rate of viscosity increase of the varnish obtained from the aminosuccinic acid resin according to the invention. The polyol corresponds to formula (III):

[0052] R4-(OH)n(III)

[0053] in:

[0054] R4 represents a saturated, linear, branched or (mono- or poly-)cyclic hydrocarbon chain containing at least 2 carbon atoms, preferably at least 4 carbon atoms, more preferably at least 5 carbon atoms, and generally less than 36 carbon atoms, and

[0055] 2≤n≤6, preferably 2≤n≤3, and more preferably n is equal to 2.

[0056] The hydrocarbon chain R4 may in particular be interrupted by one or more functional groups selected from the group consisting of ethers, esters, carbonates, ureas and urethanes.

[0057] The hydrocarbon chain R4 preferably contains only carbon and hydrogen atoms and is optionally interrupted and / or substituted by one or more oxygen atoms. Examples of such polyols are, in particular, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyalkylene glycols such as polyethylene glycol or polypropylene glycol (preferably having a number average molecular weight Mn in the range from 250 to 3000 g / mol, calculated from the OH number), 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, hydrogenated bisphenol A, glycerol, dipropylene glycol, tricyclodecane dimethanol, trimethylolpropane, di(trimethylolpropane), trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, erythritol, pentaerythritol, dipentaerythritol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-methyl-1,2-propanediol, sorbitol, mannitol, xylitol, isosorbide, isoidol, isomannide, methyl glucoside, polyester polyols (especially polycaprolactone polyols), polycarbonate polyols, polyorganosiloxane polyols (especially polydimethylsiloxane polyols), polyglycerols (for example glycerol oligomers, such as polyglycerol-3 (glycerol trimer) and decaglycerol), hydroxyl-terminated polybutadiene, diols derived from hydrogenated or non-hydrogenated fatty acid dimers or trimers, alkoxylated (especially ethoxylated and / or propoxylated) derivatives of the above polyols, and mixtures thereof.

[0058] During the transesterification reaction, the molar ratio of compound A to diester is in the range of 0.01 to 1.99, preferably 0.1 to 1.5 and more preferably 0.2 to 1.0. In the case of introducing a polyol at this stage, the molar ratio of the polyol to the diester is generally less than 0.6 / n, preferably less than 0.4 / n, more preferably less than 0.2 / n.

[0059] The reaction is generally carried out at a temperature of 50° C. to 300° C., preferably 80° C. to 250° C. and more preferably 150° C. to 200° C. The reaction is generally controlled by measuring the hydroxyl number of the reaction product so that the temperature is maintained for a period of time which allows to achieve a hydroxyl number of less than 10 mg KOH / g, preferably less than 5 mg KOH / g, as measured as described in the examples below.

[0060] The transesterification reaction is usually carried out in the presence of a catalyst. The catalyst can be, for example, selected from oxides and organic salts of metals such as titanium, tin, zinc, antimony or iron, for example selected from: titanium (IV) butyl oxide, tetra(2-ethylhexyl) titanate, tin (IV) oxide, dibutyltin oxide, butyltin hydroxide, dibutyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(2-ethylhexanoate), butyl stannoic acid, dibutyltin dichloride, octyltin hydroxide, zinc (IV) oxide and zinc (II) oxide.

[0061] It is also preferred that the transesterification reaction be carried out under an inert atmosphere, for example, by bubbling with nitrogen.

[0062] Reaction with amines

[0063] At the end of the above-described transesterification stage, a "heavy" polyester is obtained, which is reacted in the second stage of the process according to the invention with at least one primary polyamine and optionally at least one primary monoamine, which are hereinafter collectively referred to as "amines", unless otherwise indicated. The molar ratio of amine functions to double bonds of the diester is between 0.8 and 1.2, preferably between 0.9 and 1.1, more preferably between 0.95 and 1.05.

[0064] The monoamines and polyamines used according to the invention may be chosen from amines comprising a saturated or unsaturated (optionally aromatic), linear, cyclic or branched hydrocarbon chain to which one or more amino groups are attached. The polyamines may be chosen from diamines, triamines and tetraamines. They are preferably diamines.

[0065] The primary polyamine may in particular correspond to formula (IV):

[0066] R5-(NH2)m (IV)

[0067] in:

[0068] R5 is a saturated or unsaturated (optionally aromatic), linear, cyclic or branched chain containing at least 2 carbon atoms, preferably at least 4 carbon atoms, more preferably at least 5 carbon atoms, and generally less than 100 carbon atoms, preferably less than 40 carbon atoms, and

[0069] 2≤m≤4, preferably 2≤m≤3, and more preferably m is equal to 2.

[0070] Preferably, the R5 chain is a hydrocarbon chain optionally interrupted by one or more heteroatoms independently selected from oxygen and nitrogen.

[0071] According to a particular embodiment, the primary diamine corresponds to formula (IVa):

[0072] H2N-R5-NH2 (IVa)

[0073] wherein R5 is as defined above.

[0074] Examples of diamines may be selected from: 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,6-diaminohexane, 2-methylpentamethylenediamine, ethylenediamine, 1,2- and 1,3-propylenediamine, 2-methyl-1,2-propylenediamine, 2,2-dimethyl-1,3-propylenediamine, 1,3- and 1,4-butylenediamine, 1,3- and 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 2,5-dimethyl-2,5-hexanediamine, 2,2 ,4- or 2,4,4-trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2,4- and 2,6-hexahydrotoluenediamine, 2,4'- and 4,4'-diaminodicyclohexylmethane, 1,3- and 1,4-cyclohexanediamine, 1,3- or 1,4-bis(methylamino)cyclohexane, 1,8-p-menthanediamine, hydrazine, phenylenediamine, 2,4- and 2,6-toluenediamine, 2,3- and 3,4-toluenediamine, o-, m- or p-phenylenediamine, 2,4'- and 4,4'-diaminodiphenylmethane, benzidine and mixtures thereof. Examples of monoamines are specifically: sec-butylamine, isobutylamine, tert-butylamine, cyclohexylamine, 1,1,3,3-tetramethylbutylamine (or tert-octylamine) and mixtures thereof.

[0075] Examples of triamines are guanidine and N-(2-aminoethyl)-1,3-propylenediamine. As tetraamines, mention may in particular be made of N,N'-bis(2-aminoethyl)piperazine.

[0076] The primary polyamine may also be a polyetheramine. Polyetheramines are polyamines containing ether (—O—) bonds, more particularly ethylene oxide (—O—CH2—CH2) and / or propylene oxide (—O—CH2—CHCH3—) units.

[0077] Examples of polyetheramines are the compounds sold by Huntsman under the Jeffamine® reference numbers, in particular the Jeffamine® D, ED and EDR series. These series include, among others, the following reference numbers: Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148 and Jeffamine® EDR-176.

[0078] It has been observed that the use of monoamines alone, which are generally not very bulky, does not provide the aminosuccinic acid resins with adequate pot life and produces flaky and slightly cohesive films after drying of the resins.

[0079] The order of introduction of the above reactants is not critical provided that the monoamine (if used) is introduced before the diamine. Typically, the product of the transesterification stage is added slowly to the amine.

[0080] The reaction between the one or more amines and the product from the first stage is a Michael reaction, which is generally carried out at a temperature of 0° C. to 160° C., preferably 20° C. to 140° C. and more preferably 30° C. to 80° C. for a period of 1 to 4 hours. The reaction is preferably carried out under an inert atmosphere, for example under bubbling with nitrogen. The product obtained is generally then still kept under an inert atmosphere at ambient temperature for a period of 15 to 90 days, for example 30 to 60 days.

[0081] The above two stages can be carried out in the presence or absence of a solvent. Examples of solvents that can be used are polar organic solvents such as: ketones, in particular acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as n-butyl acetate and methoxypropyl acetate; N-methylpyrrolidone; and mixtures thereof. In an alternative form, non-polar organic solvents such as toluene and xylene can be used.

[0082] The aminosuccinic acid resin obtained at the end of the second stage described below has an amine value of less than 190 mg KOH / g, preferably less than 180 mg KOH / g, indeed even less than 150 mg KOH / g, measured as described in the examples below.

[0083] The process according to the invention makes it possible to obtain aminosuccinic acid resins.

[0084] Aminosuccinic acid resin

[0085] The present invention also relates to an aminosuccinic acid resin comprising at least one unit according to formula (VI):

[0086]

[0087] (VI)

[0088] in:

[0089] R1 is a saturated, straight or branched hydrocarbon chain containing less than 5 carbon atoms;

[0090] R3 is a saturated or unsaturated, linear, branched or (mono- or poly-)cyclic hydrocarbon chain containing more than 4 carbon atoms;

[0091] R5 is a saturated or unsaturated (optionally aromatic), linear, cyclic or branched hydrocarbon chain comprising at least 2 carbon atoms.

[0092] According to a particular embodiment, the aminosuccinic acid resin comprises at least one unit according to formula (VII):

[0093]

[0094] (VII)

[0095] wherein R1, R3 and R5 are as defined above;

[0096] R4 is a hydrocarbon chain containing at least 2 carbon atoms, as described in the process according to the invention; and

[0097] 2≤n≤6.

[0098] Aminosuccinic acid resins can be obtained in particular by the process described above.

[0099] The chains of R1, R3, R4 and R5 may in particular be as described in the process of the invention. Thus, in formulae (VI) and (VII):

[0100] R1 may in particular correspond to the R1 group present on the alkyl diester of formula (I) before the transesterification reaction;

[0101] R3 may in particular correspond to the residue of compound A of formula (II) or (IIb) used in the transesterification reaction (without the OH group);

[0102] R4, when present, may in particular correspond to the residue of a polyol of formula (III) optionally used for the transesterification reaction (without an OH group);

[0103] R5 may in particular correspond to the residue of a primary polyamine of formula (IV) (without the NH2 group).

[0104] Adhesive formulations

[0105] The aminosuccinic acid resins prepared according to the present invention can be used in adhesive formulations in combination with a crosslinking agent such as a polyisocyanate.

[0106] The present invention therefore also relates to an adhesive formulation comprising:

[0107] a) a polyisocyanate component, and

[0108] b) Components reactive toward isocyanates.

[0109] This type of formulation is a two-component formulation (also called a 2K formulation). Such a formulation is instant, that is to say it is prepared shortly before application by the end user.

[0110] The above-mentioned component b) comprises the aminosuccinic acid resin according to the invention and optionally another isocyanate-reactive compound. Examples of isocyanate-reactive compounds in addition to the aminosuccinic acid resin are compounds having one or more functional groups selected from alcohols, amines and thiols, preferably diols or diamines or amino alcohols.

[0111] The above-mentioned component a) comprises a polyisocyanate. Component a) may comprise a mixture of polyisocyanates. Within the meaning of the present invention, a polyisocyanate is a compound having at least 2 -NCO functional groups.

[0112] Component a) may comprise in particular aliphatic or aromatic polyisocyanates, preferably aliphatic polyisocyanates.

[0113] Component a) may comprise, in particular, diisocyanates, dimer or trimer forms of diisocyanates (in particular in the form of biuret, allophanate, uretdione or isocyanurate), polymeric forms of diisocyanates, extended forms of diisocyanates (in particular diisocyanates extended by reaction with polyols or diisocyanates having carbodiimide groups obtained by decarboxylation reaction between two diisocyanate molecules) or mixtures of these.

[0114] Examples of suitable polyisocyanates are: 1,4-diisocyanatobutane or tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), 1,6-diisocyanatohexane or hexamethylene diisocyanate (HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- or 1,4-diisocyanatocyclohexane, 1-isocyanato-5-isocyanatomethyl-3,3,5-trimethylcyclohexane or isophorone diisocyanate (IDPI), 2,3-, 2,4- or 2,6-diisocyanato-1-methylcyclohexane, 4,4'- or 2,4'-diisocyanatodicyclohexylmethane (HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- or 1,4-diisocyanatocyclohexane, 1-isocyanato-5-isocyanatomethyl-3,3,5-trimethylcyclohexane or isophorone diisocyanate (IDPI), 12 The polyisocyanates of the present invention are preferably HDI, 1-isocyanato-3 (4)-isocyanatomethyl-1-methyl-cyclohexane (IMCI), and also dimers, trimers, polymers and elongated forms of these, and mixtures thereof. Examples of preferred polyisocyanates are trimers of HDI and polyisocyanates prepared from 1,6-diisocyanatohexane, which contain isocyanurate groups and optionally uretdione groups. These polyisocyanates generally have an NCO content of 19% to 24% by weight, relative to the weight of the polyisocyanate.

[0115] These polyisocyanates can optionally be used in combination with polyether-modified polyisocyanates obtainable by reaction of the above-mentioned polyisocyanates with alcohol ethers or polyol ethers and polyoxyalkylene ethers, in particular polyoxyethylene ethers, for example polyethylene glycol monomethyl ether.

[0116] Typically, to obtain an adhesive formulation, the aminosuccinic acid resin and the polyisocyanate are mixed in a molar ratio of isocyanate groups to primary amine groups of 0.5:1 to 8:1, preferably 0.75:1 to 6:1, more preferably 1:1 to 4:1.

[0117] These formulations may also comprise other compounds capable of reacting with polyisocyanates, in particular polyacrylates and polyester polyols having hydroxyl functionality.

[0118] In an alternative form or in addition, they may contain additives such as fillers, colorants, thickeners, dispersants, surfactants, sedimentation inhibitors, catalysts, UV stabilizers, defoamers, leveling agents, adhesion promoters, matting agents, opacifiers, waxes and mixtures thereof. They may additionally contain one or more solvents selected from, for example, the esters, ketones and aromatic hydrocarbons listed above.

[0119] According to a preferred embodiment, the formulation comprises a colorant. The colorant may be selected from dyes, pigments and mixtures of these. The term "dye" as used herein means a colorant having a solubility of 10 mg / l or more in the medium into which it is introduced at 25°C. The term "pigment" is defined in standard DIN 55943 as a colorant that is hardly soluble in the application medium under the environmental conditions that characterize the application medium, so that its solubility in the medium at 25°C is less than 10 mg / l.

[0120] The colorant may in particular be a pigment. Organic and / or inorganic pigments may be used. If the colorant is not a self-dispersible pigment, the formulation may additionally contain a dispersant, more preferably a polymeric dispersant, as described below. The pigment may be selected from black, cyan, magenta, yellow, red, orange, violet, blue, green or brown pigments or mixtures of these. The pigment may be selected from those disclosed in Willy Herbst et al., Industrial Organic Pigments: Production, Properties, Applications, 3rd edition, Wiley-VCH, 2004, ISBN 3527305769.

[0121] Examples of specific pigments are described below, the term "CI" being used as an abbreviation for Color Index:

[0122] - carbon black;

[0123] - CI Pigment White s1, 3, 4, 5, 6, 7, 10, 11, 12, 14, 17, 18, 19, 21, 24, 25, 27, 28 and 32;

[0124] - CI Pigment Yellow 1, 3, 10, 12, 13, 14, 17, 55, 65, 73, 74, 75, 83, 93, 97, 109, 111, 120, 128, 138, 139, 150, 151, 154, 155, 180, 185 and 213;

[0125] - CI Pigment Red 17, 22, 23, 41, 48:1, 48:2, 49:1, 49:2, 52:1, 57:1, 81:1, 81:3, 88, 112, 122, 144, 146, 149, 169, 170, 175, 176, 184, 185, 188, 202, 206, 207, 210, 216, 221, 248, 251, 254, 255, 264, 270 and 272;

[0126] - CI Pigment Violet 1, 2, 19, 23, 32, 37 and 3;

[0127] - CI Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:6, 16, 56, 61 and (bridged) aluminum phthalocyanine pigments;

[0128] - CI Pigment Orange 5, 13, 16, 34, 40, 43, 59, 66, 67, 69, 71 and 73;

[0129] -CI Pigment Green 7 and 36;

[0130] -CI Pigment Brown 6 and 7;

[0131] and mixtures thereof.

[0132] The formulation may in particular have a pigment volume concentration (PVC) ranging from 3% to 60%, preferably from 5% to 50%, more preferably from 10% to 40%. The PVC may be defined as an arithmetic quantity corresponding to the percentage of the volume occupied by the pigment relative to the volume of the entire dry film obtained after application and drying of the formulation. The PVC may in particular be measured according to standard ISO 4618-1:2006.

[0133] The formulation may additionally comprise a dispersant. Dispersants can be used to disperse insoluble materials in the formulation, such as pigments or fillers.

[0134] The dispersant may especially be a polymeric dispersant.

[0135] Typical polymer dispersants are copolymers of two, three, four, five or even more monomers. The properties of the polymer dispersant depend on the properties of the monomers and their distribution in the polymer. The copolymer dispersant preferably has the following polymer composition:

[0136] - random copolymers (e.g. ABBAABAB);

[0137] - alternating copolymers (e.g. ABABABAB);

[0138] - gradient copolymers (e.g., AAABAABBABBB);

[0139] - block copolymers (e.g., AAAAABBBBBB);

[0140] - Graft copolymers (polymer backbone with polymer side chains attached to the backbone);

[0141] and mixed forms of these copolymers.

[0142] The polymeric dispersant may have a number average molecular weight Mn of 500 to 30 000 g / mol, more preferably 1500 to 10 000 g / mol.

[0143] Among commercial examples of polymeric dispersants, mention may be made of:

[0144] - Disperbyk® dispersants, available from BYK Chemie GmbH;

[0145] -Solsperse® dispersants, available from Lubrizol;

[0146] - Tego® dispersants from Evonik;

[0147] - Dispex®, Efka® and Joncryl® dispersants from BASF;

[0148] - Disponer® dispersants from Elementis.

[0149] The adhesive formulation can be applied to a variety of substrates, including wood, metal, stone, plaster, concrete, glass, fabric, leather, paper, plastics and composite materials. Application can be conventionally carried out, in particular by spraying or dipping or using a brush, roller or blade. In particular, application can be carried out to form one or more layers, preferably with a thickness of 5 to 100 μm.

[0150] The formulation thus obtained is subsequently cured at a temperature of 20 to 100°C.

[0151] The binder formulation can be a coating, a mastic or an adhesive formulation in particular. In particular, the binder formulation can be a coating formulation, more particularly a decorative coating formulation, in particular a film, a paint, a varnish, a lacquer, a stain, an adhesive primer or an ink formulation.

[0152] According to a specific embodiment, the adhesive formulation is a paint, varnish or stain formulation, in particular a finishing paint, varnish or stain formulation. Such a formulation can be applied especially indoors or outdoors, for example to wood, metal, wall or plastic.

[0153] The formulations are particularly useful for obtaining coatings (especially films, paints, varnishes, lacquers, stains, adhesive primers or inks), adhesives or mastics.

[0154] A further subject matter of the present invention is the use of the binder formulations according to the invention in order to obtain coatings (in particular films, paints, varnishes, lacquers, stains, adhesive primers or inks), mastics or putties.

[0155] The invention also relates to a coating (in particular a film, paint, varnish, lacquer, stain, adhesive primer or ink), a mastic or a putty obtained by applying and drying the binder formulation according to the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0156] [ Figure 1 ]and[ Figure 2 ] represents an example of the method according to the present invention.

[0157] Example

[0158] A better understanding of the present invention will be obtained from the following examples, which are given by way of illustration only and have no purpose of limiting the scope of the present invention as defined by the appended claims.

[0159] Example

[0160] Material

[0161] The materials used in the examples are as follows:

[0162] -DEM (diethyl maleate) from Sigma-Aldrich

[0163] -D2EHM (di(2-ethylhexyl)maleate) Mw=340 g / mol, from Sigma-Aldrich

[0164] -Butanediol from Sigma-Aldrich

[0165] -Cyclohexanol from Sigma-Aldrich

[0166] -Benzyl alcohol from Sigma-Aldrich

[0167] -TCDDM: tricyclodecanedimethanol (Mw = 196 g / mol), from Sigma-Aldrich

[0168] -ε-caprolactone from Sigma-Aldrich

[0169] -Isotridecanol, from BASF

[0170] -2EH (2-ethylhexanol) from Sigma-Aldrich

[0171] -TCDOH (tricyclodecylmethanol) from Oxea

[0172] -CHDM (cyclohexanedimethanol) from Sigma-Aldrich

[0173] -NPG (neopentyl glycol) from Sigma-Aldrich

[0174] -MBMCHA (4,4'-methylenebis(2-methylcyclohexylamine)) from TCI

[0175] -MBCHA (4,4'-methylenebis(cyclohexylamine)) from Sigma Aldrich

[0176] -CHA (cyclohexylamine) from Sigma-Aldrich

[0177] -Fascat 4100 (butylstannoic acid) from Brenntag

[0178] Measurement method

[0179] Amine value

[0180] The amine value is measured by quantitative determination with a Metrohm (848 Titrino Plus) titrator equipped with a Metrohm reference 6.0262.100 measuring probe. The sample to be analyzed is weighed in a 100 mL beaker. 50 ml of dichloromethane are added. The sample is completely dissolved by magnetic stirring. Depending on the method of use of the chosen titrator, titration is performed with 0.1 N perchloric acid in acetic acid under magnetic stirring. The amine value is calculated according to the following equation:

[0181]

[0182] in

[0183] VS = volume of titrant added to quantify sample (ml)

[0184] NT = equivalent weight of titrant (0.1 N)

[0185] W = weight of sample (g).

[0186] Hydroxyl value

[0187] The hydroxyl value is measured by quantitative determination with a Metrohm (848 TitrinoPlus) titrator equipped with a Metrohm reference 6.0229.100 measuring probe. Acid-base back titration of acetic anhydride in excess relative to the hydroxyl functional groups is performed under the following conditions: an accurate weight W (about 3 g) of the product is dissolved in exactly 10 mL of acetylation solution (a mixture of 555 mL ethyl acetate, 60 mL acetic anhydride and 7 g p-toluenesulfonic acid monohydrate). The mixture is reacted at 90° C. for 30 minutes. After cooling, about 2 mL of water is added and allowed to react at ambient temperature for 2 minutes. Then about 10 mL of hydrolysis solution (a mixture of 600 mL pyridine and 400 mL water) is added and allowed to react at ambient temperature for 5 minutes. About 60 mL of solvent (a mixture of 666 mL n-butanol and 333 mL toluene) is added. Subsequently, the excess acetic acid (released by the hydrolysis of the excess acetic anhydride relative to the hydroxyl functions to be acetylated) is quantitatively determined with methanolic potassium of an accurate normal titer of about 0.5 N (Eq / l), depending on the chosen titrator method. A blank test is also performed (same as above protocol, without the product to be analyzed). The hydroxyl value is calculated according to the following equation:

[0188]

[0189] in

[0190] VS = volume of titrant added to quantify sample (ml)

[0191] VB = Blank test volume

[0192] NT = equivalent weight of titrant (0.5 N)

[0193] W = weight of sample (g)

[0194] V Acid = Acid value determined according to the following method.

[0195] Acid value

[0196] The acid value is measured by quantitative determination with a Metrohm (848 Titrino Plus) titrator equipped with a Metrohm reference 6.0229.100 measuring probe. The sample to be analyzed is weighed in a 100 mL beaker. 50 ml of solvent (a mixture of 500 ml toluene and 500 ml methanol) is added. The sample is completely dissolved by magnetic stirring. Titration is performed with 0.1 N potassium methoxide under magnetic stirring according to the selected method of use of the titrator. The acid value is calculated according to the following equation:

[0197]

[0198] in

[0199] VS = volume of titrant added to quantify sample (ml)

[0200] NT = equivalent weight of titrant (0.1 N)

[0201] W = weight of sample (g).

[0202] Measurement of varnish viscosity

[0203] The initial viscosity of the varnish before application is measured at 25° C. on a Brookfield CAP 1000 viscometer (high shear gradient) according to standard ISO 2884, with cone 2 or 3 depending on the initial viscosity of the polyaminosuccinic acid.

[0204] Applicable period

[0205] The pot life is the time required to observe a doubling of the initial viscosity of a varnish composition. The viscosity is measured regularly over time. The combined measurements make it possible to draw a straight line, which makes it possible to calculate the pot life of the composition by linear regression. This common measurement makes it possible to know the ideal range of use of the composition without loss of application properties.

[0206] Dry thickness of varnish

[0207] The dry thickness is measured on the dry film of the varnish 24 hours after the varnish composition has been applied with a film applicator at a thickness of 150 μm wet (50 μm dry) on a QD46 steel panel (in a controlled indoor climate at 23° C. and 50% relative humidity) (according to standard NF EN ISO 2808).

[0208] Persoz hardness of varnish

[0209] The Persoz hardness is measured according to standard NF EN ISO 1522 of March 2007 on QD46 steel panels (in a room climate controlled at 23° C. and 50% relative humidity) after application of the varnish composition with a thickness of 150 μm wet (50 μm dry) using a film applicator.

[0210] The Persoz hardness was measured 24 h or 14 days after application of the clearcoat (in a room climate controlled at 23° C. and 50% relative humidity).

[0211] Example 1 (Transesterification)

[0212] DEM (344.00 g, i.e. 2.000 mol), isotridecanol (119.40 g, i.e. 0.597 mol), CHDM (7.40 g, i.e. 0.050 mol) and Fascat 4100 (0.050 g) were introduced into a reactor equipped with a distillation column, a thermometer, a dip tube for bubbling nitrogen and a stirrer with inclined blades. Nitrogen was bubbled at 30 ml / min throughout the synthesis. The temperature was brought to 170° C. and then maintained at 170° C. The ethanol formed during the transesterification reaction was distilled off. The temperature was maintained until a hydroxyl number of less than 5 mg KOH / g was obtained. The heavy maleate polyester obtained was colorless.

[0213] Example 2 (Transesterification)

[0214] DEM (454.18 g, i.e. 2.641 mol), 2EH (118.56 g, i.e. 0.912 mol), CHDM (4.75 g, i.e. 0.033 mol) and Fascat 4100 (0.055 g) were introduced into a reactor equipped with a distillation column, a thermometer, a dip tube for bubbling nitrogen and a stirrer with inclined blades. Nitrogen was bubbled at 30 ml / min throughout the synthesis. The temperature was brought to 190° C. and then maintained at 190° C. The ethanol formed during the transesterification reaction was distilled off. The temperature was maintained until a hydroxyl value of less than 10 mg KOH / g was obtained. The heavy maleate polyester obtained was colorless. The hydroxyl value measured after cooling was 7.5 mgKOH / g.

[0215] Example 3 (Transesterification)

[0216] DEM (456.76 g, i.e. 2.656 mol), 2EH (111.18 g, i.e. 0.855 mol), CHDM (9.56 g, i.e. 0.066 mol) and Fascat 4100 (0.055 g) were introduced into a reactor equipped with a distillation column, a thermometer, a dip tube for bubbling nitrogen and a stirrer with inclined blades. Nitrogen was bubbled at 30 ml / min throughout the synthesis. The temperature was brought to 190° C. and then maintained at 190° C. The ethanol formed during the transesterification reaction was distilled off. The temperature was maintained until a hydroxyl value of less than 10 mg KOH / g was obtained. The heavy maleate polyester obtained was colorless. The hydroxyl value measured after cooling was 6.9 mgKOH / g.

[0217] Example 4 (Transesterification)

[0218] DEM (166.65 g, i.e. 0.969 mol), TCDOH (160.83 g, i.e. 0.821 mol), NPG (2.52 g, i.e. 0.024 mol) and Fascat 4100 (0.040 g) were introduced into a reactor equipped with a distillation column, a thermometer, a dip tube for bubbling nitrogen and a stirrer with inclined blades. Nitrogen was bubbled at 30 ml / min throughout the synthesis. The temperature was brought to 190° C. and then maintained at 190° C. The ethanol formed during the transesterification reaction was distilled off. The temperature was maintained until a hydroxyl value of less than 5 mg KOH / g was obtained. The heavy maleate polyester obtained was colorless. The hydroxyl value measured after cooling was 2.1 mgKOH / g.

[0219] Example 5 (Transesterification)

[0220] DEM (425.70 g, i.e. 2.475 mol), isotridecanol (147.45 g, i.e. 0.737 mol), NPG (6.68 g, i.e. 0.064 mol) and Fascat 4100 (0.100 g) were introduced into a reactor equipped with a distillation column, a thermometer, a dip tube for bubbling nitrogen and a stirrer with inclined blades. Nitrogen was bubbled at 30 ml / min throughout the synthesis. The temperature was brought to 160° C. and then maintained at 160° C. The ethanol formed during the transesterification reaction was distilled off. The temperature was maintained until a hydroxyl value of less than 5 mg KOH / g was obtained. The heavy maleate polyester obtained was colorless. The hydroxyl value measured after cooling was 4.2 mg KOH / g.

[0221] Example 6 (aminosuccinic acid resin):

[0222] MBMCHA (51.87 g) is introduced into a reactor equipped with a reflux column, a dip tube for bubbling nitrogen, a thermometer, a dropping funnel and a stirrer with inclined blades. Bubble with nitrogen at 30 ml / min throughout the building-up process. The product obtained in 98.13 g embodiment 1 is introduced into a dropping funnel, then added within 1 hour while keeping the temperature below 50 ° C. The temperature is kept for another 1 hour at 50 ° C, then the contents of the reactor are transferred to an inert flask and sealed at ambient temperature for 60 days. By 1H NMR monitoring corresponding to the reduction of the area under the peak of olefinic protons (between 6.8 ppm and 6.9 ppm). The theoretical solid content of the finished product is 100%. The amine value measured after storage is 163mg KOH / g.

[0223] Example 7 (aminosuccinic acid resin):

[0224] MBMCHA (35.44 g) and CHA (1.55 g) are introduced into a reactor equipped with a reflux column, a dip tube for bubbling nitrogen, a thermometer, a dropping funnel and a stirrer with inclined blades. Bubble with nitrogen at 30 ml / min throughout the building-up process. The product obtained in 63.01 g of embodiment 2 is introduced into a dropping funnel, then added over a time of 1 hour while keeping the temperature below 50 ° C. The temperature is kept at 50 ° C for another 1 hour, then the contents of the reactor are transferred to an inert flask and kept closed at ambient temperature for 30 days. By 1H NMR monitoring the reduction of the area under the peak corresponding to olefinic protons (between 6.8 ppm and 6.9 ppm). The theoretical solid content of the finished product is 100%. The amine value measured after storage is 176 mgKOH / g.

[0225] Example 8 (aminosuccinic acid resin):

[0226] MBMCHA (37.19 g) is introduced into a reactor equipped with a reflux column, a dip tube for bubbling nitrogen, a thermometer, a dropping funnel and a stirrer with inclined blades. Bubble with nitrogen at 30 ml / min throughout the building-up process. The product obtained in 62.81 g embodiment 3 is introduced into a dropping funnel, then added over a time of 1 hour while maintaining the temperature below 50 ℃. The temperature is kept at 50 ℃ for another 1 hour, then the contents of the reactor are transferred to an inert flask and kept closed at ambient temperature for 30 days. By 1H NMR monitoring corresponding to the reduction of the area under the peak of olefinic protons (between 6.8 ppm and 6.9 ppm). The theoretical solid content of finished product is 100%. The amine value measured after storage is 175mg KOH / g.

[0227] Example 9 (aminosuccinic acid resin):

[0228] MBMCHA (57.92 g) is introduced into a reactor equipped with a reflux column, a dip tube for bubbling nitrogen, a thermometer, a dropping funnel and a stirrer with inclined blades. Bubble with nitrogen at 30 ml / min throughout the building-up process. The product obtained in 142.08 g embodiment 4 is introduced into a dropping funnel, then added within 1 hour while maintaining the temperature below 50 ° C. The temperature is kept for another 1 hour at 50 ° C, then the contents of the reactor are transferred to an inert flask and sealed at ambient temperature for 60 days. By 1H NMR monitoring corresponding to the reduction of the area under the peak of olefinic protons (between 6.8 ppm and 6.9 ppm). The theoretical solid content of finished product is 100%. The amine value measured after storage is 137 mg KOH / g.

[0229] Example 10 (aminosuccinic acid resin):

[0230] MBCHA (36.55 g) is introduced into a reactor equipped with a reflux column, a dip tube for bubbling nitrogen, a thermometer, a dropping funnel and a stirrer with inclined blades. Bubble with nitrogen at 30 ml / min throughout the synthesis. The product obtained in 75.95 g of Example 5 is introduced into a dropping funnel, then added over a period of 2 hours while maintaining the temperature below 50 ° C. The temperature is maintained at 50 ° C for another 1 hour, then the contents of the reactor are transferred to an inert flask and kept closed at ambient temperature for 30 days. By 1H NMR monitoring corresponding to the reduction of the area under the peak of olefinic protons (between 6.8 ppm and 6.9 ppm). The theoretical solid content of the finished product is 100%. The amine value measured after storage is 174 mg KOH / g.

[0231] Example 11 (aminosuccinic acid resin):

[0232] 76.09 g of the product obtained in Example 5 is introduced into a reactor equipped with a reflux column, a dip tube for bubbling nitrogen, a thermometer, a dropping funnel and a stirrer with inclined blades. Bubble with nitrogen at 30 ml / min throughout the synthesis. 3.45 g of CHA is added. The temperature is raised to 50 ° C, then kept at 50 ° C for 1 hour. 32.96 g of MBCHA is introduced into a dropping funnel, then added within 1 hour and 30 minutes, while keeping the temperature below 50 ° C. The contents of the reactor are transferred to an inert flask and kept closed at ambient temperature for 30 days. By 1H NMR monitoring the reduction of the area under the peak corresponding to olefinic protons (between 6.8 ppm and 6.9 ppm). The theoretical solid content of the finished product is 100%. The amine value measured after storage is 174 mg KOH / g.

[0233] Comparative Example 1 (using heavy diester without transesterification):

[0234] 75.00 g of D2EHM (0.2206 mol) is introduced into a reactor equipped with a reflux column, a dip tube for bubbling nitrogen, a thermometer, a dropping funnel and a stirrer with inclined blades. Bubble with nitrogen at 30 ml / min throughout the building-up process. 26.25 g of MBMCHA (0.1103 mol) is introduced into the dropping funnel, then added over 1 hour while maintaining the temperature below 50 ° C. The contents of the reactor are transferred to an inert flask and kept closed at ambient temperature for 30 days. By 1H NMR monitoring the reduction of the area under the peak corresponding to olefinic protons (between 6.8 ppm and 6.9 ppm). The theoretical solid content of the finished product is 100%. The amine value measured after storage is 122 mg KOH / g.

[0235] Comparative Example 2 (Transesterification without heavy monohydric alcohol):

[0236] DEM (420.31 g, i.e. 2.4437 mol), butanediol (38.33 g, i.e. 0.4259 mol) and Fascat 4100 (0.100 g) were introduced into a reactor equipped with a distillation column, a thermometer, a dip tube for bubbling nitrogen and a stirrer with inclined blades. Nitrogen was bubbled at 30 ml / min throughout the synthesis. The temperature was brought to 170° C. and then maintained at 170° C. The ethanol formed during the transesterification reaction was distilled off. The temperature was maintained until a hydroxyl value of less than 5 mg KOH / g was obtained.

[0237] The product that 59.06 g obtains is introduced into the reactor, and the reactor is equipped with reflux column, dip tube for bubbling nitrogen, thermometer, dropping funnel and the agitator with inclined blade. Bubble with nitrogen at 30 ml / min in the whole building-up process. 40.94 g MBMCHA is introduced into the dropping funnel, then added through 30 minutes, while keeping the temperature below 50 ℃. The content of the reactor is transferred in an inert flask and kept closed at ambient temperature for 30 days. By 1H NMR monitoring corresponding to the reduction of the area under the peak of olefinic protons (between 6.8 ppm and 6.9 ppm). The theoretical solid content of finished product is 100%. The amine value measured after storage is 193mg KOH / g.

[0238] Comparative Example 3 (Transesterification without heavy monohydric alcohol):

[0239] DEM (420.31 g, i.e. 2.4437 mol), butanediol (54.98 g, i.e. 0.6109 mol) and Fascat 4100 (0.100 g) were introduced into a reactor equipped with a distillation column, a thermometer, a dip tube for bubbling nitrogen and a stirrer with inclined blades. Nitrogen was bubbled at 30 ml / min throughout the synthesis. The temperature was brought to 170° C. and then maintained at 170° C. The ethanol formed during the transesterification reaction was distilled off. The temperature was maintained until a hydroxyl value of less than 5 mg KOH / g was obtained.

[0240] The product that 59.04 g obtains is introduced into the reactor, and the reactor is equipped with reflux column, dip tube for bubbling nitrogen, thermometer, dropping funnel and the agitator with inclined blade. Bubble with nitrogen at 30 ml / min in the whole building-up process. 40.96 g MBMCHA is introduced into the dropping funnel, then added through 30 minutes, while keeping the temperature below 50 ℃. The content of the reactor is transferred in an inert flask and kept closed at ambient temperature for 30 days. By 1H NMR monitoring corresponding to the reduction of the area under the peak of olefinic protons (between 6.8 ppm and 6.9 ppm). The theoretical solid content of finished product is 100%. The amine value measured after storage is 193mg KOH / g.

[0241] Example 12 (Transesterification with Heavy Monohydric Alcohol):

[0242] DEM (420.31 g, i.e. 2.4437 mol), benzyl alcohol (131.95 g, i.e. 1.2218 mol) and Fascat 4100 (0.100 g) were introduced into a reactor equipped with a distillation column, a thermometer, a dip tube for bubbling nitrogen and a stirrer with inclined blades. Nitrogen was bubbled at 30 ml / min throughout the synthesis. The temperature was brought to 170° C. and then maintained at 170° C. The ethanol formed during the transesterification reaction was distilled off. The temperature was maintained until a hydroxyl value of less than 5 mg KOH / g was obtained.

[0243] The product obtained by 63.04 g is introduced into a reactor, which is equipped with a reflux column, a dip tube for bubbling nitrogen, a thermometer, a dropping funnel and a stirrer with a tilted blade. Bubble with nitrogen at 30 ml / min throughout the building-up process. 36.96 g MBMCHA is introduced into a dropping funnel, then added over 30 minutes, while maintaining the temperature below 50 ° C. The contents of the reactor are transferred to an inert flask and kept closed at ambient temperature for 30 days. By 1H NMR monitoring corresponding to the reduction of the area under the peak of olefinic protons (between 6.8 ppm and 6.9 ppm). The theoretical solids content of finished product is 100%. The amine value measured after storage is 174 mg KOH / g.

[0244] Example 13 (Transesterification with Monofunctional Heavy Monohydric Alcohols and Heavy Monohydric Alcohol Precursors):

[0245] DEM (363.01 g, i.e. 2.1105 mol), TCDDM (5.17 g, i.e. 0.0264 mol), cyclohexanol (150.00 g, i.e. 1.5000 mol), ε-caprolactone (91.43 g, i.e. 0.8020 mol) and Fascat 4100 (0.100 g) were introduced into a reactor equipped with a distillation column, a thermometer, a dip tube for bubbling nitrogen and a stirrer with inclined blades. Nitrogen was bubbled at 30 ml / min throughout the synthesis. The temperature was brought to 170° C. and then maintained at 170° C. The ethanol formed during the transesterification reaction was distilled off. The temperature was maintained until a hydroxyl value of less than 5 mg KOH / g was obtained.

[0246] The product obtained by 68.18 g is introduced into a reactor, which is equipped with a reflux column, a dip tube for bubbling nitrogen, a thermometer, a dropping funnel and a stirrer with a tilted blade. Bubble with nitrogen at 30 ml / min throughout the building-up process. 31.82 g MBMCHA is introduced into a dropping funnel, then added over 30 minutes, while maintaining the temperature below 50 ° C. The contents of the reactor are transferred to an inert flask and kept closed at ambient temperature for 30 days. By 1H NMR monitoring corresponding to the reduction of the area under the peak of olefinic protons (between 6.8 ppm and 6.9 ppm). The theoretical solids content of finished product is 100%. The amine value measured after storage is 150mg KOH / g.

[0247] Example 14: Application Properties

[0248] Several resins according to the invention and comparative resins prepared as described above, as well as the resins according to the prior art mentioned below, were tested to evaluate the proportion of polyisocyanate required to obtain a varnish. According to the above protocol, various properties of the varnish were also evaluated, namely its viscosity before application, its pot life, its dry thickness and its Persoz hardness at 24h and 14 days.

[0249] The resin according to the prior art is as follows:

[0250] Comparative Example 4 - Synocure 9226BA 82: A high solids hydroxylated acrylic resin with a V of 5.4% relative to the bulk resin. OH , having a viscosity of 3000-5000 mPa.s at 25°C and a solids content of 82% in butyl acetate.

[0251] Comparative Example 5-Desmophen NH1420: aminosuccinic acid resin, relative to the bulk resin, the amine value is 201 mgKOH / g, the viscosity at 25°C is 1000 mPa.s, and the solid content is 100%.

[0252] Comparative Example 6-Desmophen NH 1520: aminosuccinic acid resin, relative to the bulk resin, with an amine value of 191 mgKOH / g, a viscosity of 1400 mPa.s at 25°C, and a solid content of 100%.

[0253] Operating conditions for preparing two-component varnishes:

[0254] The formulation of the two-component clearcoat material was produced with a stoichiometric amine / NCO ratio of the aminosuccinic resin and a stoichiometric OH / NCO ratio of the polyacrylic acid, adjusted to a solids content of 75% by volume and having a VOC value of 220 g / l.

[0255] The isocyanate used in this two-component system is Tolonate™ HDT-LV2, a low viscosity, solvent-free hexamethylene diisocyanate trimer with an NCO content of 23%, sold by Vencorex.

[0256] For aminosuccinic acid resin:

[0257] Add the aminosuccinic acid resin to a suitable container, followed by the solvent (butyl acetate), then the isocyanate.

[0258] The two-component varnish was stirred in a continuous manner for 30 seconds with a spatula and then allowed to stand for 1 minute to degas, and then its viscosity was measured and applied.

[0259] For polyacrylic acid:

[0260] The polyacrylic resin is incorporated into a suitable container, followed by 0.5% (on a resin dry basis) of a dibutyltin dilaurate (DBTDL) type catalyst, a solvent (butyl acetate), and then the isocyanate.

[0261] The two-component varnish was stirred in a continuous manner for 30 seconds with a spatula and then allowed to stand for 1 minute to degas, and then its viscosity was measured and applied.

[0262] Apply the result:

[0263] [Table 1]

[0264]

[0265] [Table 2]

[0266]

[0267] Tables 1 and 2 above show that the varnishes obtained from the resins according to the invention exhibit acceptable hardness, viscosity and pot life for 14 days with lower consumption of polyisocyanate compared to the comparative tests.

[0268] Comparative Example 1 shows that direct use of the heavy diester without a transesterification stage results in a tacky film at 24 hours and an insufficiently cured film at 14 days.

[0269] [Table 3]

[0270]

[0271] Comparative Examples 2 and 3 show the effect of increasing the amount of polyol on the initial viscosity of the formulation.

[0272] The table also shows that for the same OH / maleate ratio, the resin according to the invention (Example 12) exhibits a lower V NH The varnishes obtained additionally exhibited lower viscosity (implying the possibility of using smaller amounts of solvent), longer pot life and 1 week hardnesses that were virtually equivalent to those of the comparative varnishes.

[0273] Example 13 shows that V can be obtained using the precursor of the primary alcohol (caprolactone). NH Excellent compromise between toughness (low) and hardness (quite high).

Claims

1. A method for preparing an aminosuccinic acid resin, comprising the following stages: a) transesterifying at least one alkyl diester of formula (I) with at least one compound A selected from the group consisting of monohydric alcohols of formula (II), precursors of the latter and mixtures thereof and optionally at least one polyhydric alcohol of formula (III): R1-OOC-CH=CH-COO-R2(I) R3-OH(II) R4-(OH)n(III) wherein R1 and R2 are independently saturated, straight or branched hydrocarbon chains, each of which contains less than 5 carbon atoms; R3 represents a saturated or unsaturated, straight, branched or (mono- or poly-)cyclic hydrocarbon chain containing more than 4 carbon atoms; R4 represents a hydrocarbon chain containing at least 2 carbon atoms; and 2≤n≤6, The molar ratio of the compound A to the diester is in the range of 0.01 to 1.99, b) reacting the product of this reaction with at least one primary polyamine and optionally at least one primary monoamine, the molar ratio of amine functions to double bonds of the diester ranging from 0.8 to 1.

2.

2. The method according to claim 1, characterized in that The alkyl diester is selected from the group consisting of alkyl maleates and alkyl fumarates, for example, dimethyl maleate, diethyl maleate, dipropyl maleate, diisopropyl maleate, dibutyl maleate, di-tert-butyl maleate, diisobutyl maleate, di-sec-butyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, diisopropyl fumarate, dibutyl fumarate, di-tert-butyl fumarate, diisobutyl fumarate, di-sec-butyl fumarate and mixtures thereof.

3. The method according to claim 1 or 2, characterized in that The compound A is a monohydric alcohol selected from the group consisting of cyclohexanol, methylcyclohexanol, trimethylcyclohexanol, tert-butylcyclohexanol, benzyl alcohol, borneol, menthol, tricyclodecanol and a mixture thereof.

4. The method according to claim 1 or 2, characterized in that: The compound A corresponds to formula (IIb): (IIb) in: R' is a saturated or unsaturated, linear, branched or (mono- or poly-)cyclic hydrocarbon chain containing more than 4 carbon atoms, preferably more than 9 carbon atoms and generally less than 18 carbon atoms, R 1 and R 2 independently selected from H or alkyl, preferably H, methyl or ethyl, y is equal to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; preferably, y is equal to 1, 2, 3, 4, 5 or 6, and The range of z is 0 to 20; preferably, the range of z is 1 to 20.

5. The method according to claim 4, characterized in that The compound A corresponds to formula (IIb), wherein at least one of the following conditions is satisfied: - R' is a (mono- or poly-)cyclic hydrocarbon chain; preferably, R' is a non-aromatic monocyclic hydrocarbon chain, - z is greater than 0; preferably, z ranges from 1 to 20.

6. The method according to any one of claims 1 to 5, characterized in that The polyol is selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyalkylene glycols such as polyethylene glycol or polypropylene glycol (preferably having a number average molecular weight Mn in the range of 250-3000 g / mol, calculated from the OH number), 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, hydrogenated bisphenol A, glycerol, dipropylene glycol, tricyclodecane dimethanol, trimethylolpropane, di(trimethylolpropane), trimethylolethane, 1,2,6-hexanetriol, 1,2 , 4-butanetriol, erythritol, pentaerythritol, di(pentaerythritol), neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-methyl-1,2-propanediol, sorbitol, mannitol, xylitol, isosorbide, isoidol, isomannide, methyl glucoside, polyester polyols (especially polycaprolactone polyols), polycarbonate polyols, polyorganosiloxane polyols (especially polydimethylsiloxane polyols), polyglycerols (for example glycerol oligomers, such as polyglycerol-3 (glycerol trimer) and decaglycerol), hydroxyl-terminated polybutadiene, diols derived from hydrogenated or non-hydrogenated fatty acid dimers or trimers, alkoxylated (especially ethoxylated and / or propoxylated) derivatives of the above polyols, and mixtures thereof.

7. The method according to any one of claims 1 to 6, characterized in that The molar ratio of polyol to diester is less than 0.6 / n, preferably less than 0.4 / n, more preferably less than 0.2 / n.

8. The method according to any one of claims 1 to 7, characterized in that The polyamine is a diamine selected from the group consisting of 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,6-diaminohexane, 2-methylpentamethylenediamine, ethylenediamine, 1,2- and 1,3-propylenediamine, 2-methyl-1,2-propylenediamine, 2,2-dimethyl-1,3-propylenediamine, 1,3- and 1,4-butylenediamine, 1,3- and 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 2,5-dimethyl-2,5-hexanediamine, 2 , 2,4- or 2,4,4-trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2,4- and 2,6-hexahydrotoluenediamine, 2,4'- and 4,4'-diaminodicyclohexylmethane, 1,3- and 1,4-cyclohexanediamine, 1,3- or 1,4-bis(methylamino)cyclohexane, 1,8-p-menthanediamine, hydrazine, phenylenediamine, 2,4- and 2,6-toluenediamine, 2,3- and 3,4-toluenediamine, o-, m- or p-phenylenediamine, 2,4'- and 4,4'-diaminodiphenylmethane, benzidine and mixtures thereof.

9. The method according to any one of claims 1 to 7, characterized in that: The monoamine is selected from the group consisting of: sec-butylamine, isobutylamine, tert-butylamine, cyclohexylamine, 1,1,3,3-tetramethylbutylamine (or tert-octylamine) and mixtures thereof.

10. Aminosuccinic acid resin obtainable by the process according to any one of claims 1 to 9 and exhibiting an amine value of less than 190 mg KOH / g, preferably less than 180 mg KOH / g, even less than 150 mg KOH / g.

11. An aminosuccinic acid resin comprising at least one unit according to formula (VI): (WE) in: R1 is a saturated, straight or branched hydrocarbon chain containing less than 5 carbon atoms; R3 is a saturated or unsaturated, linear, branched or (mono- or poly-)cyclic hydrocarbon chain containing more than 4 carbon atoms; R5 is the residue of a primary polyamine; in particular, R5 is a saturated or unsaturated, linear, cyclic or branched hydrocarbon chain comprising at least 2 carbon atoms.

12. The aminosuccinic acid resin according to claim 11, characterized in that It comprises at least one unit according to formula (VII): (VII) wherein R1, R3 and R5 are as defined in claim 9; R4 is a hydrocarbon chain containing at least 2 carbon atoms; and 2≤n≤6。 13. Use of the aminosuccinic acid resin according to any one of claims 10 to 12 for the preparation of a two-component adhesive containing at least one polyisocyanate.

14. An adhesive formulation comprising the aminosuccinic acid resin according to any one of claims 10 to 12 and a polyisocyanate component.

15. Use of the binder formulation according to claim 14 for obtaining a coating, a mastic or an adhesive, in particular for obtaining a coating, more particularly for obtaining a film, a paint, a varnish, a lacquer, a stain, an adhesive primer or an ink.

16. A coating, adhesive or mastic obtained by applying and drying the binder formulation according to claim 14.

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