Diamides obtained from a mixture of diamines and at least one short-chain carboxylic acid, and their uses as thixotropic agents

Abstract

The invention relates to a diamide obtained from a particular reaction mixture, comprising at least one cycloaliphatic diamine, at least one acyclic diamine, at least one C3-C5 non-hydroxylated monocarboxylic acid, and at least one C3 to C36 hydroxylated monocarboxylic acid, which can be used as a thixotropic agent. 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, preferably selected from among paints, varnishes, inks, and gelcoats; a glue or an adhesive; a mastic; a sealing agent; a chemical sealing agent; a moulded object; an object obtained by 3D printing; preferably a coating.

Description

[0001] DESCRIPTION

[0002] Title: Diamides obtained from a mixture of diamines and at least one short carboxylic acid, and their uses as thixotropic agents

[0003] TECHNICAL FIELD

[0004] The invention relates to a diamide obtained from a particular reaction mixture, comprising at least one cycloaliphatic diamine, at least one acyclic diamine, at least one non-hydroxylated C3-C5 monocarboxylic acid and at least one hydroxylated C3 to C36 monocarboxylic acid, usable as a thixotropic agent. 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, in particular in the manufacture of a coating, chosen in particular from paints, varnishes, inks, and gelled finishing coatings ("gel coats"); of a glue or an adhesive; of a mastic; of a sealing agent; of a chemical sealant; of a molded object; of an object obtained by 3D printing; preferably of a coating.

[0005] A number of rheological additives have been used to increase the viscosity of sealant, glue or adhesive compositions, coating compositions, or molding compositions. These include polyamide powders, hydrogenated castor oil derivative powders, fumed silicas, precipitated calcium carbonates, or 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 when the user (formulator) prepares the final composition.This activation includes high-speed shearing, and heating corresponding to temperature increases of up to approximately 120°C depending on the products, for a minimum duration depending on the temperature conditions and the system, in order to develop optimal final rheological properties. The Applicant has already proposed rheology additives capable of conferring thixotropic properties to a formulation after an activation phase.

[0006] Thus, in particular in WO 2015 / 011375 a rheology additive or organogelator in the form of a diamide has been proposed, which is in powder form and is activated in an organic solvent which may be a reactive diluent or a plasticizer. This diamide is the reaction product of a cycloaliphatic diamine, an acyclic diamine, optionally an aromatic diamine, a hydroxylated fatty acid and optionally a non-hydroxylated monocarboxylic acid.

[0007] 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 coatings such as paints, to increase the resistance to sagging of the coatings obtained from these systems. In addition, it would be desirable to improve the thixotropic properties of these formulations.

[0008] In this context, it appeared to the Applicant that the use of diamides obtained from a cycloaliphatic diamine, an acyclic diamine, a C3-C5 monocarboxylic acid made it possible to prepare diamides satisfying these needs.

[0009] SUMMARY OF THE INVENTION

[0010] The present invention thus relates to a diamide obtained from a reaction mixture comprising: a) at least one C to C cycloaliphatic diamine, b) at least one C to C acyclic diamine, c) at least one C to C non-hydroxylated monocarboxylic acid, d) at least one C to C hydroxylated monocarboxylic acid.

[0011] The invention also relates to a composition comprising at least one crosslinkable organic binder and at least one diamide as defined above. It also relates to the use of the aforementioned diamide or composition in the manufacture of a coating, chosen in particular from paints, varnishes, inks and gelled finishing coatings ("gel coats"); a glue or an adhesive; a mastic; a sealing agent; a chemical sealant; a molded object; an object obtained by 3D printing; preferably a coating.

[0012] The diamide used according to the invention gives the composition containing it excellent properties characterized by a high viscosity at rest, good stability of this viscosity during storage, good resistance to sedimentation, ease of application and extrusion and good resistance to sagging after application. In addition, this rheological additive can be used in a variety of solvent-based or solvent-free formulations, including those with a high pigment and / or filler content.

[0013] DETAILED DESCRIPTION

[0014] The diamide according to the invention is obtained from a reaction mixture comprising: a) at least one C to C cycloaliphatic diamine, b) at least one C to C acyclic diamine, c) at least one C to C non-hydroxylated monocarboxylic acid, d) at least one C to C hydroxylated monocarboxylic acid.

[0015] In the context of this description, the term "diamide" includes a mixture of symmetrical and / or asymmetrical diamides resulting from the reaction of one or more diamines with one or more carboxylic acids. The reaction of one or more diamines with one or more carboxylic acids may be carried out simultaneously or sequentially. For example, all of the components may react in a single step. Alternatively, diamides may be formed separately (e.g., by reacting a first diamine with a portion of the monocarboxylic acids to form a first diamide and by reacting a second diamine with the remainder of the monocarboxylic acids to form a second diamide) before being combined to form a mixture of diamides.

[0016] The various constituents of this mixture will now be detailed. Component a) present in the reaction mixture comprises at least one C 6 to C 8 cycloaliphatic diamine. By "C 6 to C 8 cycloaliphatic diamine" is meant a compound comprising from 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 linked, bridged or fused with another non-aromatic ring.

[0017] Examples of cycloaliphatic diamines suitable as component a) include C 1 to C 12 cycloaliphatic diamines, including: cyclohexane-1,2-, -1,3- or -1,4-diamine; 2- or 4-methylcyclohexane-1,3-diamine; isophoronediamine; 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane; decahydronaphthalenediamine; bis(3-methyl-4-aminocyclohexyl)methane (BMACM); bis(4-aminocyclohexyl)methane (BACM); 1-{[4-(aminomethyl)cyclohexyl]oxy}propan-2-amine; and mixtures thereof. Preferred cycloaliphatic diamines are selected from: cyclohexane-1,3- or -1,4-diamine, 1,3- or 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, bis(4-aminocyclohexyl)methane, and mixtures thereof. More preferably, the cycloaliphatic diamine is 1,3-bis(aminomethyl)cyclohexane (or 1,3-BAC).

[0018] Component a) may in particular represent from 5 to 99%, preferably from 20 to 98%, more preferably from 50 to 95% by mole, relative to the total number of moles of components a), b) and f).

[0019] Component b) present in the reaction mixture comprises at least one C2 to C12 acyclic diamine. By "C2 to C12 acyclic diamine" is meant a compound comprising 2 to 12 carbon atoms, two primary amine groups (-NH2) and no rings. The C2 to C12 acyclic diamine generally represents at least 1% by weight, relative to the total weight of the reaction mixture. The acyclic diamine is preferably linear. It can further be saturated or unsaturated but is preferably saturated. Its amino groups can be primary, secondary or tertiary amine groups, preferably primary.

[0020] Examples of C2-C12 acyclic diamines are: ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 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, ethylenediamine and 1,6-diaminohexane, and mixtures thereof, are preferred.

[0021] Component b) may in particular represent from 1 to 95%, preferably from 2 to 80%, more preferably from 5 to 50% by mole, relative to the total number of moles of components a), b) and f).

[0022] The molar ratio of component a) to component b) may in particular range from 0.1 to 10, preferably from 1 to 9, more preferably from 2 to 8.

[0023] Component c) present in the reaction mixture comprises at least one non-hydroxylated C3-Cs monocarboxylic acid. By "non-hydroxylated C3-Cs monocarboxylic acid" is meant a compound comprising 3 to 5 carbon atoms, a single carboxy group (-COOH) and no hydroxy group (-OH). The non-hydroxylated monocarboxylic acid is preferably linear and saturated. Examples of non-hydroxylated monocarboxylic acids suitable as component c) include: propionic acid, butanoic acid, pentanoic acid, and mixtures thereof.

[0024] Component c) may in particular represent from 2 to 100% by mole, preferably from 5 to 80%, more preferably from 10 to 60% by mole, relative to the total number of moles of components c), d) and e).

[0025] Component d) present in the reaction mixture comprises at least one C3 to C36 hydroxylated monocarboxylic acid. By "C3 to C36 hydroxylated monocarboxylic acid" is meant a compound comprising from 3 to 36 carbon atoms, a single carboxy group (-COOH) and one or more hydroxy groups (-OH), preferably a single hydroxy group. This C3 to C36 hydroxylated monocarboxylic acid may be saturated or unsaturated; it is preferably saturated.

[0026] The hydroxylated monocarboxylic acid d) is preferably selected from C16 to C22 monohydroxylated monocarboxylic acids, such as: 12-hydroxystearic acid (12-HSA), 9-hydroxystearic acid (9-HSA), 10-hydroxy stearic acid (10-HSA), 14-hydroxyeicosaneic acid (14-HEA) or mixtures thereof, preferably 12-hydroxy stearic acid or a mixture of 12-hydroxystearic acid with one or more compounds selected from 9-hydroxystearic acid (9-HSA), 10-hydroxy stearic acid (10-HSA) and 14-hydroxyeicosaneic acid (14-HEA). 12-Hydroxystearic acid can be obtained by hydrogenation of castor oil followed by hydrolysis of the resulting hydrogenated castor oil. 14-Hydroxyeicosanoic acid can be derived from lesquerolic oil produced by extraction of Lesquerella seeds.Lesquerella oil is usually transesterified with methanol, then the resulting product is hydrogenated and finally hydrolyzed to give 14-hydroxyeicosanoic acid. An example of a polyhydroxy monocarboxylic acid is 9,10-dihydroxy stearic acid.

[0027] Preferably, component d) comprises, or even consists of, 12-hydroxy stearyl acid.

[0028] Component d) may in particular represent from 1 to 90% by mole, preferably from 20 to 85%, more preferably from 30 to 80% by mole, relative to the total number of moles of components c), d) and e).

[0029] Furthermore, the molar ratio of component d) to component c) is generally between 1:2 and 10:1, in particular between 1:1.8 and 7:1, more particularly from 1:1 to 5:1.

[0030] The reaction mixture may further comprise one or more optional components selected from: e) acetic acid, and / or f) at least one Ce to Cis aromatic diamine.

[0031] Component e) optionally present in the reaction mixture is acetic acid. When component e) is present in the reaction mixture, it may in particular represent from 1 to 80 mol%, preferably from 5 to 60%, more preferably from 10 to 50 mol%, relative to the total number of moles of components c), d) and e).

[0032] In one embodiment of the invention, the reaction mixture further comprises a component f) comprising at least one C 6 -C 8 aromatic diamine. By "C 6 -C 8 aromatic diamine" is meant 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 with another aromatic or non-aromatic ring. Examples of aromatic diamines include C 6 -C 8 aromatic diamines and in particular: m- or p-xylylenediamine, m- or p-phenylenediamine, m- or p-tolylenediamine, 3,4'- or 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and combinations thereof. Advantageously, m- or p-xylylenediamine (m- or p-XDA) is used, more preferably m-xylylenediamine (m-XDA).

[0033] When component f) is present in the reaction mixture, it may in particular represent 1 to 50% by mole, preferably 5 to 45%, more preferably 10 to 40% by mole, relative to the total number of moles of components a), b) and f).

[0034] The polycondensation reaction between components a), b), c), d) and optionally e) and / or f) as described above can be carried out at a temperature ranging from 140 to 250°C, preferably from 150 to 200°C. The reaction is preferably carried out under an inert atmosphere. The molar ratio between components a), b) and f) and components c), d) and e) is generally between 0.9 and 1.1 and is preferably 1:1.

[0035] The diamide obtained after the polycondensation reaction is typically in solid form. It can be micronized by mechanical grinding (ball milling, knife milling) possibly followed by sieving, or by air jet. Preferably, the diamide has a volume particle size Dv(90) less than or equal to 30 pm, preferably less than or equal to 25 pm, more preferably less than or equal to 20 pm, even more preferably less than or equal to 15 pm. In particular, the Dv(90) can be between 1 pm and 30 pm. The particle size Dv(90) is understood as the volume-based particle size distribution which comprises 90% of the particles present in a given sample. This size can in particular be determined by laser diffraction.

[0036] The amount of diamide in the binder composition may in particular range from 0.5 to 30%, in particular from 1 to 20%, more particularly from 2 to 10%, by weight of diamide relative to the total weight of said composition. The diamide may in particular be used as an organogelator. An organogelator (also called a rheological additive or thixotropic agent) is typically an organic molecule of low molecular weight (i.e. less than 2000 g / mol) which is capable of forming a reversible gel in an organic liquid, in particular at relatively low concentrations (i.e. less than 1% by weight relative to the weight of the organic liquid). An organogelator may modify the rheology of a formulation into which it is introduced. In particular, an organogelator may confer on this formulation a pseudoplastic or thixotropic effect.As a result, an organogelator 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 that does not include any organogelator.

[0037] In order to exhibit pseudoplastic or thixotropic properties, a diamide-type organogelator must be activated. This activation typically involves the application of specific heating conditions, under shear, for a certain duration.

[0038] Thus, in a first embodiment of the invention, the diamide is in micronized form, as described above, and is activated prior to its addition to or in the organic binder composition. The activation allows the self-assembly of its molecules by non-covalent bonds in order to obtain thixotropic or pseudoplastic properties. The activation of the diamide can for example be carried out by heating to a temperature of 40 to 120°C, more generally 50 to 80°C, for a period ranging from 15 minutes to one hour, in particular 20 to 30 minutes, with a shear corresponding to a tangential speed of 4 to 10 ms' 1 (i.e. approximately 1000 to 4000 rpm, for example 1500 to 3000 rpm). Alternatively, the diamide may be subjected to a shearing step at room temperature and then placed in an oven at a temperature within the ranges indicated above.

[0039] In a second embodiment, the diamide is in the form of a pre-activated paste in an organic solvent that is added to the organic binder composition. By the term "pre-activated" is meant that the organogelator has thixotropic or pseudoplastic properties. Accordingly, a pre-activated organogelator can be simply mixed into a formulation and will not require any further activation to exhibit pseudoplastic or thixotropic properties.

[0040] By "paste" or organogel is meant a reversible, non-crystalline, non-glassy solid or semi-solid (gel-like) material composed of an organic liquid trapped in a three-dimensional network based on the self-assembly of a structuring agent (in this case, a diamide) by non-covalent interactions (such as hydrogen bonds, Van der Waals interactions, n-Ti stacking ion pairing, solvophobic forces and / or by ionic coordination). These interactions lead to the formation of a 3D network of microfibrils that immobilize the organic liquid. The organogel can be stable at 25°C for several months, i.e., there is no overall phase separation. Upon 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.

[0041] In particular, the diamide can be pre-activated in an organic solvent or a mixture of organic solvents and by heating to a temperature equal to or higher than its activation temperature to allow self-assembly of its molecules by non-covalent bonds in order to obtain microfibrils.

[0042] The organic solvent may be any organic compound that is liquid at 30°C, preferably in 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 expression "a plasticizer" or "a solvent" thus covers both a single compound and a mixture of compounds, unless otherwise indicated.

[0043] As used herein, the term "solvent" means a compound capable of at least partially solubilizing the diamide, optionally under heating conditions. The solvent is preferably a polar organic solvent. A polar organic solvent is considered to be a solvent comprising at least one polar group, for example an alcohol or ester group.

[0044] As used herein, the term "reactive solvent" means a solvent that comprises a reactive functional group, i.e., a functional group capable of reacting with at least one component of the formulation (the binder composition) into which the pre-activated organogelator paste is added. For example, a reactive solvent may comprise at least one polymerizable carbon-carbon double bond and / or at least one epoxide ring.

[0045] As used herein, the term "non-reactive solvent" means a solvent that is inert to the components of the formulation into which the pre-activated organogelator paste is added. Generally, a non-reactive solvent is devoid of reactive functional groups as defined above.

[0046] As used herein, the term "plasticizer" means a compound capable of modifying the mechanical and / or thermal properties of the formulation to which the pre-activated organogelator paste is added, possibly under heating conditions. For example, a plasticizer may have one or more of the following effects: decrease in viscosity, decrease in glass transition temperature, increase in flexibility, etc.

[0047] Examples of non-reactive solvents are: xylene; alcohols such as methanol, ethanol, butanol and benzyl alcohol; cyclic saturated 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 ethoxy propionate; 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 units, 1, 3-di oxolane, 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 methyl carbonate, diphenyl carbonate, methylphenyl carbonate, dipropylene carbonate, methylpropyl carbonate, ethylpropyl carbonate, vinylene carbonate, fluoroethylene carbonate, trifluoropropylene carbonate; and mixtures thereof.;

[0048] 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.

[0049] In the case where a reactive solvent is used, it is generally selected from an ethylenically unsaturated compound (i.e., a compound comprising a polymerizable carbon-carbon double bond) or an epoxide (i.e., a compound comprising 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.

[0050] In particular, the reactive solvent may comprise one or more ethylenically unsaturated compounds selected from a (meth)acrylic monomer, a styrenic monomer, a vinyl monomer, an olefinic monomer, an unsaturated polyacid or a derivative thereof, and mixtures thereof.

[0051] As used herein, the term "(meth)acrylic monomer" means a monomer that comprises a carbon-carbon double bond conjugated to a carbonyl bond (-C(=O)-). Such monomers generally comprise a (meth)acryloyl group. Preferably, the (meth)acrylic monomer is a monofunctional (meth)acrylic monomer, i.e., it comprises only one (meth)acryloyl group. The term (meth)acryloyl group is used interchangeably to denote an acryloyl group (-C(=O)-CH=CH2) or a methacryloyl group (-C(=O)-C(CH3)=CH2).The (meth)acrylic monomer may be chosen from 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 (including dicyclopentadienyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (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 (including 2-hydroxyethyl (meth)acrylate); (meth)acrylic acid; (meth)acrylamide; (meth)acrylonitrile; and mixtures thereof.

[0052] As used herein, 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-methyl styrene, tert-butyl styrene, ortho-, meta- or para-methyl styrene, ortho-, meta- or para-ethyl styrene, o-methyl-p-isopropylstyrene, p-chlorostyrene, p-bromostyrene, o,p-dichlorostyrene, o,p-dibromostyrene, ortho-, meta- or para-methoxystyrenes, optionally substituted indenes, optionally substituted vinylnaphthalenes, acenaphthylene, diphenylethylene, vinylanthracene and mixtures thereof.

[0053] As used herein, the term "vinyl monomer" refers to a monomer that contains a vinyl group (-CH=CH2) that is not conjugated with a carbonyl group (C=O) or an aromatic group. Vinyl monomers are distinguished from olefin monomers in that they include at least one heteroatom, i.e., an atom other than carbon or hydrogen.The vinyl monomer may be chosen from vinyl halides (in particular vinyl chloride); vinyl esters (in particular 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 (in particular methyl, ethyl, butyl or isobutyl vinyl ether) and mixtures thereof.

[0054] As used herein, the term "olefinic monomer" refers to a non-aromatic hydrocarbon monomer that contains one or more carbon-carbon double bonds. The olefinic monomer may be selected from ethylene, propene, 1-butene, isobutylene, diisobutylene, 1-nonene, 1-decene, butadiene, or mixtures thereof. As used herein, the term "unsaturated polyacid" refers to a compound comprising at least one carbon-carbon double bond and at least two carboxy groups, wherein the carbon-carbon double bond is conjugated to at least one of the carboxy groups. The term "unsaturated polyacid derivative" refers to a compound capable of yielding an unsaturated polyacid in situ, for example, by hydrolysis or ring opening. Examples of suitable unsaturated polyacid derivatives include alkyl esters of unsaturated polyacids and cyclic anhydrides.The unsaturated polyacid or its derivative may be chosen from fumaric acid, maleic acid, itaconic acid, aconitic acid, mesaconic acid, their anhydrides and their mixtures.

[0055] Alternatively, the reactive solvent may be a cardanol derivative or a glycidyl ether.

[0056] As used herein, 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 by-product of cashew processing). Cardanol comprises a phenol ring substituted with an unsaturated fatty chain and can be chemically modified by various reactions. The OH group of the phenol ring can be transformed into an ester group, a phosphate group, an ether, or a glycidyl ether. Alternatively, the unsaturated fatty 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).

[0057] As used herein, the term "glycidyl ether" means a compound comprising a glycidyl ether group of the formula:

[0058] [Chem 1] 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 hexadecyl glycidyl 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, 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-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, tri cyclodecane dimethanol diglycidyl ether, isosorbide diglycidyl ether, pyrocatechol diglycidyl ether, resorcinol diglycidyl ether, cardol diglycidyl ether, 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.,

[0059] According to one embodiment, the reactive solvent is a monofunctional (meth)acrylic monomer, preferably an alkyl (meth)acrylate or a cycloaliphatic (meth)acrylate. The pre-activated organogelator paste obtained from these monomers is particularly suitable as an additive for compositions comprising, as 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. In the case where a plasticizer is used, said plasticizer is preferably chosen from a polar organic plasticizer which generally comprises at least one polar group chosen from an ether group and / or an ester group and / or an epoxy group.

[0060] The plasticizers comprising at least one ether group may be chosen 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 comprising, among others, said polyethers blocked at the chain end by a C1 (methoxy) to C4 (butoxy) alkoxy group, or by a C2 (acetate) to C4 (butyrate) ester group, 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 random copolymers and block copolymers.

[0061] The most particularly preferred polyethers 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 an Mw equal to 2000, and / or its derivatives chosen from monoesters, preferably C2 to C4 monoesters, or C1 to C4 monoethers, such as monomethoxylated or monoethoxylated polypropylene glycol.

[0062] The plasticizers comprising at least one ester group may be chosen from monoesters and / or polyesters (polyfunctional esters) obtained from C4 to C21 alcohols, from optionally alkoxylated alcohols, for example with 1 to 10 alkoxy units chosen from oxyethylene (EO) and / or oxypropylene (OP), and from mono- or polyacids with functionality ranging from 1 to 4, chosen from: i) organic acids chosen from aromatic acids having a chain length (without CO2H) ranging from Ce to Cio and / or aliphatic acids having a chain length (without -CO2H function) ranging from C4 to Cis and / or cycloaliphatic acids having a chain length (without -CO2H function) ranging from Ce to Cio, and ii) inorganic acids.

[0063] The aromatic acid esters may be selected from phthalic esters (phthalates) and trimellitic esters (trimellitates). The aliphatic acid esters may be selected from adipic esters (adipates), citric esters (citrates), sebacic esters (sebacates) and azelaic esters (azelates). The cycloaliphatic acid esters may be selected from tetrahydrophthalic esters (tetrahydrophthalates) and hexahydrophthalic esters (hexahydrophthalates). The inorganic acid esters may be selected from sulfonic esters (sulfonates), including C10 to C21 alkyl sulfonates, sulfuric esters (sulfates), sulfinic esters (sulfinates), phosphoric esters (phosphates), phosphonic esters (phosphonates) and phosphinic esters (phosphinates).

[0064] Finally, in the case where the plasticizer comprises at least one epoxy group, it may be chosen from epoxidized vegetable oils such as epoxidized soybean oil or epoxidized linseed oil, and epoxidized fatty acid alkyl esters such as epoxidized methyl oleate, epoxidized isoamyl stearate or 2-ethylhexyl stearate.

[0065] Among the preferred plasticizers, mention may be made of those comprising at least one C 6 to C 10 aromatic acid ester group, in particular plasticizers chosen from mono- and / or dialkylphthalates, and even more preferably from dialkyl phthalates, or hexahydrophthalates, in which said alkyls are identical or different and chosen from C 7 to C 8 alkyls, and preferably C 10 to C 12 alkyls. The most preferred plasticizers in this family of dialkyl (hexahydro)phthalates are diisoundecyl phthalate and diisononyl hexahydrophthalate.

[0066] Usually, 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.

[0067] The diamide as described above is added to a composition comprising at least one crosslinkable organic binder (sometimes referred to herein as a "formulation"). As used herein, the term "binder" refers to a material or substance providing plasticity and cohesion to the various constituents of a formulation after drying and / or curing. 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.The organic binder may 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, aza-Michael or thio-Michael addition, by thiol-ene or thiol-yne reaction, by cycloaddition reaction, by polycondensation).

[0068] Thus, according to one embodiment, the organic binder is crosslinkable, either chemically (by reaction with air humidity or with another molecule), or thermally (in the presence of a radical initiator such as a peroxide or an azo compound), or by oxidation-reduction (in the presence of an oxidant such as a peroxide and a reducing agent such as a ferrous compound, a carboxylic acid, sodium sulfite, sodium bisulfite, sodium metabisulfite, sodium hydroxymethanesulfinate, 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 initiator), including self-crosslinkable at room temperature. The organic binder may be crosslinkable by itself or in combination with another component of the formulation (multi-component system).

[0069] Generally, the binder comprises at least one monomer or at least one polymer (including oligomers), having at least one functionality selected from a polymerizable carbon-carbon double bond, a carbon-carbon triple bond, a reactive group allowing its self-crosslinking or its 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 above 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 (especially rosin or a resin acid), an epoxide (such as those described above for the reactive solvent), an epoxy resin, a polyol, a polymer polyol (especially a hydroxylated acrylic resin, a polyester polyol or a polyether polyol), a polyisocyanate, urea-formaldehyde, a phenolic resin, a hydrazide, an amine (especially melamine), a dicyandiamide, a hydroxyalkylamide, a silylated polymer (especially 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 (especially as described above), a styrene-acrylic resin functionalized with a reactive group (especially as described above), a poly(vinyl chloride), an elastomer of polychloroprene or SBR type or butyl rubber, and their mixtures, without this list being exhaustive.,

[0070] For example, the organic binder composition according to the invention may be a single-component mastic 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®.

[0071] In a more particular case, said crosslinkable organic binder may be chosen from a component of one of the following two-component systems: epoxy-amine or epoxy-polyamide systems comprising at least one epoxy resin comprising at least two epoxy groups and at least one amine or polyamide compound comprising 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 polyol reactive with at least one corresponding acid or anhydride.

[0072] The composition comprising the crosslinkable organic binder and the diamide described above can be used in the manufacture of a coating, chosen in particular from paints, varnishes, inks and gelled finishing coatings ("gel coats"); a glue or an adhesive; a mastic; a sealing agent; a chemical sealant; a molded object; an object obtained by 3D printing; preferably a coating. The composition can for example be applied to various substrates by spraying, for example with a gun, or with a brush or roller.

[0073] The pre-activated organogelator paste may be present in these compositions at a content ranging from 1 to 30%, and preferably from 2 to 25% by weight, and said diamide may be present in the form of dry active material (either in the form of micronized powder or as a constituent of the pre-activated paste) at a content ranging from 0.2 to 8%, and preferably from 1 to 6% by weight, relative to the weight of said formulation.

[0074] The composition may include other components, such as fillers, plasticizers, wetting agents or pigments.

[0075] In one embodiment of the invention, the composition is prepared by adding the pre-activated organogelator paste described above to the remaining constituents of said composition, then homogenizing the mixture with a kneader and / or a planetary mixer and / or a high-speed disperser, without the need, in this step, to apply a thermal activation treatment, where by "high speed" is meant tangential speeds ranging from 2 to 15 ms' 1 . This embodiment is particularly suitable for the formulation of epoxy, acrylic or alkyd resin-based paints. The end user can activate the organogelator before its introduction into said formulation or the end user can activate the organogelator in situ (directly in the formulation).

[0076] In a preferred embodiment of the invention, the diamide is introduced into the composition in micronized form and an activation step is carried out by the formulator. The activation conditions may in particular be as described above.

[0077] EXAMPLES

[0078] 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. Raw materials used

[0079] [Table 1]

[0080] Methods and tests used

[0081] Formulations are evaluated using the following tests: Sagging resistance test:

[0082] This test is performed using a sagging tester (Levelling / Sagging Tester from Sheen Instruments) to determine a coating's resistance to gravity-induced sagging. This tester, made of stainless steel and equipped with a flat blade, has notches of increasing value. The test consists of depositing different strips of paint of parallel thickness onto a contrast card using the sagging tester. The contrast card is immediately placed vertically, with the thinnest film at the top. The thickness at which the strips meet indicates the tendency to sag. Viscosity assessment:

[0083] This test is carried out using a Brookfield® RV viscometer at 25°C (rotor: S 4). The rotation speed of the rotor is set to 1 rpm (revolutions per minute) and the viscosity of each paint after stabilization is measured. The operation is repeated for speeds of 5 rpm, 10 rpm, 50 rpm and 100 rpm.

[0084] Gelling test:

[0085] This test is performed using a Kinexus Pro rheometer (Malvern). A stress sweep from 0.1 to 15,000 Pa is performed at 25°C at a frequency of 1 Hz and the elastic modulus (G' (in Pa)) is measured to assess the level of structure (i.e. strength) of the gel formed. The air gap is set to 1 mm for the plane-plane geometry used. A visual assessment of the gel appearance is also performed.

[0086] Preparation and characterization of diamides

[0087] Example 1: Diamide based on 1,3-BAC, EDA, 12-HSA, propionic acid and acetic acid

[0088] 352.00 g (1.12 mol) of 12-hydroxy stearic acid, 20.68 g (0.28 mol) of propionic acid and 16.75 g (0.28 mol) of acetic acid were introduced under a stream of nitrogen into a 1 liter round-bottomed flask equipped with a thermometer, a Dean-Stark apparatus, a condenser and a stirrer. 0.41 g of an aqueous solution of H3PO2 (50% by weight) was added.

[0089] The mixture was heated to 120°C, still under a nitrogen flow. 105.52 g (0.74 mol) of 1,3-BAC and 5.72 g (0.10 mol) of ethylenediamine were introduced dropwise, with stirring while maintaining the temperature below 140°C. After the addition of the diamines, the mixture was heated to 190°C, still under a nitrogen flow. The removed water began to accumulate in the Dean Stark apparatus from 150°C. The reaction was monitored by acid number and amine number measurements. When the acid and amine values ​​were below 10 (in mg KOH / g), the reaction mixture was cooled to 150°C and then emptied into a silicone mold. Once cooled to room temperature, the product is ground by micronization with opposing air jets.

[0090] For Examples 2 and 3, the same procedure was used, but with the proportions of reagents shown in Table 2 below: [Table 2]

[0091] Evaluation of rheological performance in a paint formulation

[0092] The prepared diamides were evaluated in high solids (or high dry extract) reactive epoxy paint formulations in xylene. 1) Preparation of paint formulations

[0093] A so-called “millbase” formulation was prepared in the proportions shown in Table 3 below and in the following manner:

[0094] The following successive operations were carried out in a dispersing bowl (Dispermill® 2075 yellow line, supplier: Erichsen) heated by a double jacket system:

[0095] 1.1) Introduction of epoxy binders, dispersant and degassing agent. Homogenization was carried out for 2 minutes at 800 rpm.

[0096] 1.2) Introduction of fillers and pigments, followed by grinding at 3000 rpm for 30 minutes using a 7 cm blade. The double-jacketed bowl allowed this step to be carried out at room temperature with a water bath at

[0097] 20°C.

[0098] 1.3) Introduction of the solvent (butanol) and homogenization. [Table 3]

[0099] 2) Activation of the diamide in the formulation

[0100] 24 hours after preparation of the millbase, the formulation was dispersed again using a 4 cm paddle at 3000 rpm. The diamide to be evaluated was introduced into the millbase and activated in situ at 55°C, for 20 minutes and at 3000 rpm.

[0101] The evaluation was carried out 24 hours after activation and 30 minutes after addition of the hardener diluted in xylene to the millbase (see Table 4).

[0102] [Table 4]

[0103] The paints thus obtained were adjusted in application viscosity with a xylene / butanol mixture (1 / 1 by weight) to about 0.4 P or about 40 mPa.s (more precisely to 0.37-0.38 P or 37-38 mPa.s) measured on cone 4 at 25°C at 2500 s' 1 using a Brookfield® CAP 1000 viscometer. The amount of 1 / 1 xylene / butanol mixture used for viscosity adjustment can vary, but generally less than 1% variation from run to run.

[0104] After adjustment, the paint was mixed / homogenized at 1500 rpm for 2 minutes and then allowed to stand for 30 minutes before evaluation 24 hours later. 3) Evaluation of the rheology of epoxy paint formulations

[0105] Different paint formulations were prepared, according to the proportions in Tables 3 and 4, with the diamides mentioned in Table 2 and at 55 °C, according to the protocol described above. The results of the sagging resistance test and rheological evaluation (viscosity and thixotropy index TI 1 / 10 and TI 5 / 50) are presented in Table 5 below.

[0106] [Table 5] These results show that a diamide according to the invention (Example 1) has better rheological performances than a diamide formed from a reaction mixture not comprising a C2-C5 monocarboxylic acid (Example 2), in particular higher sagging resistance and viscosity, as well as better thixotropic behavior. Evaluation of the gelling force in an STP Resin / Plasticizer mixture

[0107] The prepared diamides were evaluated in formulations containing an STP resin and a plasticizer.

[0108] 1) Preparation of mixtures containing 5% diamide

[0109] The formulation was prepared in the proportions shown in Table 6 below and in the following manner:

[0110] The binder, plasticizer, and diamide were introduced into a dispersing bowl (Dispermill® 2075 yellow line, supplier: Erichsen) whose temperature was regulated by a double-jacket system at 25°C. Homogenization was carried out for 5 minutes at 1000 rpm. The mixture was then placed in an oven heated to 40°C for 2 hours before evaluating the gelation properties.

[0111] [Table 6]

[0112] 2) Evaluation of gelling strength

[0113] Different mixtures were prepared, according to the proportions in Table 7, with the diamides in Table 2. The results of the gelling force evaluation are presented in Table 7 below.

[0114] [Table 7]

[0115] *The appearance of the gel was assessed visually and using G' values:

[0116] - gelled liquid (with G' > 100 Pa): "++" - viscous liquid (with 20 < G' < 100 Pa): "+"

[0117] - liquid (with G' < 20 Pa): “-”

[0118] These results show that the diamide based on cycloaliphatic diamine and acylic diamine according to the invention (Example 1) is a more efficient organogelator than its counterpart without cycloaliphatic diamine (Example 3).

Claims

CLAIMS 1. Mixture of diamides obtained from a reaction mixture comprising: a) at least one cycloaliphatic diamine in Ce to Cis, b) at least one acyclic diamine in C2 to C12, c) at least one non-hydroxylated monocarboxylic acid in C3 to Cs, d) at least one hydroxylated monocarboxylic acid in C3 to C36.

2. Mixture of diamides according to claim 1, characterized in that component a) comprises at least one C 6 to C 8 cycloaliphatic diamine chosen from: cyclohexane-1,2-, -1,3- or -1,4-diamine; 2- or 4-methylcyclohexane-1,3-diamine; isophoronediamine; 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane; decahydronaphthalenediamine; bis(3-methyl-4-aminocyclohexyl)methane; bis(4-aminocyclohexyl)methane; 1-{[4-(aminomethyl)cyclohexyl]oxy}propan-2-amine, and mixtures thereof; preferably cyclohexane-1,3- or -1,4-diamine, 1,3- or 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, bis(4-aminocyclohexyl)methane, and mixtures thereof; more preferably 1,3-bis(aminomethyl)cyclohexane.

3. Mixture of diamides according to claim 1 or 2, characterized in that component b) comprises at least one C2 to C12 acyclic diamine chosen from: ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 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 ethylenediamine and 1,6-diaminohexane, as well as mixtures thereof.

4. Mixture of diamides according to any one of claims 1 to 3, characterized in that component c) comprises at least one non-hydroxylated C3 to Cs monocarboxylic acid chosen from propionic, butanoic, pentanoic acid, or mixtures thereof.

5. Mixture of diamides according to any one of claims 1 to 4, characterized in that component d) comprises at least one C3 to C36 hydroxylated monocarboxylic acid chosen from: 12-hydroxy stearic acid, 9-hydroxy stearic acid, 10-hydroxy stearic acid, 14-hydroxyeicosaneic acid or mixtures thereof, preferably 12-hydroxy stearic acid or a mixture of 12-hydroxy stearic acid with one or more compounds chosen from 9-hydroxy stearic acid, 10-hydroxy stearic acid and 14-hydroxyeicosaneic acid.

6. Mixture of diamides according to any one of claims 1 to 5, characterized in that the reaction mixture further comprises a component e) which is acetic acid.

7. Mixture of diamides according to any one of claims 1 to 6, characterized in that the reaction mixture further comprises a component f) comprising at least one C6-C1S aromatic diamine, said C6-C1S aromatic diamine preferably being chosen from m- or p-xylylenediamine, m- or p-phenylenediamine, m- or p-tolylenediamine, 3,4'- or 4-4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and combinations thereof, preferably xylylenediamines, in particular chosen from m- and p-xylylenediamines, more preferably m-xylylenediamine.

8. Mixture of diamides according to any one of claims 1 to 7, characterized in that it is in the form of a pre-activated paste in an organic solvent.

9. Mixture of diamides according to any one of claims 1 to 8, characterized in that it is in micronized form.

10. Composition comprising at least one crosslinkable organic binder and at least one mixture of diamides according to any one of claims 1 to 9.

11. Composition according to claim 10, characterized in that the crosslinkable organic binder comprises at least one monomer or at least one polymer chosen from: an ethylenically unsaturated monomer; an ethylenically unsaturated oligomer; a 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 epoxy; an epoxy resin; a polyol; a polymer polyol, 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); an elastomer of the polychloroprene or SBR type or butyl rubber; and their mixtures.

12. Use of a mixture of diamides according to any one of claims 1 to 9 or of a composition according to claim 10 or 11, for the manufacture of a coating, chosen in particular from paints, varnishes, inks and gelled finishing coatings; of a glue or an adhesive; of a mastic; of a sealing agent; of a chemical sealant; of a molded object; of an object obtained by 3D printing; preferably of a coating.

Images