Method for preparing an aminosuccinic resin with a low amine value

Abstract

The present invention relates to a method for preparing an aminosuccinic resin, and to the aminosuccinic resin obtainable by this method, which has an amine value of less than 190 mg KOH / g. The invention also relates to the use of said aminosuccinic resin for producing two-component binders containing at least one polyisocyanate.

Description

[0001] Description

[0002] Title: Process for the preparation of a low amine number aminosuccinic resin

[0003] SUBJECT OF THE INVENTION

[0004] The present invention relates to a process for preparing an aminosuccinic resin, as well as the aminosuccinic resin obtainable according to this process, which has an amine index of less than 190 mg KOH / g. It also relates to the use of this aminosuccinic resin for the manufacture of two-component binders containing at least one polyisocyanate.

[0005] BACKGROUND OF THE INVENTION

[0006] Aminosuccinic or aspartic resins are polymers having -OC(=O)-CH2-CH(NR)-C(=O)-O- units, R being H or alkyl. These units can notably come from the addition of a primary or secondary amine to a succinic acid or a derivative thereof (notably succinic anhydride or dialkyl succinate). The combination of an aminosuccinic resin with a crosslinking agent such as a polyisocyanate makes it possible to obtain extemporaneous formulations of two-component binder. These formulations are useful for the preparation of adhesive compositions, paints or coatings, in particular to protect metal surfaces against corrosion, impacts or abrasion. These compositions find applications in particular in the automotive, wind and construction industries (floor coverings, sealing parts, etc.).

[0007] Aspartic resins are marketed by COVESTRO under the trade name Pasquick®. These aspartic resins are prepared from primary diamines sold under the trade name Desmophen® and are capable of reacting with an aliphatic polyisocyanate sold under the trade name Desmodur® to form polyureas. Their amine index is at least 190 mg KOH / g.

[0008] EP 1 516 886 also describes aspartic resins suitable for use in the manufacture of binders. These resins are obtained by a process comprising a first step of transesterification of an α,β-unsaturated C1-C9 alkyl ester, such as a maleic or fumaric acid ester, with a polyol such as butanediol or a sugar, and a second step of reacting the product thus obtained with a primary mono- or polyamine, such as cyclohexylamine or 1,6-hexanediamine, under conditions such that no primary amine group remains. The aspartic resins thus obtained have an amine number which is at least 200 mg KOH / g.

[0009] Document US-5,925,711 discloses a similar process for preparing aspartic resins, except that the oligoester obtained in the first step is formed either by reaction of an unsaturated diacid, such as maleic or fumaric acid, with a polyol and a monoalcohol, for example 1,6-hexanediol combined with n-butanol, or by transesterification of a C1-C8 alkyl diester with a polyol such as 1,6-hexanediol.

[0010] Known aspartic resins allow the production of coating compositions that adhere well to the substrate and whose mechanical properties are obtained quickly. However, they are concentrated in amine functions, which implies the use of a large quantity of polyisocyanate resin for the formulation of binders. Given the toxicity and cost of these polyisocyanate resins, it would therefore be desirable to have reactive diluents with a low amine index. It is also desirable that this property is not achieved to the detriment of the performance of the composition after application to the substrate, in particular its Persoz hardness.

[0011] SUMMARY OF THE INVENTION

[0012] The inventors have developed a process for meeting the above-mentioned needs, which uses, in the first step of preparing the aminosuccinic resin, a light diester transesterified using one or more heavy monoalcohols and optionally one or more polyols. It has been observed that the use of a heavy monoalcohol makes it possible to increase the molar mass of the diester and thus reduce the amine index of the aminosuccinic resin subsequently prepared, without significantly increasing the polydispersity (and therefore the viscosity) of the diester thus obtained, and to maintain a pot life of the mixture of the resin with a polyisocyanate which is suitable for the intended use.

[0013] The present invention thus relates to a process for preparing an aminosuccinic resin comprising the following steps: a) the transesterification of at least one alkyl diester of formula (I) using at least one compound A chosen from a mono-alcohol of formula (II), a precursor thereof and their mixtures, and optionally at least one polyol of formula (III):

[0014] RI-OOC-CH=CH-COO-R2(I)

[0015] R3-OH (II)

[0016] R4-(OH)n (III) where R1 and R2are independently saturated, linear or branched hydrocarbon chains each containing less than 5 carbon atoms; R3denotes a saturated or unsaturated, linear, branched or (mono or poly)cyclic hydrocarbon chain containing more than 4 carbon atoms; R4 denotes a hydrocarbon chain containing at least 2 carbon atoms; and 2 < n < 6, in a molar ratio of compound A to the diester ranging from 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, in a molar ratio between the amine functions and the double bonds of the diester ranging from 0.8 to 1.2.

[0017] It also relates to an aminosuccinic resin capable of being obtained using this process and having an amine index of less than 190 mg KOH / g.

[0018] It also relates to the use of this aminosuccinic resin for the manufacture of two-component binders containing at least one polyisocyanate.

[0019] The invention also relates to a binder formulation comprising the aforementioned aminosuccinic resin and a polyisocyanate component.

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

[0021] Finally, the invention also relates to a coating, an adhesive or a sealant obtained by applying and drying the aforementioned binder formulation. DETAILED DESCRIPTION

[0022] Process of a friendly resin

[0023] The invention relates to a process for preparing an aminosuccinic resin comprising essentially two steps, namely a first step of transesterification and a second step of reacting the product thus obtained with an amine.

[0024] The first step of this process comprises the transesterification of at least one alkyl diester using at least one compound A chosen from a mono-alcohol, a precursor of a mono-alcohol and their mixtures, and optionally at least one polyol.

[0025] The alkyl diester has the formula (I):

[0026] RI-OOC-CH=CH-COO-R2(I) in which Ri and R2 are independently saturated, linear or branched hydrocarbon chains that each contain less than 5 carbon atoms.

[0027] For the purposes of the present invention, the term "hydrocarbon chain" may in particular designate a chain comprising carbon and hydrogen atoms. A hydrocarbon chain may further comprise one or more heteroatoms (i.e. atoms other than carbon and hydrogen), in particular one or more heteroatoms chosen from O, N and S. These heteroatoms may be incorporated within the chain (i.e. between two carbon atoms) and / or may be incorporated as a substituent on the chain. In particular, a hydrocarbon chain may be interrupted by one or more functions chosen from ether, amine, thioether, ester, amide, thioester, carbonate, urea and urethane.

[0028] It is preferred that the hydrocarbon chains R 1 and R 2 are chains consisting solely of carbon or hydrogen atoms. Examples of such diesters (or "light diesters") include alkyl maleates and fumarates such as: dimethyl maleate, diethyl maleate, dipropyl maleate, diisopropyl maleate, dibutyl maleate, di-tert-butyl maleate, di- / so-butyl maleate, di-sec-butyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, diisopropyl fumarate, dibutyl fumarate, di-tert-butyl fumarate, di- / so-butyl fumarate, di-sec-butyl fumarate, and mixtures thereof.

[0029] For its part, the mono-alcohol responds to the formula (II):

[0030] R3-OH (II) in which R3 denotes 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. It is preferred that the hydrocarbon chain R3 contains only carbon and hydrogen atoms and is optionally interrupted and / or substituted by one or more oxygen atoms.

[0031] The hydrocarbon chain R3 is preferably a (mono or poly)cyclic hydrocarbon chain, more preferably a non-aromatic monocyclic hydrocarbon chain. For the purposes of the invention, a (mono or poly)cyclic hydrocarbon chain is a chain comprising at least one cycle (preferably a non-aromatic cycle) 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 is preferably devoid of oxyethylene units, more preferably the hydrocarbon chain R3 is devoid of an ether function.

[0032] Examples of such alcohols (so-called "heavy alcohols") include: pentanol, methylbutanol, dimethylpropanol, hexanol, methylpentanol, ethylbutanol, diethylpropanol, cyclohexanol, heptanol, methylcyclohexanol, octanol, ethylhexanol, nonanol, trimethylcyclohexanol, decanol, tert-butyl cyclohexanol, tridecanol, isotridecanol, dodecanol, butoxyethanol, benzyl alcohol, borneol, menthol, tricyclodecyl methanol, methoxy polyethylene glycol, and mixtures thereof. Particularly preferred heavy alcohols include: cyclohexanol, methylcyclohexanol, trimethylcyclohexanol, tert-butyl cyclohexanol, benzyl alcohol, borneol, menthol, tricyclodecyl methanol, and mixtures thereof.

[0033] In one embodiment of the invention, compound A may comprise a precursor of a monoalcohol, i.e. a compound capable of forming a monoalcohol under the conditions of the transesterification reaction (in particular 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 the transesterification reaction. Said precursor may also be used in a mixture with a monoalcohol, in particular a heavy monoalcohol as defined above. Said precursor may in particular be a lactone such as γ-butyrolactone, 6-valerolactone or ε-caprolactone or a cyclic diester. A cyclic diester may in particular be a cyclic diester of any α-hydroxy acid (AAH). In particular, the cyclic diester may be a cyclic dimer of two identical AAHs or a combination of two different AAHs.For example, the cyclic diester can be formed by two glycolic acid molecules, thus giving a glycolide, or two lactic acid molecules, thus forming a lactide, or one glycolic acid molecule and one lactic acid molecule. It is understood that all isomeric forms of AAH can be used to form the cyclic diester. In particular, the cyclic diester can have the following formula (IIa):. wherein Ra, Rb, Rc and Rd are independently selected from H, methyl or ethyl.

[0034] Examples of cyclic diesters are a lactide (Ra and Rc = H and Rb and Rd = methyl) or a glycolide (Ra, Rb, Rc and Rd = H).

[0035] According to a preferred embodiment, compound A corresponds to the formula (llb): in which:

[0036] 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,

[0037] R 1 and R 2 are independently selected from H, or alkyl, preferably H, methyl or ethyl, y is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, preferably y is 1, 2, 3, 4, 5 or 6, and z is from 0 to 20, preferably z is from 1 to 20.

[0038] 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' is preferably devoid of oxyethylene units, more preferably the hydrocarbon chain R' is devoid of ether function.

[0039] According to a particularly preferred embodiment, compound A corresponds to formula (II b) in which at least one of the following conditions is fulfilled:

[0040] 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.

[0041] When z is greater than 0, compound A may in particular be a mono-alcohol resulting from the reaction between a mono-alcohol (in particular a heavy mono-alcohol as defined above) and a precursor of a mono-alcohol chosen from a lactone and a cyclic diester.

[0042] A polyol may optionally be present in the reaction mixture to adjust the rate of viscosity increase of the varnish obtained from the aminosuccinic resin according to the invention. This polyol corresponds to formula (III):

[0043] R4-(OH)n (III) in which:

[0044] R4 denotes a saturated, linear, branched or (mono or poly)cyclic hydrocarbon chain containing at least 2 carbon atoms, preferably at least 4 carbon atoms and more preferably at least 5 carbon atoms, and generally less than 36 carbon atoms, and

[0045] 2 < n < 6, preferably 2 < n < 3 and more preferably n is equal to 2.

[0046] The hydrocarbon chain R4 may in particular be interrupted by one or more functions chosen from ether, ester, carbonate, urea and urethane.

[0047] It is preferred that the hydrocarbon chain R4 contains only carbon and hydrogen atoms and is optionally interrupted and / or substituted by one or more oxygen atoms. Examples of such polyols include: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 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 with a number-average molecular weight Mn, calculated from the OH number, ranging from 250 to 3000 g / mol), 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, hydrogenated bisphenol A, glycerol, diglycerol, 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, isoidide, isomannide, methyl glucoside, polyester polyols (especially polycaprolactone polyol), polycarbonate polyols, polyorganosiloxane polyols (especially polydimethylsiloxane polyol), polyglycerols such as glycerol oligomers such as Polyglycerol-3 (glycerol trimer) and decaglycerol, a hydroxy-terminated polybutadiene, a diol derived from a dimer or trimer of hydrogenated or non-hydrogenated fatty acid, alkoxylated (especially ethoxylated and / or propoxylated) derivatives of the above-mentioned polyols, and mixtures thereof.,

[0048] In the transesterification reaction, the molar ratio of compound A to diester ranges from 0.01 to 1.99, preferably from 0.1 to 1.5 and more preferably from 0.2 to 1.0. In the case where a polyol is introduced in this step, the molar ratio of polyol to diester is generally less than 0.6 / n, preferably less than 0.4 / n and more preferably less than 0.2 / n.

[0049] This reaction is generally carried out at a temperature of 50 to 300°C, preferably 80 to 250°C and more preferably 150 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 time allowing a hydroxyl number of less than 10 mg KOH / g, preferably less than 5 mg KOH / g, to be reached, as measured as described in the examples below. The transesterification reaction is generally carried out in the presence of a catalyst.The catalyst may for example be chosen from oxides and organic salts of metals such as titanium, tin, zinc, antimony or iron, for example from: titanium(IV) butoxide, tetrakis(2-ethylhexyl) titanate, tin(IV) oxide, dibutyltin oxide, butyltin oxide hydroxide, dibutyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(2-ethylhexanoate), butylstannoic acid, dibutyltin dichloride, octyltin hydroxide, zinc(IV) oxide and zinc(II) oxide.

[0050] It is further preferred that the transesterification reaction be carried out under an inert atmosphere, for example under nitrogen bubbling.

[0051] Reaction with an amine

[0052] At the end of the transesterification step described above, a so-called "heavy" polyester is obtained which is reacted, in the second step of the process according to the invention, with at least one primary polyamine and optionally at least one primary monoamine, hereinafter referred to together as "the amine", unless otherwise indicated. The molar ratio between the amine functions and the double bonds of the diester ranges from 0.8 to 1.2, preferably from 0.9 to 1.1 and more preferably from 0.95 to 1.05.

[0053] The mono- and polyamines used according to the invention may be chosen from amines comprising a linear, cyclic or branched, saturated or unsaturated (optionally aromatic) hydrocarbon chain, to which one or more amino groups are linked. The polyamine may be chosen from diamines, triamines and tetramines. It is preferably a diamine.

[0054] The primary polyamine may in particular correspond to the formula (IV):

[0055] R5-(NH2)m (IV) in which:

[0056] Rs is a linear, cyclic or branched, saturated or unsaturated (optionally aromatic) chain comprising at least 2 carbon atoms, preferably at least 4 carbon atoms and more preferably at least 5 carbon atoms, and generally less than 100 carbon atoms, preferably less than 40 carbon atoms, and 2 < m < 4, preferably 2 < m < 3 and more preferably m is equal to 2.

[0057] It is preferred that the Rs chain is a hydrocarbon chain optionally interrupted by one or more heteroatoms independently selected from oxygen and nitrogen.

[0058] According to a particular embodiment, the primary diamine corresponds to the formula (IVa): H2N-R5-NH2 (IVa) in which R5 is as defined above.

[0059] Examples of diamines may be chosen from: l-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), bis-(4-aminocyclohexyl)methane, bis-(4-amino-3-methylcyclohexyl)methane, 1,6-diamino hexane, 2-methyl pentamethylene diamine, ethylene diamine, 1,2- and 1,3-propanediamines, 2-methyl-l,2-propanediamine, 2,2-dimethyl-l,3-propanediamine, 1,3- and 1,4-butanediamines, 1,3- and 1,5-pentanediamines, 2-methyl-l,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-hexahydrotoluylenediamines, 2,4'- and 4,4'-diamino-dicyclohexylmethanes, 1,3- and 1,4-cyclohexanediamines, 1,3- or 1,4-bis(methylamino)-cyclohexane, 1,8-p-menthanediamine, hydrazine, phenylenediamine, 2,4- and 2,6-toluylenediamines, 2,3- and 3,4-toluylenediamines, o-, m- or p-xylylenediamines, 2,4'- and 4,4'-diaminodiphenyl methanes, benzidine, and mixtures thereof. Examples of monoamines include: sec-butylamine, isobutylamine, tert-butylamine, cyclohexylamine, 1,1,3,3-tetramethyl butylamine (or tert-octylamine) and mixtures thereof.,

[0060] Examples of triamines are guanidine and N-(2-aminoethyl)-1,3-propanediamine. Examples of tetramines include N,N'-di-(2-aminoethyl)piperazine.

[0061] The primary polyamine may also be a polyetheramine. A polyetheramine is a polyamine comprising ether linkages (-O-), more particularly ethylene oxide (-O-CH2-CH2) and / or propylene oxide (-O-CH2-CHCH3-) units. Examples of polyetheramines are the compounds marketed by Hunstmann under the reference Jeffamine®, in particular the Jeffamine® D, ED and EDR series. These series include in particular the following references: Jeffamine®D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, Jeffamine® EDR-176.

[0062] It was observed that the use of monoamines alone, which are generally not very hindered, did not allow the aminosuccinic resin to have a sufficient pot life and led to friable and poorly cohesive films after drying of this resin.

[0063] The order of introduction of the above reactants is not critical, as long as the monoamines, if used, are introduced before the diamines. Generally, the product of the transesterification step is added slowly to the amine.

[0064] The reaction between the amine(s) and the product of the first step is a Michael reaction, which is generally carried out at a temperature of 0 to 160°C, preferably 20 to 140°C and more preferably 30 to 80°C, for a period of 1 to 4 hours. It is preferred that this reaction be carried out under an inert atmosphere, for example under nitrogen bubbling. The product obtained is generally then kept at room temperature for a period of 15 to 90 days, for example 30 to 60 days, always under an inert atmosphere.

[0065] The two steps described above can be carried out in the presence or absence of a solvent. Examples of suitable solvents are polar organic solvents such as: ketones, including acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as n-butyl acetate and methoxypropyl acetate; N-methylpyrrolidone; and mixtures thereof. Alternatively, non-polar organic solvents such as toluene and xylene can be used.

[0066] The amine index of the aminosuccinic resin obtained at the end of the second step described below is less than 190 mg KOH / g, preferably less than 180 mg KOH / g or even less than 150 mg KOH / g, as measured as described in the examples below. The process according to the invention makes it possible to obtain an aminosuccinic resin.

[0067] Amino succinic resin

[0068] The invention also relates to an aminosuccinic resin comprising at least one unit according to formula (VI): in which:

[0069] Ri is a saturated, linear or branched hydrocarbon chain that contains less than 5 carbon atoms;

[0070] R3 is a saturated or unsaturated, linear, branched or (mono or poly)cyclic hydrocarbon chain containing more than 4 carbon atoms;

[0071] Rs is a linear, cyclic or branched, saturated or unsaturated (possibly aromatic) hydrocarbon chain comprising at least 2 carbon atoms.

[0072] According to a particular embodiment, the aminosuccinic resin comprises at least one unit according to formula (VII): in which Ri, R3 and R5 are as defined previously;

[0073] R4 is a hydrocarbon chain containing at least 2 carbon atoms as described in the process according to the invention; and

[0074] 2 < n < 6. The aminosuccinic resin can in particular be obtained by the process described above.

[0075] The chains R1, R3, R4 and R5 may in particular be as described in the process according to the invention. Thus, in formulas (VI) and (VII):

[0076] Ri may in particular correspond to the group Ri which is present on the alkyl diester of formula (I) before the transesterification reaction;

[0077] R3 may in particular correspond to the residue of compound A of formula (II) or (IIb) (without the OH group) used in the transesterification reaction;

[0078] R4, when present, may in particular correspond to the residue of the polyol of formula (III) (without the OH groups) possibly used in the transesterification reaction;

[0079] Rs may in particular correspond to the primary polyamine residue of formula (IV) (without the NH2 groups).

[0080] Binder formulations

[0081] The aminosuccinic resins prepared according to the invention can be used in binder formulations, in combination with a crosslinking agent such as a polyisocyanate.

[0082] Thus, the present invention also relates to a binder formulation comprising: a) a polyisocyanate component, and b) an isocyanate-reactive component.

[0083] This type of formulation is a two-component formulation (also called a 2K formulation). Such a formulation is extemporaneous, meaning it is prepared shortly before its application by the end user.

[0084] Component b) above comprises the aminosuccinic resin according to the invention and optionally another isocyanate-reactive compound. Examples of isocyanate-reactive compounds other than the aminosuccinic resin are compounds having one or more functions chosen from alcohol, amine and thiol, preferably diols or diamines or amino alcohols. Component a) above comprises a polyisocyanate. Component a) may comprise a mixture of polyisocyanates. For the purposes of the present invention, a polyisocyanate is a compound having at least 2 -NCO functions.

[0085] Component a) may in particular comprise an aliphatic or aromatic polyisocyanate, preferably an aliphatic polyisocyanate.

[0086] Component a) may in particular comprise a diisocyanate, a dimeric or trimeric form of a diisocyanate (in particular biuret, allophanate, uretdione, isocyanurate) a polymeric form of a diisocyanate, an elongated form of a diisocyanate (in particular a diisocyanate elongated by reaction with a polyol or a diisocyanate having a carbodiimide group obtained by decarboxylation reaction between 2 diisocyanate molecules) or a mixture thereof.

[0087] 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-diiso-cyanatocyclohexane, 1-isocyanato-5-isocyanatomethyl-3,3,5-trimethyl-cyclohexane or isophorone diisocyanate (IPDI), 2,3-, 2,4- or 2,6-diisocyanato-1-methylcyclohexane, 4,4'- or 2,4'- diisocyanatodicyclohexylmethane (H12MDI), l-isocyanato-3(4)-isocyanatomethyl-l-methyl- cyclohexane (I MCI ), as well as dimeric, trimeric, polymeric and extended forms thereof and mixtures thereof. Examples of preferred polyisocyanates are trimers of HDI, as well as polyisocyanates prepared from 1,6-diisocyanato-hexane, which contain isocyanurate groups and optionally uretdione groups.These polyisocyanates typically have an NCO content of 19 to 24% by weight, based on the weight of the polyisocyanate.

[0088] These polyisocyanates may optionally be used in combination with polyether-modified polyisocyanates, which may be obtained by reacting the above-mentioned polyisocyanates with an alcohol or polyol ether of polyoxyalkylene, in particular polyoxyethylene, such as polyethylene glycol monomethyl ether.

[0089] Generally, to obtain the binder formulations, the aminosuccinic resin and the polyisocyanate are mixed in a molar ratio of isocyanate groups to primary amine groups ranging from 0.5:1 to 8:1, preferably from 0.75:1 to 6:1 and more preferably from 1:1 to 4:1.

[0090] These formulations may also include other compounds that may react with polyisocyanates, including hydroxyl-functional polyacrylates and polyester polyols.

[0091] Alternatively or additionally, they may comprise additives such as fillers, colorants, thickeners, dispersants, surfactants, anti-settling agents, catalysts, UV stabilizers, anti-foaming agents, leveling agents, adhesion promoters, matting agents, opacifying agents, waxes and mixtures thereof. They may further comprise one or more solvents, selected for example from the esters, ketones and aromatic hydrocarbons listed above.

[0092] According to a preferred embodiment, the formulation comprises a colorant. A colorant may be selected from a dye, a pigment and mixtures thereof. 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 DIN 55943, as a colorant which is practically insoluble in the application medium under the ambient conditions which characterize it, and whose solubility is therefore less than 10 mg / l in this medium at 25°C.

[0093] The colorant may in particular be a pigment. Organic and / or inorganic pigments may be used. If the colorant is not a self-dispersing pigment, the formulations may further contain a dispersant, more preferably a polymeric dispersant, as described below. The pigment may be selected from a black, cyan, magenta, yellow, red, orange, violet, blue, green, brown pigment or a mixture thereof. The pigment may be selected from those disclosed by HERBST, Willy, et al. Industrial Organic Pigments, Production, Properties, Applications. 3rd edition. Wiley - VCH, 2004. ISBN 3527305769.

[0094] Examples of particular pigments are described below, with the term "Cl" being used as an abbreviation for Colour Index:

[0095] - carbon black;

[0096] - Cl White Pigment 1, 3, 4, 5, 6, 7, 10, 11, 12, 14, 17, 18, 19, 21, 24, 25, 27, 28 and 32;

[0097] - Cl 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;

[0098] - Cl 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;

[0099] - Cl Pigment Violet 1, 2, 19, 23, 32, 37 and 3;

[0100] - Cl Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:6, 16, 56, 61 and aluminum phthalocyanine pigments (bridged);

[0101] - Cl Pigment Orange 5, 13, 16, 34, 40, 43, 59, 66, 67, 69, 71 and 73;

[0102] - Cl Pigment Green 7 and 36;

[0103] - Cl Brown Pigment 6 and 7; and their mixtures.

[0104] 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 pigments in relation 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 the ISO 4618-1:2006 standard.

[0105] The formulation may further comprise a dispersant. The dispersant may be used to disperse an insoluble material such as a pigment or filler in the formulation.

[0106] The dispersant may in particular be a polymer dispersant.

[0107] Typical polymer dispersants are copolymers of two, three, four, five, or even more monomers. The properties of polymer dispersants depend on both the nature of the monomers and their distribution in the polymer. Copolymer dispersants preferably have the following polymer compositions:

[0108] - random copolymer (e.g. ABBAABAB);

[0109] - alternating copolymer (e.g. ABABABAB);

[0110] - gradient copolymer (e.g., AAABAABBABBB);

[0111] - block copolymers (e.g., AAAAABBBBBB);

[0112] - graft copolymers (polymer backbone with polymer side chains attached to the backbone); and mixed forms of these copolymers.

[0113] The polymeric dispersant may have a number average molecular weight Mn of between 500 and 30,000 g / mol, more preferably between 1500 and 10,000 g / mol.

[0114] Commercial examples of polymeric dispersants include:

[0115] - DISPERBYK® dispersants available from BYK CHEMIE GMBH;

[0116] - SOLSPERSE® dispersants available from LUBRIZOL;

[0117] - TEGO® DISPERSE dispersants from EVONIK;

[0118] - DISPEX®, EFKA® and JONCRYL® dispersants from BASF;

[0119] - DISPONER® dispersants from ELEMENTIS.

[0120] The binder formulation can be applied to a wide variety of substrates, including wood, metal, stone, plaster, concrete, glass, fabric, leather, paper, plastic, composite. Application can be carried out conventionally, such as by spraying, dipping, or using a brush, roller, or blade. Application can be carried out in particular to form one or more layers, preferably having a thickness of 5 to 100 μm.

[0121] The resulting formulation is then hardened at a temperature of 20 to 100°C.

[0122] The binder formulation may in particular be a coating, sealant or adhesive formulation. In particular, the binder formulation may be a coating formulation, more particularly a decorative coating formulation, in particular a film, paint, varnish, lacquer, stain, adhesion primer or ink formulation. According to a particular embodiment, the binder formulation is a paint, varnish or stain formulation, in particular a finishing paint, varnish or stain formulation. Such a formulation may in particular be applied indoors or outdoors, for example on wood, metal, a wall or plastic.

[0123] The formulation can in particular be used to obtain a coating (in particular a film, a paint, a varnish, a lacquer, a stain, an adhesion primer or an ink), an adhesive or a sealant.

[0124] Another subject of the invention relates to the use of the binder formulation according to the invention, to obtain a coating (in particular a film, a paint, a varnish, a lacquer, a stain, an adhesion primer or an ink), an adhesive or a mastic.

[0125] The invention also relates to a coating (in particular a film, a paint, a varnish, a lacquer, a stain, an adhesion primer or an ink), an adhesive or a sealant obtained by applying and drying the binder formulation according to the invention.

[0126] BRIEF DESCRIPTION OF THE FIGURES

[0127] [Fig 1] and [Fig. 2] represent examples of methods according to the invention.

[0128] EXAMPLES

[0129] The invention will be better understood in light of the following examples, which are given purely for illustrative purposes and are not intended to limit the scope of the invention, defined by the appended claims.

[0130] Materials

[0131] The materials used in the examples are described below:

[0132] DEM (diethyl maleate) from Sigma-Aldrich

[0133] D2EHM (di-2ethyl hexyl maleate) Mw =340g / mol from Sigma-Aldrich Butanediol from Sigma-Aldrich

[0134] Cyclohexanol from Sigma-Aldrich

[0135] - Benzyl Alcohol from Sigma-Aldrich

[0136] - TCDDM: tricyclodecyl dimethanol (Mw=196g / mol) from Sigma-Aldrich e-Caprolactone from Sigma-Aldrich

[0137] Isotridecanol from BASF

[0138] 2EH (2-ethyl hexanol) from Sigma-Aldrich

[0139] - TCDOH (tricyclodecyl methanol) from OXEA

[0140] CHDM (cyclohexane dimethanol) from Sigma-Aldrich

[0141] NPG (Neopentyl glycol) from Sigma-Aldrich

[0142] MBMCHA (4,4'-methylenebis-(2-methylcyclohexylamine)) from TCI

[0143] MBCHA (4,4'-methylenebis-(cyclohexylamine)) from Sigma Aldrich

[0144] CHA (cyclohexylamine) from Sigma-Aldrich

[0145] Fascat 4100 (butyl stanoic acid) from BRENNTAG

[0146] Measurement methods

[0147] Amine index

[0148] The amine index is measured by titration with a Metrohm titrator (848 Titrino plus) equipped with a Metrohm measuring probe reference 6.0262.100. The sample to be analyzed is weighed into a 100 ml beaker. 50 ml of dichloromethane is added. The sample is completely dissolved by magnetic stirring. Titration is carried out under magnetic stirring with 0.1 N perchloric acid in acetic acid, according to the chosen method for using the titrator. The amine index is calculated according to the following equation:

[0149] VE X NT X 56.1 kmineOgKOH / g) = - - -

[0150] M with

[0151] VE = Volume of titrant poured for sample dosage (mL)

[0152] NT = Normality of the titrant (0.1 N)

[0153] M = Mass of the sample (g). Hydroxyl number

[0154] The hydroxyl number is measured by titration with a Metrohm titrator (848 Titrino plus) equipped with a Metrohm measuring probe reference 6.0229.100. An acid-base titration is carried out in return for the excess of acetic anhydride relative to the hydroxy functions under the following conditions: the product, of exact mass M (approximately 3 grams) is dissolved in exactly 10 ml of acetylating solution (mixture of 555 ml of ethyl acetate, 60 ml of acetic anhydride and 7 g of para-toluenesulfonic acid monohydrate). The reaction is left to react for 30 minutes at 90°C. After cooling, approximately 2 ml of water is added and left to react for 2 minutes at room temperature. Then add about 10 ml of hydrolyzing solution (mixture of 600 ml of pyridine and 400 ml of water) and leave to react for 5 minutes at room temperature. Add about 60 ml of solvent (mixture of 666 ml of n-butanol and 333 ml of toluene).The excess acetic acid (released by the hydrolysis of the acetic anhydride in excess of the hydroxy functions to be acetylated) is then measured with methanolic potash of normal N (Eq / I) exact titration of approximately 0.5N, according to the method of using the titrimeter chosen. A blank test (identical to the protocol above without the product to be analyzed) is also carried out. The hydroxyl index is calculated according to the following equation:.

[0155] (VE - VB) X NT X 56.1

[0156] I0H(m K0H / g) = 1 Acid + - - - -

[0157] M with

[0158] VE = Volume of titrant poured for sample dosage (mL)

[0159] VB = Blank Test Volume

[0160] NT = Normality of the titrant (0.5 N)

[0161] M = Mass of the sample (g). lAcid = Acid number determined according to the method below.

[0162] Acid number

[0163] The acid number is measured by titration with a Metrohm titrator (848 titrino plus) equipped with a Metrohm measuring probe reference 6.0229.100. The sample to be analyzed is weighed into a 100 ml beaker. 50 ml of solvent (mixture of 500 ml of toluene and 500 ml of methanol) is added. The sample is completely dissolved by magnetic stirring. Titration is carried out under magnetic stirring with 0.1 N methanolic potash, according to the chosen method of using the titrator. The acid number is calculated according to the following equation: X 56.1 - with

[0164] VE = Volume of titrant poured for sample dosage (mL)

[0165] NT = Normality of the titrant (0.1 N)

[0166] M = Mass of the sample (g).

[0167] Measuring varnish viscosity

[0168] The initial viscosity of the varnish before application is measured on a CAP 1000 Brookfield viscometer (high shear gradient) according to ISO 2884 standard, with a cone 2 or 3 depending on the initial viscosity of the polyaminosuccinic acid, at 25°C.

[0169] Pot life:

[0170] Pot life is the time required to observe a doubling of the initial viscosity of a varnish composition. Viscosity is measured regularly over time. All of the measurements allow a straight line to be drawn, which allows the pot life of the composition to be calculated by linear regression. This common measurement allows the ideal range of use of the composition to be determined without losing its application properties.

[0171] Dry thickness of varnish:

[0172] The dry thickness is measured on a dry film of varnish 24 hours after application (according to standard NF EN ISO 2808) with a filmograph of a varnish composition with a thickness of 150pm wet (50pm dry) on a QD46 steel plate (in an air-conditioned room at 23°C, and 50% relative humidity).

[0173] Persoz varnish hardness:

[0174] Persoz hardness is measured according to the NF EN ISO 1522 standard of March 2007 after application with a filmograph of a varnish composition with a thickness of 150pm wet (50pm dry) on a QD46 steel plate (in an air-conditioned room at 23°C, and 50% relative humidity). Persoz hardness is measured 24 hours or 14 days after application of the varnish (in an air-conditioned room at 23°C, and 50% relative humidity). 1 (tra

[0175] DEM (344.00 g or 2.000 mol), isotridecanol (119.40 g or 0.597 mol), CHDM (7.40 g or 0.050 mol) and Fascat 4100 (0.050 g) were introduced into a reactor equipped with a distillation column, a thermometer, a nitrogen bubbling rod and an inclined blade stirrer. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. The temperature is raised and then maintained at 170 °C. The ethanol formed during the transesterification reaction is distilled. The temperature is maintained until a hydroxyl number of less than 5 mg KOH / g is obtained. The heavy maleate polyester obtained is colorless.

[0176] DEM (454.18 g or 2.641 mol), 2EH (118.56 g or 0.912 mol), CHDM (4.75 g or 0.033 mol) and Fascat 4100 (0.055 g) were introduced into a reactor equipped with a distillation column, a thermometer, a nitrogen bubbling rod and an inclined blade stirrer. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. The temperature is raised and then maintained at 190 ° C. The ethanol formed during the transesterification reaction is distilled. The temperature is maintained until a hydroxyl number of less than 10 mg KOH / g is obtained. The heavy maleate polyester obtained is colorless. The hydroxyl number measured after cooling is 7.5 mg KOH / g.

[0177] DEM (456.76 g or 2.656 mol), 2EH (111.18 g or 0.855 mol), CHDM (9.56 g or 0.066 mol) and Fascat 4100 (0.055 g) were introduced into a reactor equipped with a distillation column, a thermometer, a nitrogen bubbling rod and an inclined blade stirrer. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. The temperature is raised and then maintained at 190 ° C. The ethanol formed during the transesterification reaction is distilled. The temperature is maintained until a hydroxyl number of less than 10 mg KOH / g is obtained. The heavy maleate polyester obtained is colorless. The hydroxyl number measured after cooling is 6.9 mg KOH / g.

[0178] DEM (166.65 g or 0.969 mol), TCDOH (160.83 g or 0.821 mol), NPG (2.52 g or

[0179] 0.024 mol) and Fascat 4100 (0.040 g) were introduced into a reactor equipped with a distillation column, a thermometer, a nitrogen bubbling rod and an inclined blade stirrer. Nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. The temperature is raised and then maintained at 190 ° C. The ethanol formed during the transesterification reaction is distilled. The temperature is maintained until a hydroxyl number of less than 5 mg KOH / g is obtained. The heavy maleate polyester obtained is colorless. The hydroxyl number measured after cooling is 2.1 mg KOH / g.

[0180] DEM (425.70 g or 2.475 mol), isotridecanol (147.45 g or 0.737 mol), NPG (6.68 g or 0.064 mol) and Fascat 4100 (0.100 g) were introduced into a reactor equipped with a distillation column, a thermometer, a nitrogen bubbling rod and an inclined blade stirrer. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. The temperature is raised and then maintained at 160 ° C. The ethanol formed during the transesterification reaction is distilled. The temperature is maintained until a hydroxyl number of less than 5 mg KOH / g is obtained. The heavy maleate polyester obtained is colorless. The hydroxyl number measured after cooling is 4.2 mg KOH / g.

[0181] MBMCHA (51.87 g) is introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. 98.13 g of the product obtained in Example 1 is introduced into the dropping funnel and then added over a period of 1 hour while maintaining the temperature below 50°C. The temperature is maintained at 50°C for a further 1 hour and then the contents of the reactor are transferred into an inert bottle and kept closed at room temperature for 60 days. The reduction of the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is monitored by NMR. 1 H. The theoretical dry extract of the finished product is 100%. The amine index measured after storage is 163 mg KOH / g.

[0182] MBMCHA (35.44 g) and CHA (1.55 g) are introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. 63.01 g of the product obtained in Example 2 is introduced into the dropping funnel and then added over a period of 1 hour while maintaining the temperature below 50°C. The temperature is maintained at 50°C for a further 1 hour and then the contents of the reactor are transferred into an inert flask and kept closed at room temperature for 30 days. The reduction of the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is monitored by NMR. 1 H. The theoretical dry extract of the finished product is 100%. The amine index measured after storage is 176 mg KOH / g.

[0183] MBMCHA (37.19 g) is introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. 62.81 g of the product obtained in Example 3 is introduced into the dropping funnel and then added over a period of 1 hour while maintaining the temperature below 50°C. The temperature is maintained at 50°C for a further 1 hour and then the contents of the reactor are transferred into an inert bottle and kept closed at room temperature for 30 days. The reduction of the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is monitored by NMR. 1 H. The theoretical dry extract of the finished product is 100%. The amine index measured after storage is 175 mg KOH / g.

[0184] MBMCHA (57.92 g) is introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. 142.08 g of the product obtained in Example 4 is introduced into the dropping funnel and then added over a period of 1 hour while maintaining the temperature below 50°C. The temperature is maintained at 50°C for a further 1 hour and then the contents of the reactor are transferred into an inert bottle and kept closed at room temperature for 60 days. The reduction of the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is monitored by NMR. 1 H. The theoretical dry extract of the finished product is 100%. The amine index measured after storage is 137 mg KOH / g. 10 (ami resin

[0185] MBCHA (36.55 g) is introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. 75.95 g of the product obtained in Example 5 is introduced into the dropping funnel and then added over a period of 2 hours while maintaining the temperature below 50°C. The temperature is maintained at 50°C for a further 1 hour and then the contents of the reactor are transferred into an inert bottle and kept closed at room temperature for 30 days. The reduction of the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is monitored by NMR. 1 H. The theoretical dry extract of the finished product is 100%. The amine index measured after storage is 174 mg KOH / g.

[0186] 76.09 g of the product obtained in Example 5 is introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. Nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. 3.45 g of CHA is added. The temperature is raised and then maintained at 50°C for

[0187] 1 hour. 32.96 g of MBCHA is introduced into the dropping funnel and then added over a period of 1 hour 30 minutes while maintaining the temperature below 50°C. The contents of the reactor are transferred into an inert bottle and kept closed at room temperature for 30 days. The reduction of the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is monitored by NMR. 1 H. The theoretical dry extract of the finished product is 100%. The amine value measured after storage is 174 mg KOH / g. corn :if 1 of a heavy diester without

[0188] 75.00g of D2EHM (0.2206 mol) is introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. 26.25g of MBMCHA (0.1103 mol) is introduced into the dropping funnel and then added over a period of 1h while maintaining the temperature below 50°C. The contents of the reactor are transferred into an inert flask and kept closed at room temperature for 30 days. The reduction of the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is monitored by NMR. 1 H. The theoretical dry extract of the finished product is 100%. The amine index measured after storage is 122 mg KOH / g.

[0189] Comparative example 2 (transesterification without heavy monoalcohol):

[0190] DEM (420.31 g or 2.4437 mol), butanediol (38.33 g or 0.4259 mol) and Fascat 4100 (0.100 g) were introduced into a reactor equipped with a distillation column, a thermometer, a nitrogen bubbling rod and an inclined blade stirrer. Nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. The temperature is raised and then maintained at 170 °C. The ethanol formed during the transesterification reaction is distilled. The temperature is maintained until a hydroxyl number of less than 5 mg KOH / g is obtained.

[0191] 59.06 g of the product obtained are introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. 40.94 g of MBMCHA is introduced into the dropping funnel and then added over a period of 30 minutes while maintaining the temperature below 50°C. The contents of the reactor are transferred into an inert bottle and kept closed at room temperature for 30 days. The reduction of the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is monitored by NMR 1 H. The theoretical dry extract of the finished product is 100%. The amine index measured after storage is 193 mg KOH / g.

[0192] Comparative example s (transesterification without heavy monoalcohol):

[0193] DEM (420.31 g or 2.4437 mol), butanediol (54.98 g or 0.6109 mol) and Fascat 4100 (0.100 g) were introduced into a reactor equipped with a distillation column, a thermometer, a nitrogen bubbling rod and an inclined blade stirrer. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. The temperature is raised and then maintained at 170 °C. The ethanol formed during the transesterification reaction is distilled. The temperature is maintained until a hydroxyl number of less than 5 mg KOH / g is obtained.

[0194] 59.04 g of the product obtained are introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. 40.96 g of MBMCHA is introduced into the dropping funnel and then added over a period of 30 minutes while maintaining the temperature below 50°C. The contents of the reactor are transferred into an inert bottle and kept closed at room temperature for 30 days. The reduction of the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is monitored by NMR 1 H. The theoretical dry extract of the finished product is 100%. The amine index measured after storage is 193 mg KOH / g. ransesterification with monoalcohol

[0195] DEM (420.31 g or 2.4437 mol), benzyl alcohol (131.95 g or 1.2218 mol) and Fascat 4100 (0.100 g) were introduced into a reactor equipped with a distillation column, a thermometer, a nitrogen bubbling rod and an inclined blade stirrer. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. The temperature is raised and then maintained at 170 ° C. The ethanol formed during the transesterification reaction is distilled. The temperature is maintained until a hydroxyl number of less than 5 mg KOH / g is obtained.

[0196] 63.04 g of the product obtained are introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. 36.96 g of MBMCHA is introduced into the dropping funnel and then added over a period of 30 minutes while maintaining the temperature below 50°C. The contents of the reactor are transferred into an inert bottle and kept closed at room temperature for 30 days. The reduction of the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is monitored by NMR 1 H. The theoretical dry extract of the finished product is 100%. The amine index measured after storage is 174 mg KOH / g.

[0197] Example 13 (transesterification with monofunctional heavy monoalcohol and heavy monoalcohol precursor):

[0198] DEM (363.01 g or 2.1105 mol), TCDDM (5.17 g or 0.0264 mol), cyclohexanol (150.00 g or 1.5000 mol), e-caprolactone (91.43 g or 0.8020 mol) and Fascat 4100 (0.100 g) were introduced into a reactor equipped with a distillation column, a thermometer, a nitrogen bubbling rod and a tilted blade stirrer. A nitrogen bubbling of 30 ml / minute was imposed throughout the synthesis. The temperature was raised and then maintained at 170 ° C. The ethanol formed during the transesterification reaction was distilled.

[0199] The temperature is maintained until a hydroxyl number of less than 5 mg KOH / g is obtained.

[0200] 68.18 g of the product obtained are introduced into a reactor equipped with a reflux column, a nitrogen bubbling rod, a thermometer, a dropping funnel and a stirrer with inclined blades. A nitrogen bubbling of 30 ml / minute is imposed throughout the synthesis. 31.82 g of MBMCHA is introduced into the dropping funnel and then added over a period of 30 minutes while maintaining the temperature below 50°C. The contents of the reactor are transferred into an inert bottle and kept closed at room temperature for 30 days. The reduction of the area under the peaks corresponding to the ethylenic protons (between 6.8 and 6.9 ppm) is monitored by NMR 1 H. The theoretical dry extract of the finished product is 100%. The amine index measured after storage is 150 mg KOH / g.

[0201] Example 14: Application Properties

[0202] 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 in order to evaluate the proportion of polyisocyanate necessary to obtain a varnish. Different properties of this varnish were also evaluated, namely its viscosity before application, its pot life, its dry thickness and its Persoz hardness at 24 hours and at 14 days, following the protocols described above.

[0203] The resins according to the prior art were as follows:

[0204] Comparative Example 4 - SYNOCURE 9226 BA 82: High solids hydroxylated acrylic resin with an IOH of 5.4% relative to the resin mass with a viscosity (3000-5000 mPa.s at 25°C) and a solids content of 82% in butyl acetate.

[0205] Comparative Example 5 - DESMOPHEN NH 1420: Amino succinic resin with an amine index of 201 mg KOH / g relative to the resin mass with a viscosity of 1000 mPa.s at 25°C and a dry extract of 100%.

[0206] Comparative Example 6 - DESMOPHEN NH1520: Amino succinic resin with an amine index of 191 mg KOH / g relative to the bulk resin with a viscosity of 1400 mPa.s at 25°C and a solids content of 100%. Operating conditions for formulating the two-component varnish:

[0207] The formulations of the two-component varnishes are made with a stoichiometric ratio of Amine / NCO for aminosuccinic resins and a stoichiometric ratio of OH / NCO for polyacrylics, adjusted to 75% dry extract by volume, containing a VOC value of 220g / L.

[0208] The isocyanate used in this two-component system is Tolonate™ HDT-LV2, which is a solvent-free, low-viscosity, hexamethylene diisocyanate trimer with an NCO level of 23%, marketed by Vencorex.

[0209] For aminosuccinic resins:

[0210] In a suitable container, the aminosuccinic resin is incorporated, followed by the solvent (butyl acetate) and then the isocyanate.

[0211] The two-component varnish is stirred vigorously for 30 seconds with a spatula, then left to stand for one minute to de-bubble before measuring its viscosity and applying it.

[0212] For polyacrylics:

[0213] In a suitable container, the polyacrylic resin is incorporated, followed by 0.5% (dry on resin) of dibutyltin dilaurate (DBTDL) catalyst, the solvent (butyl acetate) and then the isocyanate.

[0214] The two-component varnish is stirred vigorously for 30 seconds with a spatula, then left to stand for one minute to de-bubble before measuring its viscosity and applying it.

[0215] Application results:

[0216] [Table 1]

[0217] [Table 2]

[0218] Tables 1 and 2 above show that the varnishes obtained from the resins according to the invention have acceptable 14-day hardnesses, viscosities and pot lives, with lower polyisocyanate consumption compared to the comparative tests. Comparative example 1 shows that the direct use of a heavy diester without a transesterification phase gives a film that is sticky at 24 hours and insufficiently hardened at 14 days. [Table 3]

[0219] Comparative Examples 2 and 3 show the impact of increasing the amount of polyol on the initial viscosity of the formulation. This table also shows that, for an identical OH / maleic ester ratio, the resin according to the invention (Example 12) has a lower INH than the resin of Comparative Example 3. The varnish obtained also has a lower viscosity (implying the possibility of using a smaller amount of solvent), a longer pot life and a hardness at 1 week practically equivalent to those of the comparative varnish. Example 13 shows that excellent compromises between INH (low) and hardness (rather high) can be obtained with primary alcohol precursors (caprolactone).

Claims

Claims 1. Process for the preparation of an aminosuccinic resin comprising the following steps: a) the transesterification of at least one alkyl diester of formula (I) using at least compound A chosen from a mono-alcohol of formula (II), a precursor thereof and mixtures thereof, and optionally at least one polyol of formula (III): RI-OOC-CH=CH-COO-R2(I) R3-OH (II) R4-(OH)n (III) where R1 and R2 are independently saturated, linear or branched hydrocarbon chains each containing less than 5 carbon atoms; R3 denotes a saturated or unsaturated, linear, branched or (mono or poly)cyclic hydrocarbon chain containing more than 4 carbon atoms; R4 denotes a hydrocarbon chain containing at least 2 carbon atoms; and 2 < n < 6, in a molar ratio of compound A to the diester ranging from 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, in a molar ratio between the amine functions and the double bonds of the diester ranging from 0.8 to 1.

2.

2. Method according to claim 1, characterized in that the alkyl diester is chosen from: alkyl maleates and fumarates such as: dimethyl maleate, diethyl maleate, dipropyl maleate, diisopropyl maleate, dibutyl maleate, di-tert-butyl maleate, di- / so-butyl maleate, di-sec-butyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, diisopropyl fumarate, dibutyl fumarate, di-tert-butyl fumarate, di- / so-butyl fumarate, di-sec-butyl fumarate, and mixtures thereof.

3. Method according to claim 1 or 2, characterized in that compound A is a monoalcohol chosen from: cyclohexanol, methylcyclohexanol, trimethylcyclohexanol, tert-butyl cyclohexanol, benzyl alcohol, borneol, menthol, tricyclodecyl methanol, and mixtures thereof.

4. Process according to claim 1 or 2, characterized in that compound A corresponds to formula (II b): in which: 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 are independently selected from H, or alkyl, preferably H, methyl or ethyl, y is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, preferably y is 1, 2, 3, 4, 5 or 6, and z is from 0 to 20, preferably z is from 1 to 20.

5. Process according to claim 4, characterized in that compound A corresponds to formula (II b) in which at least one of the following conditions is fulfilled: 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. Method according to any one of claims 1 to 5, characterized in that the polyol is chosen from: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 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 with a number-average molecular weight Mn, calculated from the OH number, ranging from 250 to 3000 g / mol), 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, bisphenol Hydrogenated, glycerol, diglycerol, tricyclodecane dimethanol, trimethylolpropane, di(trimethylolpropane), trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, erythritol, pentaerythritol, di(pentaerythritol), neopentyl glycol, 2-butyl-2-ethyl-l,3-propanediol, 2-methyl-l,3-propanediol, 2-methyl-l,2-propanediol, sorbitol,mannitol, xylitol, isosorbide, isoidide, isomannide, methyl glucoside, polyester, polyols (in particular polycaprolactone polyol), polycarbonate polyols, polyorganosiloxane polyols (in particular polydimethylsiloxane polyol), polyglycerols such as glycerol oligomers such as Polyglycerol-3 (glycerol trimer) and decaglycerol, a hydroxy-terminated polybutadiene, a diol derived from a dimer or trimer of hydrogenated or non-hydrogenated fatty acid, alkoxylated derivatives (in particular ethoxylated and / or propoxylated) of the polyols mentioned above, and mixtures thereof.

7. Process 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 and more preferably less than 0.2 / n.

8. Method according to any one of claims 1 to 7, characterized in that the polyamine is a diamine chosen from: l-amino-3-aminomethyl-3,5,5-trimethyl cyclohexane (IPDA), bis-(4-aminocyclohexyl)-methane, bis-(4-amino-3-methylcyclohexyl)methane, 1,6-diamino hexane, 2-methyl pentamethylene diamine, ethylene diamine, 1,2- and 1,3-propanediamines, 2-methyl-l,2-propanediamine, 2,2-dimethyl-l,3-propanediamine, 1,3- and 1,4-butanediamines, 1,3- and 1,5-pentanediamines, 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-hexahydrotoluylenediamines, 2,4'- and 4,4'-diamino-dicyclohexylmethanes, 1,3- and 1,4-cyclohexane diamines, 1,3- or 1,4-bis(methylamino)-cyclohexane, 1,8-p-menthane diamine, hydrazine, phenylenediamine, 2,4- and 2,6-toluylene diamines, 2,3- and 3,4-toluylenediamines, o-, m- or p-xylylenediamines, 2,4'- and 4,4'-diaminodiphenylmethanes, benzidine and mixtures thereof.

9. Process according to any one of claims 1 to 8, characterized in that the monoamine is chosen from: sec-butylamine, isobutylamine, tert-butylamine, cyclohexylamine, 1,1,3,3-tetramethyl butylamine (or tert-octylamine) and mixtures thereof.

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

11. Aminosuccinic resin comprising at least one unit according to formula (VI): in which Ri is a saturated, linear or branched hydrocarbon chain that contains 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 linear, cyclic or branched, saturated or unsaturated hydrocarbon chain comprising at least 2 carbon atoms.

12. Aminosuccinic resin according to claim 11, characterized in that it comprises at least one unit according to formula (VII): wherein R1, R3 and Rs 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 resin according to any one of claims 10 to 12 for the manufacture of two-component binders containing at least one polyisocyanate.

14. Binder formulation comprising the aminosuccinic 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 sealant or an adhesive, in particular for obtaining a coating, more particularly for obtaining a film, a paint, a varnish, a lacquer, a stain, an adhesion primer or an ink.

16. Coating, adhesive or sealant obtained by applying and drying the binder formulation according to claim 14.

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