Compositions based on polymerizable components and thixotropic additives

Abstract

The present invention relates to a composition based on polymerizable components and thixotropic additives, as well as to a two-component system containing said composition, and to a method for producing a cross-linked product from said composition. The invention also relates to the use of an additive for increasing the viscosity and / or imparting thixotropic properties to polymerizable components.

Description

Technical Field

[0001] The present invention relates to a composition based on a polymerizable component and on a thixotropic additive, and also to a two-component system containing said composition, and to a process for preparing a crosslinked product from said composition. The invention also relates to the use of the additive for increasing the viscosity of the polymerizable component and / or imparting thixotropic properties thereto. Background Art

[0002] Compositions based on (meth)acrylate functional compounds are widely used in many fields, such as coatings, adhesives and composite materials. The use of rheological additives to increase the viscosity of compositions based on (meth)acrylate functional compounds advantageously makes it possible to facilitate the storage, handling and use of these compositions. Furthermore, the phenomenon of sedimentation of fillers in compositions based on (meth)acrylate functional compounds leads to inhomogeneities in the properties of the materials obtained therefrom; it is proposed to provide anti-settling properties to limit this phenomenon.

[0003] However, the use of compositions based on (meth)acrylate functionalized compounds requires special precautions, since these compounds, especially (meth)acrylate functionalized monomers, can have a high saturated vapor pressure and evaporate easily. This results in variations in the concentration of the composition and requires the installation of specialized equipment to capture the released vapors.

[0004] Existing technology for rheological additives, especially for fatty acid diamides and silica, is suitable for solving this problem, but requires activation by heat and / or high shear, which causes self-heating to occur.

[0005] Rheology modifiers based on diurea-diurethanes are good alternatives to those rheology additives because they are liquids and do not require a high temperature activation step. Thus, they can be easily and directly introduced into the composition to be thickened at ambient temperature (20-25°C).

[0006] Patent application EP 3 381 961 A1 describes a molding composition prepared from a composition of monomers containing a thixotropic additive based on diurea-diurethane. However, the thixotropic additive described in this application contains salts such as lithium chloride or surfactants. Lithium salts can cause corrosion problems when the composition is applied to a metal substrate and can generate uncontrolled species due to their Lewis acidity. Furthermore, lithium salts, in particular LiCl, are toxic compounds, and formulations containing them are subject to current regulations on the classification, labeling and packaging of chemicals.

[0007] There is therefore a need for new compositions based on (meth)acrylate-functional compounds and on thixotropic additives comprising diurea-diurethane compounds which contain neither salts nor surfactants, are stable, are easily prepared without a distillation step of residual diisocyanates and have rheological properties which are at least equal to, or even better than, comparable additives from the prior art.

[0008] After extensive research and study, applicants have developed compositions that meet this need. Summary of the invention

[0009] The present invention relates to a composition comprising:

[0010] a) a polymerizable component comprising a (meth)acrylate-functional compound;

[0011] b) a thixotropic additive comprising a diurea-diurethane compound;

[0012] Component b) contains less than 0.1 mol of salt per urea group in component b).

[0013] The invention also relates to a two-component system comprising:

[0014] - a first kit comprising a free radical initiator;

[0015] - a second kit comprising a composition according to the invention and optionally an activator of a free radical initiator;

[0016] Place the first box separately from the second box.

[0017] The invention also relates to a process for preparing a cross-linked product, comprising the following steps:

[0018] - mixing the composition according to the invention with a free radical initiator and optionally an activator for the free radical initiator;

[0019] - Applying the obtained mixture to a substrate.

[0020] The invention also relates to the use of an additive comprising a diurea-diurethane compound and containing less than 0.1 mol of salt per urea group in the additive for increasing the viscosity and / or imparting thixotropic properties to a polymerizable component comprising a (meth)acrylate-functional compound. DETAILED DESCRIPTION

[0021] definition

[0022] In this patent application, the terms "comprising (including) a" and "comprising (including) an" mean "comprising (including) one or more (one or more)".

[0023] Unless otherwise stated, weight percentages in a compound or composition are relative to the weight of the compound or composition.

[0024] The term "diurea-diurethane" refers to a compound having two urea functional groups and two carbamate functional groups.

[0025] The term "diurethane compound" refers to a compound having two carbamate functional groups and no urea functional group.

[0026] The term "polyurea-diurethane compound" refers to a compound having two carbamate functional groups and at least four urea functional groups.

[0027] The term "urea functionality" or "urea group" refers to the sequence -NH-C(=O)-NH-.

[0028] The term "carbamate functionality" or "carbamate group" refers to the sequence -NH-C(=O)-O- or -OC(=O)-NH-.

[0029] The term "solvent" refers to a liquid that has the property of dissolving, diluting, or reducing the viscosity of other substances without chemically modifying the substances and without modifying itself.

[0030] The term "aprotic solvent" refers to a solvent that does not have acidic hydrogen atoms. In particular, an aprotic solvent does not contain hydrogen atoms bonded to heteroatoms (O, N or S).

[0031] The term "salt" refers to an ionic compound. Salts may be inorganic or organic, preferably inorganic. Within the meaning of the present invention, the term "salt" does not include ionic surfactants.

[0032] The term "surfactant" refers to a compound capable of changing the surface tension between two surfaces. Surfactants may in particular be amphiphilic compounds, that is to say they have two parts of different polarity, a lipophilic part (which retains fatty substances) which is non-polar, and another hydrophilic (water-miscible) part which is polar.

[0033] The term "alkyl" refers to a group of the formula -C n H 2n+1 The alkyl group may be linear or branched. 30 The alkyl group refers to an alkyl group having from 1 to 30 carbon atoms.

[0034] The term "alkenyl" refers to a monovalent acyclic hydrocarbon group having one or more C=C double bonds. The alkenyl group may be linear or branched. 30 The alkenyl group refers to an alkenyl group having from 2 to 30 carbon atoms.

[0035] The term "cycloalkyl" refers to a monovalent cyclic hydrocarbon group. Cycloalkyl groups can be saturated or unsaturated. Cycloalkyl groups are non-aromatic. 12 The cycloalkyl group refers to a cycloalkyl group having from 5 to 12 carbon atoms.

[0036] The term "aryl" refers to a monovalent aromatic hydrocarbon group. 12 The aryl group refers to an aromatic group having from 6 to 12 carbon atoms.

[0037] The term "arylalkyl" refers to an alkyl group substituted with an aryl group.

[0038] The term "aliphatic" refers to a non-aromatic acyclic compound or group. It may be linear or branched, saturated or unsaturated, and substituted or unsubstituted. It may contain one or more bonds / functional groups, for example selected from ethers, esters, amines and mixtures thereof.

[0039] The term "cycloaliphatic" refers to a non-aromatic compound or radical containing a ring having only carbon atoms as ring atoms. It may be substituted or unsubstituted.

[0040] The term "aromatic" refers to compounds or groups containing aromatic rings, that is to say conforming to Hückel's rule for aromaticity, in particular compounds containing phenyl groups. They may be substituted or unsubstituted. They may contain one or more bonds / functional groups as defined for the term "aliphatic".

[0041] The term "araliphatic" refers to a compound or radical that contains an aliphatic portion and an aromatic portion.

[0042] The term "heterocycle" refers to a compound or group comprising a ring having as a ring atom at least one heteroatom selected from N, O and / or S. It may be substituted or unsubstituted. It may be aromatic or non-aromatic.

[0043] Component a) - (Meth)acrylate functionalized compounds

[0044] The composition according to the invention comprises a polymerizable component, also referred to as component a). Component a) may in particular comprise all polymerizable compounds of the composition according to the invention. In particular, component a) may in particular comprise all ethylenically unsaturated compounds of the composition according to the invention. These compounds may in particular be intended to polymerize, in particular by free-radical polymerization.

[0045] For the purposes of the present invention, "ethylenically unsaturated compounds" refer to compounds containing polymerizable carbon-carbon double bonds. 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. The polymerizable carbon-carbon double bond is generally within a group selected from the following: acrylates (including cyanoacrylates), methacrylates, acrylamides, methacrylamides, styrenes, maleates, fumarates, itaconates, allyls, propenyls, vinyls and corresponding combinations, preferably selected from acrylates, methacrylates and vinyls, more preferably selected from acrylates and methacrylates. The carbon-carbon double bonds of benzene rings are not considered polymerizable carbon-carbon double bonds.

[0046] Component a) comprises a (meth)acrylate-functional compound. Component a) may comprise a mixture of (meth)acrylate-functional compounds.

[0047] As used herein, the term "(meth)acrylate functionalized compound" refers to a compound comprising at least one (meth)acryloxy group, in particular an acryloxy group. The term "(meth)acryloxy group" encompasses an acryloxy (-O-CO-CH=CH2) group and a methacryloxy (-O-CO-C(CH3)=CH2) group.

[0048] The total amount of (meth)acrylate-functional compounds in component a) may be from 20% to 100% by weight, in particular from 30% to 100% by weight, from 40% to 100% by weight, from 50% to 100% by weight, from 60% to 100% by weight, from 70% to 100% by weight, from 80% to 100% by weight, from 90% to 100% by weight, based on the weight of component a). According to one embodiment, component a) contains no polymerizable compounds other than (meth)acrylate-functional compounds.

[0049] Component a) may comprise, in particular, a (meth)acrylate-functionalized compound selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and mixtures thereof. In particular, component a) may comprise (meth)acrylate-functionalized monomers and optionally (meth)acrylate-functionalized oligomers.

[0050] Component a) may comprise in particular (meth)acrylate-functional monomers. Component a) may comprise a mixture of (meth)acrylate-functional monomers.

[0051] The (meth)acrylate functional monomer may have a molecular weight of less than 600 g / mol, specifically from 70 to less than 550 g / mol, more specifically from 80 to 450 g / mol, more specifically from 90 to 350 g / mol.

[0052] The (meth)acrylate-functional monomer may have 1 to 6 (meth)acryloyloxy groups, in particular 1 to 4 (meth)acryloyloxy groups.

[0053] The (meth)acrylate functional monomer may comprise a mixture of (meth)acrylate functional monomers having different functional groups. For example, the (meth)acrylate functional monomer may comprise a mixture of (meth)acrylate functional monomers containing a single acryloxy or methacryloyloxy group per molecule (referred to herein as "mono (meth)acrylate functional monomer") and (meth)acrylate functional monomers containing 2 or more, preferably 2 to 6 acryloxy and / or methacryloyloxy groups per molecule (referred to herein as "multi (meth)acrylate functional monomer").

[0054] Component a) may in particular comprise mono(meth)acrylate-functional monomers. Component a) may in particular comprise a mixture of mono(meth)acrylate-functional monomers. Mono(meth)acrylate-functional monomers may advantageously act as reactive diluents and reduce the viscosity of the composition according to the invention.

[0055] Examples of suitable mono(meth)acrylate functionalized monomers include, but are not limited to, (meth)acrylic acid, mono(meth)acrylates of aliphatic alcohols (the alcohol may be linear or branched and may be a mono-, di- or polyol, provided that only one hydroxyl group is (meth)acrylated); mono(meth)acrylates of cycloaliphatic or heterocyclic alcohols; mono(meth)acrylates of aromatic alcohols (such as phenols, including alkylated phenols); mono(meth)acrylates of alkylaryl alcohols (such as benzyl alcohol); mono(meth)acrylates of oligomeric and polymeric glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol and polypropylene glycol); mono(meth)acrylates of monoalkyl ethers of ethylene glycol and oligomeric glycols; caprolactone mono(meth)acrylate; and alkoxylated (e.g., ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.

[0056] Component a) may in particular comprise a mono(meth)acrylate-functionalized monomer selected from the group consisting of: (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-pentyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; isodecyl (meth)acrylate; n-dodecyl (meth)acrylate; ( tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; 3-hydroxypropyl (meth)acrylate; 4-hydroxybutyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2-ethoxypropyl (meth)acrylate; 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; hydration Glyceryl (meth)acrylate; benzyl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; phenol (meth)acrylate; nonylphenol (meth)acrylate; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; tricyclodecane methanol (meth)acrylate; tert-butyl cyclohexyl (meth)acrylate; trimethyl cyclohexyl (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; polyethylene glycol monomethyl ether (meth)acrylate; hydroxyethyl -butyl carbamate (meth)acrylate; 3-(2-hydroxyalkyl) oxazolidinone (meth)acrylate; (2,2-dimethyl-1,3-dioxolan-4-yl) (meth)acrylate methyl; (2-ethyl-2-methyl-1,3-dioxolan-4-yl) (meth)acrylate methyl; 1,3-dioxan-5-yl (meth)acrylate; (1,3-dioxolan-4-yl) (meth)acrylate methyl; glycerol carbonate (meth)acrylate; and alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.

[0057] In particular, component a) may comprise, in particular, a mono(meth)acrylate-functionalized monomer selected from the group consisting of: (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-pentyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; n-dodecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; cyclohexyl (meth)acrylate; trimethylcyclohexyl (meth)acrylate; methyl (meth)acrylate; glycidyl (meth)acrylate; benzyl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; (2,2-dimethyl-1,3-dioxolan-4-yl) (meth)acrylate methyl ester; (2-ethyl-2-methyl-1,3-dioxolan-4-yl) (meth)acrylate methyl ester; 1,3-dioxan-5-yl (meth)acrylate; (1,3-dioxolan-4-yl) (meth)acrylate methyl ester; and alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.

[0058] More particularly, component a) may comprise, inter alia, methyl methacrylate, optionally as a mixture with at least one further (meth)acrylate-functional compound.

[0059] Component a) may comprise, in particular, poly(meth)acrylate-functional monomers.

[0060] Examples of multi-(meth)acrylate functional monomers include acrylate and methacrylate esters of polyols (organic compounds containing two or more, for example 2 to 6, hydroxyl groups per molecule). Specific examples of suitable polyols are ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5- Pentanediol, 3,3-dimethyl-1,5-pentanediol, neopentyl glycol, 2,4-diethyl-1,5-pentanediol, cyclohexanediol, cyclohexane-1,4-dimethanol, norbornene dimethanol, norbornene dimethanol, tricyclodecanediol, tricyclodecane dimethanol, hydrogenated bisphenol A, B, F or S, hydrogenated bisphenol A, B, F or S, trimethylolmethane, trimethylolethane, trimethylolpropane, di(trihydroxy) methyl propane), trihydroxyethylpropane, pentaerythritol, di(pentaerythritol), glycerol, di-, tri- or tetraglycerol, polyglycerol, di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol, di-, tri- or tetrabutylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly(ethylene glycol-co-propylene glycol), sugar alcohols (i.e. erythritol, threitol, arabitol, xylitol, ribitol, mannitol, sorbitol, dulcitol, fucitol or iditol), dianhydrohexitol (i.e. isosorbide, isomannite or isoidose), tris(2-hydroxyethyl)isocyanurate, polybutadiene polyols, and alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof and derivatives obtained by ring-opening polymerization of a lactone (e.g. ε-caprolactone) initiated with one of the above-mentioned polyols. Such polyols may be fully or partially esterified (with (meth)acrylic acid, (meth)acrylic anhydride, (meth)acryloyl chloride, etc.), provided that they contain at least two (meth)acryloyloxy functional groups per molecule.

[0061] In particular, component a) may comprise, inter alia, a multi-(meth)acrylate-functionalized monomer selected from the group consisting of: bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate; polypropylene glycol di(meth)acrylate. Ester; polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4-butanediol di(meth)acrylate; 1,5-pentanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate; 1,8-octanediol di(meth)acrylate; 1,9-nonanediol di(meth)acrylate; 1,10-decanediol di(meth)acrylate 1,12-dodecanediol di(meth)acrylate ; Neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; Polybutadiene di(meth)acrylate; Cyclohexane-1,4-dimethanol di(meth)acrylate; Tricyclodecane dimethanol di(meth)acrylate; Glycerol di(meth)acrylate; Glycerol tri(meth)acrylate; Trimethylolethane tri(meth)acrylate; Trimethylolethane di(meth)acrylate; Trimethylolpropane tri(meth)acrylate; Trimethylolpropane di(meth)acrylate; Pentaerythritol di(meth)acrylate; Pentaerythritol tri(meth)acrylate ) acrylate, pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) di(meth)acrylate; di(trimethylolpropane) tri(meth)acrylate; di(trimethylolpropane) tetra(meth)acrylate; sorbitol penta(meth)acrylate; di(pentaerythritol) tetra(meth)acrylate; di(pentaerythritol) penta(meth)acrylate; di(pentaerythritol) hexa(meth)acrylate; tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.

[0062] More particularly, component a) may comprise, inter alia, a multi(meth)acrylate-functional monomer selected from: 1,6-hexanediol di(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; and mixtures thereof.

[0063] Component a) may comprise from 0 to 100% by weight, in particular from 5 to 100% by weight, from 10 to 100% by weight, from 15 to 100% by weight, from 20 to 95% by weight, from 25 to 95% by weight, from 30 to 95% by weight, from 35 to 90% by weight, from 40 to 90% by weight, or from 50 to 90% by weight, of (meth)acrylate-functional monomers, based on the weight of component a). Component a) can comprise from 0 wt % to 60 wt %, from 5 wt % to 60 wt %, from 10 wt % to 60 wt %, from 15 wt % to 60 wt %, from 20 wt % to 60 wt %, from 25 wt % to 60 wt %, from 30 wt % to 60 wt %, from 35 wt % to 60 wt %, from 40 wt % to 60 wt %, or from 45 wt % to 60 wt % of the (meth)acrylate-functional monomer, based on the weight of component a). As a variant, component a) may comprise from 60% to 100% by weight, from 65% to 100% by weight, from 70% to 100% by weight, from 75% to 100% by weight, from 80% to 100% by weight, from 85% to 100% by weight, from 90% to 100% by weight, from 95% to 100% by weight of (meth)acrylate-functional monomers, based on the weight of component a).

[0064] Component a) may comprise in particular (meth)acrylate-functional oligomers. Component a) may comprise a mixture of (meth)acrylate-functional oligomers.

[0065] The (meth)acrylate functionalized oligomer may be selected to enhance properties such as flexibility, strength and / or modulus of the product obtained by polymerization of the composition according to the invention.

[0066] The (meth)acrylate functionalized oligomer may have 1 to 18 (meth)acryloyloxy groups, specifically 2 to 6 (meth)acryloyloxy groups, more specifically 2 to 6 acryloyloxy groups.

[0067] The (meth)acrylate functional monomer may have a number average molecular weight greater than or equal to 600 g / mol, specifically 800 to 15000 g / mol, more specifically 1000 to 5000 g / mol.

[0068] In particular, component a) may comprise, inter alia, a (meth)acrylate-functionalized oligomer selected from the group consisting of: (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized epoxy oligomers, (meth)acrylate-functionalized polyether oligomers, (meth)acrylate-functionalized polydiene oligomers, (meth)acrylate-functionalized polycarbonate oligomers, (meth)acrylate-functionalized polyester oligomers; (meth)acrylate-functionalized acrylic oligomers; and mixtures thereof.

[0069] (Meth)acrylate-functional urethane oligomers (sometimes also referred to as "urethane (meth)acrylate oligomers") suitable for use in the polymerizable compositions of the present invention include urethanes based on at least one polyol, on at least one polyisocyanate and on at least one hydroxy-functional and (meth)acrylate-functional compound (also known as hydroxy-functional (meth)acrylate).

[0070] (Meth)acrylate functionalized urethane oligomers can be prepared by reacting a polyisocyanate (e.g., a diisocyanate or triisocyanate, which is aliphatic, cycloaliphatic, heterocyclic, or aromatic) with a polyol (particularly a polyester polyol, a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, a polyorganosiloxane polyol, or a polydiene polyol such as a polybutadiene polyol, all corresponding combinations) to form an isocyanate-terminated oligomer, which is then reacted with a hydroxyl-functionalized (meth)acrylate (such as hydroxyethyl (meth)acrylate) to provide terminal (meth)acrylate groups. For example, the (meth)acrylate functionalized urethane oligomer can contain two, three, four, or more (meth)acrylate functional groups per molecule. Other addition sequences can also be used to prepare (meth)acrylate functionalized urethane oligomers. For example, a hydroxy-functional (meth)acrylate can first be reacted with a polyisocyanate to obtain an isocyanate-functional (meth)acrylate, which can then be reacted with a polyol. As a variant, all components can be combined and reacted simultaneously.

[0071] Examples of suitable (meth)acrylate functionalized epoxy oligomers include reaction products of (meth)acrylic acid (or the corresponding synthetic equivalents, such as acid chlorides, alkyl esters or anhydrides) and epoxy resins comprising at least one epoxide group, in particular at least one group selected from glycidyl ethers, glycidyl esters and combinations thereof. The epoxy resins may be selected in particular from bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resins, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-1,4-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis(3,4- Cyclohexene oxide), dicyclopentadiene diepoxide, ethylene glycol di(3,4-epoxycyclohexyl methyl) ether, ethylene bis(3,4-epoxycyclohexane carboxylate), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, by adding one or more alkylene oxides to aliphatic polyols Polyglycidyl ethers of polyether polyols obtained by using alcohols such as ethylene glycol, propylene glycol and glycerol, diglycidyl esters of aliphatic long-chain dibasic acids, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these compounds, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxybutyl stearic acid, epoxyoctyl stearic acid, epoxidized linseed oil, epoxidized polybutadiene, etc.

[0072] Suitable (meth)acrylate functionalized polyether oligomers include, but are not limited to, the reaction products of (meth)acrylic acid (or the corresponding synthetic equivalents, such as acid chlorides, alkyl esters or anhydrides) and at least one polyether alcohol corresponding to a polyether polyol, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or copolymers thereof. Suitable polyether alcohols may be linear or branched materials containing ether bonds and terminal hydroxyl groups. Polyether alcohols may be prepared by ring-opening polymerization of cyclic ethers such as tetrahydrofuran or alkylene oxides (e.g., ethylene oxide and / or propylene oxide) with a starter molecule. Suitable starter molecules include water, polyhydroxy-functionalized materials, polyester polyols and amines.

[0073] Provided (meth)acrylate functionalized polydiene oligomers include, for example, the reaction product of (meth)acrylic acid (or the corresponding synthetic equivalent, such as acid chloride, alkyl ester or anhydride) and a hydroxyl terminated polydiene polyol, especially a hydroxyl terminated polybutadiene polyol.

[0074] Provided (meth)acrylate functionalized polycarbonate oligomers include, for example, the reaction product of (meth)acrylic acid (or the corresponding synthetic equivalent, such as the chlorinated acid, alkyl ester or anhydride) and a hydroxyl terminated polycarbonate polyol.

[0075] The (meth)acrylic acid functionalized polydiene oligomers provided include, for example, the reaction product of (meth)acrylic acid (or the corresponding synthetic equivalent, such as acid chloride, alkyl ester or anhydride) and a hydroxyl-terminated polyester polyol. The reaction process can be carried out so that the hydroxyl groups of the polyester polyol are all or substantially all (meth)acrylic acid esterified, especially in the case where the polyester polyol is difunctional. The polyester polyol can be prepared by the polycondensation reaction of a polyhydroxy-functional component (especially a diol) and a poly(carboxylic acid)-functional compound (especially a dicarboxylic acid and anhydride). The polyhydroxy-functional and poly(carboxylic acid)-functional components can each have a linear, branched, cycloaliphatic or aromatic structure and can be used alone or as a mixture.

[0076] Suitable (meth)acrylate functionalized acrylic oligomers (sometimes also known in the art as "acrylic oligomers") include oligomers that can be described as materials having an acrylic backbone, which are functionalized by one or more (meth)acrylate groups (which can be at the end of the oligomer or pendant to the acrylic backbone). The acrylic backbone can be a homopolymer, a random copolymer, or a block copolymer composed of repeating units of acrylic monomers. The acrylic monomers can be any monomeric (meth)acrylate, such as C1-C6 alkyl (meth)acrylates and functionalized (meth)acrylates such as (meth)acrylates with hydroxyl, carboxylic acid and / or epoxy groups. The acrylic (meth)acrylate oligomers may be prepared using any procedure known in the art, such as oligomerization of monomers, at least a portion of which are functionalized with hydroxyl, carboxylic acid and / or epoxy groups (e.g., hydroxyalkyl (meth)acrylates, (meth)acrylic acid, glycidyl (meth)acrylates), to obtain a functionalized oligomeric intermediate, which is subsequently reacted with one or more (meth)acrylate containing reactants to introduce the desired (meth)acrylate functional groups.

[0077] In particular, component a) may comprise, inter alia, a (meth)acrylate functionalized oligomer selected from the group consisting of: (meth)acrylate functionalized urethane oligomers, (meth)acrylate functionalized polydiene oligomers, (meth)acrylate functionalized acrylic oligomers; and mixtures thereof.

[0078] Component a) may comprise from 0 to 100% by weight, in particular from 5 to 100% by weight, from 10 to 100% by weight, from 15 to 100% by weight, from 20 to 95% by weight, from 25 to 95% by weight, from 30 to 95% by weight, from 35 to 90% by weight, from 40 to 90% by weight, or from 50 to 90% by weight, of the (meth)acrylate-functional oligomer, based on the weight of component a). Component a) may comprise from 0 to 60 wt %, from 5 to 60 wt %, from 10 to 60 wt %, from 15 to 60 wt %, from 20 to 60 wt %, from 25 to 60 wt %, from 30 to 60 wt %, from 35 to 60 wt %, from 40 to 60 wt %, or from 45 to 60 wt %, based on component a), of the (meth)acrylate-functional oligomer. As a variation, component a) may comprise from 60% to 100% by weight, from 65% to 100% by weight, from 70% to 100% by weight, from 75% to 100% by weight, from 80% to 100% by weight, from 85% to 100% by weight, from 90% to 100% by weight, or from 95% to 100% by weight of (meth)acrylate-functional oligomers, based on the weight of component a).

[0079] According to a particular embodiment, component a) comprises:

[0080] - from 10 wt % to 100 wt %, from 20 wt % to 100 wt %, from 30 wt % to 100 wt %, from 40 wt % to 95 wt %, or from 50 wt % to 90 wt % of (meth)acrylate functional monomers; and

[0081] - from 0 to 90 wt %, from 0 to 80 wt %, from 0 to 70 wt %, from 5 to 60 wt %, or from 10 to 50 wt % of (meth)acrylate functionalized oligomer.

[0082] Component b) - Thixotropic additive

[0083] The composition according to the invention comprises a thixotropic additive, also referred to as component b). The thixotropic additive is used in particular to increase the viscosity of the composition according to the invention and / or to impart thixotropic properties thereto. For the purposes of the present invention, the term "imparting thixotropic properties to the composition" means increasing the viscosity of the composition when it is at rest (no shear pressure is applied) and reducing the viscosity of the composition in a reversible manner using a memory history or in a time-dependent manner when the composition is subjected to shear pressure. The increase and decrease in viscosity can be determined relative to a control composition not comprising any thixotropic additive.

[0084] Component b) comprises a diurea-diurethane compound. Component b) may comprise a mixture of polyurea-diurethane compounds. Component b) may further comprise an aprotic solvent.

[0085] Component b) is stable, although it contains little or no salt. Component b) contains less than 0.1 mol of salt per urea group in component b) (excluding any aprotic solvent). The number of urea groups is determined relative to all compounds contained in component b) (excluding any aprotic solvent). The (one or more) diurea-diurethane compounds contain 2 urea groups. If component b) contains 1 mol of (one or more) diurea-diurethane compounds and no other compounds having at least one urea group are present in component b), component b) contains less than 0.2 mol of salt.

[0086] In particular, component b) may contain from 0 to less than 0.1 mol, or from 0 to 0.09 mol, or from 0 to 0.07 mol, or from 0 to 0.05 mol, or from 0 to 0.03 mol, or from 0 to 0.01 mol, or from 0 to 0.001 mol of salt per urea group in component b) (excluding any aprotic solvent).

[0087] More particularly, component b) may contain less than 1 wt.-%, or from 0 to 0.9 wt.-%, or from 0 to 0.7 wt.-%, or from 0 to 0.5 wt.-%, or from 0 to 0.25 wt.-%, or from 0 to 0.2 wt.-%, or from 0 to 0.15 wt.-%, or from 0 to 0.09 wt.-%, or from 0 to 0.03 wt.-% LiCl, relative to the weight of component b) (excluding any aprotic solvent).

[0088] More particularly, component b) may contain less than 1.6 wt.-%, or from 0 wt.-% to 1.4 wt.-%, or from 0 wt.-% to 1.1 wt.-%, or from 0 wt.-% to 0.8 wt.-%, or from 0 wt.-% to 0.4 wt.-%, or from 0 wt.-% to 0.3 wt.-%, or from 0 wt.-% to 0.25 wt.-%, or from 0 wt.-% to 0.15 wt.-%, or from 0 wt.-% to 0.05 wt.-% LiNO 3 , relative to the weight of component b) (excluding any aprotic solvent).

[0089] The salt may be selected in particular from metal salts, ionic liquids and ammonium salts. In particular, the salt may be a metal salt selected from halides, acetates, formates or nitrates. More particularly, the salt may be a lithium salt. Still more particularly, the salt may be a lithium salt selected from LiCl, LiNO3, LiBr and mixtures thereof.

[0090] Component b) may be particularly stable without the addition of stabilizers such as in particular surfactants. According to a specific embodiment, component b) according to the invention contains less than 0.1 mol of surfactant per urea group in component b).

[0091] In particular, component b) contains from 0 to 0.1 mol, or from 0 to 0.08 mol, or from 0 to 0.06 mol, or from 0 to 0.04 mol, or from 0 to 0.02 mol, or from 0 to 0.01 mol, or from 0 to 0.001 mol of surfactant (excluding any aprotic solvent) per urea group in component b).

[0092] More particularly, component b) may contain less than 3 wt.%, or from 0 wt.% to 2.8 wt.%, or from 0 wt.% to 2.4 wt.%, or from 0 wt.% to 2 wt.%, or from 0 wt.% to 1.6 wt.%, or from 0 wt.% to 1.2 wt.%, or from 0 wt.% to 1 wt.%, or from 0 wt.% to 0.5 wt.%, or from 0 wt.% to 0.1 wt.%, or from 0 wt.% to 0.01 wt.% of surfactant, relative to the weight of component b) (excluding any aprotic solvent).

[0093] The surfactant may in particular be chosen from anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants and mixtures thereof. The surfactant may in particular have an HLB of from 8 to 12.

[0094] Examples of anionic surfactants are sulfonates, sulfates, sulfosuccinates, phosphates and carboxylates. Examples of cationic surfactants are quaternary ammonium salts (especially tetraalkylammonium salts and quaternary ammonium esters or esterases). Examples of nonionic surfactants are alkoxylated (especially ethoxylated and / or propoxylated) fatty alcohols, alkyl glycosides, esters of fatty acids (especially glycol esters, glycerides, sorbitol esters or sucrose esters of fatty acids) and alkoxylated (especially ethoxylated and / or propoxylated) esters of fatty acids. Examples of zwitterionic surfactants are betaines, imidazolines, sultaines, phospholipids and amine oxides.

[0095] Component b) may have an NCO index of less than 0.5 mg KOH / g, particularly less than 0.2 mg KOH / g, more particularly less than 0.1 mg KOH / g, still more particularly 0 mg KOH / g. The NCO index may be measured according to the method described below.

[0096] Diurea-diurethane compounds

[0097] Component b) comprises a diurea-diurethane compound. Component b) may comprise a mixture of diurea-diurethane compounds.

[0098] The diurea-diurethane compound may correspond to a compound of formula (I):

[0099]

[0100] wherein R', R2 and R3 groups are as defined below.

[0101] Preferably, the compound of formula (I) does not contain a tertiary amine functional group or a quaternary ammonium salt functional group.

[0102] The compound(s) of formula (I) may in particular correspond to the reaction product of at least one alcohol of formula R′—OH, at least one diisocyanate of formula OCN—R 2 —NCO, and at least one diamine of formula H 2 N—R 3 —NH 2 .

[0103] Component b) may particularly comprise 5 to 80 mol %, in particular 15 to 75 mol %, more particularly 25 to 65 mol % of compounds of formula (I), relative to the total molar amount of compounds having one or more functional groups selected from urea, urethane and mixtures thereof (excluding any aprotic solvent).

[0104] R' Group

[0105] The compound of formula (I) contains two R' groups. The R' groups of the same compound of formula (I) may be the same or different. Component b) may contain a mixture of compounds of formula (I) having the same R' groups. Component b) may contain a mixture of compounds of formula (I) that are different in terms of R' groups. For example, some compounds of the mixture may have the same R' groups, and some compounds of the mixture may have different R' groups.

[0106] Each R' group may be derived from the use of an alcohol of formula R'-OH to form (one or more) diurea-diurethane compounds of formula (I). The R' group may correspond to the residue of an alcohol of formula R'-OH in the absence of an OH group. The R' groups of formula R'-OH and the corresponding alcohols described below are also suitable for use in the process described below for preparing diurea-diurethane compounds.

[0107] Each R' is independently selected from alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, -[(CR a R b ) n -O] m -Y and ·-[(CR c R d ) p -C(=O)O] q -Z;

[0108] The symbol · represents the point of attachment to the carbamate group of formula (I);

[0109] Y and Z are independently selected from alkyl, alkenyl, cycloalkyl, aryl and arylalkyl;

[0110] R a , R b , R c and R d Independently selected from H and methyl, especially H;

[0111] Each n is independently equal to 2, 3 or 4, in particular n is 2;

[0112] m ranges from 1 to 30, in particular m ranges from 2 to 25;

[0113] p ranges from 3 to 5, in particular p is 5;

[0114] q ranges from 1-20, in particular q ranges from 2-10.

[0115] The R' group can be an alkyl group, especially C1 to C 30 Examples of suitable alkyl groups are methyl, propyl, 1-methylethyl, butyl, X 1-2 -Methylpropyl, pentyl, X 1-3-Methylbutyl, hexyl, X 1-4 -Methylpentyl, heptyl, X 1-5 -Methylhexyl, octyl, X 1-6 -Methylheptyl, 2-ethylhexyl, nonyl, X 1-7 -Methyloctyl, decyl, X 1-8 -Methylnonyl, undecyl, X 1-9 -Methyldecyl, dodecyl, X 1-10 -Methylundecyl, tridecyl, X 1-11 -Methyldodecyl, 2,5,9-trimethyldecyl, tetradecyl, X 1-12 -Methyltridecyl, pentadecyl, X 1-13 -Methyltetradecyl, hexadecyl, X 1-14 -Methylpentadecyl, heptadecyl, X 1-15 -Methylhexadecyl, octadecyl, X 1-16 -Methyl heptadecyl, nonadecyl, X 1-17 -Methyloctadecyl, eicosyl, X 1-18 -Methyl nonadecyl, heneicosyl, X 1-19 -Methyleicosyl, docosyl, X 1-20 -methylheneicosyl, 2-propylheptyl, 2-propylnonyl, 2-pentylnonyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl, 6-methyldodecyl and isomers thereof, wherein X a-b represents an integer that can take any value from a to b, X a-b Indicates the position of the substituent in the alkyl group. 1-11 -Methyldodecyl groups are dodecyl groups substituted with methyl groups in the 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11 positions, for example 11-methyldodecyl or 2-methyldodecyl. The term "isomer" is understood to mean that the alkyl groups contain the same number of carbon atoms but have different substitution schemes, for example ethyl substituents replace methyl substituents or a greater number of methyl substituents. Thus, 2,5,9-trimethyldodecyl groups are isomers of 11-methyldodecyl or 2-methyldodecyl groups. The alkyl groups mentioned above can be particularly bound to a carbamate group in the 1 position. Thus, 2,5,9-trimethyldodecyl groups can be represented by the following formula:

[0116]

[0117] Therein the broken line represents the point of attachment to the carbamate group of the compound of formula (I).

[0118] The R' group can be an alkenyl group, especially a C2 to C 30 Examples of suitable alkenyl groups are hex-Y 2-5 -Alkenyl, heptyl-Y 2-6 -Alkenyl, octyl-Y 2-7 -Alkenyl, nonyl-Y 2-8 -Alkenyl, Decyl-Y 2-9 -alkenyl, undecyl-Y 2-10 -alkenyl, dodeca-Y 2-11 -alkenyl, tridecan-Y 2-12 -alkenyl, tetradeca-Y 2-13 -Alkenyl, Hexadecene 2-15 -alkenyl, octadecyl- 2-17 -alkenyl, eicosyl 2-19 -alkenyl, dioctyl- 2-21 -alkenyl, hepta-8,11-dienyl, octa-9,12-dienyl, nonadeca-10,13-dienyl, eicos-11,14-dienyl, eicos-13,16-dienyl, octa-5,9,12-trienyl, octa-6,9,12-trienyl, octa-9,12,15-trienyl, octa-9,11,13-trienyl, eicos-8,11,14-trienyl and eicos-11,14,17-trienyl, wherein Y a-b represents an integer that can take any value from a to b, Y a-b Indicates the position of the double bond in the alkenyl group. 2-5 -Alkenyl groups are hexenyl groups in which the double bond may be in the 2, 3, 4 or 5 position, which corresponds to hex-2-enyl, hex-3-enyl, hex-4-enyl and hex-5-enyl groups. The alkenyl groups mentioned above may in particular be bonded to the carbamate group in the 1 position. Thus, a hex-2-enyl group may be represented by the formula:

[0119]

[0120] Therein the broken line represents the point of attachment to the carbamate group of the compound of formula (I).

[0121] The R' group can be a cycloalkyl group, especially a C5 to C 12 Cycloalkyl. Examples of suitable cycloalkyl groups are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl.

[0122] The R' group can be an aromatic group, especially a C6 to C 12 Aryl. Examples of suitable aryl groups are phenyl, naphthyl, biphenyl, o-, m- or p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-xylyl and mesityl.

[0123] The R' group can be an arylalkyl group, especially a C7 to C 12 Arylalkyl. Examples of suitable arylalkyl groups are benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl and 2-phenylbutyl.

[0124] The R' group can be -[(CR a R b ) n -O] m -Y group, wherein:

[0125] Y is selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl and arylalkyl;

[0126] R a and R b Independently selected from H and methyl, especially H;

[0127] Each n is independently equal to 2, 3 or 4, in particular n is 2;

[0128] m ranges from 1 to 30, in particular m ranges from 2 to 25;

[0129] ·-[(CR a R b ) n -O] m Examples of -Y groups are alkoxylated derivatives of the alkyl, alkenyl, cycloalkyl, aryl and alkylaryl groups described above. Polyethylene glycols, polypropylene glycols, co-(ethylene glycol / propylene glycol) and polytetramethylene glycols containing terminal groups selected from the alkyl, alkenyl, cycloalkyl, aryl and arylalkyl groups described above are particularly suitable. These groups are obtainable in particular by reacting an alcohol R'OH having an R' group as described above with a cyclic compound selected from ethylene oxide, propylene oxide, tetrahydrofuran and mixtures thereof.

[0130] The R' group can be -[(CR c R d ) p -C(=O)O] q -Z group, wherein:

[0131] Z is selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl and arylalkyl;

[0132] R c and R d Independently selected from H and methyl, especially H;

[0133] p ranges from 3 to 5, in particular p is 5;

[0134] q ranges from 1-20, in particular q ranges from 2-10.

[0135] ·-[(CR c R d ) p -C(=O)O] q Examples of -Z groups are esterified derivatives of the alkyl, alkenyl, cycloalkyl, aryl and arylalkyl groups described above. Polyesters containing terminal groups selected from the group consisting of alkyl, alkenyl, cycloalkyl, aryl and arylalkyl groups as described above are particularly suitable. These groups are obtainable in particular by reacting an alcohol R'OH having an R' group as described above with a lactone selected from the group consisting of γ-butyrolactone, δ-valerolactone, ε-caprolactone and mixtures thereof.

[0136] According to one embodiment, each R' is independently selected from alkyl and -[(CR a R b ) n -O] m -Y, as defined above. In particular, each R' is independently selected from a linear or branched C1-C 30 Alkyl and -[CH2-CH2-O] m -Y, where Y is C1-C 24 alkyl and m ranges from 1 to 25. More particularly, each R' is independently selected from a branched C8-C 20 Alkyl and -[CH2-CH2-O] m -Y, wherein Y is a C1-C6 alkyl group and m ranges from 2 to 20.

[0137] Still more particularly, each R' is independently selected from octyl, X 1-6 -Methylheptyl, 2-ethylhexyl, nonyl, X 1-7 -Methyloctyl, decyl, X 1-8 -Methylnonyl, undecyl, X 1-9 -Methyldecyl, dodecyl, X 1-10 -Methylundecyl, tridecyl, X 1-11 -Methyldodecyl, 2,5,9-trimethyldecyl, tetradecyl, X 1-12 -Methyltridecyl, pentadecyl, X 1-13 -Methyltetradecyl, hexadecyl, X 1-14 -Methylpentadecyl, heptadecyl, X 1-15 -Methylhexadecyl, octadecyl, X 1-16 -Methyl heptadecyl, nonadecyl, X 1-17 -Methyloctadecyl, eicosyl, X 1-18 -Methyl nonadecanyl, heneicosyl, X 1-19 -Methyleicosyl, docosyl, X 1-20-methylheneicosyl, 2-propylheptyl, 2-propylnonyl, 2-pentylnonyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 2-octyldodecyl, 2-decyltetradecyl, 6-methyldodecyl and isomers thereof, -[CH2-CH2-O]3-(CH2)3-CH3, and -[CH2-CH2-O] m -CH3, wherein m=2 to 20.

[0138] The compounds of formula (I) may have identical or different R' groups. The compounds of formula (I) may have R' groups with different molecular weights. The compounds of formula (I) may have R' groups with different chemical properties, in particular hydrophilicity.

[0139] Component b) may comprise compounds of formula (I) in which the R' groups are identical. Component b) may comprise compounds of formula (I) in which the R' groups are different. Component b) may comprise compounds of formula (I) in which the R' groups are identical and compounds of formula (I) in which the R' groups are different.

[0140] Component b) may especially comprise compounds of formula (I) in which the R' groups are identical. The R' groups may be identical and correspond to R1, which is a linear or branched C1-C 30 Alkyl, especially linear or branched C8-C 20 Alkyl, more particularly branched C8-C 20 Alkyl is as described above.

[0141] Component b) may in particular comprise a mixture of compounds of formula (I), said mixture containing at least one compound of formula (I) in which the R' groups are different. The mixture may contain at least one compound of formula (I) in which the R' groups have different molecular weights. The mixture may contain at least one compound of formula (I) in which the R' groups have different chemical properties, in particular hydrophilicity.

[0142] Thixotropic additives comprising compounds of formula (I) in which the R' groups are different can be obtained in particular by using a mixture of at least 2 different alcohols R'-OH, in particular corresponding to R4-OH and R5-OH, to form the compound(s) of formula (I).

[0143] In particular, the mixture of compounds of formula (I) may contain:

[0144] at least one compound of formula (I) in which the R' groups are different, one of the R' groups corresponding to R4 and the other R' group corresponding to R5;

[0145] - optionally compounds of formula (I) in which the R' groups are identical and correspond to R4;

[0146] - optionally compounds of formula (I) in which the R' groups are identical and correspond to R5;

[0147] R4 and R5 are as defined above for R'.

[0148] The mixture of compounds of formula (I) may in particular comprise compounds of formula (Ia), optionally as a mixture with compounds of formula (Ib) and / or compounds of formula (Ic):

[0149]

[0150] in:

[0151] All R4 groups are the same and as defined above for R';

[0152] All R5 groups are the same and as defined above for R';

[0153] The R4 group is different from the R5 group.

[0154] The R4 group may be more hydrophobic than the R5 group; and / or the R5 group may have a higher molecular weight than the molecular weight of the R4 group.

[0155] The molecular weight of R4 and R5 groups can be different. Particularly, the R4 group can have a molecular weight lower than the molecular weight of the R5 group. More particularly, the difference between the molecular weight of the R4 group and the molecular weight of the R5 group can be at least 50, at least 100, at least 150, at least 200, at least 300 or at least 350 g / mol.

[0156] The chemical nature of the R4 and R5 groups may be different. In particular, the R4 group may be more hydrophobic than the R5 group.

[0157] The R4 and R5 groups may be of the formula -[(CR a R b ) n -O] m -Y group, Y, R a , R b , n and m are as defined above. Alternatively, the R4 group may be a linear or branched C1-C 30 Alkyl, and the R5 group can be of the formula -[(CR a R b ) n -O] m -Y group, where Y, R a , R b , n and m are as defined above.

[0158] The total molar amount of R5 groups, in particular the least hydrophobic groups and / or the groups with the highest molecular weight, may in particular account for more than 20%, in particular from 25% to 95%, 30% to 90%, 35% to 85%, or 40% to 80% of the total molar amount of R4 and R5 groups of all products having one or more functional groups selected from urea, carbamate and mixtures thereof in component b) (excluding any aprotic solvent).

[0159] Component b) may in particular comprise a mixture of compounds of formula (I), the mixture containing at least two different compounds of formula (I) in which the R' groups are different. The mixture may contain at least two different compounds of formula (I) in which the R' groups have different molecular weights. The mixture may contain at least two different compounds of formula (I) in which the R' groups have different chemical properties, in particular hydrophilicity.

[0160] Thixotropic additives comprising at least two compounds of formula (I) in which the R' groups are different can be obtained in particular by using a mixture of at least 3 different alcohols R'-OH, in particular corresponding to R4-OH, R5-OH and R6-OH, to form the diurea-diurethane compound(s) of formula (I).

[0161] Mixtures of compounds of formula (I) may contain:

[0162] at least one compound of formula (I) in which the R' groups are different, one of the R' groups corresponding to R4 and the other R' group corresponding to R5; and

[0163] at least one compound of formula (I) in which the R' groups are different, one of the R' groups corresponding to R4 and the other R' group corresponding to R6;

[0164] - optionally compounds of formula (I) in which the R' groups are different, one of the R' groups corresponding to R5 and the other R' group corresponding to R6;

[0165] - optionally compounds of formula (I) in which the R' groups are identical and correspond to R4;

[0166] - optionally compounds of formula (I) in which the R' groups are identical and correspond to R5;

[0167] - optionally compounds of formula (I) in which the R' groups are identical and correspond to R6;

[0168] R4, R5 and R6 are as defined above for R'.

[0169] The mixture of compounds of formula (I) may in particular comprise a compound of formula (Ia), a compound of formula (Id) and optionally one or more compounds of formula (Ib), (Ic), (Ie) or (If) represented below:

[0170]

[0171] in:

[0172] All R4 groups are the same and as defined above for R';

[0173] All R5 groups are the same and as defined above for R';

[0174] All R6 groups are the same and as defined above for R';

[0175] The R4 group is different from the R5 group.

[0176] The R4 group is different from the R6 group.

[0177] The R5 group is different from the R6 group.

[0178] The R4 group may be more hydrophobic than the R5 group and / or the R6 group; and / or the R4 group may have a lower molecular weight than the molecular weight of the R5 group and / or the molecular weight of the R6 group.

[0179] The molecular weights of the R4, R5 and R6 groups may be different. In particular, the R4 group may have a molecular weight lower than the molecular weight of the R5 group; and / or the R4 group may have a molecular weight lower than the molecular weight of the R6 group; and / or the R5 group may have a molecular weight lower than the molecular weight of the R6 group. More particularly, the R4 group has a molecular weight lower than the molecular weights of the R5 and R6 groups. Still more particularly, the difference between the molecular weight of the R4 group and the molecular weight of the R5 group; and / or the difference between the molecular weight of the R4 group and the molecular weight of the R6 group; and / or the difference between the molecular weight of the R5 group and the molecular weight of the R6 group may be at least 50, at least 100, at least 150, at least 200, at least 300 or at least 350 g / mol.

[0180] The R4, R5 and R6 groups may have different chemical properties. In particular, the R4 group may be more hydrophobic than the R5 group; and / or the R4 group may be more hydrophobic than the R6 group; and / or the R5 group may be more hydrophobic than the R6 group. More particularly, the R4 group is more hydrophobic than the R5 and R6 groups.

[0181] The R4 group can be a linear or branched C1-C 30 alkyl, and the R5 and R6 groups may be of the formula -[(CR a R b ) n-O] m -Y group, Y, R a , R b , n and m are as defined above.

[0182] The total molar amount of R5 and R6 groups, in particular the least hydrophobic groups and / or the groups with the highest molecular weight, may in particular account for more than 20%, in particular from 25% to 95%, 30% to 90%, 35% to 85% or 40% to 80% of the total molar amount of R4, R5 and R6 groups of all products having one or more functional groups selected from urea, carbamate and mixtures thereof in component b) (excluding any aprotic solvent).

[0183] According to a preferred embodiment, more than 20 mol %, in particular from 25 to 95 mol %, 30 to 90 mol %, 35 to 85 mol %, or 40 to 80 mol % of all R' groups contained in the compound(s) of formula (I) are hydrophilic groups, in particular -[(CR a R b ) n -O] m -Y group.

[0184] The R' group may in particular be the residue of one or more alcohols of the formula R'-OH in the absence of an OH group. The alcohol R'-OH may in particular be selected from C1 to C 30 Alkanes, C2 to C 30 Olefins, C5 to C 12 Cycloalkanes, C6 to C 12 Aromatic hydrocarbons, C7 to C 12 Arylalkanes, HO-[(CR a R b ) n -O] m -Y and HO-[(CR c R d ) p -C(=O)O] q -Z.

[0185] Y and Z are independently selected from C1 to C 30 Alkyl, C2 to C 30 Alkenyl, C5 to C 12 Cycloalkyl, C6 to C 12 Aryl and C7 to C 12 Arylalkyl;

[0186] R a , R b , R c and Rd Independently selected from H and methyl, especially H;

[0187] Each n is independently equal to 2, 3 or 4, in particular n is 2;

[0188] m ranges from 1 to 30, in particular m ranges from 2 to 25;

[0189] p ranges from 3 to 5, in particular p is 5;

[0190] q ranges from 1-20, in particular q ranges from 2-10.

[0191] C1 to C 30 The alkane may be selected in particular from octan-1-ol, octan-2-ol, X 1-6 -methylheptane-1-ol, 2-ethylhexane-1-ol, nonane-1-ol, X 1-7 -Methyloctan-1-ol, decan-1-ol, X 1-8 -Methylnonane-1-ol, undecane-1-ol, X 1-9 -Methyldecane-1-ol, dodecan-1-ol, X 1-10 -Methylundecane-1-ol, tridecane-1-ol, X 1-11 -Methyl dodecan-1-ol, 2,5,9-trimethyl decan-1-ol, tetradecan-1-ol, X 1-12 -Methyltridecane-1-ol, pentadecane-1-ol, X 1-13 -methyltetradecane-1-ol, hexadecane-1-ol, X 1-14 -Methylpentadecan-1-ol, heptadecan-1-ol, X 1-15 -Methylhexadecan-1-ol, octadecane-1-ol, X 1-16 -Methylheptadecan-1-ol, nonadecan-1-ol, X 1-17 -Methyloctadecane-1-ol, eicosan-1-ol, X 1-18 -Methylnonadecan-1-ol, heneicosane-1-ol, X 1-19 -Methyleicosan-1-ol, docosan-1-ol, X 1-20 -methyl heneicosane-1-ol, 2-propyl heptane-1-ol, 2-propyl nonane-1-ol, 2-pentyl nonane-1-ol, 2-butyl octane-1-ol, 2-butyl decane-1-ol, 2-hexyl octane-1-ol, 2-hexyl decane-1-ol, 2-octyl decane-1-ol, 2-hexyl dodecane-1-ol, 2-octyl dodecane-1-ol, 2-decyl tetradecane-1-ol, 6-methyl dodecane-1-ol and isomers thereof, wherein X a-b represents an integer that can take any value from a to b, X a-bIndicates the position of the alkyl substituent on the alkane. 1-11 -Methyldodecan-1-ol is a dodecane substituted by an OH group in position 1 and by a methyl group in position 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, for example 2-methyldodecan-1-ol or 11-methyldodecan-1-ol. The term "isomer" is understood to mean that the alkane contains the same number of carbon atoms but has a different substitution scheme, for example ethyl substituents instead of methyl substituents or a greater number of methyl substituents. Thus, 2,5,9-trimethyldodecan-1-ol is an isomer of 2-methyldodecan-1-ol and 11-methyldodecan-1-ol. Preferably, the C1 to C2 substituted by the OH group 30 The alkane is selected from 11-methyldodecan-1-ol and 2,5,9-trimethyldodecan-1-ol.

[0192] C2 to C 30 The olefin may be selected in particular from Y 2-5 -Hexen-1-ol, Y 2-6 -heptene-1-ol, Y 2-7 -Octene-1-ol, Y 2-8 -nonen-1-ol, Y 2-9 -Decen-1-ol, Y 2-10 -Undecene-1-ol, Y 2-11 -Dodecene-1-ol, Y 2-12 -Tridecene-1-ol, Y 2-13 -Tetradecene-1-ol, Y 2-15 -Hexadecene-1-ol, Y 2-17 -Octadecen-1-ol, Y 2-19 -eicosene-1-ol, Y 2-21 -eicosene-1-ol, heptadeca-8,11-diene-1-ol, octadeca-9,12-diene-1-ol, nonadeca-10,13-diene-1-ol, eicosene-11,14-diene-1-ol, eicosene-13,16-diene-1-ol, octadeca-5,9,12-triene-1-ol, octadeca-6,9,12-triene-1-ol, octadeca-9,12,15-triene-1-ol, octadeca-9,11,13-triene-1-ol, eicosene-8,11,14-triene-1-ol, eicosene-11,14,17-triene-1-ol, wherein Y a-b represents an integer that can take any value from a to b, Y a-b Indicates the position of the double bond in the olefin. 2-5 -Hexen-1-ol is a hexene substituted by OH in the 1-position, wherein the double bond may be in the 2-, 3-, 4- or 5-position.

[0193] C5 to C 12The cycloalkane may in particular be chosen from cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, cyclodecanol, cycloundecanol and cyclododecanol, preferably cyclopentanol and cyclohexanol.

[0194] C6 to C 12 The aromatic hydrocarbons may in particular be chosen from phenol, 1- or 2-naphthol, 2-, 3- or 4-phenylphenol, 2-, 3- or 4-methylphenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenol and 2,4,6-, 2,3,5- or 2,3,6-trimethylphenol.

[0195] C7 to C 12 The arylalkane may in particular be chosen from benzyl alcohol, 2-phenylethane-1-ol, 3-phenylpropane-1-ol, 4-phenylbutane-1-ol, and 2-phenylbutane-1-ol, preferably benzyl alcohol and 2-phenylethane-1-ol.

[0196] Alcohol HO-[(CR a R b ) n -O] m -Y may be selected in particular from C1 to C 30 Alkoxylated derivatives of alkanes, C2 to C substituted with OH groups as defined above 30 Alkoxylated derivatives of olefins, C5 to C substituted with OH groups as defined above 12 Alkoxylated derivatives of cycloalkanes, C6 to C substituted with OH groups as defined above 12 Alkoxylated derivatives of aromatic hydrocarbons, C7 to C substituted with OH groups as defined above 12 Alkoxylated derivatives of arylalkanes. The alkoxylated derivatives may in particular be ethoxylated, propoxylated and / or butoxylated derivatives, preferably ethoxylated derivatives. Preferably, the alcohol HO-[(CR a R b ) n -O] m -Y is chosen from polyethylene glycol monomethyl ether (MPEG), polyethylene glycol monoethyl ether and polyethylene glycol monobutyl ether; more preferably MPEG having a number average molecular weight from 200 to 1000 g / mol (in particular MPEG-250, MPEG-350, MPEG-400, MPEG-450, MPEG-500, MPEG-550, MPEG-650 or MPEG-750), or triethylene glycol monobutyl ether (also known as butyl triglycol (BTG).

[0197] Alcohol HO-[(CR c R d )p -C(=O)O] q -Z may in particular be a C1 to C 30 polyester derivatives of alkanes, C2 to C substituted by OH groups as defined above 30 Polyester derivatives of olefins, C5 to C substituted by OH groups as defined above 12 The polyester derivatives of cycloalkanes, C6 to C6 substituted by OH groups as defined above 12 A polyester derivative of an aromatic hydrocarbon, a C7 to C16 hydrocarbon substituted with an OH group as defined above 12 Polyester derivatives of arylalkanes. The polyester derivatives may in particular comprise a polyester moiety obtained by ring-opening polymerization of a lactone, preferably selected from the group consisting of gamma-butyrolactone, delta-valerolactone, epsilon-caprolactone and mixtures thereof.

[0198] R2 Group

[0199] The compound of formula (I) contains two R2 groups. The R2 groups of the compounds of the same formula (I) may be the same or different. Component b) may comprise a mixture of compounds of formula (I) with the same R2 groups. Component b) may comprise a mixture of compounds of formula (I) in which the R2 groups are different. For example, some compounds of the mixture may have the same R2 groups, and some compounds of the mixture may have different R2 groups.

[0200] Each R2 group may be derived from the use of a diisocyanate of the formula OCN-R2-NCO to form (one or more) diurea-diurethane compounds of formula (I). The R2 group may correspond to the residue of a diisocyanate of the formula OCN-R2-NCO in the absence of an NCO group. The R2 groups of the formula OCN-R2-NCO described below and the corresponding diurethanes are also suitable for use in the process according to the invention.

[0201] Each R2 is independently a divalent group selected from aliphatic groups, cycloaliphatic groups, aromatic groups and araliphatic groups.

[0202] According to one embodiment, each R2 is independently an aromatic group.

[0203] In particular, each R2 is independently an aromatic group having the formula:

[0204]

[0205] wherein the symbol · represents the point of attachment to the urea or urethane group of formula (I).

[0206] More particularly, each R2 is independently an aromatic group having one of the following formulae:

[0207]

[0208] wherein the symbol · represents the point of attachment to the urea or urethane group of formula (I).

[0209] Component b) may in particular have more than 85 mol %, more than 90 mol %, more than 95 mol %, more than 97 mol %, more than 98 mol %, more than 99 mol %, or 100 mol % of all R2 groups contained in the compound(s) of formula (I) being aromatic groups of the formula:

[0210]

[0211] wherein the symbol · represents the point of attachment to the urea or urethane group of formula (I).

[0212] In particular, component b) may have from 86 to 100 mol%, from 90 to 100 mol%, from 95 to 100 mol%, from 97 to 100 mol%, from 98 to 100 mol%, from 99 to 100 mol%, or 100 mol% of all R2 groups contained in the compound(s) of formula (I) which are aromatic groups of the formula:

[0213]

[0214] wherein the symbol · represents the point of attachment to the urea or urethane group of formula (I).

[0215] The R2 group is bonded on one side to a urethane group (deriving from the reaction between an isocyanate group of the diisocyanate OCN-R2-NCO and an OH group of the alcohol R′OH) and on the other side to a urea group (deriving from the reaction between another isocyanate group of the diisocyanate OCN-R2-NCO and an NH2 group of the diamine H2N-R3-NH2).

[0216] Still more particularly, each R2 is independently an aromatic group of the formula:

[0217]

[0218] wherein the symbol ★ represents the point of attachment to the carbamate group of formula (I), and the symbol represents the point of attachment to the urea group of formula (I).

[0219] When the R2 group is asymmetric, one side of the R2 group preferably binds to the carbamate group and the other side preferably binds to the urea group. Without wishing to be bound by any one theory, the applicant company assumes that the least hindered side of the R2 group preferably binds to the carbamate group.

[0220] Component b) may in particular have more than 60 mol %, more than 65 mol %, more than 70 mol %, more than 75 mol %, more than 80 mol %, more than 85 mol %, or more than 90 mol % of all R2 groups contained in the compound(s) of formula (I) being aromatic groups of the formula:

[0221]

[0222] wherein the symbol ★ represents the point of attachment to the carbamate group of formula (I), and the symbol represents the point of attachment to the urea group of formula (I).

[0223] In particular, component b) may have from 61 to 100 mol%, from 65 to 100 mol%, from 70 to 100 mol%, from 75 to 100 mol%, from 80 to 100 mol%, from 85 to 100 mol%, or from 90 to 100 mol% of all R2 groups contained in the compound(s) of formula (I) which are aromatic groups of the formula:

[0224]

[0225] wherein the symbol ★ represents the point of attachment to the carbamate group of formula (I), and the symbol represents the point of attachment to the urea group of formula (I).

[0226] The R2 group may in particular be the residue of one or more diisocyanates of the formula OCN-R2-NCO in the absence of an NCO group. The diisocyanate of the formula OCN-R2-NCO may be toluene diisocyanate (TDI). TDI may be in the form of one or more isomers selected from toluene-2,4-diisocyanate and toluene-2,6-diisocyanate.

[0227] In the context of the present invention, it is advantageous to use TDI containing a high proportion of toluene-2,4-diisocyanate, in fact even TDI containing only toluene-2,4-diisocyanate. The applicant company assumes that the asymmetry of this compound can reduce the amount of by-products in component b), in particular compounds of formula (II). This makes it possible to obtain compounds of formula (I) having a high proportion, or even consisting only of R2 groups according to the following formula:

[0228]

[0229] wherein the symbol ★ represents the point of attachment to the carbamate group of formula (I), and the symbol represents the point of attachment to the urea group of formula (I).

[0230] In particular, the diisocyanate of the formula OCN-R2-NCO is a TDI containing more than 85 mol%, more than 90 mol%, more than 95 mol%, more than 97 mol%, more than 98 mol%, more than 99 mol%, or 100 mol% of toluene-2,4-diisocyanate, based on the total amount of toluene diisocyanate isomers. More particularly, the diisocyanate of the formula OCN-R2-NCO is a TDI containing from 86 to 100 mol%, from 90 to 100 mol%, from 95 to 100 mol%, from 97 to 100 mol%, from 98 to 100 mol%, from 99 to 100 mol%, or 100 mol% of toluene-2,4-diisocyanate, based on the total amount of toluene diisocyanate isomers. Preferably, the diisocyanate of the formula OCN-R2-NCO is a TDI containing 100 mol% of toluene-2,4-diisocyanate, based on the total amount of toluene diisocyanate isomers.

[0231] R3 group

[0232] The compound of formula (I) contains an R3 group. Component b) may comprise a mixture of compounds of formula (I) having the same R3 group. Component b) may comprise a mixture of compounds of formula (I) in which the R3 groups are different.

[0233] Each R3 group may be derived from the use of a diamine of the formula H2N-R3-NH2 to form the (one or more) biurea-dicarbamate compounds of formula (I). The R3 group may correspond to the residue of the diamine of the formula H2N-R3-NH2 in the absence of the NH2 groups. The R3 groups and the corresponding diamines of the formula H2N-R3-NH2 described below also apply to the process according to the invention.

[0234] Each R3 is independently a divalent group selected from aliphatic groups, cycloaliphatic groups, aromatic groups, araliphatic groups and heterocyclic groups.

[0235] According to a particular embodiment, each R3 is independently selected from C2-C 24 alkylene, -(CR h R i ) s -[A-(CR j R k ) t u -, -(CR l R m ) v -CY-(CR n R o ) w -, and -(CR p R q ) x -CY-(CH2)​y -CY-(CR r R s ) z -group;

[0236] in:

[0237] A is O or NX;

[0238] R h , R i , R j , R k , R l , R m , R n , R o , R p , R q , R r and R s Independently selected from H and methyl, especially H;

[0239] X is C1 to C6 alkyl, especially methyl or ethyl;

[0240] CY is a ring selected from phenyl, cyclohexyl, naphthyl, decahydronaphthyl, piperazinyl, triazinyl and pyridinyl, said ring being unsubstituted or substituted with 1 to 3 C1-C4 alkyl groups;

[0241] s ranges from 2 to 4, in particular s is 2;

[0242] t ranges from 2 to 4, in particular t is 2;

[0243] u ranges from 1 to 30;

[0244] v, w, x, y and z independently range from 0 to 4.

[0245] Each R3 may in particular be selected from C2-C 24 Alkylene and -(CR l R m ) v -CY-(CR n R o ) w -group;

[0246] Especially selected from C2-C 18 Alkylene and -(CH2) v -CY-(CH2) w -, wherein CY is a cyclohexyl group or a benzene ring, the ring is unsubstituted or substituted with 1 to 3 C1-C4 alkyl groups, and v and w range from 0 to 1.

[0247] More particularly, each R3 may be a group selected from C2-C6 alkylene and a group having the formula:

[0248]

[0249] wherein the symbol · represents the point of attachment to the urea group of the compound of formula (I).

[0250] Component b) may in particular have more than 85 mol %, more than 90 mol %, more than 95 mol %, more than 97 mol %, more than 98 mol %, more than 99 mol %, or 100 mol % of all R3 groups contained in the compound(s) of formula (I) being groups of the formula:

[0251]

[0252] In particular, component b) may have from 86 to 100 mol%, from 90 to 100 mol%, from 95 to 100 mol%, from 97 to 100 mol%, from 98 to 100 mol%, from 99 to 100 mol%, or 100 mol% of all R3 groups contained in the compound(s) of formula (I) which are groups of the formula:

[0253]

[0254] The (one or more) R3 groups may in particular be the residue of (one or more) diamines of the formula H2N-R3-NH2 in the absence of NH2 groups. The diamines of the formula H2N-R3-NH2 may be selected from C2 to C 24 Aliphatic diamine, C6 to C 18 Cycloaliphatic diamines, C6 to C 24 Aromatic diamines, C7 to C 26 Aromatic aliphatic diamines and C3 to C 18 Heterocyclic diamines.

[0255] C2 to C 24Aliphatic diamines are diamines of the formula H2N-R3-NH2 in which R3 is an aliphatic group containing from 2 to 24 carbon atoms. The aliphatic diamines may be linear or branched, preferably linear. The aliphatic diamines may be polyetheramines, that is to say diamines of the formula H2N-R3-NH2 in which R3 contains ether (-O-) bonds, more particularly oxyethylene (-O-CH2-CH2) and / or oxypropylene (-O-CH2-CHCH3-) units. The aliphatic diamines may be polyalkyleneimines, that is to say diamines of the formula H2N-R3-NH2 in which R3 is interrupted by one or more tertiary amines (-NX-, wherein X is a C1 to C6 alkyl). The aliphatic diamines may be interrupted by one or more tertiary amine groups. Examples of suitable linear aliphatic diamines are 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine and mixtures thereof; preferably 1,2-ethylenediamine, 1,5-pentamethylenediamine and 1,6-hexamethylenediamine. Examples of suitable branched aliphatic diamines are 1,2-propylenediamine, 2,2-dimethyl-1,3-propanediamine, 2-butyl-2-ethyl-1,5-pentanediamine and mixtures thereof. Examples of polyetheramines are sold by Huntsman under the trade name Compounds with the number D, ED and EDR series (diamines). These series include in particular the following designations: D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-2003, EDR-148 and EDR- 176. An example of a polyalkylene imine is 3,3'-diamino-N-methyldipropylamine.

[0256] C6 to C 18 Cycloaliphatic diamines are diamines of the formula H2N-R3-NH2 in which R3 is a cycloaliphatic radical containing from 6 to 18 carbon atoms. Examples of suitable cycloaliphatic diamines are 1,2-, 1,3- or 1,4-diaminocyclohexane, 2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine, isophoronediamine, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, diaminodecahydronaphthalene, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, bis(aminomethyl)norbornane and mixtures thereof;

[0257] Preferred are 1,3- or 1,4-bis(aminomethyl)cyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, isophoronediamine and 4,4′-diaminodicyclohexylmethane.

[0258] C6 to C 24 Aromatic diamines are diamines of the formula H2N-R3-NH2 in which R3 is an aromatic group containing from 6 to 24 carbon atoms. Examples of suitable aromatic diamines are o-, m- and p-phenylenediamine, o-, m- and p-toluenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and mixtures thereof; preferably o-, m- and p-phenylenediamine.

[0259] C7 to C 26 Aromatic aliphatic diamines are diamines of the formula H2N-R3-NH2 in which R3 contains an aromatic aliphatic group having from 7 to 26 carbon atoms. Examples of suitable aromatic aliphatic diamines are o-, m- and p-xylylenediamine, 4,4'-diaminodiphenylmethane and mixtures thereof; preferably o-, m- and p-xylylenediamine.

[0260] C3 to C 18 Heterocyclic diamines are diamines of the formula H2N-R3-NH2 in which R3 contains a heterocyclic group having from 3 to 18 carbon atoms. Examples of suitable heterocyclic diamines are 1,2-diaminopiperazine, 1,4-diaminopiperazine, 1,4-bis(3-aminopropyl)piperazine, 2,3-, 2,6- and 3,4-diaminopyridine, 2,4-diamino-1,3,5-triazine and mixtures thereof.

[0261] Aprotic solvents

[0262] Component b) may further comprise an aprotic solvent. Component b) may comprise a mixture of aprotic solvents.

[0263] According to one embodiment, the aprotic solvent is selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N,N,N',N'-tetramethylurea and mixtures thereof. In particular, the aprotic solvent is selected from dimethyl sulfoxide, N-butylpyrrolidone and mixtures thereof.

[0264] Component b) may in particular comprise from 20% to 95% by weight, in particular from 40% to 80% by weight and more particularly from 50% to 70% by weight of aprotic solvent, relative to the weight of component b).

[0265] Diurethane compounds

[0266] Component b) may further comprise a diurethane compound. Component b) may comprise a mixture of diurethane compounds.

[0267] The diurethane compound may be a by-product of the process for the preparation of component b) as described below. This is because the reaction between a diisocyanate of the formula OCN-R2-NCO and an alcohol of the formula R'-OH to form a monoisocyanate adduct of the formula R'-OC(=O)-NH-R2-NCO may also form a diurethane when the alcohol is in a stoichiometric excess relative to the diisocyanate.

[0268] Without wishing to be bound by any one theory, the Applicant Company assumes that the dicarbamate stabilizes component b) and reduces the amount of by-products obtained during its preparation. The presence of the dicarbamate in component b) eliminates or greatly reduces the amount of salts, in particular the amount of lithium salts, or the amount of surfactants, relative to the thixotropic additives of the prior art.

[0269] The diurethane compound may in particular correspond to a compound of formula (II):

[0270]

[0271] wherein R' and R2 are as defined above for the compound of formula (I).

[0272] According to a specific embodiment, component b) comprises from 20 to 95 mol %, in particular from 25 to 85 mol %, more particularly from 35 to 75 mol % of compounds of formula (II), relative to the total molar amount of compounds having one or more functional groups selected from urea, carbamate and mixtures thereof (excluding any aprotic solvent).

[0273] Polyurea-diurethane compounds

[0274] Component b) may further comprise a polyurea-diurethane compound. Component b) may comprise a mixture of polyurea-diurethane compounds.

[0275] The polyurea-diurethane compound may be obtained in particular as a by-product of the process for the preparation of component b) as described below. This is because the reaction between the monoisocyanate adduct of the formula R'-OC(=O)-NH-R2-NCO and the diamine of the formula H2N-R3-NH2 can also form polyurea-diurethane when the reaction medium contains a diisocyanate of the formula OCN-R2-NCO. The diisocyanate may be in particular a residual diisocyanate from the reaction between the diisocyanate of the formula OCN-R2-NCO and the alcohol of the formula R'-OH in order to form the monoisocyanate adduct of the formula R'-OC(=O)-NH-R2-NCO.

[0276] The polyurea-diurethane compound may in particular correspond to a compound of formula (III):

[0277]

[0278] wherein R', R2 and R3 are as defined above for the compound of formula (I);

[0279] z ranges from 1 to 10.

[0280] Since the polyurea-diurethane compound is generally solid, it is advantageous to limit its amount in component b). Although the residual diisocyanate content can be reduced by carrying out a distillation step before the reaction between the monoisocyanate adduct and the diamine, this represents a non-negligible cost and requires specific equipment. Component b) has a low content of polyurea-diurethane compounds, although its preparation process does not require a distillation step of the residual diisocyanate. This can be achieved in particular by adjusting the molar ratios of the reactants used in the process for the preparation of component b), as described below.

[0281] According to a specific embodiment, component b) contains less than 4 mol %, in particular from 3.0 to 1.5 mol %, from 2.0 to 1.0 mol %, or from 1.0 to 0 mol % of a compound of formula (III), relative to the total molar amount of compounds having one or more functional groups selected from urea, carbamate and mixtures thereof (excluding any aprotic solvent).

[0282] Process for preparing thixotropic additives

[0283] Component b) can be prepared according to the process described below.

[0284] The process for preparing component b) comprises step a), step b) and optionally one or more further steps which may occur before step a), between step a) and step b), and / or after step b).

[0285] Step a) is a step during which at least one diisocyanate of the formula OCN-R2-NCO is reacted with at least one alcohol of the formula R'-OH to form at least one monoisocyanate adduct of the formula R'-OC(=O)-NH-R2-NCO.

[0286] Step b) is a step during which at least one monoisocyanate adduct obtained in step a) is reacted with at least one diamine of formula H2N-R3-NH2 to form at least one compound of formula (I):

[0287]

[0288] in:

[0289] Each R' is independently selected from alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, -[(CR a R b ) n -O] m -Y and ·-[(CR c R d ) p -C(=O)O] q -Z;

[0290] The symbol · represents the point of attachment to the carbamate group of formula (I);

[0291] Each R2 is independently a divalent group selected from aliphatic groups, cycloaliphatic groups, aromatic groups and araliphatic groups;

[0292] Each R3 is independently a divalent group selected from aliphatic groups, cycloaliphatic groups, aromatic groups, araliphatic groups and heterocyclic groups;

[0293] Y and Z are independently selected from alkyl, alkenyl, cycloalkyl, aryl and arylalkyl;

[0294] R a , R b , R c and R d Independently selected from H and methyl, especially H;

[0295] Each n is independently equal to 2, 3 or 4, in particular n is 2;

[0296] m ranges from 1 to 30, in particular m ranges from 2 to 25;

[0297] p ranges from 3 to 5, in particular p is 5;

[0298] q ranges from 1-20, in particular q ranges from 2-10.

[0299] The R', R2 and R3 groups, the diisocyanates of the formula OCN-R2-NCO, the alcohols of the formula R'-OH and the diamines of the formula H2N-R3-NH2 may in particular be as defined above for the compounds of formula (I). The specific embodiments described for the compounds of formula (I) also apply to the process for preparing component b).

[0300] Step a) can be carried out in particular by gradually adding at least one alcohol to a reactor containing at least one diisocyanate. The at least one diisocyanate can be in particular in a molten state. The rate of addition of the at least one alcohol can be controlled to limit the exotherm. In particular, the rate of addition of the at least one alcohol can be controlled to keep the temperature of the reaction medium at less than or equal to 60°C, in particular from 20°C to 60°C, from 25°C to 55°C, or from 30°C to 40°C.

[0301] Step a) is carried out with a molar ratio of the total amount of alcohols to the total amount of diisocyanates of from 1.10 to 1.80. In particular, the molar ratio of the total amount of alcohols to the total amount of diisocyanates in step a) ranges from 1.20 to 1.60, more particularly from 1.25 to 1.45, still more particularly from 1.30 to 1.40.

[0302] The ratio of alcohol to diisocyanate in step a) can limit the amount of diisocyanate remaining at the end of step a). The amount of diisocyanate remaining at the end of step a) corresponds to the amount of diisocyanate introduced in step a) that has not reacted with the at least one alcohol. Controlling the amount of diisocyanate remaining at the end of step a) can advantageously limit the formation of insoluble substances during step b), in particular compounds of formula (III) as described above. According to a specific embodiment, the amount of diisocyanate remaining in the reaction mixture at the end of step a) is less than 6 mol%, in particular from 0 to 5 mol%, from 0.01 to 4.5 mol%, or from 0.05 to 4 mol%, relative to the molar amount of all compounds having one or more functional groups selected from carbamate, isocyanate and mixtures thereof.

[0303] The ratio of alcohol to diisocyanate in step a) advantageously makes it possible to avoid the implementation of a step for removing residual diisocyanate. This is because the amount of residual diisocyanate at the end of step a) is sufficiently low and no excessive formation of insoluble substances, in particular compounds of formula (III) as described above, will be generated during step b). According to a specific embodiment, the process for preparing component b) does not include a distillation step of residual diisocyanate, in particular does not include a distillation step of residual diisocyanate between step a) and step b).

[0304] The ratio of alcohol to diisocyanate in step a) may result in the formation of one or more diurethane compounds as described above. The diurethane compound may in particular be obtained from the reaction between an alcohol of formula R'-OH and a monoisocyanate adduct of formula R'-OC(=O)-NH-R2-NCO. Thus, the reaction mixture obtained in step a) may comprise a monoisocyanate adduct of formula R'-OC(=O)-NH-R2-NCO and a compound of formula (II):

[0305]

[0306] wherein R' and R2 are as defined above.

[0307] Without wishing to be bound by any one theory, the Applicant Company assumes that the presence of the diurethane compound in component b) stabilizes the urea bonds formed during step b). Thus, the amount of stabilizer (in particular salt, such as lithium salt or surfactant) added in step b) can be greatly reduced, or even eliminated, compared to the processes of the prior art.

[0308] When the addition of the at least one alcohol is complete, step a) may be continued until the NCO index of the reaction mixture reaches the theoretical NCO index. The NCO index at the end of step a) may in particular be less than 200 mg KOH / g. In particular, the NCO index at the end of step a) may be from 5 to 150 mg KOH / g, from 25 to 125 mg KOH / g, from 50 to 100 mg KOH / g, or from 60 to 80 mg KOH / g. The NCO index at the end of step a) may in particular be measured according to the method described below. The theoretical NCO index at the end of step a) may in particular be calculated according to the method described below.

[0309] Step b) can be carried out in particular by gradually adding the mixture obtained in step a) to a reactor containing at least one diamine and optionally an aprotic solvent and / or a salt. The rate of addition of the mixture obtained in step a) can be controlled to limit the exotherm. In particular, the rate of addition of the mixture obtained in step a) can be controlled to keep the temperature of the reaction medium below 80°C or equal to 80°C, in particular from 20°C to 80°C, from 30°C to 70°C, or from 40°C to 60°C.

[0310] When the addition of the at least one monoisocyanate adduct is completed, step b) may be continued until the NCO index of the reaction mixture reaches the desired value. The NCO index of the thixotropic additive obtained by the process for preparing component b) may be in particular less than 0.5 mg KOH / g, in particular less than 0.2 mg KOH / g, more particularly less than 0.1 mg KOH / g, and more particularly 0 mg KOH / g. The NCO index of the thixotropic additive may be determined in particular according to the method described in patent application No. PCT / EP2021 / 084323.

[0311] Step b) is carried out with less than 0.2 mol of salt per mole of diamine. In particular, step b) is carried out in the presence of from 0 to 0.19, from 0 to 0.15, from 0 to 0.1, from 0 to 0.05, from 0 to 0.02, from 0 to 0.01, or 0 mol of salt per mole of diamine used. The salt may in particular be as defined above for component b).

[0312] Step b) can be carried out in the presence of less than 0.2 mol of surfactant per mole of diamine used. In particular, step b) can be carried out in the presence of from 0 to 0.19, from 0 to 0.15, from 0 to 0.1, from 0 to 0.05, from 0 to 0.02, from 0 to 0.01, or 0 mol of surfactant per mole of diamine used. The surfactant can in particular be as defined above for component b).

[0313] The molar ratio of the total amount of monoisocyanate adducts to the total amount of diamines in step b) may range from 1.8 to 2.2. In particular, the molar ratio of the total amount of monoisocyanate adducts to the total amount of diamines in step b) ranges from 1.9 to 2.1, more particularly from 1.95 to 2.05, still more particularly from 1.98 to 2.02.

[0314] A solvent may be added in step a) and / or in step b) and / or between step a) and step b) to reduce the viscosity of the composition and to dissolve the compound obtained. In particular, step a) and / or step b) may be carried out in the presence of an aprotic solvent. The viscosity of the reaction medium obtained at the end of step a) may be reduced by adding an aprotic solvent. The aprotic solvent may in particular be as defined above for component b).

[0315] The process for preparing component b) can be carried out using an alcohol or a mixture of alcohols in step a).

[0316] According to a first embodiment, in step a), the at least one diisocyanate is reacted with a single alcohol of formula R1-OH to form at least one monoisocyanate adduct of formula R1-OC(=O)-NH-R2-NCO, and

[0317] In step b), the product obtained in step a) is reacted with at least one diamine of formula H2N-R3-NH2 to form at least one compound of formula (I'):

[0318]

[0319] in

[0320] The R1 groups are the same and as defined above for R';

[0321] R2 and R3 are as defined above.

[0322] The alcohol R1-OH in the first embodiment may in particular be a linear or branched C1-C 30 alkyl.

[0323] According to a second embodiment, in step a), the at least one diisocyanate is reacted with at least two different alcohols of the formula R4-OH and R5-OH to form a mixture of at least two monoisocyanate adducts of the formula R4-OC(=O)-NH-R2-NCO and R5-OC(=O)-NH-R2-NCO, and

[0324] In step b), the mixture obtained in step a) is reacted with at least one diamine of formula H2N-R3-NH2 to form at least one compound of formula (Ia), optionally as a mixture with a compound of formula (Ib) and / or a compound of formula (Ic):

[0325]

[0326] in:

[0327] All R4 groups are the same and as defined above for R';

[0328] All R5 groups are the same and as defined above for R';

[0329] The R4 group is different from the R5 group.

[0330] The R4 and R5 radicals, and also the alcohols of the formula R4-OH and R5-OH, may in particular be as defined above for the compounds of formula (I).

[0331] In a second embodiment, the alcohol R4-OH may be more hydrophobic than the alcohol R5-OH; and / or the alcohol R5-OH may have a higher molecular weight than the molecular weight of the alcohol R4-OH.

[0332] In a second embodiment, the molecular weights of the alcohols R4-OH and R5-OH may be different. In particular, R4-OH may have a molecular weight lower than the molecular weight of R5-OH. More particularly, the difference between the molecular weight of R4-OH and the molecular weight of R5-OH may be at least 50, at least 100, at least 150, at least 200, at least 300, or at least 350 g / mol.

[0333] In a second embodiment, the chemical nature of R4-OH and R5-OH may be different. In particular, the alcohol R4-OH may be more hydrophobic than the alcohol R5-OH.

[0334] In a second embodiment, the alcohols R4-OH and R5-OH may be of the formula HO-[(CR a Rb ) n -O] m -Y alcohol, Y, R a , R b , n and m are as defined above. Alternatively, the alcohol R4-OH may be a linear or branched C1-C 30 alkyl, and the alcohol R5-OH may be of the formula HO-[(CR a R b ) n -O] m -Y alcohol, wherein Y, R a , R b , n and m are as defined above.

[0335] In a second embodiment, the total molar amount of alcohols R5-OH, in particular the least hydrophobic alcohol and / or the alcohol with the highest molecular weight, may in particular account for more than 20%, in particular from 25% to 95%, from 30% to 90%, from 35% to 85%, or from 40% to 80% of the total molar amount of alcohols R4-OH and R5-OH introduced in step a).

[0336] In a second embodiment, the alcohol R5-OH, in particular the least hydrophobic alcohol and / or the alcohol with the highest molecular weight, can be reacted in particular with a diisocyanate before the alcohol R4-OH, in particular the most hydrophobic alcohol and / or the alcohol with the lowest molecular weight, is introduced into the reaction mixture of step a).

[0337] According to a third embodiment, in step a), a diisocyanate is reacted with a mixture of at least three different alcohols of the formula R4-OH, R5-OH and R6-OH to form at least three monoisocyanate adducts of the formula R4-OC(=O)-NH-R2-NCO, R5-OC(=O)-NH-R2-NCO and R6-OC(=O)-NH-R2-NCO, and

[0338] In step b), the mixture obtained in step a) is reacted with at least one diamine of formula H2N-R3-NH2 to form a compound of formula (Ia), a compound of formula (Id) and optionally one or more compounds of formula (Ib), (Ic), (Ie) or (If) represented below:

[0339]

[0340] in:

[0341] All R4 groups are the same and as defined above for R';

[0342] All R5 groups are the same and as defined above for R';

[0343] All R6 groups are the same and as defined above for R';

[0344] The R4 group is different from the R5 group.

[0345] The R4 group is different from the R6 group.

[0346] The R5 group is different from the R6 group.

[0347] The R4, R5 and R6 radicals, and also the alcohols of the formula R4-OH, R5-OH and R6-OH, may in particular be as defined above for the compounds of formula (I).

[0348] In a third embodiment, the alcohol R4-OH may be more hydrophobic than the alcohol R5-OH and / or the alcohol R6-OH; and / or the alcohol R4-OH may have a molecular weight lower than the molecular weight of the alcohol R5-OH and / or the molecular weight of the alcohol R6-OH.

[0349] In a third embodiment, the molecular weights of the alcohols R4-OH, R5-OH and R6-OH may be different. In particular, R4-OH may have a molecular weight lower than the molecular weight of R5-OH; and / or R4-OH may have a molecular weight lower than the molecular weight of R6-OH; and / or R5-OH may have a molecular weight lower than the molecular weight of R6-OH. More particularly, the alcohol R4-OH has a molecular weight lower than the molecular weights of the alcohols R5-OH and R6-OH. Still more particularly, the difference between the molecular weight of R4-OH and the molecular weight of R5-OH; and / or the difference between the molecular weight of R4-OH and the molecular weight of R6-OH; and / or the difference between the molecular weight of R5-OH and the molecular weight of R6-OH may be at least 50, at least 100, at least 150, at least 200, at least 300, or at least 350 g / mol.

[0350] The alcohols R4-OH, R5-OH and R6-OH may have different chemical properties. In particular, R4-OH may be more hydrophobic than R5-OH; and / or R4-OH may be more hydrophobic than R6-OH; and / or R5-OH may be more hydrophobic than R6-OH. More particularly, the alcohol R4-OH is more hydrophobic than the alcohols R5-OH and R6-OH.

[0351] In a third embodiment, the alcohol R4-OH may be a linear or branched C1-C 30 alkyl, and the alcohols R5-OH and R6-OH may be of the formula HO-[(CR a R b ) n -O] m -Y alcohol, Y, R a , R b , n and m are as defined above.

[0352] The total molar amount of alcohols R5-OH and R6-OH, in particular the least hydrophobic alcohol and / or the alcohol with the highest molecular weight, may in particular account for more than 20%, in particular from 25% to 95%, from 30% to 90%, from 35% to 85%, or from 40% to 80% of the total molar amount of alcohols R4-OH, R5-OH and R6-OH introduced in step a).

[0353] Before the alcohol R4-OH, in particular the most hydrophobic alcohol and / or the alcohol with the lowest molecular weight, is introduced into the reaction mixture of step a), the alcohols R5-OH and R6-OH, in particular the least hydrophobic alcohol and / or the alcohol with the highest molecular weight, can be reacted in particular with a diisocyanate.

[0354] Composition

[0355] The composition according to the invention comprises a polymerizable component as described above and a thixotropic additive.

[0356] The composition may especially comprise from 50% to 99.95% by weight, in particular from 70% to 99.9% by weight, more particularly from 80% to 99.8% by weight, still more particularly from 90% to 99.75% by weight, of component a), relative to the weight of the composition.

[0357] The thixotropic additive may in particular be added in an amount sufficient to increase the viscosity of the composition according to the invention and / or to impart thixotropic properties thereto.

[0358] The composition may especially comprise from 0.05 to 50% by weight, in particular from 0.1 to 30% by weight, more particularly from 0.2 to 20% by weight, still more particularly from 0.25 to 10% by weight, of component b), relative to the weight of the composition.

[0359] The composition may in particular have a higher viscosity at low shear (0.01 s) at 25° C. than a composition not comprising component b) or comprising an insufficient amount of component b). -1 ) is measured.

[0360] According to a specific embodiment, the composition is a coating composition, a molding composition, a mastic composition, an adhesive composition, a liquid waterproofing composition, a composite material composition, a chemical sealing composition, or a dental material composition.

[0361] The composition according to the invention may further comprise one or more additional components selected from fillers, plasticizers, wetting agents, pigments, antioxidants, free radical inhibitors, UV absorbers, light stabilizers and mixtures thereof.

[0362] The composition according to the invention may comprise a filler, in particular a filler selected from mineral fillers, and organic fillers or mixtures thereof. In particular, the composition may comprise a mineral filler, especially selected from gravel, marble, granite, quartz, diatomaceous earth, feldspar, mica, gypsum, glass beads, rock dust, limestone, ceramics, clay, loam, carbon black, graphite, sand, silicon dioxide, aluminum oxide, titanium dioxide, magnesium oxide, zirconium dioxide, talc, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zirconium hydroxide, calcium phosphate, calcium carbonate, calcium sulfate, barium sulfate and mixtures thereof.

[0363] The composition may comprise an organic filler, in particular selected from polymer particles such as polyolefin particles (in particular polyethylene, polytetrafluoroethylene or polypropylene particles), polyester particles, polyether particles, (meth)acrylic polymer particles (in particular polymethyl methacrylate particles), urethane particles, polyamide particles (in particular type), styrene-maleic acid copolymer particles; natural or synthetic waxes such as paraffin wax, microcrystalline wax, ceresin wax, montan wax, beeswax, candelilla wax, carnauba wax, rice bran wax, Japan wax, soybean wax, rapeseed wax, palm wax, spermaceti, shea butter, cocoa butter, tristearin, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated cottonseed oil, hydrogenated rapeseed oil, hydrogenated soybean oil, hydrogenated palm oil; gums such as guar gum and xanthan gum; and mixtures thereof.

[0364] The composition may especially comprise from 0% to 70% by weight, in particular from 10% to 60% by weight, more particularly from 20% to 50% by weight of filler relative to the weight of the composition.

[0365] The composition according to the invention may comprise a reinforcement, more particularly a reinforcement chosen from vegetable fibers, glass fibers, carbon fibers, carbon nanotubes, polyester fibers, aramid fibers and mixtures thereof.

[0366] The composition may especially comprise from 0% to 70% by weight, in particular from 10% to 60% by weight, more particularly from 20% to 50% by weight, of reinforcement relative to the weight of the composition.

[0367] The composition according to the invention may comprise a tackifying resin; in particular an optionally modified rosin.

[0368] The composition according to the invention may further comprise a free radical initiator. The free radical initiator may in particular initiate the polymerization of component a).

[0369] The free-radical initiator may especially be a peroxide compound or an azo compound, in particular a peroxide.

[0370] Azo compounds are compounds comprising an azo group of the formula -N=N-. An example of a suitable azo compound is azobisisobutyronitrile (AIBN).

[0371] Peroxide compounds are compounds containing a peroxide group of formula -OO-. The peroxide compound may be selected in particular from hydrogen peroxide, hydroperoxide (ROOH), dialkyl or alkylaryl peroxide (ROO-R'), peracid (RC(=O)-OOH), peroxyester (RC(=O)-OO-R'), diacyl peroxide (RC(=O)-OOC(=O)-R'), peroxycarbonate (ROC(=O)-OOC(=O)-O-R'), peroxyketone (derived from the reaction between ketone and hydrogen peroxide or hydroperoxide), and mixtures thereof, R and R' being independently aliphatic, cycloaliphatic or aromatic groups. The peroxide compound may advantageously be in a stabilized form, in particular in an aqueous phase, in a plasticizer or in an organic solvent.

[0372] Examples of suitable peroxide compounds are dibenzoyl peroxide, dilauroyl peroxide, diisopropyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, tert-butyl peroxyoctanoate, tert-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl peroxymaleate, and mixtures thereof.

[0373] In particular, the free radical initiator may be benzoyl peroxide.

[0374] The composition may especially comprise a free radical initiator in an amount sufficient to obtain complete polymerization of component a). In particular, the composition may comprise from 0.05% to 10% by weight, from 0.1% to 5% by weight, from 0.5% to 5% by weight, or from 0.5% to 3% by weight of free radical initiator, relative to the weight of component a).

[0375] The composition according to the invention may further comprise an activator for the free radical initiator. The free radical initiator activator may in particular make it possible to activate the free radical initiator at ambient temperature (20-25° C.) to initiate the polymerization of component a). The free radical initiator activator may in particular comprise a tertiary amine or a redox coupling.

[0376] In order to prevent any premature polymerization of the composition according to the invention, a free-radical initiator may be brought into contact with component a) just before the composition is applied by the end user.

[0377] Thus, the present invention may also relate to a two-component system comprising:

[0378] - a first kit comprising a free radical initiator;

[0379] - a second kit comprising a composition according to the invention and optionally an activator of a free radical initiator;

[0380] Place the first box separately from the second box.

[0381] The container of the first box and the container of the second box are intended to be in slight contact before applying the composition to the substrate.

[0382] The invention also relates to a process for preparing a cross-linked product, comprising the following steps:

[0383] - mixing the composition according to the invention with a free radical initiator and optionally an activator for the free radical initiator to form a mixture;

[0384] - Applying the obtained mixture to a substrate.

[0385] The crosslinked product may especially be a coating, a molding, a mastic, an adhesive, a liquid waterproofing system, a composite material, a chemical sealing system, or a dental material.

[0386] The mixture may be applied in particular to the surface of a substrate to be coated or waterproofed. Alternatively, the mixture may be applied to the surface of a substrate intended to be adhered to another substrate. Alternatively, the mixture may be applied to fill a gap between two adjacent substrates or to fill holes in the surface of a substrate. Alternatively, the mixture may be applied to a substrate comprising reinforcing fibers to form a composite material. Alternatively, the mixture may be applied to a substrate in the form of a mold.

[0387] The invention also relates to the use of an additive for increasing the viscosity and / or imparting thixotropic properties to a polymerizable component comprising a (meth)acrylate-functionalized compound, the additive comprising a diurea-diurethane compound and containing less than 0.1 mol of salt per urea group in the additive (excluding any aprotic solvent). The additive may especially correspond to component b) as described above for the composition according to the invention. The polymerizable component may especially correspond to component a) as described above for the composition according to the invention.

[0388] The invention is illustrated by the following non-limiting examples.

[0389] Example

[0390] Starting Materials

[0391] [Table 1]

[0392]

[0393]

[0394] Thixotropic Additive 1 (TA1) According to the Invention

[0395] The thixotropic additive 1 according to the invention was prepared as described in Example 8 (diurea-diurethane-based additive without LiCl) of the patent application filed under No. PCT / EP2021 / 084323.

[0396] Thixotropic Additive 2 (TA2) According to the Invention

[0397] The thixotropic additive 2 according to the invention corresponds to the commercially available product from Arkema LA-377 (diurea-diurethane based additive without LiCl).

[0398] Comparison with Thixotropic Additive C1 (TAC1)

[0399] Comparative thixotropic additive C1 corresponds to the commercially available product from Arkema LA-350 (a diurea-diurethane based additive containing more than 0.1 mol % LiCl per urea group).

[0400] Comparison with Thixotropic Additive C2 (TAC2)

[0401] Comparative thixotropic additive C2 corresponds to the commercially available product from BYK D-420 (a diurea-diurethane based additive containing more than 0.1 mol % LiCl per urea group).

[0402] Preparation of composition

[0403] Compositions based on (meth)acrylate-functional monomers

[0404] The composition was prepared using a high-speed disperser equipped with a deflocculator in a 50 ml flask. The components, namely 1 g of thixotropic additive and 19 g of (meth)acrylate functionalized monomer, were introduced into the flask. Subsequently, the mixture was homogenized by stirring at 1000 rpm for 1 minute at 20° C. After this dispersion stage, the mixture was placed at 20° C. for at least 10 min without stirring.

[0405] The components used to prepare the compositions are described in the following table (1% by weight of thixotropic additive relative to the weight of the composition):

[0406] [Table 2]

[0407] TA 1 TA 2 TA C1 TA C2 MMA SR238 SR351 SR295 SR531 Example 1a X X Example 1b X X Example 1c X X Example 1d X X Example 2a X X Example 2b X X Example 2c X X Example 2d X X Example 2e X X Example C1a X X Example C1b X X Example C1c X X Example C1d X X Example C1e X X Example C2a X X Example C2b X X Example C2c X X Example C2d X X Example C2e X X

[0408] Compositions based on (meth)acrylate functional monomers and (meth)acrylate functional oligomers

[0409] The composition was prepared using a high-speed dispersing machine equipped with a deflocculant in a 250 ml flask. (Meth)acrylate functionalized compounds (i.e. 97.7 g of MMA and 2.3 g of CN981) were introduced and stirred at 20°C until a homogeneous mixture was obtained. The desired amount of thixotropic additive TA 2 was then added to the flask. The mixture was then homogenized by stirring at 20°C with a high-speed dispersing machine equipped with a deflocculant for 5 minutes at 1500 rpm. After this dispersion stage, the mixture was placed at 20°C for at least 10 min without stirring.

[0410] The amounts of thixotropic additive used to prepare the compositions are described in the following table (weight % of thixotropic additive relative to the weight of the composition):

[0411] [Table 3]

[0412] %TA 2 Example 3 1 Example 4 2 Example 5 9.8 Example 6 16.8

[0413] Compositions based on (meth)acrylate-functional compounds

[0414] The series of compositions based on (meth)acrylate-functional compounds were prepared in 50 ml flasks according to a protocol similar to that described for Examples 1a to C2e. The desired amounts of thixotropic additive TA 2 and resin 190 is introduced into the flask. Subsequently, the mixture is homogenized by stirring at 800 rpm for 30 seconds at 20° C. using a high-speed disperser equipped with a deflocculant. After this dispersion stage, the mixture is left at 20° C. for at least 10 min without stirring.

[0415] The amounts of thixotropic additive used to prepare the compositions are described in the following table (weight % of thixotropic additive relative to the weight of the composition):

[0416] [Table 4]

[0417] %TA 2 Example 7 0 Example 8 0.125 Example 9 0.25 Example 10 0.5 Embodiment 11 1

[0418] (Meth)acrylate-functionalized monomers and (meth)acrylate-functionalized oligomers and fillers Composition

[0419] For these compositions, a mixture of (meth)acrylate-functional compounds was prepared in advance as follows: 97.7 g of MMA and 2.3 g of CN981 were introduced into a 250 ml flask and stirred at 20° C. using a high-speed disperser equipped with a deflocculant until a homogeneous mixture was obtained. Subsequently, the desired amount of 10AV filler and use the same high-speed disperser equipped with a deflocculant to disperse for 10 minutes at 2000rpm. Subsequently, in a 50ml flask, the desired amount of thixotropic additive TA 2 and the previously prepared MMA / CN981 / filler are introduced into the flask. The mixture is then homogenized by stirring for 5 minutes at 1500rpm using a high-speed disperser equipped with a deflocculant at 20°C. After this dispersion stage, the mixture is placed at 20°C for at least 10min without stirring.

[0420] The components used to prepare the compositions are described in the following table (weight % relative to the weight of the composition):

[0421] [Table 5]

[0422] %MMA / CN981 %filler %TA 2 Example 12 50 50 0 Embodiment 13 49.5 49.5 1 Embodiment 14 49 49 2 Embodiment 15 48.5 48.5 3

[0423] Characterization of composition

[0424] Visual Representation

[0425] The performance of the thixotropic additives was evaluated by visual characterization of the compositions after having been placed at 20° C. (without stirring) for 1 h, 24 h, or 1 week.

[0426] To allow comparison of samples, the evaluation levels are defined as follows.

[0427] [Table 6]

[0428]

[0429] The visual evaluation of the compositions of Examples 1a to 11 is described in detail in the following table:

[0430] [Table 7]

[0431]

[0432]

[0433] The visual evaluation of the compositions of Examples 12 to 15 is detailed in the following table:

[0434] [Table 8]

[0435] 5h 5h 24h 24h 1 week 1 week Gelation settlement Gelation settlement Gelation settlement Example 12 0 S- 0 S- 0 S- Embodiment 13 0 S- 0 S- 0 S- Embodiment 14 3 S+ 3 S+ 3 S+ Embodiment 15 3 S+ 3 S+ 3 S+

[0436] Viscosity measurement

[0437] Viscosity measurement according to standard NF EN ISO 2555 The viscometer is operated at 22°C (spindle: S63). The cylindrical spindle rotates around its axis at a constant rotation speed in the product to be tested. The resistance exerted by the liquid on the spindle depends on the viscosity of the product. This resistance causes the rotation spring to twist, which is reflected in the viscosity value.

[0438] The viscosity of the compositions of Examples 7 to 11 measured at 22° C. after 24 h is detailed in the following table:

[0439] [Table 9]

[0440]

[0441] *5 / 50 thixotropic index corresponds to the ratio of viscosity at 5 rpm to viscosity at 50 rpm.

[0442] The viscosity of the compositions of Examples 12 and 14 measured at 22° C. after one week is detailed in the following table:

[0443] [Table 10]

[0444]

Claims

1. A composition comprising: a) a polymerizable component comprising a (meth)acrylate-functional compound; b) a thixotropic additive comprising a diurea-diurethane compound; Characteristically, component b) contains less than 0.1 mol of salt per urea group in component b) (excluding any aprotic solvent).

2. The composition according to claim 1, characterized in that component a) comprises a (meth)acrylate-functionalized compound selected from (meth)acrylate-functionalized monomers, (meth)acrylate-functionalized oligomers, and mixtures thereof; in particular component a) comprises (meth)acrylate-functionalized monomers and optionally (meth)acrylate-functionalized oligomers.

3. The composition according to claim 1 or 2, characterized in that component a) comprises a mono(meth)acrylate-functionalized monomer selected from the group consisting of: (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-pentyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-decyl (meth)acrylate; isodecyl (meth)acrylate; (meth)acrylate ) n-dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; 3-hydroxypropyl (meth)acrylate; 4-hydroxybutyl (meth)acrylate; 2-methoxyethyl (meth)acrylate; 2-ethoxyethyl (meth)acrylate; 2-ethoxypropyl (meth)acrylate; 3-ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate 2-Phenoxyethyl (meth)acrylate; phenol (meth)acrylate; nonylphenol (meth)acrylate; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; tricyclodecane methanol (meth)acrylate; tert-butyl cyclohexyl (meth)acrylate; trimethyl cyclohexyl (meth)acrylate; diethylene glycol monomethyl ether (meth)acrylate; diethylene glycol monobutyl ether (meth)acrylate; triethylene glycol monoethyl ether (meth)acrylate; polyethylene glycol monomethyl ether (meth)acrylate ; hydroxyethyl-butyl carbamate (meth)acrylate; 3-(2-hydroxyalkyl)oxazolidinone (meth)acrylate; (2,2-dimethyl-1,3-dioxolan-4-yl) (meth)acrylate methyl ester; (2-ethyl-2-methyl-1,3-dioxolan-4-yl) (meth)acrylate methyl ester; 1,3-dioxan-5-yl (meth)acrylate; (1,3-dioxolan-4-yl) (meth)acrylate methyl ester; glycerol carbonate (meth)acrylate; and alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.

4. The composition according to any one of claims 1 to 3, characterized in that component a) comprises a mono(meth)acrylate-functionalized monomer selected from the group consisting of: (meth)acrylic acid; methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; isopropyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-pentyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; n-dodecyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; cyclohexyl (meth)acrylate esters; trimethylcyclohexyl (meth)acrylate; glycidyl (meth)acrylate; benzyl (meth)acrylate; 2-phenoxyethyl (meth)acrylate; cyclic trimethylolpropane formal (meth)acrylate; isobornyl (meth)acrylate; (2,2-dimethyl-1,3-dioxolan-4-yl) (meth)acrylate methyl ester; (2-ethyl-2-methyl-1,3-dioxolan-4-yl) (meth)acrylate methyl ester; 1,3-dioxolan-5-yl (meth)acrylate; (1,3-dioxolan-4-yl) (meth)acrylate methyl ester; and alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.

5. The composition according to claim 1, wherein component a) comprises methyl methacrylate, optionally as a mixture with at least one other (meth)acrylate-functional compound.

6. The composition according to any one of claims 1 to 5, characterized in that component a) comprises a multi-(meth)acrylate-functionalized monomer selected from the group consisting of: bisphenol A di(meth)acrylate; hydrogenated bisphenol A di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; triethylene glycol di(meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate; propylene glycol di(meth)acrylate; dipropylene glycol di(meth)acrylate; tripropylene glycol di(meth)acrylate; tetrapropylene glycol di(meth)acrylate ; Polypropylene glycol di(meth)acrylate; Polytetramethylene glycol di(meth)acrylate; 1,2-butanediol di(meth)acrylate; 2,3-butanediol di(meth)acrylate; 1,3-butanediol di(meth)acrylate; 1,4-butanediol di(meth)acrylate; 1,5-pentanediol di(meth)acrylate; 1,6-hexanediol di(meth)acrylate; 1,8-octanediol di(meth)acrylate; 1,9-nonanediol di(meth)acrylate; 1,10-decanediol di(meth)acrylate 1,12-dodecanediol di(meth)acrylate; neopentyl glycol di(meth)acrylate; 2-methyl-2,4-pentanediol di(meth)acrylate; polybutadiene di(meth)acrylate; cyclohexane-1,4-dimethanol di(meth)acrylate; tricyclodecane dimethanol di(meth)acrylate; glycerol di(meth)acrylate; glycerol tri(meth)acrylate; trimethylolethane tri(meth)acrylate; trimethylolethane di(meth)acrylate; trimethylolpropane tri(meth)acrylate; trimethylolpropane di(meth)acrylate; pentaerythritol di(meth)acrylate; pentaerythritol dimethylolpropane) tetra(meth)acrylate; sorbitol penta(meth)acrylate; dipentaerythritol tetra(meth)acrylate; dipentaerythritol penta(meth)acrylate; dipentaerythritol hexa(meth)acrylate; tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate; and alkoxylated (e.g. ethoxylated and / or propoxylated) derivatives thereof; and mixtures thereof.

7. The composition according to any one of claims 1 to 6, characterized in that component a) comprises a multi-(meth)acrylate-functionalized monomer selected from the group consisting of: 1,6-hexanediol di(meth)acrylate; trimethylolpropane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate; and mixtures thereof.

8. The composition according to any one of claims 1 to 7, characterised in that component a) comprises a (meth)acrylate-functionalised oligomer selected from the group consisting of (meth)acrylate-functionalised urethane oligomers, (meth)acrylate-functionalised epoxy oligomers, (meth)acrylate-functionalised polyether oligomers, (meth)acrylate-functionalised polydiene oligomers, (meth)acrylate-functionalised polycarbonate oligomers, (meth)acrylate-functionalised polyester oligomers; (meth)acrylate-functionalised acrylic oligomers; and mixtures thereof.

9. The composition according to any one of claims 1 to 8, characterized in that component a) comprises a (meth)acrylate-functionalized oligomer selected from the group consisting of: (meth)acrylate-functionalized urethane oligomers, (meth)acrylate-functionalized polydiene oligomers, (meth)acrylate-functionalized acrylic oligomers; and mixtures thereof.

10. The composition according to any one of claims 1 to 9, characterized in that component a) comprises: - from 10 wt % to 100 wt %, from 20 wt % to 100 wt %, from 30 wt % to 100 wt %, from 40 wt % to 95 wt %, or from 50 wt % to 90 wt % of (meth)acrylate functional monomers; and - from 0 to 90 wt %, from 0 to 80 wt %, from 0 to 70 wt %, from 5 to 60 wt %, or from 10 to 50 wt % of (meth)acrylate functionalized oligomer.

11. The composition according to any one of claims 1 to 10, characterized in that component b) comprises a diurea-diurethane compound of formula (I) or a mixture of diurea-diurethane compounds of formula (I): in Each R' is independently selected from alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, -[(CR a R b ) n -O] m -Y and ·-[(CR c R d ) p -C(=O)O] q -Z; The symbol · represents the point of attachment to the carbamate group of formula (I); Each R2 is independently a divalent group selected from aliphatic groups, cycloaliphatic groups, aromatic groups and araliphatic groups; Each R3 is independently a divalent group selected from aliphatic groups, cycloaliphatic groups, aromatic groups, araliphatic groups and heterocyclic groups; Y and Z are independently selected from alkyl, alkenyl, cycloalkyl, aryl and arylalkyl; R a , R b , R c and R d Independently selected from H and methyl, especially H; Each n is independently equal to 2, 3 or 4, in particular n is 2; m ranges from 1 to 30, in particular m ranges from 2 to 25; p ranges from 3 to 5, in particular p is 5; q ranges from 1-20, in particular q ranges from 2-10.

12. The composition according to any one of claims 1 to 11, characterized in that component b) contains from 0 to less than 0.1 mol, or from 0 to 0.09 mol, or from 0 to 0.07 mol, or from 0 to 0.05 mol, or from 0 to 0.03 mol, or from 0 to 0.02 mol, or from 0 to 0.01 mol of salt per urea group in component b).

13. The composition according to any one of claims 1 to 12, characterized in that the salt of component b) is selected from metal salts, ionic liquids and ammonium salts; in particular, the salt is a metal salt selected from halides, acetates, formates or nitrates; more particularly, the salt is a lithium salt; even more particularly, the salt is a lithium salt selected from LiCl, LiNO3, LiBr and mixtures thereof.

14. The composition according to claim 1, wherein component b) contains less than 0.1 mol of surfactant per urea group in component b).

15. Composition according to any one of claims 1 to 14, characterised in that the NCO index of component b) is less than 0.5 mg KOH / g, in particular less than 0.2 mg KOH / g, more particularly less than 0.1 mg KOH / g, still more particularly 0 mg KOH / g.

16. The composition according to any one of claims 1 to 15, characterized in that component b) comprises 5 to 80 mol %, in particular 15 to 75 mol %, more particularly 25 to 65 mol % of diurea-diurethane compounds, relative to the total molar amount of compounds having one or more functional groups selected from urea, urethane and mixtures thereof.

17. The composition according to any one of claims 1 to 16, characterized in that component b) further comprises at least one diurethane compound of formula (II): in R' and R2 are as defined in claim 11.

18. Composition according to claim 17, characterized in that component b) comprises 20 to 95 mol %, in particular 25 to 85 mol %, more particularly 35 to 75 mol % of diurethane compounds of formula (II), relative to the total molar amount of compounds having one or more functional groups selected from urea, carbamate and mixtures thereof, excluding any aprotic solvent.

19. The composition according to any one of claims 11 to 18, characterized in that each R' is independently selected from alkyl and -[(CR a R b ) n -O] m -Y; in particular, each R' is independently selected from a linear or branched C1-C 30 Alkyl and -[CH2-CH2-O] m -Y, where Y is C1-C 24 alkyl and m ranges from 1 to 25; more particularly each R' is independently selected from a branched C8-C 20 Alkyl and -[CH2-CH2-O] m -Y, wherein Y is a C1-C6 alkyl group and m ranges from 2 to 20.

20. A composition according to any one of claims 11 to 19, characterised in that each R2 is independently an aromatic group; in particular an aromatic group having the formula: More particularly, an aromatic group according to one of the following formulae: wherein the symbol · represents the point of attachment to the urea or urethane group of formula (I); Still more particularly, an aromatic group according to one of the following formulae: in, The symbol ★ represents the point of attachment to the urethane group of formula (I), and the symbol ╪ represents the point of attachment to the urea group of formula (I).

21. The composition according to any one of claims 11 to 20, characterized in that more than 85 mol %, more than 90 mol %, more than 95 mol %, more than 97 mol %, more than 98 mol %, more than 99 mol %, or 100 mol % of all R2 groups contained in the diurea-diurethane compounds of formula (I) are aromatic groups of the following formula: wherein the symbol · represents the point of attachment to the urea or urethane group of formula (I); In particular, more than 60 mol%, more than 65 mol%, more than 70 mol%, more than 75 mol%, more than 80 mol%, more than 85 mol%, or more than 90 mol% of all R2 groups contained in the diurea-diurethane compound of formula (I) are aromatic groups of the following formula: in, The symbol ★ represents the point of attachment to the urethane group of formula (I), and the symbol ╪ represents the point of attachment to the urea group of formula (I).

22. The composition according to any one of claims 11 to 21, characterized in that each R3 is independently a group selected from the group consisting of: C2-C 24 Alkylene, -(CR h R i ) s -[A-(CR j R k ) t u -and​ -(CR l R m ) v -CY-(CR n R o ) w -、and -(CR p R q ) x -CY-(CH2) y -CY-(CR r R s ) z -; in: A is O or NX; R h , R i , R j , R k , R l , R m , R n , R o , R p , R q , R r and R s Independently selected from H and methyl, especially H; X is C1 to C6 alkyl, especially methyl or ethyl; CY is a ring selected from phenyl, cyclohexyl, naphthyl, decahydronaphthyl, piperazinyl, triazinyl and pyridinyl, said ring being unsubstituted or substituted with 1 to 3 C1-C4 alkyl groups; s ranges from 2 to 4, especially s is 2; t ranges from 2 to 4, especially t is 2; u ranges from 1 to 30; v, w, x, y and z independently range from 0 to 4.

23. The composition according to any one of claims 11 to 22, characterized in that each R3 is independently a group selected from the group consisting of: C2-C 24 Alkylene, -(CR l R m ) v -CY-(CR n R o ) w -; Especially selected from C2-C 18 Alkylene and -(CH2) v -CY-(CH2) w -, wherein CY is a cyclohexyl or benzene ring, the ring is unsubstituted or substituted with 1 to 3 C1-C4 alkyl groups, and v and w range from 0 to 1; More particularly, a group selected from C2-C6 alkylene and a group having the formula: wherein the symbol · represents the point of attachment to the urea group of formula (I).

24. A composition according to any one of claims 11 to 23, characterised in that component b) is obtainable by a process comprising the following steps: a) reacting at least one diisocyanate of formula OCN-R2-NCO with at least one alcohol of formula R'-OH to form at least one monoisocyanate adduct of formula R'-OC(=O)-NH-R2-NCO, the molar ratio of the total amount of alcohol to the total amount of diisocyanate ranging from 1.10 to 1.80, in particular from 1.20 to 1.60, more particularly from 1.25 to 1.45, still more particularly from 1.30 to 1.40; b) reacting the at least one monoisocyanate adduct obtained in step a) with at least one diamine of formula H2N-R3-NH2 in the presence of less than 0.2 mol of metal salt per mole of diamine used to form at least one diurea-diurethane compound of formula (I) in R', R2 and R3 are as defined in claim 11.

25. Composition according to claim 24, characterised in that step b) is carried out in the presence of from 0 to 0.19, from 0 to 0.15, from 0 to 0.1, from 0 to 0.05, from 0 to 0.02, from 0 to 0.01, or 0 mol of salt per mole of diamine used.

26. Composition according to claim 24 or 25, characterised in that step b) is carried out in the presence of less than 0.2, in particular from 0 to 0.19, from 0 to 0.15, from 0 to 0.1, from 0 to 0.05, from 0 to 0.02, from 0 to 0.01 or 0 mol of surfactant per mole of diamine used.

27. Composition according to any one of claims 24 to 26, characterised in that it does not comprise a distillation step of residual diisocyanates, in particular between step a) and step b).

28. Composition according to any one of claims 24 to 27, characterised in that the amount of diisocyanate remaining in the reaction mixture at the end of step a) is less than 6 mol %, in particular from 0 to 5 mol %, from 0.01 to 4.5 mol %, or from 0.05 to 4 mol %, relative to the molar amount of all compounds having one or more functional groups selected from urethane and isocyanate.

29. The composition according to any one of claims 24 to 28, characterized in that step a) and / or step b) is carried out in the presence of an aprotic solvent.

30. The composition according to any one of claims 1 to 29, characterized in that component b) further comprises an aprotic solvent; in particular an aprotic solvent selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-butylpyrrolidone, N,N,N',N'-tetramethylurea and mixtures thereof; more particularly an aprotic solvent selected from dimethyl sulfoxide or N-propylpyrrolidone.

31. The composition according to any one of claims 1 to 30, characterized in that component b) comprises 20% to 95% by weight, in particular 40% to 80% by weight, more particularly from 50% to 70% by weight, of aprotic solvent, relative to the weight of component b).

32. A composition according to any one of claims 1 to 31, characterised in that it comprises from 0.05 to 50% by weight, in particular from 0.1 to 30% by weight, more particularly from 0.2 to 20% by weight, still more particularly from 0.25 to 10% by weight, of component b), relative to the weight of the composition.

33. The composition according to any one of claims 1 to 32, characterized in that the composition is a coating composition, a molding composition, a cement composition, an adhesive composition, a liquid waterproofing composition, a composite material composition, a chemical sealing composition, or a dental material composition.

34. Composition according to any one of claims 1 to 33, characterised in that the composition further comprises a filler, in particular a filler chosen from mineral fillers, organic fillers and mixtures thereof.

35. The composition according to any one of claims 1 to 34, characterized in that the composition further comprises a reinforcement, in particular a reinforcement selected from plant fibers, glass fibers, carbon fibers, carbon nanotubes, polyester fibers, aramid fibers and mixtures thereof.

36. Composition according to any one of claims 1 to 35, characterised in that the composition further comprises a tackifying resin; in particular an optionally modified rosin resin.

37. The composition according to any one of claims 1 to 36, characterized in that the composition further comprises a free radical initiator, in particular an azo compound or a peroxide compound.

38. Composition according to claim 37, characterised in that the composition further comprises an activator for a free radical initiator, in particular a tertiary amine or a redox coupling.

39. A two-component system, characterized in that it comprises: - a first kit comprising a free radical initiator; - a second kit comprising a composition according to any one of claims 1 to 38 and optionally an activator of a free radical initiator; Place the first box separately from the second box.

40. A process for preparing a cross-linked product comprising the following steps: - mixing a composition according to any one of claims 1 to 38 with a free radical initiator and optionally an activator for the free radical initiator; - Applying the obtained mixture to a substrate.

41. Use of an additive for increasing the viscosity and / or imparting thixotropic properties to a polymerizable component comprising a (meth)acrylate-functional compound, the additive comprising a diurea-diurethane compound and containing less than 0.1 mol of salt per urea group in the additive.

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