Diamides obtained from propionic acid and uses thereof as thixotropic agents

Abstract

The invention relates to a diamide that can be used as a thixotropic agent and that is based on 12-hydroxystearic acid and propionic acid in combination with at least two particular diamines. The invention also relates to a composition comprising this diamide and at least one crosslinkable organic binder, as well as to the uses of this diamide or of this composition, in particular in the manufacture of a coating, selected in particular from among paints, varnishes, inks, and gelled coatings ("gel coats"); a glue or an adhesive; a mastic; a sealing agent; a chemical sealing agent; a molded object; an object obtained by 3D printing; preferably a coating or a mastic, more preferably a mastic.

Description

[0001] Diamides obtained from propionic acid and their uses as thixotropic agents

[0002] TECHNICAL FIELD

[0003] The invention relates to a diamide usable as a thixotropic agent, which is based on 12-hydroxystearic acid and propionic acid in association with at least two particular diamines. It also relates to a composition comprising this diamide and at least one crosslinkable organic binder, as well as the uses of this diamide or this composition, particularly in the manufacture of a coating, selected especially from paints, varnishes, inks, and gel coats; an adhesive; a sealant; a sealant; a chemical sealant; a molded object; or an object obtained by 3D printing; preferably a coating or a sealant, more preferably a sealant.

[0004] A number of rheological additives have been used to increase the viscosity of sealants, glues or adhesives, coatings, and molding compounds. These include polyamide powders, hydrogenated castor oil derivative powders, fumed silica, precipitated calcium carbonates, and ground calcium carbonates. Inorganic fillers require very high-speed dispersion of the mixture and present stability and sedimentation problems over time, resulting in negative effects on the mechanical properties of the final system. Polyamide powders and hydrogenated castor oil derivative powders, on the other hand, require system activation by the user (formulator) during the final formulation process to develop optimal rheological properties.

[0005] The Applicant has already proposed rheology additives capable of conferring thixotropic properties to a formulation after an activation phase.

[0006] Thus, a rheology additive or organogestor consisting of a diamide, in powder form, activated in an organic solvent (which may be a reactive diluent or a plasticizer), has been proposed, notably in WO 2015 / 011375. This diamide is the reaction product of an acyclic diamine, possibly an aromatic diamine, a hydroxylated fatty acid, and possibly a non-hydroxylated monocarboxylic acid. An example of such a diamide is prepared from meta-xylylene diamine, ethylene diamine, hexamethylene diamine, and 12-hydroxystearic acid. For its part, document EPI 162242 describes a diamide based on ethylene diamine and / or hexamethylene diamine, 12-hydroxystearic acid and a linear monocarboxylic acid whose hydrocarbon chain (excluding the COOH group) contains 3 to 7 carbon atoms, therefore a C4-C8 acid.

[0007] Other diamides have been described by the Applicant (WO2025 / 132127), comprising at least one cycloaliphatic diamine, at least one acyclic diamine (in particular ethylenediamine or 1,6-diaminohexane, and mixtures thereof), at least one non-hydroxylated C3-C5 monocarboxylic acid, and at least one hydroxylated C3-C36 monocarboxylic acid, preferably 12-hydroxystearic acid. An example of such a diamide is prepared from 1,3-BAC, ethylenediamine, 12-hydroxystearic acid, and a mixture of propionic and acetic acids. Other diamides are cited in applications EP3328938 and EP4289886.

[0008] Although these solutions have proven satisfactory in most of the applications envisaged, it remains necessary for certain applications, and in particular in the formulation of sealants, to propose rheological additives of the diamide type capable of being activated at low temperature, typically below 60°C, to form a three-dimensional network exhibiting a higher modulus of elasticity than that obtained with prior art diamides.

[0009] In this context, the Applicant has developed specific diamides to meet this need.

[0010] SUMMARY OF THE INVENTION

[0011] The present invention thus relates to a diamide based on: a) at least one diamine selected from linear C2 to C4 diamines, b) at least one diamine selected from linear Ce to C12 diamines, aromatic Ce-Cis diamines and mixtures thereof, c) propionic acid, and d) 12-hydroxystearic acid, containing a mixture of diamides of formulas (1) and (2): A1-C(=O)NH-DA1-NH(C=O)-A2 (1) A1-C(=O)NH-DA2-NH(C=O)-A2 (2) wherein:

[0012] Al is an ethyl group (-CH2-CH3),

[0013] A2 is a group (-(CH2)IO-CH(OH)-(CH2)5-CH3), DA1 is a linear alkylene group from C2 to C4,

[0014] DA2 is a linear Ce to C12 alkylene group or a Ce-Cis arylene group or a Ce to Cis alkylene-arylene-alkylene group or a Ce to Cis arylene-alkylene-arylene group or a Ce to Cis arylene-O-arylene group.

[0015] The invention also relates to a composition comprising at least one crosslinkable organic binder and at least one diamide as defined above.

[0016] It also relates to the use of the aforementioned diamide or composition for the manufacture of a coating, chosen in particular from gelled paints, varnishes, inks and finishing coatings; a glue or adhesive; a sealant; a sealing agent; a chemical sealant; a molded object; an object obtained by 3D printing; preferably a coating or a sealant, more preferably a sealant.

[0017] The invention also relates to the use of the aforementioned diamide as a thixotropic agent.

[0018] DETAILED DESCRIPTION

[0019] The diamide according to the invention is based on: a) at least one diamine selected from linear diamines in C2 to C4, b) at least one diamine selected from linear diamines in Ce to C12, aromatic diamines in Ce-Cis and their mixtures, c) propionic acid, d) 12-hydroxystearic acid.

[0020] In the context of this description, the term "diamide" includes a mixture of asymmetric diamides and possibly symmetric diamides, resulting from the reaction of one or more diamines with one or more carboxylic acids.

[0021] The diamide is based on components a) to d). It can notably be obtained by the reaction of components a) to d). In other words, the diamide contains units resulting from the reaction of components a) to d).

[0022] In particular, the diamide according to the invention contains a mixture of asymmetric diamides, i.e. diamides of formulas (1) and (2):

[0023] A1-C(=O)NH-DA1-NH(C=O)-A2 (1) A1-C(=O)NH-DA2-NH(C=O)-A2 (2) in which:

[0024] Al is an ethyl group (-CH2-CH3),

[0025] A2 is a 12-hydroxyheptadecyl group (-(CH2)IO-CH(OH)-(CH2)5-CH3),

[0026] DA1 is a linear alkylene group in the C2 to C4 position,

[0027] DA2 is a linear Ce to C12 alkylene group or a Ce-Cis arylene group or a Ce to Cis alkylene-arylene-alkylene group or a Ce to Cis arylene-alkylene-arylene group or a Ce to Cis arylene-O-arylene group.

[0028] For the purposes of the present invention, an alkylene group is a divalent group derived from an alkyl group by abstracting two hydrogen atoms. A linear C2-C4 alkylene can, in particular, be represented by the following formula: -(CH2) n - in which n goes from 2 to 4. A linear Ce alkylene at C12 can notably be represented by the following formula: -(CH2) m - in which m ranges from 6 to 12.

[0029] For the purposes of this invention, an arylene group is a divalent group derived from an aryl by the removal of two hydrogen atoms. A Ce to cis arylene comprises 6 to 18 carbon atoms. Examples of arylenes include phenylene, tolylene, naphthylene, and biphenylene.

[0030] This mixture may also contain one or more symmetrical diamides selected from those of formula (3) to (6) and their mixtures:

[0031] A1-C(=O)NH-DA1-NH(C=O)-A1 (3), A2-C(=O)NH-DA1-NH(C=O)-A2 (4), A1-C(=O)NH-DA2-NH(C=O)-A1 (5), A2-C(=O)NH-DA2-NH(C=O)-A2 (6), in which Al, A2, DA1 and DA2 are as defined above.

[0032] The different compounds used in the synthesis of diamide will now be detailed.

[0033] Component a) comprises or consists of at least one linear diamine in C2 to C4, selected in particular from ethylenediamine (EDA), 1,3-diaminopropane, 1,4-diaminobutane and mixtures thereof. Preferably, it is ethylenediamine.

[0034] Component b) comprises or consists of at least one diamine selected from linear Ce-12 diamines, aromatic Ce-cis diamines, and mixtures thereof. The linear Ce-12 diamine may be saturated or unsaturated but is preferably saturated. Examples of linear Ce-12 diamines include 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and mixtures thereof. Of these, 1,6-diaminohexane or hexamethylenediamine (HMD A) is preferred.

[0035] The term "Ce-Cis aromatic diamine" refers to a compound comprising 6 to 18 carbon atoms, two primary amine groups (-NH2), and at least one aromatic ring, preferably at least one 6-membered aromatic ring, which may be bonded or fused to another aromatic or non-aromatic ring. The Ce-Cis aromatic diamine may be selected, in particular, from m- or p-xylylenediamine, m- or p-phenylenediamine, m- or p-tolylenediamine, 3,4'- or 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, and mixtures thereof, preferably from m- and p-xylylenediamines. More preferably, it is m-xylylenediamine (m-XDA).

[0036] In one embodiment of the invention, the molar ratio of component a) to component b) may in particular range from 0.1 / 99.9 to 50 / 50, preferably from 0.5 / 99.5 to 30 / 70, more preferably from 1 / 99 to 15 / 95.

[0037] Component c) consists of propionic (or propanoic) acid.

[0038] Component d) consists of 12-hydroxystearic acid (12-HSA), which can be obtained by hydrogenating castor oil followed by hydrolyzing the resulting hydrogenated castor oil.

[0039] The molar ratio of component c) to component d) may in particular range from 20 / 80 to 80 / 20, preferably from 30 / 70 to 70 / 30, more preferably from 40 / 60 to 60 / 40.

[0040] In a preferred embodiment of the invention, the reagents used in the synthesis of the diamide do not include cycloaliphatic diamine, in particular Ce to Cis cycloaliphatic diamine.

[0041] The term "cis-Ce cycloaliphatic diamine" refers to a compound comprising 6 to 18 carbon atoms, two primary amine groups (-NH2), and at least one non-aromatic ring. The cycloaliphatic diamine preferably comprises at least one 6-membered non-aromatic ring, which may be bonded, bridged, or fused to another non-aromatic ring. An example of a cis-Ce cycloaliphatic diamine is 1,3-bis(aminomethyl)cyclohexane (or 1,3-BAC). To prepare the diamide, components a), b), c), and d) can be reacted in various ways. For example, in one embodiment, a reaction mixture containing all these components can be prepared and then subjected to a polycondensation reaction.In a second embodiment, a first reaction mixture containing components a), c), and d) can be prepared, and a polycondensation reaction carried out to obtain a first diamide. A second reaction mixture containing components b), c), and d) can then be prepared and a polycondensation reaction carried out to obtain a second diamide, and the diamides thus obtained can then be mixed. In this preferred embodiment, the weight ratio of the first diamide to the second diamide can range from 70 / 30 to 99 / 1, preferably from 80 / 20 to 98 / 2, and more preferably from 90 / 10 to 97 / 3.

[0042] In all cases, the polycondensation reaction can be carried out at a temperature ranging from 140 to 250°C, preferably from 150 to 200°C. It is generally conducted under an inert atmosphere.

[0043] The diamide obtained after the polycondensation reaction comprises the same constituents, regardless of the synthesis route followed, and is typically in solid form. It can be micronized by mechanical milling (in particular ball milling or knife milling), possibly followed by sieving, or by air jet milling. Preferably, the diamide has a volumetric particle size Dv(90) less than or equal to 50 pm, preferably less than or equal to 30 pm, more preferably less than or equal to 25 pm, even more preferably less than or equal to 20 pm, and even better, less than or equal to 15 pm. Furthermore, Dv(90) can be greater than or equal to 1 pm. The particle size Dv(90) is understood as the volume-based particle size distribution that includes 90% of the particles present in a given sample. This size can, in particular, be determined by laser diffraction.

[0044] Diamide can be used, in particular, as an organo-freezer. An organo-freezer (also called a rheological additive or thixotropic agent) is typically a low molecular weight organic molecule (less than 2000 g / mol) capable of forming a reversible gel in an organic liquid, especially at relatively low concentrations (i.e., less than 1% by weight relative to the weight of the organic liquid). An organo-freezer can modify the rheology of a formulation into which it is introduced. In particular, an organo-freezer can impart a pseudoplastic or thixotropic effect to the formulation. Consequently, an organo-freezer can increase the viscosity of the formulation when the formulation is at rest (no shear stress is applied). The viscosity of the formulation decreases when the formulation is subjected to shear stress.The increase and decrease in viscosity can be determined relative to a control formulation containing no organo-freezer.

[0045] In order to exhibit pseudoplastic or thixotropic properties, a diamide-type organofreezer must be activated. This activation generally involves applying specific heating conditions under shear for a certain duration.

[0046] Thus, in a first embodiment of the invention, the diamide is in micronized form, as described above, and is activated within the organic binder composition to which it is added. This activation allows its molecules to self-assemble through non-covalent bonds in order to obtain thixotropic or pseudoplastic properties. The diamide can, for example, be activated by heating it to a temperature of 40 to 120°C, more generally 50 to 80°C, for a period of 15 minutes to one hour, particularly 20 to 30 minutes, with a shear rate corresponding to a tangential velocity of 4 to 10 m / s². 1 (i.e., approximately 1000 to 4000 rpm, for example 1500 to 3000 rpm). Alternatively, the diamide can be subjected to a shearing step at room temperature and then placed in an oven at a temperature within the ranges indicated above.

[0047] In a second embodiment, the diamide is pre-activated in an organic solvent to obtain a pre-activated paste, which is then added to the organic binder composition. The term "pre-activated" means that the organogestor possesses thixotropic or pseudoplastic properties. Consequently, a pre-activated organogestor can be simply mixed into a formulation and will not require any further activation to exhibit pseudoplastic or thixotropic properties.

[0048] The term "paste" or organogel refers to a reversible, non-crystalline, and non-glassy solid or semi-solid (gelatinous) material composed of an organic liquid trapped within a three-dimensional network. This network is based on the self-assembly of a structuring agent (in this case, a diamide) through non-covalent interactions (such as hydrogen bonds, Van der Waals interactions, n-7i stacking ion pairing, solvophobic forces, and / or ionic coordination). These interactions lead to the formation of a 3D network of microfibrils that immobilize the organic liquid. The organogel can remain stable at 25°C for several months, meaning that there is no overall phase separation. During heating and / or stirring, the 3D network can be reversibly fragmented, the organogel can become less viscous, and when heating and / or stirring stops, the 3D network of microfibrils can reform.In particular, the diamide can be pre-activated in an organic solvent or a mixture of organic solvents, by heating to a temperature equal to or above its activation temperature to allow the self-assembly of its molecules by non-covalent bonds in order to obtain microfibrils.

[0049] The organic solvent can be any organic compound that is liquid at 30°C, preferably within the temperature range of 0°C to 30°C. The organic solvent may comprise one or more plasticizers, one or more reactive solvents, one or more non-reactive solvents, or mixtures thereof. In this description, the term "a plasticizer" or "a solvent" thus covers both a single compound and a mixture of compounds, unless otherwise specified.

[0050] As used here, the term "solvent" refers to a compound capable of at least partially solubilizing the diamide, possibly under heating conditions. The solvent is preferably a polar organic solvent. A solvent is considered polar organic solvent if it contains at least one polar group, for example, an alcohol or ester group.

[0051] As used here, the term "reactive solvent" refers to a solvent that contains a reactive functional group, that is, a functional group capable of reacting with at least one component of the formulation (the binder composition) to which the pre-activated organo-freezer paste is added. For example, a reactive solvent may contain at least one polymerizable carbon-carbon double bond and / or at least one epoxide ring.

[0052] As used here, the term "non-reactive solvent" refers to a solvent that is inert with respect to the components of the formulation into which the pre-activated organo-freezer paste is added. Generally, a non-reactive solvent lacks reactive functional groups as defined above.

[0053] As used here, the term "plasticizer" refers to a compound capable of modifying the mechanical and / or thermal properties of the formulation to which the pre-activated organofreezer paste is added, possibly under heating conditions. For example, a plasticizer may have one or more of the following effects: decreased viscosity, decreased glass transition temperature, increased flexibility, etc.

[0054] Examples of non-reactive solvents include: xylene; alcohols such as methanol, ethanol, butanol, and benzyl alcohol; saturated cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, and decalin; alkyl esters of monocarboxylic acids such as methyl formate, methyl acetate, ethyl acetate, butyl acetate, hexyl acetate, heptyl acetate, methyl propionate, ethyl propionate, amyl propionate, and ethyl ethoxypropionate; alkyl esters of dicarboxylic acids, such as methyl glutarate, methyl succinate and methyl adipate; lactones, such as γ-butyrolactone; ethers, such as dimethoxyethane (DME), oligoethylene glycol methyl ethers of 2 to 5 oxyethylene motifs, 1,3-dioxolane, dioxane, dibutyl ether and tetrahydrofuran;ketones such as cyclohexanone; phosphoric acid esters or sulfite esters; nitriles, such as acetonitrile, pyruvonitrile, propionitrile, methoxypropionitrile, dimethylaminopropionitrile, butyronitrile, isobutyronitrile, valeronitrile, pivalonitrile, isovaleronitrile, glutaronitrile, methoxyglutaronitrile, 2-methylglutaronitrile, 3-methylglutaronitrile, adiponitrile and malononitrile; Carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl and methyl carbonate, diphenyl carbonate, methylphenyl carbonate, dipropylene carbonate, methylpropyl carbonate, ethylpropyl carbonate, vinylene carbonate, fluoroethylene carbonate, trifluoropropylene carbonate; and mixtures thereof.

[0055] Examples of non-reactive solvent mixtures are mixtures of xylene with ethanol or butanol, for example in a weight ratio of 1:1 to 4:1.

[0056] When a reactive solvent is used, it is generally chosen from an ethylenically unsaturated compound (i.e., a compound containing a polymerizable carbon-carbon double bond) or an epoxide (i.e., a compound containing an epoxy ring). A polymerizable carbon-carbon double bond is a carbon-carbon double bond that can react with another carbon-carbon double bond in a polymerization reaction. Specifically, the reactive solvent may include one or more ethylenically unsaturated compounds chosen from a (meth)acrylic monomer, a styrenic monomer, a vinyl monomer, an olefinic monomer, an unsaturated polyacid or a derivative thereof, and mixtures thereof.

[0057] As used here, the term "(meth)acrylic monomer" refers to a monomer that includes a carbon-carbon double bond conjugated to a carbonyl bond (-C(=O)-). Such monomers generally include a (meth)acryloyl group. Preferably, the (meth)acrylic monomer is a monofunctional (meth)acrylic monomer, that is, it includes only one (meth)acryloyl group. The term (meth)acryloyl group is used interchangeably to refer to an acryloyl group (-C(=O)- CTUCTL) or a methacryloyl group.

[0058] (-C(=O)-C(CH3)=CH2). The (meth)acrylic monomer can be chosen from among the alkyl (meth)acrylates (in particular methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate or 2-ethylhexyl (meth)acrylate); cycloaliphatic (meth)acrylates (in particular dicyclopentadienyl (meth)acrylate, norbomyl (meth)acrylate, isobomyl (meth)acrylate (IBO(M)A), tert-butyl cyclohexanol (meth)acrylate (TBCH(M)A), tricyclodecane methanol mono(meth)acrylate and 3,3,5-trimethylcyclohexanol (meth)acrylate (TMCH(M)A); hydroxyalkyl (meth)acrylates (in particular 2-hydroxyethyl (meth)acrylate); (meth)acrylic acid; (meth)acrylamide; (meth)acrylonitrile; and mixtures thereof.

[0059] As used here, the term "styrenic monomer" refers to a monomer that contains a carbon-carbon double bond in the alpha position relative to an aromatic ring. The styrenic monomer may be selected from styrene, alpha-methylstyrene, tert-butylstyrene, ortho-, meta- or para-methylstyrene, ortho-, meta- or para-ethylstyrene, o-methyl-p-isopropylstyrene, p-chlorostyrene, p-bromostyrene, o,p-dichlorostyrene, o,p-dibromostyrene, ortho-, meta- or para-methoxystyrenes, possibly substituted indenes, possibly substituted vinylnaphthalenes, acenaphthylene, diphenylethylene, vinylanthracene, and mixtures thereof.

[0060] As used here, the term "vinyl monomer" refers to a monomer that contains a vinyl group (-CH=CH2) that is not conjugated to a carbonyl group (C=O) or an aromatic group. Vinyl monomers are distinguished from olefmic monomers in that they include at least one heteroatom, that is, an atom other than carbon or hydrogen.The vinyl monomer can be chosen from among the vinyl halides (in particular vinyl chloride); vinyl esters (including vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl pentanoate, vinyl hexanoate, vinyl octanoate, vinyl 2-ethylhexanoate, vinyl pelargonate, vinyl laurate, vinyl stearate and vinyl versatate, i.e. esters of branched monocarboxylic acids having 6, 9, 10 or 11 carbon atoms (available in particular under the references VeoVa® EH, VeoVa® 9, VeoVa® 10 or VeoVa® 11 from the company Hexion); vinyl ethers (including methyl, ethyl, butyl or isobutyl vinyl ether) and their mixtures.

[0061] As used here, the term "olefmic monomer" refers to a nonaromatic hydrocarbon monomer containing one or more carbon-carbon double bonds. The olefmic monomer may be selected from ethylene, propene, 1-butene, isobutylene, diisobutylene, 1-nonene, 1-decene, butadiene, or mixtures thereof. As used here, the term "polyunsaturated acid" refers to a compound containing at least one carbon-carbon double bond and at least two carboxy groups, with the carbon-carbon double bond conjugated to at least one of the carboxy groups. The term "polyunsaturated acid derivative" refers to a compound capable of yielding a polyunsaturated acid in situ, for example, by hydrolysis or ring opening. Examples of suitable polyunsaturated acid derivatives include alkyl esters of polyunsaturated acids and cyclic anhydrides.The unsaturated polyacid or its derivative may be chosen from fiimaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, their anhydrides and mixtures thereof.

[0062] Alternatively, the reactive solvent can be a cardanol derivative or a glycidyl ether. As used here, the term "cardanol derivative" refers to a compound obtained by chemical modification of cardanol. Cardanol is a bio-based phenolic lipid extracted from cashew nuts (a byproduct of cashew nut processing). Cardanol comprises a phenol ring substituted with an unsaturated fatty acid chain and can be chemically modified by various reactions. The OH group of the phenolic ring can be converted to an ester group, a phosphate group, an ether, or a glycidyl ether. Alternatively, the unsaturated fatty acid chain can be epoxidized. Examples of suitable cardanol derivatives include {3-[(8E)-pentadec-8-en-l-yl]phenoxymethyl}oxirane (Cardolite NC-513) or [(7Z)-pentadec-7-en-l-yl]phenol (Cardolite® NX-2022).

[0063] As used here, the term "glycidyl ether" refers to a compound comprising a glycidyl ether group of formula:

[0064] Glycidyl ethers can be obtained by reacting an alcohol or polyol with epichlorohydrin. Examples of suitable glycidyl ethers include C4-C20 alkyl glycidyl ethers (such as octyl, decyl, dodecyl, tetradecyl, or hexadecylglycidyl ether), 1,2- or 1,3-propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether 2-methyl-1,3-propanediol diglycidyl ether, neopentylglycol diglycidyl ether, 2,2-diethyl-1,3-propanediol 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-pentanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolmethane triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, di(trimethylolpropane) tetraglycidyl ether, pentaerythritol diglycidyl ether, cyclohexane diglycidyl ether, cyclohexane-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, hydrogenated bisphenol diglycidyl ether, bisphenol diglycidyl ether, glycidyloxypropyl trimethoxysilane and mixtures thereof.

[0065] In one embodiment, the reactive solvent is a monofunctional (meth)acrylic monomer, preferably an alkyl (meth)acrylate or a cycloaliphatic (meth)acrylate. The pre-activated organo-freezer paste obtained from these monomers is particularly suitable as an additive for compositions comprising, as an organic binder, a component of a two-component epoxy / amine reactive system, in which the reactive solvent is capable of reacting with the amine of the epoxy / amine system.

[0066] In the case where a plasticizer is used, said plasticizer is preferably chosen from a polar organic plasticizer which generally includes at least one polar group chosen from an ether group and / or an ester group and / or an epoxy group.

[0067] Plasticizers comprising at least one ether group may be selected from polyethers, such as homopolymers and / or copolymers of ethylene oxide and / or propylene oxide and / or a mixture of said polyethers (homopolymers and / or copolymers) and / or derivatives thereof, these derivatives including, among others, said polyethers blocked at the end of the chain by an alkoxy group from C1 (methoxy) to C4 (butoxy), or by an ester group from C2 (acetate) to C4 (butyrate), said polyethers having a weight-average molecular weight Mw ranging from 150 to 6000 and preferably from 1000 to 3000. The term "copolymer" should be interpreted as including both statistical copolymers and block copolymers.

[0068] The polyethers most particularly preferred are polyethers which are homopolymers of propylene oxide (polypropylene glycols) with a weight average molecular mass Mw ranging from 1000 to 3000, and more particularly polypropylene glycol (PPG) with Mw equal to 2000, and / or its derivatives chosen from among the monoesters, preferably C2 to C4 monoesters, or Ci to C4 monoethers, such as monomethoxylated or monoethoxylated polypropylene glycol.

[0069] Plasticizers comprising at least one ester group may be selected from monoesters and / or polyesters (polyfunctional esters) obtained from C4 to C21 alcohols, possibly alkoxylated alcohols, for example with 1 to 10 alkoxy motifs selected from oxyethylene (OE) and / or oxypropylene (OP), and from mono- or polyacids of functionality from 1 to 4, selected from: i) organic acids selected from aromatic acids having a chain length (without CO2H) from Ce to C10 and / or aliphatic acids having a chain length (without -CO2H function) from C4 to Cis and / or cycloaliphatic acids having a chain length (without -CO2H function) from Ce to C10, and ii) inorganic acids.

[0070] Aromatic acid esters can be selected from phthalic (phthalates) and trimellitic (trimellitates) esters. Aliphatic acid esters can be selected from adipic (adipates), citric (citrates), sebacic (sebacates), and azelaic (azelates) esters. Cycloaliphatic acid esters can be selected from tetrahydrophthalic (tetrahydrophthalates) and hexahydrophthalic (hexahydrophthalates) esters. Inorganic acid esters can be selected from sulfonic (sulfonate) esters, including C21-alkylsulfonates, sulfuric (sulfates), sulfinic (sulfinates) esters, phosphoric (phosphates), phosphonic (phosphonates), and phosphinic (phosphinates) esters.

[0071] Finally, in the case where the plasticizer includes at least one epoxy group, it can be chosen from epoxidized vegetable oils such as epoxidized soybean oil or epoxidized linseed oil, and epoxidized alkyl esters of fatty acids such as epoxidized methyl oleate, epoxidized isoamyl stearate or 2-ethylhexyl stearate.

[0072] Preferred plasticizers include those containing at least one C1 to C10 aromatic acid ester group, particularly mono- and / or dialkyl phthalates, and even more preferably dialkyl phthalates or hexahydrophthalates, in which the alkyl groups are identical or different and are chosen from C7 to Cis alkyls, and preferably C12 to C10 alkyls. The most preferred plasticizers in this family of dialkyl (hexahydro)phthalates are diisoundecyl phthalate and diisononyl hexahydrophthalate. Typically, the diamide is present in a weight ratio, relative to the organic solvent, ranging from 1:1 to 1:10, and preferably from 1:3 to 1:6.

[0073] The diamide according to the invention is added to a composition comprising at least one crosslinkable organic binder (sometimes referred to herein as the "formulation"). As used herein, the term "binder" refers to a material or substance that ensures the plasticity and cohesion of the various constituents of a formulation after drying and / or hardening. As used herein, the term "organic binder" refers to a binder comprising carbon and hydrogen atoms. As used herein, the term "crosslinkable organic binder" refers to an organic binder that is capable of forming one or more covalent bonds with itself and / or with another molecule.

[0074] The organic binder can be an ethylenically unsaturated binder crosslinkable by radical means or an organic binder crosslinkable by chemical reaction (in particular by epoxy-amine reaction, by alcohol-isocyanate reaction, by amine-isocyanate reaction, by carbonyl-amine reaction, by carbonyl-hydrazide reaction, by Michael addition, by aza-Michael or by thio-Michael addition, by thiol-ene or thiol-yne reaction, by cycloaddition reaction, by polycondensation).

[0075] Thus, according to one embodiment, the organic binder is crosslinkable either chemically (by reaction with atmospheric moisture or with another molecule), thermally (in the presence of a radical initiator such as a peroxide or an azo compound), by redox reaction (in the presence of an oxidant such as a peroxide and a reductant such as a ferrous compound, a carboxylic acid, sodium sulfite, sodium bisulfite, sodium metabisulfite, sodium hydroxymethanesulfinate, or rongalite), or by irradiation under radiation such as UV radiation (in the presence of at least one photoinitiator) and / or EB radiation (electron beam, without an initiator), including self-crosslinking at room temperature. The organic binder can be crosslinkable on its own or in combination with another component of the formulation (multi-component system).

[0076] In general, the binder comprises at least one monomer or at least one polymer (including oligomers), having at least one functionality selected from among a polymerizable carbon-carbon double bond, a carbon-carbon triple bond, a reactive group enabling its self-crosslinking or reaction with another component of the formulation, and combinations thereof. Examples of suitable reactive groups are amino, amido, hydroxyl, thiol, epoxy, oxetane, carboxyl, carbonyl, urea, cyclic carbonate, cyclic anhydride, silyl, isocyanate, azide, and combinations thereof. It may thus comprise at least one monomer or at least one polymer selected from: an ethylenically unsaturated monomer (such as those described previously for the reactive solvent), an ethylenically unsaturated oligomer, an unsaturated polymer (in particular an unsaturated polyester, an alkyd resin, a uralkyd, or a modified alkyd),an oleoresin (in particular rosin or resin acid), an epoxide (such as those described above for the reactive solvent), an epoxy resin, a polyol, a polyol polymer (in particular a hydroxylated acrylic resin, a polyester polyol or a polyether polyol), a polyisocyanate, urea-formaldehyde, a phenolic resin, a hydrazide, an amine (in particular melamine), a dicyandiamide, a hydroxyalkylamide, a silylated polymer (in particular a silylated polyurethane, a silylated polysiloxane, a silylated polysulfide, a silylated polyether, a silylated polyether / urethane, a silylated polyester, a silylated polybutadiene), an acrylic resin functionalized with a reactive group (in particular as described above), a styrene-acrylic resin functionalized with a reactive group (in particular as described above), a poly(vinyl chloride), a type elastomer Polychloroprene, SBR, butyl rubber, and mixtures thereof, without this list being exhaustive.

[0077] For example, the organic binder composition according to the invention can be a single-component sealant composition based on silylated polymer and preferably based on silylated polyether or silylated polyurethane, such as the products marketed by KANEKA under the names MS POLYMER® and SILYL®.

[0078] Alternatively, said crosslinkable organic binder may be selected from a component of one of the following two-component systems: epoxy-amine or epoxy-polyamide systems comprising at least one epoxy resin having at least two epoxy groups and at least one amine or polyamide compound having at least two amine groups (resulting in particular from the condensation of an acid dimer with a polyamine); polyurethane systems comprising at least one polyisocyanate and at least one polyol; polyol-melamine systems in which the polyol is optionally a hydroxylated acrylic resin, a polyester or a polyether polyol; polyester systems based on at least one epoxy or a reactive polyol with at least one corresponding acid or anhydride.

[0079] The composition comprising the crosslinkable organic binder and the diamide according to the invention can be used in the manufacture of a coating, selected in particular from among gelled paints, varnishes, inks and finishing coatings ("gel coats"); an adhesive; a sealant; a waterproofing agent; a chemical sealant; a molded object; an object obtained by 3D printing; preferably a coating or a sealant, more preferably a sealant. Sealants can in particular be used for structural bonding such as the bonding of concrete elements in civil engineering (as in the construction of bridges or concrete buildings) or for jointing or caulking gaps between two building elements.

[0080] The composition according to the invention can, for example, be applied to various substrates by spraying, for example with a gun, brush or roller.

[0081] The pre-activated organofreezer paste may be present in these compositions at a content of 1 to 30%, and preferably 2 to 25% by weight, and said diamide may be present as dry active material (either as micronized powder or as a constituent of the pre-activated paste) at a content of 0.1 to 10% by weight, preferably 0.2 to 8%, preferably 0.5 to 8% by weight, more preferably 1 to 6% by weight, relative to the weight of said composition.

[0082] The composition may include various additives suited to its use. Thus, in the case of a sealant, it may include: fillers or extenders, such as calcium carbonate or silica, which are added to reduce cost, increase viscosity, and improve mechanical properties; plasticizers, such as phthalates or adipates, to soften the sealant and increase its flexibility; curing agents or crosslinkers, such as peroxides or isocyanates, to initiate or accelerate the polymerization of the sealant; catalysts; pigments and dyes, such as titanium dioxide or carbon black; antioxidants; antimicrobial agents, such as triclosan to prevent the growth of mold and bacteria; coupling agents or adhesion promoters, such as organic silanes, to strengthen the sealant's adhesion to substrates; and flame retardants, such as aluminum hydroxides.UV stabilizing agents; dehydrating agents, intended to accelerate the evaporation of solvents in solvent-based sealants; solvents or diluents, such as xylene or acetates, which allow the viscosity of the sealant to be adjusted and thus facilitate its application; and mixtures thereof.

[0083] In one embodiment of the invention, the composition is prepared by adding the pre-activated organofreezer paste described above to the remaining constituents of said composition, and then homogenizing the mixture with a mixer and / or a planetary mixer and / or a high-speed disperser, without the need, at this stage, to apply a thermal activation treatment, where "high speed" means tangential speeds ranging from 2 to 15 ms. 1This embodiment is particularly well-suited to the formulation of epoxy, acrylic, or alkyd resin-based paints. The end user can activate the organo-freezer before its introduction into the formulation, or the end user can activate the organo-freezer in situ (directly within the formulation). In a preferred embodiment of the invention, the diamide is introduced into the composition as a micronized powder, and an activation step is performed by the formulator. The activation conditions may, in particular, be as described above. EXAMPLES

[0084] The invention will be better understood in light of the examples below, which are given for purely illustrative purposes and are not intended to limit its scope.

[0085] Raw materials used [Table 1]

[0086] Preparation of diamides

[0087] Example 1: Amide based on ethylenediamine, 12-HSA and propanoic acid

[0088] In a 1-liter round-bottom flask equipped with a thermometer, a Dean-Stark flask, a condenser, and a stirrer, 115.21 g of ethylenediamine (1.92 mol), 142.25 g of propanoic acid (1.92 mol), and 592.54 g (1.92 mol) of 12-hydroxystearic acid are introduced under a stream of nitrogen. The mixture is heated to 190°C, still under a stream of nitrogen. The water removed begins to accumulate in the Dean-Stark flask at 150°C. The reaction is monitored by measuring the acid and amine values. When the acid value is less than 6 mg KOH / g, the reaction mixture is cooled to 150°C and then discharged into a silicone mold. Once cooled to room temperature, the product is ground by opposed-jet micronization.

[0089] Example 2: Amide based on m-xylylenediamine, 12-HSA and propanoic acid

[0090] The same procedure was used with the following proportions: 157.50 g of m-xylylenediamine (1.16 mole), 85.66 g of propanoic acid (1.16 mole) and 256.84 g (1.16 mole) of 12-hydroxystearic acid.

[0091] Example 3: Amide based on hexamethylenediamine, 12-HSA and propanoic acid

[0092] The same procedure was used with the following proportions: 275.14 g of hexamethylenediamine (1.90 mole), 140.33 g of propanoic acid (1.90 mole) and 584.54 g (1.90 mole) of 12-hydroxystearic acid.

[0093] We also prepared mixtures of these diamides in the following proportions: [Table 2]

[0094] Evaluation of rheological performance

[0095] The rheological performance of the thixotropic additives described above was compared in the same simplified sealant formulation. The formulations obtained from the diamides in EXAMPLES 1-8 are respectively designated Fl to F8.

[0096] 1) Preparation of formulations

[0097] The sealant formulations are prepared using a NETZSCH PML1 planetary disperser with a twin-blade agitator. Temperature regulation and control are achieved using a Huber® ministat 230 cryothermostat consisting of a double-jacketed heat exchanger. Vacuum is maintained by a Fisherbrant® FVRD8 rotary vane pump.

[0098] First, 250g of binder is mixed with 165g of plasticizer for 5 minutes at 25°C and 200 rpm. Then, 35g of the diamide is added, and stirring is continued under the same conditions. The extender (500g), pigment (25g), and UV stabilizers (50g) are then introduced into the mixture. The diamide is activated in situ by heating the mixture to 45°C for 30 minutes with stirring at 800 rpm, after which the desiccant (7g) is added. After 5 minutes of mixing at 25°C and 200 rpm, the adhesion promoter (5g) is added, and mixing is continued under the same conditions. Finally, the catalyst (3g) is introduced. After cooling for 5 minutes at 25°C and 200 rpm, a putty formulation is obtained.

[0099] 2) Evaluation of gelling strength

[0100] The performance of formulations Fl to F8 is evaluated by measuring the elastic modulus (G') after aging for one week at 50°C to account for complete rheological development. Indeed, although all compositions were activated equally to initiate the formation of the rheological network, the complete network is not yet fully established with this simple activation, and maturation at 50°C is required to achieve intrinsic performance.

[0101] The tests are performed on the NETZSCH KINEXUS® ULTRA+ controlled-stress rheometer. A stress sweep from 0.1 to 15,000 Pa is carried out at 25°C at a frequency of 1 Hz. The air gap is set at 1 mm for the planar-planar geometry used, namely parallel sandblasted plates with a diameter of 20 mm. The temperature is controlled by the Peltier effect.

[0102] The maximum value of the elastic modulus is recorded on the plateau.

[0103] The results are presented in Table 3 below.

[0104] [Table 3]

[0105] These results show that the diamides according to the invention (Examples 4-6 and 7-8) are more effective organogeators than diamides obtained from a single amine (Examples 1-3). Furthermore, the higher the proportion of MXDA-based diamide, compared to the EDA-based diamide, the better the properties obtained (Formulation F4 vs. F5 and F6), which is surprising given the poorer performance of the diamide obtained from MXDA alone (Example 2), compared to the diamide obtained from EDA alone (Example 1).

Claims

DEMANDS 1. Diamide based on: a) at least one diamine selected from linear diamines in C2 to C4, b) at least one diamine selected from linear diamines in Ce to C12, aromatic diamines in Ce-Cis and mixtures thereof, c) propionic acid, d) 12-hydroxystearic acid, containing a mixture of diamides of formulas (1) and (2): A1-C(=O)NH-DA1-NH(C=O)-A2 (1) A1-C(=O)NH-DA2-NH(C=O)-A2 (2) in which: Al is an ethyl group (-CH2-CH3), A2 is a group (-(CH2)io-CH(OH)-(CH2)5-CH3), DA1 is a linear alkylene group in the C2 to C4 position, DA2 is a linear Ce to C12 alkylene group or a Ce-Cis arylene group or a Ce to Cis alkylene-arylene-alkylene group or a Ce to Cis arylene-alkylene-arylene group or a Ce to Cis arylene-O-arylene group.

2. Diamide according to claim 1, characterized in that component a) comprises or is constituted by at least one linear C2 to C4 diamine selected from: ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane and mixtures thereof, preferably ethylene diamine.

3. Diamide according to any one of claims 1 to 2, characterized in that component b) comprises or is constituted by at least one linear Ce to C12 diamine selected from: 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane and mixtures thereof, preferably 1,6-diaminohexane.

4. Diamide according to any one of claims 1 to 2, characterized in that component b) comprises or is constituted by at least one Ce-Cis aromatic diamine selected from m- or p-xylylenediamine, m- or p-phenylenediamine, m- or p-tolylenediamine, 3,4'- or 4-4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and mixtures thereof, preferably selected from m- and p-xylylene diamines, more preferably m-xylylene diamine.

5. Diamide according to any one of claims 1 to 4, characterized in that the molar ratio of component c) to component d) ranges from 20 / 80 to 80 / 20, preferably from 30 / 70 to 70 / 30, more preferably from 40 / 60 to 60 / 40.

6. Diamide according to any one of claims 1 to 5, characterized in that it is in micronized form or in the form of a paste pre-activated in an organic solvent or a mixture of organic solvents, by heating to a temperature equal to or greater than its activation temperature, preferably the diamide is in micronized form.

7. Diamide according to any one of claims 1 to 6, characterized in that the reaction mixture is devoid of cycloaliphatic diamine.

8. Composition comprising at least one crosslinkable organic binder and at least one diamide according to any one of claims 1 to 7.

9. Composition according to claim 8, characterized in that the crosslinkable organic binder comprises at least one monomer or at least one polymer selected from: an ethylenically unsaturated monomer; an ethylenically unsaturated oligomer; an unsaturated polymer, in particular an unsaturated polyester, an alkyd resin, a uralkyd or a modified alkyd; an oleoresin, in particular rosin or a resin acid; an epoxide; an epoxy resin; a polyol; a polyol polymer, in particular a hydroxylated acrylic resin, a polyester polyol or a polyether polyol; a polyisocyanate; urea-formaldehyde; a phenolic resin; a hydrazide; an amine, in particular melamine; a dicyandiamide; a hydroxyalkylamide; a silylated polymer, in particular a silylated polyurethane, a silylated polysiloxane, a silylated polysulfide, a silylated polyether, a silylated polyether / urethane, a silylated polyester, a silylated polybutadiene; an acrylic resin functionalized with a reactive group;a styrene-acrylic resin functionalized with a reactive group; a poly(vinyl chloride); a polychloroprene or SBR type elastomer or butyl rubber; and mixtures thereof.

10. Composition according to claim 8 or 9, characterized in that the diamide represents from 0.1 to 10% by weight, preferably from 0.2 to 8% by weight, preferably from 0.5 to 8% by weight, more preferably from 1 to 6% by weight, relative to the total weight of said composition.

11. Use of a diamide according to any one of claims 1 to 7 or of a composition according to any one of claims 8 to 10 for the manufacture of a coating, selected in particular from gelled paints, varnishes, inks and finishing coatings; of a glue or adhesive; of a sealant; of a sealing agent; of a chemical sealant; of a molded object; of an object obtained by 3D printing; preferably of a coating or of a sealant, more preferably of a sealant.

12. Use of a diamide according to any one of claims 1 to 7 as a thixotropic agent.

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