CROSSLINKABLE COMPOSITION BY MICHAEL ADDITION

Abstract

The present invention relates to a real Michael addition (RMA) crosslinkable composition, more particularly a solvent-free crosslinkable composition, usable in all types of coatings, including paint. The present invention also relates to a method for preparing a crosslinked product by applying and crosslinking the composition to at least one substrate. In particular, the present invention uses a Michael acceptor component having an α,β-unsaturated group functionality ranging from 1 to 2 in a crosslinkable composition to achieve real Michael addition (RMA) crosslinking, for example used in combination with another Michael acceptor component of higher α,β-unsaturated group functionality.

Description

Title of the invention: Michael addition crosslinkable composition Field of invention

[0001] The present invention relates to a real Michael addition (RMA) crosslinkable composition, more particularly a solvent-free crosslinkable composition, usable for preparing a coating, a paint, a varnish, an ink, a molded object, a waterproofing membrane, a chemical seal, an adhesive, a polymeric concrete or a composite. The present invention also relates to a method for preparing a crosslinked product by applying and crosslinking the composition to at least one substrate. Technical background

[0002] Durable and highly crosslinked coatings can be obtained using true Michael addition (RMA) chemistry. RMA crosslinkable compositions typically comprise a Michael donor component A and a Michael acceptor component B that react and crosslink with each other in the presence of a basic catalyst component. The catalyst component must be strong enough to abstract a proton from component A to form the carbanion donor component B.

[0003] EP 0326723 A1 (Rohm and Haas Company) describes crosslinkable compositions based on the Michael reaction comprising a catalyst component derived from the reaction of an epoxide with a tertiary amine. The catalyst components are brought into contact before use, which then activates the crosslinking of the donor and acceptor components. All the disclosed formulations further comprise organic solvents indicated as being capable of improving the pot life and gloss of the coatings, and which are also used to lower the viscosity of the formulations before use.

[0004] WO 2011 / 124665 A1 and WO 2013 / 050622 A1 (Nuplex Resins BV) describe the use of a catalyst comprising a latent strong base for the Michael addition based on substituted carbonate salts. When the composition is applied to a substrate, the carbonate salts release carbon dioxide, thereby generating a strong base capable of catalyzing (or initiating) the Michael reaction between components A and B. The base is either a hydroxide or an alkoxide. The crosslinkable compositions described in these documents also all comprise an organic solvent whose role is to adjust the viscosity of the formulations before use so that they can be easily applied to the substrates by the for- emulator.

[0005] A major drawback of the systems described in the prior art is that they contain organic solvents and thus generate volatile organic compounds (VOCs). Eliminating the presence of solvents in crosslinkable compositions, or even reducing their quantity, is nevertheless not easy, because high solids content systems have reduced pot lives and extended curing speeds, which does not correspond to market expectations.

[0006] The present invention aims in particular to solve these problems.

[0007] In particular, one of the objects of the present invention is to propose com crosslinkable positions which exhibit satisfactory hardness properties and acceptable yellowing while having a viscosity such that they can be easily applied by the formulator to the surface of the substrates without having to add organic solvents. Summary of the invention

[0008] A first subject of the present invention relates to a crosslinkable composition, in particular a composition crosslinkable by adding a catalyst component C.

[0009] The crosslinkable composition according to the invention comprises:

[0010] a) a Michael A donor component;

[0011] b) a Michael B acceptor component comprising:

[0012] - a Michael B1 acceptor component having a group functionality a,[3-unsaturated ranging from 1 to 2; and

[0013] - optionally a Michael B2 acceptor component having a functionality in group a,[3-unsaturated greater than or equal to 3;

[0014] c) optionally a catalyst component C.

[0015] A second object of the present invention relates to a process for preparing a crosslinked product, characterized in that the process comprises: a. the preparation of a composition by bringing components A, B1, B2 and C into contact; b. applying the composition to at least a portion of a surface of a substrate; and c. crosslinking the composition, preferably at a temperature ranging from 0 to 60°C;

[0016] wherein components A, B1, B2 and C are as defined in the present description.

[0017] A third object of the present invention relates to the use of a Michael acceptor component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2 in a crosslinkable composition for carrying out crosslinking by addition of Actual Michael (RMA), the crosslinkable composition comprising less than 2% by weight of non-reactive organic solvent relative to the total weight of the composition.

[0018] A fourth object of the present invention relates to the use of a combination of a Michael acceptor component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2 and a Michael acceptor component B2 having an α,[3-unsaturated group functionality greater than or equal to 3 in a crosslinkable composition for carrying out real Michael addition (RMA) crosslinking.

[0019] A fifth subject of the present invention relates to the use of the crosslinkable composition according to the invention for preparing a coating, a paint, a varnish, an ink, a molded object, a waterproofing membrane, a chemical seal, an adhesive, a polymeric concrete or a composite. Detailed description

[0020] In the context of the present invention:

[0021] - the expression “between ... and ...” (for example, a range of values) must be understood to include the limits (e.g., the limit values ​​of that range of values);

[0022] - the expression “includes a / an” must be understood as meaning “includes at minus one / one”;

[0023] - any description relating to an embodiment is applicable and inter interchangeable with all other embodiments of the invention; and

[0024] - when an element or component is included in and / or chosen and / or selected in a list of elements or components, it is to be understood that that individual element or component may be chosen / selected and combined with other individual elements, or may be chosen / selected to constitute a subgroup of two or more explicitly listed elements or components; also, any element or component cited in a list of elements or components may be omitted from that list. Crosslinkable composition

[0025] A first subject of the present invention relates to a crosslinkable composition, in particular a composition crosslinkable by adding a catalyst component C.

[0026] The crosslinkable composition according to the invention comprises: a. a Michael A donor component; b. a Michael B acceptor component comprising: - a Michael B1 acceptor component having group functionality a,[3-unsaturated ranging from 1 to 2; and - optionally a Michael B2 acceptor component having a group functionality α,[3-unsaturated greater than or equal to 3;

[0027] c) optionally a catalyst component C.

[0028] The crosslinkable composition according to the invention may in particular be a solvent-free composition.

[0029] In the context of the present invention, the term “solvent-free composition” means a composition comprising less than 2% by weight, less than 1% by weight, less than 500 ppm, less than 200 ppm, less than 50 ppm or less than 1 ppm of non-reactive organic solvent, relative to the total weight of the composition. The solvent content can in particular be determined according to the method described below.

[0030] In the context of the present invention, the term "solvent" means an organic compound which is liquid at 0°C and which has a boiling point, measured at 101.325 kPa, of less than 250°C.

[0031] In the context of the present invention, the term “organic solvent” means a solvent having carbon atoms.

[0032] In the context of the present invention, the term "non-reactive organic solvent" means an organic solvent which remains unchanged during the crosslinking process, i.e. it is non-reactive with respect to the components of the crosslinkable composition. Consequently, components A and B of the crosslinkable composition according to the invention do not fall within the definition of "non-reactive organic solvent" mentioned above.Examples of non-reactive organic solvents are alkanes, halogenated hydrocarbons, alcohols, glycols, esters, ethers, glycol ethers, aldehydes, ketones, and aromatic hydrocarbons, including hexane, heptane, dichloromethane, methanol, ethanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, diethyl ether, ethylene glycol n-butyl ether, formaldehyde, acetaldehyde, acetone, 2-butanone (MEK), butyl acetate, ethyl acetate, benzene, toluene, xylene, or ethylbenzene. Michael A donor component

[0033] The crosslinkable composition according to the present invention comprises a Michael A donor component (component A hereinafter).

[0034] Component A is such that it comprises at least one Michael donor compound A. Compound A may in particular be in the form of a monomer comprising at least one Michael donor group, or of a polymer comprising at least one Michael donor group. When compound A is a polymer, said polymer may for example be a polyester, a polyurethane, a poly(meth)acrylate, an epoxy polymer, a polyamide, a polyesteramide, a polyvinyl polymer, or a mixture of these polymers. Preferably, when compound A is a polymer, it is a polyester.

[0035] The crosslinkable composition according to the present invention may comprise a component A comprising several distinct Mickaël donor A compounds, for example two, three or four distinct A compounds.

[0036] Each compound A comprises at least one Michael donor group. A Michael donor group is a group having a labile proton alpha to a carbonyl function. Each compound A may comprise several Michael donor groups, for example two, three or four Michael donor groups. These groups may be the same or different. Examples of Michael donor groups are a malonate group and an acetoacetate group.

[0037] Preferably, component A comprises a compound with a malonate group and is referred to herein as component A1. Component A may comprise several A1 compounds, for example 2, 3 or 4 distinct A1 compounds.

[0038] According to one embodiment, the component Al comprises a polymer having at least one malonate group, said polymer being chosen from a polyester, a polyurethane, a poly(meth)acrylate, an epoxy polymer, a polyamide, a polyesteramide, a polyvinyl polymer, and mixtures thereof.

[0039] The malonate group may in particular be a dialkyl malonate group chosen from a dimethyl malonate, a diethyl malonate, a di-n-propyl malonate, a diisopropyl malonate, a di-n-butyl malonate, a diisobutyl malonate, a di-tert-butyl malonate, a dilauryl malonate, a di-2-ethylhexyl malonate, and mixtures thereof.

[0040] According to one embodiment, component Al comprises a compound selected from a dialkyl malonate, a polymer having at least one malonate group, and mixtures thereof.

[0041] Preferably, component Al comprises a polyester having at least one malonate group.

[0042] According to one embodiment, component A has a residual content of non-reactive organic solvent of less than 2% by weight, less than 1% by weight, less than 500 ppm, less than 200 ppm, less than 50 ppm or less than 1 ppm, relative to the total weight of component A. The solvent content can in particular be determined according to the method described below.

[0043] When component A comprises a polymer, the latter is preferably prepared according to a solvent-free process (in other words a process not using a non-reactive organic solvent as defined above), i.e. no compound having the following three cumulative properties: 1 / be present from the beginning to the end of the reaction, possibly added during the process, 2 / unchanged during the process, i.e. non-reactive with respect to the reagents involved, and 3 / must be eliminated at the end of the process in the case where the product of the reaction must be in its pure form. Michael B acceptor component

[0044] The crosslinkable composition according to the present invention comprises a Michael B acceptor component (component B hereinafter).

[0045] Component B may in particular comprise a Michael acceptor component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2, and / or a Michael acceptor component B2 having an α,[3-unsaturated group functionality greater than or equal to 3.

[0046] For the purposes of the present invention, an α,[3-unsaturated group is a group comprising a carbon-carbon double bond in the α,[3 position of a carbonyl function, in particular in the α,[3 position of a group of formula -C(=O)-R in which R is H, halogen, alkyl, aryl, OH, O-alkyl, -O-aryl, NRaRb, -OC(=O)-alkyl and Ra and Rb are independently H, alkyl or aryl.

[0047] According to one embodiment, component B comprises only component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2 or only Michael acceptor component B2 having an α,[3-unsaturated group functionality greater than or equal to 3.

[0048] According to another embodiment, component B comprises component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2 and component B2 having an α,[3-unsaturated group functionality greater than or equal to 3.

[0049] According to one embodiment of the present invention, component B1 has a viscosity of less than 100 mPa.s, as measured at 23°C according to the method described below. For example, according to this embodiment, component B1 has a viscosity of less than 50 mPa.s, preferably less than 30 mPa.s, more preferably less than 15 mPa.s.

[0050] Component B1 of the present invention may comprise one or more distinct Michael donor compounds, each having an α,[3-unsaturated group functionality ranging from 1 to 2.

[0051] Component B1 of the present invention may in particular comprise one or more compounds having at least one (meth)acrylate group (preferably at least one acrylate group), one or more compounds having at least one (meth)acrylamide group, one or more vinyl ketones, one or more maleates, one or more fumarates, one or more mesaconates and / or one or more itaconates. Compound B1 may comprise several distinct compounds, for example a mixture of compounds comprising 1 or 2 (meth)acrylate groups and compounds comprising 1 or 2 other unsaturations.

[0052] According to one embodiment, component B1 comprises a compound chosen from a monomer having 1 (meth)acrylate group, a monomer having 2 (meth)acrylate groups, a maleate, an itaconate, a fumarate and mixtures thereof. Preferably, component B1 comprises a compound selected from a monomer having 1 (meth)acrylate group, a monomer having 2 (meth)acrylate groups, and mixtures thereof. More preferably, component B1 comprises a monomer having 2 (meth)acrylate groups.

[0053] According to one embodiment, component B1 comprises a compound selected from a monomer having 1 acrylate group, a monomer having 2 acrylate groups, a maleate, an itaconate, a fumarate and mixtures thereof. Preferably, component B1 comprises a compound selected from a monomer having 1 acrylate group, a monomer having 2 acrylate groups, and mixtures thereof. More preferably, component B1 comprises a monomer having 2 acrylate groups.

[0054] According to one embodiment, component B1 comprises a monomer having 1 (meth)acrylate group selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-octyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, n-hexadecyl (meth)acrylate, n-octadecyl (meth)acrylate, oleyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate,2-ethoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenol (meth)acrylate, nonylphenol (meth)acrylate, trimethylolpropane formalin cyclic (meth)acrylate, isobutyl (meth)acrylate, tricyclodecanemethanol (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, (poly)caprolactone (meth)acrylate, n-butyl acryloyloxy ethyl carbamate,3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate, (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (1,3-dioxan-5-yl)methyl (meth)acrylate, (1,3-dioxolan-4-yl)methyl (meth)acrylate, glycerol carbonate (meth)acrylate; , as well as alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof. Acrylated derivatives of the aforementioned compounds are particularly preferred.

[0055] According to one embodiment, component B1 comprises a monomer having 2 (meth)acrylate groups chosen from bisphenol A di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, di-, tri-, tetra- or polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, di-, tri-, tetra- or polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,2-butanediol di(meth)acrylate, 2,3-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-2,4-pentanediol di(meth)acrylate,polybutadiene di(meth)acrylate, cyclohexane-1,4-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate; as well as alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof. Acrylated derivatives of the aforementioned compounds are particularly preferred.

[0056] According to one embodiment, component B1 comprises a maleate chosen from dimethyl maleate, diethyl maleate, di-n-propyl maleate, diisopropyl maleate, di-n-butyl maleate, diisobutyl maleate, di-tert-butyl maleate, and mixtures thereof.

[0057] According to one embodiment, component B1 comprises an itaconate selected from dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, diisopropyl itaconate, di-n-butyl itaconate, diisobutyl itaconate, di-tert-butyl itaconate, and mixtures thereof.

[0058] According to one embodiment, component B1 comprises a fumarate chosen from dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, diisopropyl fumarate, di-n-butyl fumarate, diisobutyl fumarate, di-tert-butyl fumarate, and mixtures thereof.

[0059] Preferably, component B1 comprises at least one monomer having 2 acrylate groups chosen from di-, tri-, tetra- or polyethylene glycol diacrylate, di-, tri-, tetra- or polypropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, 3-methyl-1,5-pentanediol diacrylate, neopentyl glycol diacrylate, cyclohexane-1,4-dimethanol diacrylate and mixtures thereof.

[0060] Component B2 of the present invention may comprise one or more distinct Michael donor compounds, each having an α,[3-unsaturated] group functionality greater than or equal to 3.

[0061] According to one embodiment, component B2 comprises a compound selected from a monomer having at least 3 (meth)acrylate groups, an oligomer having at least 3 (meth)acrylate groups, and mixtures thereof; preferably, a monomer having at least 3 (meth)acrylate groups. In particular, component B2 may comprise a compound selected from a monomer having at least 3 acrylate groups, an oligomer having at least 3 acrylate groups, and mixtures thereof; preferably, a monomer having at least 3 acrylate groups.

[0062] According to one embodiment, component B2 comprises at least one compound having 3, 4, 5 or 6 (meth)acrylate groups; preferably, at least one compound having 3 or 4 (meth)acrylate groups. In particular, component B2 may comprise at least one compound having 3, 4, 5 or 6 acrylate groups; preferably, at least one compound having 3 or 4 acrylate groups.

[0063] According to one embodiment, component B2 comprises at least one monomer having at least 3 (meth)acrylate groups chosen from glycerol tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, sorbitol penta(meth)acrylate, di(pentaerythritol) hexa(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate; as well as alkoxylated (for example, ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof. Acrylated derivatives of the compounds mentioned above are particularly preferred.

[0064] According to one embodiment, component B2 comprises an oligomer having at least 3 (meth)acrylate groups chosen from urethane oligomers functionalized with a (meth)acrylate, epoxy oligomers functionalized with a (meth)acrylate, polyether oligomers functionalized with a (meth)acrylate, polyester oligomers functionalized with a (meth)acrylate, (meth)acrylic oligomers functionalized with a (meth)acrylate, polydiene oligomers functionalized with a (meth)acrylate, polycarbonate oligomers functionalized with a (meth)acrylate, polyamide oligomers functionalized with a (meth)acrylate, and mixtures thereof.

[0065] Preferably, component B2 comprises at least one monomer having 3 or 4 acrylate groups chosen from glycerol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, di(trimethylolpropane) tetraacrylate and mixtures thereof.

[0066] When the crosslinkable composition according to the invention comprises a component B1 and a component B2, the mass ratio between the component B1 and the component B2 may in particular be between 1:0.1 and 1:100, preferably from 1:0.2 to 1:20, more preferably from 1:1 to 1:10.

[0067] According to one embodiment, the average functionality in the α,[3-unsaturated group of component B varies between 1.5 and 6, preferably between 2 and 4. Catalyst component C

[0068] The crosslinkable composition according to the present invention optionally comprises a catalyst component C.

[0069] According to one embodiment, the catalyst component C comprises at least one latent strong base. In particular, the catalyst component C may comprise several latent strong bases, for example 2, 3 or 4 latent strong bases.

[0070] According to the present invention, a latent strong base is a blocked base which becomes activated once all or part of the components of the crosslinkable composition are brought into contact with each other and / or once the composition is applied to a substrate. Activation of the base makes it possible to generate a strong base capable of catalyzing (or initiating) the Michael reaction between components A and B.

[0071] The latent strong base may in particular be a substituted carbonate salt of the following formula (1):

[0072] [Chem.l] o X* O—C—-O—R (1)

[0073] in which

[0074] R is hydrogen, alkyl or aralkyl; in particular, R is C1-C4 alkyl;

[0075] X+ represents a cation; in particular, X+ represents a cation originating from an alkali metal or an alkaline earth metal, a quaternary ammonium of formula (R')4N+ or a phosphonium of formula (R')4P+, each R1 being independently chosen from H, an alkyl, an aryl or an alkaryl.

[0076] For the purposes of the present invention:

[0077] - the term "alkyl" denotes a monovalent saturated acyclic hydrocarbon group of formula -CnH2n+i in which n is 1 to 100. An alkyl group may be straight or branched. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 2,2-dimethylbutyl, n-heptyl, 2-ethylhexyl and the like;

[0078] - the term “aryl” denotes an optionally substituted aromatic group. Aryl groups may contain any number of carbon atoms in the ring, such as C6, C7, C8, C9, C10, C11, C12, C13, C14, C15 or C16, as well as C6-8, C6-12 or C6-20. Aryl may contain a single ring (e.g., phenyl) or multiple rings, at least one ring being aromatic. Aryl groups may be monocyclic, fused to form bicyclic (e.g. benzocyclohexyl) or tricyclic groups, or linked by a bond to form a biaryl group. Examples include phenyl, benzyl, naphthyl, biphenyl, phenanthrenyl and naphthacenyl. Aryl groups may also include saturated linear and branched aliphatic hydrocarbyl thereby forming an araliphatic group. Araliphatic groups used herein generally comprise at least one aromatic moiety (e.g. one, two or three aromatic rings, optionally substituted) and at least one non-aromatic moiety (e.g. a C1-20 (hetero)alkylene group or a C1-20 (hetero)alkenylene group);

[0079] - the term "aralkyl" denotes an aryl substituted by an alkyl group; an example of aralkyl group is tolyl.

[0080] Such a base is activated by the release of CO2, thus generating an anion RO“ which is capable of removing a proton from the donor component A.

[0081] The latent strong base may also be a substituted carbonate salt of formula (1) in which R is a polymer, and / or the cation X+ is a quaternary ammonium of formula (R2)4N+ or a phosphonium of formula (R2)4P+, in which at least one R 2 is a polymer.

[0082] According to one embodiment of the present invention, component C is a quaternary alkylammonium carbonate. The component may then in particular be chosen from tetrahexylammonium methylcarbonate, tetradecyltrihexylammonium methylcarbonate, tetradecylammonium methylcarbonate, tetrabutylammonium methylcarbonate, tetrabutylammonium ethylcarbonate, benzyltrimethylammonium methylcarbonate or trihexylmethylammonium methylcarbonate or trioctylmethylammonium methylcarbonate, and mixtures or combinations thereof.

[0083] According to another embodiment, the catalyst component C is a catalyst system SC comprising: - an epoxy component Cl; and - a nucleophilic component C2.

[0084] The catalyst system SC is capable of generating a strong base in order to catalyze (or initiate) the Michael reaction between components A and B. The strong base is generated by bringing components C1 and C2 into contact. Thus, components C1 and C2 are intended to be brought into contact shortly before application of the crosslinkable composition by an end user.

[0085] The epoxy component Cl (or component Cl hereinafter) is such that it comprises at least one compound having at least 1 epoxy group. This compound may comprise several epoxy groups, for example two, three or four epoxy groups. The epoxy component Cl may, itself, comprise several distinct epoxy compounds, comprising each one or more epoxy groups. Preferably, component Cl is liquid at 25°C.

[0086] The Cl component may in particular comprise at least one compound selected from a glycidyl ether, a glycidyl ester, a cycloaliphatic epoxide (in particular a compound having an epoxy group fused with an aliphatic ring such as cyclohexyl) and combinations thereof. The Cl component may comprise several of these compounds, for example 2, 3 or 4 distinct Cl compounds.

[0087] According to one embodiment, the component Cl may in particular comprise a compound chosen from 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxycyclohexane, a glycidyl ether of a C4-C26 aliphatic or aromatic monoalcohol (in particular ethanol glycidyl ether, isopropanol glycidyl ether, butan-1-ol glycidyl ether, tert-butanol glycidyl ether, 2-ethylhexanol glycidyl, dodecan-1-ol glycidyl ether, phenol glycidyl ether, cresol glycidyl ether, 2-methoxyphenol glycidyl ether, p-nonylphenol glycidyl ether, 4-tert-butylphenol glycidyl ether, benzyl alcohol glycidyl ether, cardanol glycidyl ether such as Cardolite Ultra LITE 513 marketed by Cardolite),a glycidyl ester of a C4-C26 aliphatic or aromatic monobasic acid (in particular 4-tert-butylbenzoic acid glycidyl ester, oleic acid glycidyl ester, linolenic acid glycidyl ester, palmitic acid glycidyl ester, stearic acid glycidyl ester, neodecanoic acid glycidyl ester or versatic acid glycidyl ester such as Cardura E10P marketed by Hexion), methyl 9,10-epoxystearate, ethyl 9,10-epoxystearate, butyl 9,10-epoxystearate, 2-ethylhexyl 9,10-epoxystearate, n-octyl 9,10-epoxystearate, diglycidyl ether, 1,2,3,4-diepoxybutane, 1,2,4,5-diepoxypentane, 1,2,5,6-diepoxyhexane, 1,2,7,8-diepoxyoctane, 1,2,9,10-diepoxydecane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether,hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, novolac epoxy resin (obtained by epoxidation of condensation products of phenolic derivatives, in particular m- / p-cresol, 2,5-dimethylphenol, bisphenol A or cardanol, with formaldehyde), glycidyl (meth)acrylate functionalized (meth)acrylic resin, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, , bis(3,4-epoxycyclohexylethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, m-ethylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexylmethyl)ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), ethylene glycol diglycidyl ether, 1,2- or 1,3-propylene glycol diglycidyl ether, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 2-methyl-1,3-propanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 2,2-diethyl-1,3-propane diol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, 3,3-dimethyl-1,5-pentanediol diglycidyl ether, 2,4-diethyl-1,5-pentanediol diglycidyl ether, 3,3-butylethyl-1,5-pentane diol, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly-glycidyl ethers of a polyether polyol (obtained by the addition of one or more alkylene oxides to an aliphatic polyhydric alcohol, such as ethylene glycol, propylene glycol, and glycerol), glycerol triglycidyl ether, tri-methylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, di(trimethylolpropane) tetraglycidyl ether, pentaerythritol tetra-glycidyl ether, cyclohexane-1,2 or 1,4-dicarboxylate diglycidyl ester, diglycidyl ester 4-cyclohexene-1,2-dicarboxylate, cyclohexane-1,2 or 1,4-diol diglycidyl ether, cyclohexane-1,2 or 1,4-dimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether, isosorbide diglycidyl ether, pyrocatechol diglycidyl ether,resorcinol diglycidyl ether, cardol diglycidyl ether, phloroglucinol triglycidyl ether, pyrogallol triglycidyl ether, tris(hydroxyphenyl)methane triglycidyl ether, tris(hydroxyphenyl)ethane triglycidyl ether, diglycidyl esters of long-chain aliphatic dibasic acids, diglycidyl esters of ortho-, iso- or terephthalic acid, diglycidyl esters of tetrahydrophthalic acid, diglycidyl esters of hexahydrophthalic acid, epoxidized vegetable oil (in particular epoxidized soybean oil, epoxidized linseed oil), epoxidized polybutadiene, triglycidyl isocyanurate, as well as alkoxylated derivatives (in particular ethoxylated and / or propoxylated) thereof, and mixtures thereof.

[0088] Preferably, component C1 comprises a compound selected from versatic acid glycidyl ester, cardanol glycidyl ether, bisphenol A diglycidyl ether, 1,4-butanediol diglycidyl ether, isosorbide diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, novolac epoxy resin and mixtures thereof.

[0089] In addition to the epoxy component C1, the catalyst system SC also comprises a nucleophilic component C2.

[0090] Component C2 may in particular comprise a nucleophilic compound. For the purposes of the present invention, a nucleophilic compound is a compound capable of opening an epoxide ring of component C1, thus generating a strong base in order to catalyze (or initiate) the Michael reaction between the donor A and acceptor B components.

[0091] In particular, the nucleophilic compound may have an imidazole function or a tertiary amine function having a pka > 8, preferably a pKa > 8.5.

[0092] The tertiary amine function may in particular correspond to the formula -NRaRb (1) in which Ra and Rb, identical or different, represent a C1-C4 alkyl or a cycloalkyl, or else Ra and Rb form a C2-C6 heterocycle.

[0093] The imidazole function can in particular correspond to the following formula (2):

[0094] [Chem.2] Rc Rd .f

[0095] wherein Rc, Rd and Re are independently selected from H, alkyl, aryl and al-kylaryl or Rc and Rd, together with the carbon atoms to which they are bonded, may form a ring.

[0096] Component C2 may in particular comprise at least one compound chosen from triethylamine, triethanolamine, N,N-dimethyl-n-octadecylamine, dimethylglucamine, N-methylpiperidine, 1,4-dimethylpiperazine, 1-, 3-, or 4-methylimidazole, N-methylimidazole, 6-dimethylamino-l-hexanol, 1-ethylpyrrolidine, 1-butylpyrrolidine, bis(2-hydroxyethyl)amino-tris(hydroxymethyl)methane, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0097] Other examples of nucleophilic compounds are phosphines, phosphites or thiols. Special embodiments

[0098] According to one embodiment, the molar ratio of the Michael acceptor groups of component B to the Michael donor groups of component A is between 1:1 and 3:1, for example between 1.1:1 and 2.9:1 or between 1.2:1 and 2.8:1.

[0099] According to one embodiment, the mixture of components A and B has a viscosity of less than 1500 mPa.s at 23°C. The mixture of components A and B may, for example, have a viscosity of less than 1300 mPa.s at 23°C, less than 1100 mPa.s at 23°C, less than 1000 mPa.s at 23°C, or less than 900 mPa.s at 23°C. viscosity of the mixture of components A and B can be measured according to the method described below.

[0100] According to one embodiment, the composition according to the invention comprises: a. an Al component; b. a component B comprising a component B1 and a component B2; and c. optionally a catalyst component C.

[0101] According to another embodiment, the composition according to the invention comprises: a. an Al component; b. a component B comprising a component B1 and a component B2; and c. a catalyst component C.

[0102] According to one embodiment, the composition according to the invention comprises:

[0103] a) as component A: a polyester having at least one malonate group and having a residual solvent content of less than 2% by weight;

[0104] b) as component B:

[0105] - a monomer having 2 (meth)acrylate groups, preferably 2 acrylate groups; and

[0106] - a monomer having 3 or 4 (meth)acrylate groups, preferably 3 or 4 groups acrylate;

[0107] c) optionally as component C: a latent strong base.

[0108] According to another embodiment, the composition according to the invention comprises:

[0109] a) as component A: a polyester having at least one malonate group and having a residual solvent content of less than 2% by weight;

[0110] b) as component B:

[0111] - a monomer having 2 (meth)acrylate groups, preferably 2 acrylate groups; and

[0112] - a monomer having 3 or 4 (meth)acrylate groups, preferably 3 or 4 groups acrylate;

[0113] c) optionally as component C: a catalyst system SC comprising:

[0114] - an epoxy component Cl; and

[0115] - a nucleophilic component C2.

[0116] According to one embodiment, the composition according to the invention comprises: a. from 20 to 80%, in particular from 30 to 60%, by weight of Al component; b. from 2 to 60%, in particular from 5 to 40%, by weight of component Bl; and from 2 to 80%, in particular from 10 to 60%, by weight of reactive component B2; c. from 0 to 20%, in particular from 1 to 15%, by weight of component C;

[0117] the quantities by weight being expressed relative to the total weight of the composition.

[0118] According to one embodiment, the composition is crosslinkable by bringing components A, B and C into contact and has a hardness index greater than 200, as measured 24 hours after contact. The Persoz hardness can in particular be measured according to the method described below. Composition in several parts

[0119] The crosslinkable composition according to the invention may be in several parts, in particular in 2 or 3 separate parts. The parts are intended to be brought into contact shortly before the application of the crosslinkable composition by an end user. Thus, the crosslinkable composition according to the invention may be in several parts distributed in separate compartments, in particular in the form of a kit, so that the constituents do not react before their use. In particular, the crosslinkable composition according to the invention may be in 2 parts, P1 and P2.

[0120] According to one embodiment, the composition according to the invention is characterized in that:

[0121] - it is in two parts PI and P2: • a first part PI comprising components A, B1 and B2; and • a second part P2 comprising component C; or

[0122] - it is in two parts PI' and P2': • a first part PI' comprising components A and B1; and • a second part P2' comprising components B2 and C. Process for the preparation of a crosslinked product

[0123] The present invention also relates to a process for preparing a crosslinked product, characterized in that the process comprises: a. the preparation of a composition by bringing components A, B and C into contact; b. applying the composition to at least a portion of a surface of a substrate; and c. crosslinking the composition, preferably at a temperature ranging from 0 to 60°C;

[0124] wherein components A, B and C are as defined above.

[0125] Use of component B1 for RMA crosslinking

[0126] The present invention also relates to the use of a Michael acceptor component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2 in a crosslinkable composition for carrying out real Michael addition (RMA) crosslinking. According to a preferred embodiment of this use, the crosslinkable composition comprises less than 2% by weight of non-reactive organic solvent relative to the total weight of the composition.

[0127] According to one embodiment, the use is characterized in that component B1 has a viscosity of less than 100 mPa.s. The viscosity of component B1 can in particular be measured according to the method described below.

[0128] All the characteristics described previously in connection with component B1 are applicable to the present use for RMA crosslinking.

[0129] Use of a combination of acceptor components B1 and B2 for RMA crosslinking

[0130] The present invention also relates to the use of a combination of a Michael acceptor component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2 and a Michael acceptor component B2 having an α,[3-unsaturated group functionality greater than or equal to 3 in a crosslinkable composition to achieve true Michael addition (RMA) crosslinking.

[0131] According to one embodiment, the use is characterized in that the crosslinkable composition comprises less than 2% by weight of non-reactive organic solvent relative to the total weight of the composition.

[0132] All the characteristics described previously in connection with components B1 and B2 are applicable to the present use for RMA crosslinking. Uses of crosslinkable composition

[0133] The present invention further relates to the use of the crosslinkable composition as described above for preparing a coating, a paint, a varnish, an ink, a molded object, a waterproofing membrane, a chemical seal, an adhesive, a polymeric concrete or a composite. EXAMPLES

[0134] The invention will now be described in more detail with reference to the following examples, the purpose of which is merely illustrative and not intended to limit the scope of the invention. Materials

[0135] NPG: neopentyl glycol from Sigma-Aldrich

[0136] BEPD: 2-butyl-2-ethyl-1,3-propanediol from Sigma-Aldrich

[0137] DMM: dimethyl malonate from Sigma-Aldrich

[0138] Fascat 4100: n-butylstannonic acid from BRENNTAG

[0139] SR238 or HDD A: 1,6-hexanediol diacrylate from Sartomer

[0140] SR355 or DiTMPTA: Sartomer di(trimethylolpropane) tetraacrylate

[0141] SR351 or TMPTA: trimethylolpropane triacrylate from Sartomer

[0142] SR454 or TMP3EOTA: ethoxylated trimethylolpropane triacrylate from Sartomer

[0143] Succinimide from Sigma-Aldrich

[0144] TB AH: tetrabutylammonium hydroxide 40% in water from Sigma-Aldrich

[0145] DEC: Sigma-Aldrich diethyl carbonate Preparation of Al polyester:

[0146] The raw materials composing the polyester and their proportions are identical to the polyester Al of patent application WO 2011 / 124665 AL However, the mode The procedure followed does not involve any solvent and the nature of the transesterification catalyst is modified: 127.83 g of NPG (1.2291 mol), 196.77 g of BEPD (1.2298 mol), 275.40 g of DMM (2.0864 mol) and 0.30 g of Fascat 4100 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 brought to then maintained at 145°C. The methanol formed during the transesterification reaction is distilled.

[0147] The synthesis is stopped when the contents of the reactor become lower than its final theoretical mass (FTM), i.e. 466.77 g. The actual final mass measured before stopping the synthesis was 465.50 g.

[0148] A proton NMR analysis of the product obtained shows the total disappearance of the malonate functions. Preparation of catalyst Cl:

[0149] Catalyst Cl is prepared according to the procedure described in application WO 2013 / 050622 A1 from 59.4 g of TB AH (40% in water), 13.5 g of DEC and 14.5 g of isopropanol.

[0150] Preparation of comparative and inventive formulations Formulation 1:

[0151] In a first bottle, 9.06 g of polyester Al and 8.91 g of SR355 (diTMPTA) are mixed. The viscosity of the varnish obtained is measured at 23°C according to the method: “measurement of the viscosity of a varnish with a viscosity lower than 5000 mPa.s” described below.

[0152] 1.20 g of catalyst Cl and 0.120 g of succinimide are introduced into a test tube. After hermetically sealing the tube, the constituents are mixed until the succinimide is completely dissolved.

[0153] The contents of the test tube are then added to the first bottle and mixed. After applying the mixture obtained with a filmograph, the Persoz hardness is measured after 24 hours. Formulations 2 to 6:

[0154] For these formulations, we proceed in the same way as example 1. Analytical methods Solvent content:

[0155] Solvent content may be calculated based on the amount by weight of solvent added in a formulation relative to the total weight of the formulation.

[0156] The solvent content can also be measured according to ISO 11890-2:2020.

[0157] Measurement of the viscosity of a varnish having a viscosity less than 5000 mPa.s:

[0158] The viscosity of a varnish (mixture of components A and B) before application is measured at 23°C on a CAP 1000 Brookfield viscometer (high shear rate) according to ISO 2884-1:1999, with a cone adapted to the viscosity measured.

[0159] Measurement of the viscosity of a monomer before a viscosity lower than 200 mPa.s:

[0160] The viscosity of a monomer (in particular component Bl) is measured at 23°C according to the ISO 3219:1993 standard with a Brookfield LVT DVII+ viscometer and an S18 spindle.

[0161] Calculation of the final theoretical mass (FTM) of the contents of a reactor during the synthesis of a malonate-functionalized polyester:

[0162] The following calculation is used when the polyester is obtained from a dialkyl malonate, one or more polyols and a catalyst.

[0163] MTF = MI-2 *MA *Nmalo

[0164] with

[0165] MTF: final theoretical mass

[0166] MI: initial mass of the reactor contents before heating.

[0167] MA: molar mass of the distilled alcohol

[0168] Nmalo: number of moles of malonate functions introduced into the reactor.

[0169] Calculation of the theoretical malonate function rate Hmalo in mgKOH / g) after the synthesis of a polyester:

[0170] Imalo is calculated according to the following equation:

[0171] [Math.6]

[0172] Calculation of the average functionality in malonate functions (Fmalo) after the synthesis of a polyester:

[0173] The following calculation is used when the polyester is obtained from a dialkyl malonate, one or more polyols and a catalyst.

[0174] [Math.7] Fmalo =

[0175] n represents the number of different polyols introduced during the synthesis and

[0176] n; represents the number of moles of each of the polyols introduced.

[0177] Determination of the unsaturation / malonate (DL / malonate) molar ratio in a formulation:

[0178] The level of α,[3-unsaturated groups] is first determined by proton NMR in each of the Michael acceptor compounds of the formulation in the presence of an internal standard (dimethyl orthophthalate). The level of α,[3-unsaturated groups] and the calculated malonate level are used to determine the unsaturation / malonate (DL / malonate) molar ratio in the varnish (mixture comprising components A + B) or the for mulation (mixture comprising components A + B + C). The DL / malonate ratio therefore takes into account the impurities present in the acrylic monomers. Persoz hardness measurement:

[0179] Persoz hardness is measured according to the NF EN ISO 1522 standard of March 2007 after application with a filmograph of a composition with a thickness of 150 pm wet (50 pm dry) on a QD46 steel plate (in an air-conditioned room at 23°C, and 50% relative humidity). Results

[0180] The results are detailed in the table below

[0181] [Tables 1] Comparative formulations Formulations according to the invention 1 2 3 4 5 6 Polyester Al 9.06 9.06 9.06 9.06 9.06 9.06 SR355 8.91 / 1.96 / 5.61 / SR351 / 7.81 / / / 6.33 SR454 / / 8.58 / / / SR238 / / / 8.39 3.10 1.59 Catalyst Cl 1.20 1.20 1.20 1.20 1.20 1.20 Succinimide 0.12 0.12 0.12 0.12 0.12 0.12 Viscosity of the varnish (components A + B) at 23°C (mPa.s) 4530 1580 800 112 800 800 Molar ratio DL / malonate 1.75 1.75 1.75 1.75 1.75 1.75 Persoz hardness 24h 289 253 115 26 282 255

[0182] Formulations 1 and 2 produce resins with good hardness but their high viscosity makes their application difficult which can cause surface defects.

[0183] Formulation 3 shows that it is possible to achieve a varnish viscosity in the desired range by dilution with a high functionality acrylate (SR454) but the hardness obtained is insufficient.

[0184] Formulation 4 shows that excessive use of a low functionality, low viscosity acrylate (SR238 or HDD A) leads to a complete loss of hardness properties.

[0185] The comparison between formulations 1 and 5 on the one hand, then between 2 and 6 on the other hand, shows that a very significant reduction in viscosity is obtained by adding a low-functionality, low-viscosity acrylate, which allows application to the surface of the substrate without having to add solvents, and without compromising the hardness properties of the resin obtained.

[0186] These results can be transposed to formulations comprising a catalyst which does not contain added solvent.

Claims

Claims

1. A crosslinkable composition comprising: a) a Michael donor component A; b) a Michael acceptor component B comprising: - a Michael acceptor component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2; and - optionally a Michael acceptor component B2 having an α,[3-unsaturated group functionality greater than or equal to 3; c) optionally a catalyst component C.

2. Composition according to claim 1, characterized in that the composition comprises less than 2% by weight of non-reactive organic solvent, relative to the total weight of the composition.

3. Composition according to any one of the preceding claims, characterized in that component B1 has a viscosity of less than 100 mPa.s, as measured at 23°C according to ISO 3219:1993 with a Brookfield LVT DVII+ viscometer and an S18 spindle.

4. Composition according to any one of the preceding claims, characterized in that component B comprises component B1 and component B2.

5. Composition according to claim 4, characterized in that the mass ratio between component B1 and component B2 is between 1:0.1 and 1:100, preferably from 1:0.2 to 1:20, more preferably from 1:1 to 1:

10.

6. A composition according to any one of the preceding claims, characterized in that the molar ratio of the Michael acceptor groups of component B to the Michael donor groups of component A is between 1:1 and 3:

1.

7. Composition according to any one of the preceding claims, characterized in that component A comprises a compound with a malonate group Al.

8. Composition according to claim 7, characterized in that the component Al comprises a compound selected from a dialkyl malonate, a polymer having at least one malonate group, and mixtures thereof.

9. Composition according to any one of the preceding claims, characterized in that component B1 comprises a compound chosen from a monomer having 1 (meth)acrylate group, a monomer having 2 (meth)acrylate groups, a maleate, an itaconate, a fumarate and mixtures thereof; preferably, a compound selected from a monomer having 1 (meth)acrylate group, a monomer having 2 (meth)acrylate groups, and mixtures thereof; more preferably, a monomer having 2 (meth)acrylate groups.

10. A composition according to any one of the preceding claims, characterized in that component B2 comprises a compound selected from a monomer having at least 3 (meth)acrylate groups, an oligomer having at least 3 (meth)acrylate groups, and mixtures thereof; preferably, a monomer having at least 3 (meth)acrylate groups.

11. Composition according to any one of the preceding claims, characterized in that component C comprises at least one latent strong base.

12. Composition according to any one of claims 1 to 10, characterized in that component C is a catalyst system SC comprising: - an epoxy component Cl; and - a nucleophilic component C2.

13. A composition according to any preceding claim, characterized in that the composition comprises: a. a component Al; b. a component B comprising a component B1 and a component B2; and c. a component C.

14. Composition according to any one of the preceding claims, characterized in that the composition comprises: a) from 20 to 80%, in particular from 30 to 60%, by weight of component A1; b) from 2 to 60%, in particular from 5 to 40%, by weight of component B1; and from 2 to 80%, in particular from 10 to 60%, by weight of reactive component B2; c) from 0 to 20%, in particular from 1 to 15%, by weight of component C; the amounts by weight being expressed relative to the total weight of the composition.

15. A composition according to any preceding claim, ca- characterized in that the composition is in 2 parts PI and P2: - the first part PI comprising the components A, B1 and B2; and - the second part P2 comprising the component C; or in that the composition is in 2 parts PI' and P2': - the first part PI' comprising the components A and B1; and - the second part P2' comprising the components B2 and C.

16. Composition according to any one of the preceding claims, characterized in that the mixture of components A and B has a viscosity of less than 1500 mPa.s at 23°C, as measured with a CAP 1000 Brookfield viscosimeter according to standard ISO 2884-1:1999.

17. Composition according to any one of the preceding claims, characterized in that the average functionality in the α,[3-unsaturated group of component B ranges from 1.5 to 6, preferably from 2 to 4.

18. Composition according to any one of the preceding claims, characterized in that the composition comprises: a. as component A: a polyester having at least one malonate group and having a residual solvent content of less than 2% by weight, b. as component B: - a monomer having 2 (meth)acrylate groups, preferably 2 acrylate groups; and - a monomer having 3 or 4 (meth)acrylate groups, preferably 3 or 4 acrylate groups; c) optionally as component C: a strong latent base or a catalyst system SC comprising an epoxy component C1 and a nucleophilic component C2.

19. A process for preparing a crosslinked product, characterized in that the process comprises: a. preparing a composition by bringing components A, B and C, as defined in any one of the preceding claims, into contact with each other. of the preceding claims; b. applying the composition to at least a portion of a surface of a substrate; and c. crosslinking the composition, preferably at a temperature ranging from 0 to 60°C.

20. Use of a Michael acceptor component B1 having an α,[3-unsaturated] group functionality ranging from 1 to 2 in a crosslinkable composition for performing real Michael addition (RMA) crosslinking.

21. Use of a combination of a Michael acceptor component B1 having an α,[3-unsaturated group functionality ranging from 1 to 2 and a Michael acceptor component B2 having an α,[3-unsaturated group functionality greater than or equal to 3 in a crosslinkable composition for performing true Michael addition (RMA) crosslinking.

22. Use according to claim 20 or 21, characterized in that the crosslinkable composition comprises less than 2% by weight of non-reactive organic solvent relative to the total weight of the composition.

23. Use of the crosslinkable composition according to any one of claims 1 to 18, for preparing a coating, a paint, a varnish, an ink, a molded object, a waterproofing membrane, a chemical seal, an adhesive, a polymeric concrete or a composite.