Wet-crosslinkable composition

Abstract

The present invention relates to a wet-crosslinkable composition comprising: a polyurethane P1 comprising at least two isocyanate groups; polyurethane P2 comprising at least one isocyanate group and one group having the following formula (I): [chemical 17]-N (H)-C (= O)-X-R1-Si (R2) p (OR3) 3-p (I) wherein:-X represents S or NR4, R4 represents H, alkyl, aryl or cycloalkyl; -R1 represents a divalent hydrocarbon group comprising from 1 to 12 carbon atoms; -p is an integer equal to 0, 1 or 2, preferably 0 or 1; -each R2, which may be the same or different, represents a linear or branched alkyl group comprising from 1 to 4 carbon atoms; -each R3, which may be identical or different, represents a linear or branched alkyl group comprising from 1 to 4 carbon atoms; the composition is characterized in that the mass ratio of polyurethane P1: polyurethane P2 is in the range of 50: 50 to 99: 1.

Description

TECHNICAL FIELD

[0001] The present invention relates to a moisture-crosslinkable composition, which can be particularly used in the building field, and which is able to form, after crosslinking, a joint with good mechanical properties. BACKGROUND

[0002] Various polymer-based compositions exist on the market, which can be used in many fields, in particular as sealants. Sealants make it possible to assemble (or connect or bond) two substrates, which can be chosen from the most diverse materials, and can also serve as sealing joints. Sealants provide the assembly thus obtained with advantageous mechanical properties of solidity, elasticity and / or flexibility, as well as fluid-tightness.

[0003] For example, polymer-based compositions can be used as sealants in the construction, shipbuilding or transport fields (for example, road, maritime, railway or aerospace transport).

[0004] Among the desired properties of a construction sealant, mention can be made especially of its ability to adhere to various substrates, its resistance to weather conditions (UV, ozone, water), its elasticity, etc. The ability to move is a property closely linked to the modulus of elasticity. The modulus of elasticity makes it possible to predict the extension or compression properties of a sealant. The modulus is generally the ratio between the force (stress) required to stretch a sealant and the cross-section of the material at a certain point (usually 100%). The elongation is the length to which the sealant can be extended, expressed as a percentage of its initial size. The modulus has a direct influence on the ability to elongate, since the lower the tensile strength, the more easily the mastic can be stretched.

[0005] It is advantageous to seek a sealant with high deformation and resilience (elastic recovery) ability, to accommodate significant movements without generating too high a tension on the sealant or the substrate.

[0006] In addition, unlike mercapto-silanes or amino-silanes, it is common practice to use adhesion promoters of the epoxy-silane type (and derivatives thereof) in polyurethane-based sealants, which do not react directly with the isocyanate functions of the polyurethane. Epoxy-silanes react with amine functions resulting from the reaction of isocyanate functions with water. However, epoxy-silanes and their derivatives are generally small molecules, the content of which must be limited in view of their chemical classification, and which can be prohibited in the future.

[0007] There is therefore a need for a new composition suitable for the preparation of a sealant, which exhibits a good compromise between good mechanical properties, good elastic properties (elongation and elastic recovery) and good adhesion properties.

[0008] Composition

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

[0010] - a polyurethane P1 comprising at least two isocyanate groups;

[0011] - a polyurethane P2 comprising at least one isocyanate group and one group of formula (I):

[0012] - N(H)-C(=0)-X-R 1 - Si(R 2 ) p (OR 3 ) 3-p (I)

[0013] wherein:

[0014] - X represents S or NR 4 , R 4 represents H, an alkyl group, an aryl group or a cycloalkyl group;

[0015] - R 1 represents a divalent hydrocarbon group comprising from 1 to 12 carbon atoms;

[0016] - p is an integer equal to 0, 1 or 2, preferably 0 or 1 ;

[0017] - each R 2 , which can be identical or different, represents a linear or branched alkyl group comprising from 1 to 4 carbon atoms;

[0018] - each R 3 , which can be identical or different, represents a linear or branched alkyl group comprising from 1 to 4 carbon atoms;

[0019] The composition is characterized in that the mass ratio of polyurethane P1 : polyurethane P2 is in the range of 50:50 to 99:1.

[0020] Preferably, in the composition, the mass ratio of polyurethane P1 : polyurethane P2 is from 70:30 to 99:1, more preferably from 80:20 to 99:1.

[0021] Polyurethane P1

[0022] Preferably, polyurethane P1 comprises at least two isocyanate groups in terminal position.

[0023] Polyurethane P1 is preferably obtained by a process comprising a step E1 of polyaddition reaction:

[0024] i) a composition comprising at least one polyol; and

[0025] ii) a composition comprising at least one polyisocyanate;

[0026] in an amount such that the NCO / OH molar ratio (r 1 ) is greater than 1.

[0027] In the context of the invention, unless otherwise stated, r 1 is the NCO / OH molar ratio corresponding to the number of isocyanate groups (NCO) to the number of hydroxyl groups (OH), carried respectively by all the polyisocyanates and polyols present in the reaction medium of step E1.

[0028] Preferably, the NCO / OH molar ratio (r1) is in the range 1.0 to 2.0, preferably 1.2 to 2.0.

[0029] polyol

[0030] The term "polyol" should be understood to mean a compound comprising at least two hydroxyl groups (-OH).

[0031] The polyols used according to the application can be chosen from those having a number-average molecular weight (Mn) of between 50 and 50 000 g / mol, preferably between 100 and 20 000 g / mol, preferentially between 500 and 20 000 g / mol and advantageously between 500 and 5 000 g / mol.

[0032] Their hydroxyl functionality can range from 2 to 6, preferably from 2 to 3. The hydroxyl functionality is the average number of hydroxyl functions per mole of polyol.

[0033] The polyols that can be used can be chosen from polyester polyols, polyether polyols, polyene polyols, polycarbonate polyols, poly(ether carbonate) polyols and mixtures thereof.

[0034] The polyols that can be used can be chosen from aromatic polyols, aliphatic polyols, araliphatic polyols and mixtures of these compounds.

[0035] The polyester polyols can be chosen from polyester diols and polyester triols, preferably polyester diols.

[0036] Among the polyester polyols, examples that can be mentioned include:

[0037] - polyester polyols of natural origin, such as castor oil;

[0038] - polyester polyols obtained by polycondensation of:

[0039] - one or more aliphatic (linear, branched or cyclic) or aromatic polyols, such as monoethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, butylene glycol,

[0040] 1,6-hexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, neopentyl glycol, cyclohexanedimethanol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, sucrose, glucose, sorbitol, pentaerythritol, mannitol, N-methyldiethanolamine, triethanolamine, fatty alcohol dimers, fatty alcohol trimers, and mixtures thereof, with

[0041] - one or more polycarboxylic acids or ester or anhydride derivatives thereof, such as 1,6-hexanedioic acid (adipic acid), dodecanedioic acid, azelaic acid, sebacic acid, hexanedioic acid, 1,18-octadecanediolic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, fatty acid dimers, fatty acid trimers, and mixtures of these acids, unsaturated anhydrides such as maleic anhydride or phthalic anhydride, or lactones such as caprolactone;

[0042] - inter-ester polyols obtained by polycondensation of one or more hydroxy acids (such as ricinoleic acid) with diols (examples that can be mentioned include Vertellus D-1000 and D-2000).

[0043] The polyester polyols mentioned above can be prepared by conventional methods and most of them are commercially available.

[0044] Among the polyester polyols, mention can be made, for example, of the following products having a hydroxyl functionality equal to 2: 0240 (sold by Union Carbide), which is a polycaprolactone having a number-average molecular weight of about 2000 g / mol, a melting point of about 50°C, 7381 (sold by Evonik), having a number-average molecular weight of about 3500 g / mol, a melting point of about 65°C, 7360 (sold by Evonik), which is obtained by condensation of adipic acid with hexanediol, has a number-average molecular weight of about 3500 g / mol, a melting point of about 55°C; 3008 (sold by the company Polysciences), having a number-average molar mass Mn of about 1060 g / mol, a hydroxyl value ranging from 102 to 112 mg KOH / g. It is the product of the condensation of adipic acid, diethylene glycol and monoethylene glycol.

[0045] The polyether polyols that can be used according to the application are preferably chosen from polyoxyalkylene polyols, the linear or branched alkylene moiety of which comprises from 1 to 4 carbon atoms, more preferentially from 2 to 3 carbon atoms.

[0046] More preferentially, the polyether polyols that can be used according to the application are preferably chosen from polyoxyalkylene diols or polyoxyalkylene triols, the linear or branched alkylene moiety of which comprises from 1 to 4 carbon atoms, more preferentially from 2 to 3 carbon atoms, and mixtures thereof.

[0047] Examples of polyoxyalkylene diols or triols that can be used according to the application can be mentioned: polyoxypropylene diols or triols having a number average molecular weight (Mn) of between 500 g / mol and 12000 g / mol (also known as polypropylene glycol (PPG) diols or triols); polyoxyethylene diols or triols having a number average molecular weight (Mn) of between 500 g / mol and 12000 g / mol (also known as polyethylene glycol (PEG) diols or triols); and mixtures thereof.

[0048] The polyether polyols mentioned above can be prepared by conventional methods and are widely commercially available. They can be prepared by polymerization of the corresponding alkylene oxides in the presence of a basic catalyst, such as potassium hydroxide, or a catalyst based on a double metal / cyanide complex.

[0049] As examples of polyether diols, mention can be made of the polyoxypropylene diols sold under the names P1010 by Dow Chemical, having a number average molecular weight (Mn) of around 1020 g / mol, a hydroxyl number of about 110 mg KOH / g, or P2000 by Dow Chemical, having a number average molecular weight of around 2040 g / mol, a hydroxyl number of about 55 mg KOH / g.

[0050] The polyene polyols that can be used according to the application can preferably be chosen from polyenes comprising hydroxyl end groups, and their corresponding hydrogenated or epoxidized derivatives.

[0051] Preferably, the polyene polyols that can be used according to the application are chosen from polybutadienes comprising hydroxyl end groups, optionally hydrogenated or epoxidized. Preferably, the polyene polyols that can be used according to the application are chosen from butadiene homopolymers and copolymers comprising hydroxyl end groups, optionally hydrogenated or epoxidized.

[0052] In the context of the present application, the term "hydroxyl end group" of a polyene polyol is understood to mean a hydroxyl group located at the end of the polyene polyol main chain, unless otherwise specified.

[0053] The hydrogenated derivatives mentioned above can be obtained by total or partial hydrogenation of the double bonds of a polydiene comprising hydroxyl end groups, and are thus saturated or unsaturated.

[0054] The epoxidized derivatives mentioned above can be obtained by chemoselective epoxidation of the double bonds of the polyene main chain comprising hydroxyl end groups, and thus comprise at least one epoxide group on their main chain.

[0055] Examples of polyene polyols that can be mentioned include saturated or unsaturated butadiene homopolymers comprising hydroxyl end groups, optionally epoxidized, such as those sold by Cray Valley under the names or .

[0056] The polycarbonate polyol may be selected from polycarbonate diols or triols.

[0057] As examples of polycarbonate diols, mention may be made of the polycarbonate diols sold by Novomer. Polyol212-20, its number average molecular weight (M n ) is equal to 2000 g / mol, and its hydroxyl value is 56 mgKOH / g, and Polyol C1090, C-2090 and C-3090 sold by Kuraray have a number average molecular weight (M n ) is 1000 to 3000 g / mol, and the hydroxyl value is 35 to 118 mgKOH / g.

[0058] Preferably, the polyurethane P1 is obtained from a composition i) comprising one or more polyether polyols.

[0059] Preferably, the polyurethane P1 is obtained from a composition i) comprising a mixture of polyether diols and polyether triols.

[0060] polyisocyanates

[0061] The term "polyisocyanate" refers to a compound containing at least two isocyanate groups (-NCO).

[0062] The polyisocyanate may be selected from diisocyanates, triisocyanates and mixtures thereof.

[0063] Among the diisocyanates, examples that can be mentioned include isophorone diisocyanate (IPDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate) (4,4'-HMDI), norbornane diisocyanate, norbornene diisocyanate, 1,4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, 1,5-diisocyanato-2-methylpentane (MPDI), 1,6-diisocyanato-2,4,4-trimethylhexane, 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), (2,5)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (2,5-NBDI), (2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (2,6-NBDI), 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6-XDI), 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6-XDI), xylene diisocyanate (XDI) (in particular m-xylylene diisocyanate (m-XDI)), toluene diisocyanate (in particular 2,4-toluene diisocyanate (2,4-TDI) and / or 2,6-toluene diisocyanate (2,6-TDI)), diphenylmethane diisocyanate (in particular 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and / or 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), tetramethylxylylene diisocyanate (TMXDI) (in particular tetramethyl(m-)xylylene diisocyanate), a PDI allophanate (n = 5) or a HDI allophanate (n = 6) of formula (Y) below, for example:

[0064]

[0065] in which p is an integer from 1 to 2, q is an integer from 0 to 9 and preferably from 2 to 5, Rc represents a saturated or unsaturated, cyclic or acyclic, linear or branched hydrocarbon chain comprising from 1 to 20 carbon atoms, preferably from 6 to 14 carbon atoms, R d represents a linear or branched divalent alkylene radical having from 2 to 4 carbon atoms, and preferably a divalent propylene radical;

[0066] and mixtures thereof.

[0067] Among the triisocyanates, examples that can be mentioned include isocyanurates, biurets and adducts of diisocyanates and triols.

[0068] The isocyanurates can be used in the form of technical mixtures of (poly)isocyanurates, the purity of which is greater than or equal to 70% by weight.

[0069] Examples of diisocyanate trimers that can be mentioned include:

[0070] - isocyanurate trimers of hexamethylene diisocyanate (HDI):

[0071]

[0072] - isocyanurate trimers of isophorone diisocyanate (IPDI):

[0073]

[0074] Examples of adducts of diisocyanates and triols that can be used according to the application can mention the adduct of m-xylylene diisocyanate (m-XDI) and a triol. Such adducts can generally be obtained by carrying out an addition reaction using the compounds. The method of such addition reactions is described, for example, in EP3101044.

[0075] The triol used is preferably a trimethylolalkane, including an alkane comprising from 1 to 20 carbon atoms and 3 hydroxymethyl groups, such as trimethylolmethane, trimethyloloethane, trimethylolpropane, trimethylol(n-butane), trimethylol(isobutane), trimethylol(sec-butane), trimethylol(tert-butane), trimethylolpentane, trimethylolhexane, trimethylolheptane, trimethyloloctane, trimethylolnonane, trimethyloldecane, trimethylolundecane and trimethyloldodecane.

[0076] More preferentially, among the triols that can be used to obtain the adduct of m-XDI and a triol, mention can be made of glycerol of formula HOH2C-CHOH-CH2OH, trimethylolmethane (TMM) of formula HC(CH2-OH)3, trimethyloloethane (TME) of formula H3C-C(CH2-OH)3 and trimethylolpropane (TMP) of formula CH3-CH2-C(CH2-OH)3.

[0077] The MDI can be in the form of an isomer or a mixture of isomers, such as 4,4'-MDI and / or 2,4'-MDI.

[0078] The TDI can be in the form of an isomer or a mixture of isomers, such as 2,4-TDI and / or 2,6-TDI.

[0079] The diisocyanates that can be used are widely available on the market. For example, mention can be made of the TX, corresponding to 2,4-TDI with a purity of approximately 95%; sold by Vencorex T100, corresponding to 2,4-TDI with a purity higher than 99% by weight; sold by Covestro I, corresponding to IPDI; or sold by Dow M125, corresponding to MDI containing at least 97% of 4,4'-MDI.

[0080] Preferably, the polyisocyanate is chosen from diisocyanates.

[0081] Preferably, the polyisocyanate is chosen from toluene diisocyanates (in particular 2,4-toluene diisocyanate (2,4-TDI) and / or 2,6-toluene diisocyanate (2,6-TDI)), diphenylmethane diisocyanates (in particular 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and / or 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI) (in particular meta-xylylene diisocyanate (m-XDI)).

[0082] Preferably, the polyurethane P1 is obtained by a process comprising a step E1 of polyaddition reaction comprising:

[0083] i) a composition comprising a polyether diol and a polyether triol;

[0084] ii) a composition comprising a diisocyanate chosen from toluene diisocyanates, diphenylmethane diisocyanates, isophorone diisocyanate, xylylene diisocyanate.

[0085] Step E1

[0086] During step E1, the polyaddition reaction can be carried out at a temperature of between 50°C and 100°C, for example at a temperature of between 60°C and 80°C.

[0087] The polyaddition reaction of step E1 can be carried out in the presence or in the absence of at least one reaction catalyst.

[0088] The catalyst can be any catalyst known to the person skilled in the art for catalysing the formation of polyurethanes by reaction of at least one polyisocyanate with at least one polyol.

[0089] The catalyst can be used in an amount ranging up to 0.3% by weight relative to the weight of the reaction medium of step E1.

[0090] The reaction of step E1 can also be carried out in the presence of a solvent. The solvent can be selected from esters, ketones, aromatics and mixtures thereof. The solvent can be added during step E1 ) or can come from the starting reactants dissolved in said solvent. The solvent can be selected from, for example, esters, ketones, aromatics and mixtures thereof. The solvent can be selected from, for example, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and mixtures thereof.

[0091] The NCO group content of the polyurethane P1 is preferably comprised between 0.5% and 10%, more preferably between 1% and 8%.

[0092] The composition according to the application preferably comprises between 5% and 60% by weight of polyurethane P1 relative to the total weight of the composition, still more preferably between 10% and 50% by weight.

[0093] Polyurethane P2

[0094] The polyurethane P2 preferably comprises terminal isocyanate groups and end groups of formula (I):

[0095] -N(H)-C(=0)-X-R 1 -Si(R 2 ) p (OR 3 ) 3-p (I)

[0096] wherein:

[0097] -X represents S or NR 4 , R 4 represents H or an alkyl group or an aryl group or a cycloalkyl group;

[0098] -R 1 represents a divalent hydrocarbon group comprising from 1 to 12 carbon atoms;

[0099] -p is an integer equal to 0, 1 or 2, preferably an integer equal to 0 or 1 ;

[0100] -R 2 , which can be identical or different, represent a linear or branched alkyl group comprising from 1 to 4 carbon atoms;

[0101] -R 3 , which can be identical or different, represent a linear or branched alkyl group comprising from 1 to 4 carbon atoms.

[0102] Preferably, the polyurethane P2 comprises a group of formula (I) wherein:

[0103] -X represents S; and / or

[0104] -R 1 represents a linear or branched alkylene group comprising from 1 to 6 carbon atoms; and / or

[0105] - p represents 0; and / or

[0106] - R 3 which can be identical or different, represent a methyl or ethyl group.

[0107] More preferably, the polyurethane P2 comprises a radical of formula (I) in which:

[0108] - X represents S; and

[0109] - R 1 represents a linear or branched alkylene radical comprising from 1 to 6 carbon atoms; and

[0110] - p represents 0; and

[0111] - R 3 which can be identical or different, represent a methyl or ethyl group.

[0112] The polyurethane P2 is preferably obtained by a process comprising a step E2 of reacting a composition comprising the polyurethane P1 with at least one organosilane of formula (II) below:

[0113] H-X-R 1 -Si(R 2 ) p (OR 3 ) 3-p (II)

[0114] in an amount such that the NCO / XH molar ratio (r2) ranges from 70 to 200, preferably from 90 to 140.

[0115] Step E2

[0116] Step E2 can be carried out at a temperature ranging from 23°C to 80°C.

[0117] The reaction of step E2 can be carried out in the presence or in the absence of at least one reaction catalyst.

[0118] The catalyst can be any catalyst known to the person skilled in the art. The amount of catalyst can be used in the range up to 0.3% by weight relative to the weight of the reaction medium of step E2.

[0119] The reaction of step E2 can also be carried out in the presence of a solvent. The solvent can be chosen from esters, ketones, aromatic compounds and mixtures thereof. The solvent can be added during step E1 or step E2, or can come from the starting reactants dissolved in said solvent. The solvent can be chosen, for example, from ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and mixtures thereof.

[0120] In the context of the present invention, unless otherwise indicated, r2 is the NCO / XH molar ratio, which corresponds to the molar ratio of the number of isocyanate groups to the number of XH groups carried by all the isocyanates (in particular the polyurethane P1) and organosilanes present in the reaction medium of step E2, respectively.

[0121] The organosilane of formula (II) may be selected from the group consisting of 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, N-butyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, and mixtures thereof.

[0122] The organosilanes are commercially available, for example from Evonik. 1189, or sold by Momentive A1110, or sold by Evonik MTMO.

[0123] The organosilanes of formula (II) are preferably selected from those wherein:

[0124] -X means S; and / or

[0125] -R 1 represents a straight-chain or branched alkylene group containing 1 to 6 carbon atoms; and / or

[0126] -p means 0; and / or

[0127] -R 3 They may be the same or different and represent a methyl group or an ethyl group.

[0128] More preferably, the organosilane of formula (II) is selected from those wherein:

[0129] -X means S; and

[0130] -R 1 represents a straight-chain or branched alkylene group containing 1 to 6 carbon atoms; and

[0131] -p means 0; and

[0132] -R 3which can be the same or different, represent a methyl or ethyl group.

[0133] More preferentially, the organosilane of formula (II) is chosen from 3- mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and mixtures thereof.

[0134] The composition according to the application comprises a polyurethane P2 in an amount less than or equal to 4% by weight relative to the total weight of the composition.

[0135] More preferentially, the composition comprises a polyurethane P2 in an amount less than or equal to 3% by mass relative to the total weight of the composition.

[0136] The polyurethane P2 preferably has a weight average molecular weight (Mw) of between 5000 g / mol and 100000 g / mol, more preferentially between 8000 g / mol and 60000 g / mol, more preferentially between 10000 g / mol and 40000 g / mol.

[0137] The weight average molecular weight of the polymers can be measured by methods well known to those skilled in the art, for example by NMR or by size exclusion chromatography using polystyrene standards.

[0138] According to a preferred embodiment, the composition according to the application comprises between 5% and 60% by weight of a mixture of polyurethanes P1 and P2 relative to the total weight of the composition.

[0139] Rheological agent

[0140] The composition according to the application preferably comprises at least one rheological agent.

[0141] The rheological agent is preferably a thixotropic agent. A thixotropic agent generally affects the thixotropy of the composition. Thixotropy refers to the property of certain compositions to decrease in viscosity when a constant force is applied (for example shear force under constant stress), the viscosity returning to its initial state after an appropriate time when the stress is removed. The greater the force, the lower the viscosity.

[0142] In particular, the thixotropic agent can be chosen from:

[0143] - PVC plastisols, corresponding to suspensions of PVC in plasticizers that are miscible with PVC, which can in particular be obtained in situ by heating to a range of 60°C to 80°C. These plastisols can in particular be those described in the book “Polyurethane Sealants” by Robert M. Evans (ISBN 0-87762-998-6);

[0144] - fumed silica;

[0145] - suspensions of biureas generated from the reaction of diisocyanates with primary aliphatic amines in plasticizers;

[0146] - a wax derived from castor oil, such as the BYTAC® available from Elementis R;

[0147] - an amide wax, preferably micronized amide wax, such as the BYTANOL® sold by Arkema SLX, SLW or SUPER, or the BYTAC® available from Elementis AS8053 or MAX, or RHEOBYK 7503 sold by BYK; and

[0148] - mixtures thereof.

[0149] Preferably, the thixotropic agent is chosen from amide waxes, suspensions in plasticizer of bis-ureas resulting from the reaction of diisocyanates with primary aliphatic amines, and mixtures thereof.

[0150] Preferably, the thixotropic agent is chosen from suspensions in plasticizer of bis-ureas resulting from the reaction of diisocyanates with primary aliphatic amines.

[0151] The suspension of bis-urea in plasticizer preferably comprises:

[0152] - from 1 to 40% by weight, relative to the total weight of the suspension, of bis-urea resulting from the reaction of diisocyanate with primary aliphatic amine having a molar mass of less than 500 g / mol, and

[0153] - from 60 to 99% by weight, relative to the total weight of the suspension, of plasticizer chosen from alkyl phthalates, pentaerythritol tetrapentanoate, esters of alkyl sulfonic acids and phenols, diisononyl 1,2-cyclohexane dicarbonates, 3,3'-[methylenebis(oxy methylene)]bis[heptane], dioctyl carbonate, and mixtures thereof,

[0154] The suspension is a suspension of solid particles of bis-urea in a continuous phase of plasticizer.

[0155] Advantageously, the bis-urea is obtained by reacting a n-alkyl amine comprising from 1 to 22 carbon atoms, preferably n-butyl amine, with a diisocyanate of formula NCO-R 6 -NCO, in which R 6 is chosen from one of the following divalent radicals, the following formulae showing the two free valences:

[0156] - i) the divalent radical derived from isophorone:

[0157]

[0158] - ii) the divalent radical 4,4'-methylenebis(cyclohexyl):

[0159]

[0160] - iii) divalent radicals derived from toluene 2,4-diisocyanate (or 2,4-TDI) or toluene 2,6-diisocyanate (or 2,6-TDI), each of which formula is:

[0161]

[0162] - iv) divalent radicals derived from diphenylmethylene 4,2'-diisocyanate (or 4,2'-MDI) or diphenylmethylene 4,4'-diisocyanate (or 4,4'-MDI), each of which has the chemical formula:

[0163]

[0164] - v) hexamethylene radical: -(CH2)6-,

[0165] - vi) m-xylylene:

[0166] and

[0167] - vii) hexahydro-m-xylylene:

[0168]

[0169] Preferably, R 6 is a divalent radical derived from 4,2'-MDI or 4,4'-MDI, more preferably 4,4'-MDI.

[0170] More preferably, the biuret is obtained by reaction of n-butylamine with a diisocyanate of formula NCO-R 6 -NCO, wherein R 6 is a divalent radical derived from 4,2'-MDI or 4,4'-MDI, preferably 4,4'-MDI.

[0171] As indicated above for this embodiment, the plasticizer used in the biuret suspension is selected from the group consisting of alkyl phthalates, pentaerythritol tetrapentanoate, esters of alkyl sulfonic acids and phenols, diisononyl 1,2-cyclohexane dicarbonates, 3,3'-[methylenebis(oxy methylene)]bis[heptane], dioctyl carbonate and mixtures thereof.

[0172] The alkyl phthalates preferably form the group consisting of diisodecyl phthalate (DIDP), bis(2-propylheptyl) phthalate and mixtures thereof.

[0173] Advantageously, the plasticizer is chosen from alkyl phthalates, preferably from diisodecyl phthalate, di(2-propylheptyl) phthalate and mixtures thereof, more preferably diisodecyl phthalate.

[0174] According to a preferred embodiment, the suspension of biuret in plasticizer consists of:

[0175] - from 1 to 40% by weight of biuret obtained from the reaction of a diisocyanate with a primary aliphatic amine having a molar mass of less than 500 g / mol, and

[0176] - from 60 to 99% by weight of plasticizer, chosen from alkyl phthalates, pentaerythritol tetrapentanoate, esters of alkyl sulfonic acids and phenols, diisononyl 1,2-cyclohexane dicarboxylate, 3,3'-[methylenebis(oxy methylene)]bis[heptane], dioctyl carbonate and mixtures thereof, relative to the total weight of the suspension,

[0177] The suspension is a suspension of solid particles of biuret in a continuous phase of plasticizer, and the biuret and the plasticizer are as described above, including the embodiments.

[0178] Advantageously, the suspension comprises, and preferably consists of, from 5 to 30% by weight of biuret and from 70 to 95% by weight of plasticizer, the percentages being relative to the total weight of the suspension. The biuret and the plasticizer are as described above, including the embodiments.

[0179] The suspension of biuret in plasticizer can be prepared according to the following process.

[0180] The reaction of the primary aliphatic amine with the diisocyanate is highly exothermic. In order to prevent the decomposition of the biuret produced by the large amount of heat generated by the reaction, the primary aliphatic amine and the diisocyanate are each dissolved in a plasticizer, then they are brought together so that the plasticizer acts as a heat sink. The two solutions of primary aliphatic amine and diisocyanate in plasticizer are advantageously introduced into the reactor separately by means of injectors at a pressure of 40 to 200 bar, preferably 80 to 120 bar, so that the two solutions are brought into contact in the state of spray liquid. The amounts of reactants correspond preferably to a (mole number of primary aliphatic amine) / (mole number of diisocyanate) ratio of about 2. The biuret produced by the reaction is dispersed in the form of solid particles in a continuous phase of plasticizer, the Brookfield viscosity of the corresponding suspension, measured at a temperature of 23°C, being generally between 1 and 50 Pa.s, preferably between 10 and 25 Pa.s.

[0181] The term "waxes derived from castor oil" is understood to mean waxes obtained from castor oil, in particular hydrogenated castor oil.

[0182] "Amide wax" refers to a wax comprising one or more compounds containing at least one amide group. In particular, amide waxes are obtainable from one or more organic acids (eg fatty acids) and one or more (di)amines.

[0183] The amide wax is preferably micronized, ie has an average particle size of less than 1 mm. The average particle size of the amide wax is advantageously less than 500 μm, preferably less than 100 μm, more preferably less than 10 μm.

[0184] In this context, the average particle size advantageously corresponds to the d50 particle size, ie the maximum dimension of 50% of the smallest particles by volume, and can be measured using a particle size analyzer, in particular by laser diffraction on a Malvern machine (for example according to standard ISO 13320).

[0185] Unless otherwise stated, the standards referred to throughout this patent application are those in effect on the filing date of the patent application.

[0186] Preferably, the content of the rheological agent in the composition is 1 to 45 wt %, more preferably 5 to 40 wt %, more preferably 10 to 35 wt %, relative to the total weight of the composition.

[0187] Filler

[0188] The composition according to the invention preferably comprises at least one filler.

[0189] The filler may be selected from mineral fillers, organic fillers and mixtures thereof, preferably mineral fillers.

[0190] As an example of a mineral filler, any mineral filler commonly used in the field of adhesive compositions can be used. These fillers are generally in the form of particles of various geometric shapes. For example, they can be spherical, fibrous or irregular in shape.

[0191] The mineral filler may be selected from clay, quartz, carbonate fillers, kaolin, gypsum, hollow mineral microspheres, zeolites, and mixtures thereof.

[0192] Among the hollow mineral microspheres, mention may be made of hollow glass microspheres, more particularly those made of soda-lime borosilicate or aluminosilicate.

[0193] Preferably, the mineral filler is selected from the group consisting of carbonate fillers, zeolites and mixtures thereof.

[0194] Advantageously, the carbonate filler is selected from alkali metal or alkaline earth metal carbonates and mixtures thereof.Preferably, the carbonate filler comprises calcium carbonate, more preferably, the carbonate filler is ground calcium carbonate and / or fatty acid coated calcium carbonate (the latter preferably being precipitated).

[0195] When the calcium carbonate is coated with a fatty acid, the calcium carbonate particles can be rendered completely or partially hydrophobic. Furthermore, the fatty acid coating acts as a hydrophobic coating which prevents the calcium carbonate from absorbing the components of the composition and rendering it ineffective. The hydrophobic coating of the calcium carbonate represents from 0.1 wt% to 3.5 wt% of the total weight of the calcium carbonate.

[0196] Preferably, the fatty acid coating the calcium carbonate comprises, or consists of, more than 50 wt% of stearic acid, relative to the total weight of the fatty acid.

[0197] Among the alkali metal or alkaline-earth metal carbonates, mention can be made of chalk BL 200TB (DV50 = 9 microns) sold by Omya, Socal 312 (hydrophobized calcium carbonate with a DV50 of 1 micron) sold by Solvay or Omya BSH (hydrophobized calcium carbonate) sold by Omya.

[0198] Advantageously, the zeolite is chosen from synthetic zeolites of type A, type X and / or type Y, preferably of type A, and has a pore size of between and , preferably of between

[0199] The average particle size of the mineral filler can range from 10 nm to 400 pm; preferably from 20 nm to 100 pm, more preferably from 30 nm to 50 pm.

[0200] As examples of organic fillers, mention can be made of any organic and in particular polymeric filler commonly used in the field of adhesive compositions.

[0201] For example, polyvinyl chloride (PVC), polyolefins, rubber, ethylene / vinyl acetate (EVA), expandable or non-expandable hollow thermoplastic polymer microspheres (for example hollow vinylidene chloride / acrylonitrile microspheres) and / or aramid fibers (for example ) can be used.

[0202] The PVC can be a PVC homopolymer and / or a PVC copolymer, preferably a PVC homopolymer.

[0203] As examples of PVC copolymers, mention can be made of copolymers obtained by polymerization of vinyl chloride with one or more monomers chosen from acrylonitrile, ethylene, propylene, vinylidene chloride and / or vinyl acetate, in particular vinyl acetate.

[0204] The particle size of the PVC filler can vary between 0.05 pm and 0.8 pm, preferably between 0.1 pm and 0.5 pm. The particle size can be measured by electron microscopy, in particular scanning electron microscopy.

[0205] The PVC filler can be obtained by emulsion.

[0206] There are various types of PVC fillers on the market.

[0207] Expandable or non-expandable hollow microspheres made of thermoplastic polymers can also be used. Hollow microspheres made of vinylidene chloride / acrylonitrile are particularly worthy of mention.

[0208] Preferably, the composition according to the application comprises at least a carbonate filler, preferably calcium carbonate, and a PVC filler.

[0209] Preferably, the composition according to the application comprises 5 to 50% by weight of filler, preferably 5 to 40% by weight, relative to the total weight of the composition.

[0210] Other additives

[0211] The composition according to the application can also comprise at least one additive chosen from plasticizers, solvents, UV stabilizers, antifoams, adhesion promoters and mixtures thereof.

[0212] Preferably, the composition comprises an additive chosen from plasticizers.

[0213] The additive chosen from plasticizers can be any plasticizer commonly used in the field of adhesive compositions.

[0214] The additive chosen from plasticizers can for example be chosen from diisodecyl phthalate, diisononyl phthalate (DINP), esters of alkyl sulfonic acids and phenols, for example , diisononyl hexahydrophthalate, pentakis pentanovyl pentaerythritol, and mixtures thereof.

[0215] The content of additive chosen from plasticizers can range up to 10% by weight relative to the total weight of the composition.

[0216] The solvent can be chosen from aliphatic hydrocarbons (for example pentane, hexane, heptane, octane, nonane, decane, dodecane, isohexane, isooctane, isododecane, tetradecane, dodecylbenzene, cyclohexane, kerosene and naphthene), aromatic hydrocarbons (for example benzene, toluene, xylene, alkylbenzene, solvent naphtha, phenylxylylethane and diisopropyl naphthalene), halogenated hydrocarbons (for example carbon tetrachloride, chloroform, dichloromethane, bromoethane, trichloroethylene, tetrachloroethylene, trifluoroethylene, tetrafluoroethylene, trichlorotrifluoroethylene and tetrachlorodifluoroethylene) and mixtures thereof, preferably chosen from aromatic hydrocarbons, in particular diisopropyl naphthalene.

[0217] The content of solvent can range up to 10% by weight of the total weight of the composition, preferably 0 to 5% by weight.

[0218] The composition according to the application can comprise up to 1 % by weight of one or more UV stabilizers (or antioxidants) relative to the total weight of the composition.

[0219] The UV stabilizers are generally added in order to protect the composition from degradation due to reactions with oxygen which are liable to occur under the effect of heat or light. These compounds can include antioxidants capable of scavenging free radicals.

[0220] The UV stabilizers (or antioxidants) can be chosen from benzotriazoles, benzophenones, "hindered" amines, such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (CAS No: 41556-26-7), methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (CAS No: 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-bis(a,a-dimethylbenzyl) diphenylamine, and mixtures thereof.

[0221] The person skilled in the art generally uses a defoaming agent (or antifoam agent) to enable rapid elimination of the bubbles formed during the preparation and application of compositions comprising a component comprising a polyisocyanate.

[0222] The defoaming agent can be any defoaming agent commonly used in the field of adhesive compositions.

[0223] For example, the defoaming agent can be a polysiloxane, an aldehyde imine and / or an oxazolidine, in particular a polysiloxane.

[0224] The content of defoaming agent can range from 0 to 2% by weight of the total weight of the two-component composition, preferably from 0 to 1 % by weight.

[0225] The adhesion promoter can be chosen from aminoalkoxysilanes (such as (3- aminopropyl)trimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropyltrimethoxysilane), mercaptoalkoxysilanes, epoxyalkoxysilanes (such as (3-glycidyloxypropyl)trimethoxysilane), and mixtures thereof.

[0226] Preferably, the composition does not comprise an aminosilane.

[0227] Preferably, the composition does not comprise an ethoxymercaptosilane, and more preferentially, the composition does not comprise a mercaptosilane.

[0228] Preferably, the composition according to the application comprises less than 4% by weight of polyurethane containing two silanized terminal functions (without isocyanate function), relative to the total weight of the composition, preferably less than 2% by weight, more preferably less than 1.5% by weight.

[0229] Preferably, the content of residual polyisocyanate in the composition (resulting from the preparation of polyurethanes P1 and P2) is less than or equal to 0.5% by weight relative to the total weight of said composition.

[0230] The composition according to the application can be prepared by simply mixing its ingredients.

[0231] Use of the composition

[0232] The application also relates to the use of the composition as defined above as an adhesive, in particular as a semi-structural adhesive, as a sealant or as a coating.

[0233] In particular, the application relates to the use of the composition as defined above as an adhesive, sealant or coating in the field of construction, in the field of manufacturing means of transport (for example the automotive, railway, aerospace or shipbuilding industry).

[0234] The composition according to the application comprises the embodiments and preferred features as described above.

[0235] The composition according to the application advantageously has at least one of the following advantages:

[0236] - after crosslinking, it results in a joint with an elongation at break greater than 300%, more preferentially greater than or equal to 400%, more preferentially greater than or equal to 600%;

[0237] - after crosslinking, it results in a joint with an elastic recovery greater than or equal to 70%;

[0238] - after crosslinking, it results in a joint with a modulus at 100% elongation less than or equal to 1 MPa;

[0239] - it has a low content of residual polyisocyanate resulting from the preparation of polyurethanes P1 and P2 (preferably less than or equal to 0.5% by weight relative to the total weight of said composition).

[0240] The person skilled in the art knows how to determine the elongation at break of a composition. For example, the elongation at break can be measured according to standard ISO 37.

[0241] The elastic recovery can be measured according to standard ISO 11600 of 2002 (reference standard ISO 7389 of 2002) and at a constant rate equal to 5.5 mm / min.

[0242] The modulus at 100% elongation can be measured according to standard ISO 8339.

[0243] In particular, the elastic recovery and the elongation at break can be measured as described in the following example 4.

[0244] Method of assembling a substrate

[0245] The present application also relates to a method of assembling substrates, comprising:

[0246] - applying a composition as defined above to at least one surface of the substrates to be assembled, then

[0247] - bringing the substrates into contact.

[0248] The composition according to the present application is as described above, including the embodiments and preferred features.

[0249] It is understood that during the application step and the contact step, the composition according to the present application is in uncured state.

[0250] The substrates can be identical or different.

[0251] The substrates concerned are numerous, for example inorganic substrates, such as concrete, metals and / or alloys (such as aluminium alloys, steel, non-ferrous metals and plated metals), and / or organic substrates, such as wood, and / or plastics (such as PVC, polycarbonates, PMMA, polyethylene, polypropylene, polyesters, epoxy resins).

[0252] Article

[0253] The present application also relates to an article comprising a composition according to the present application (cured or uncured) which binds at least two substrates of said article.

[0254] The composition according to the present application is as described above, including the embodiments and preferred features.

[0255] The article can be obtained by the method of assembling substrates according to the present application (including the embodiments and preferred features).

[0256] Said substrates are preferably as described above for the method of assembling substrates according to the present application.

[0257] All the embodiments described above can be combined with each other. In particular, the various aforementioned compositions, and especially the preferred options, can be combined with each other.

[0258] In the context of the present application, the term "between x and y" or "ranging from x to y" is to be understood as the interval including the endpoints x and y. For example, the range "between 0% and 25%" includes in particular the values 0% and 25%.

[0259] The following examples are merely illustrative of the present application and should not be construed as limiting the scope of the application. Example

[0260] The ingredients used are as follows:

[0261] - PVC powder obtained from emulsion (homopolymer);

[0262] - IPDI (Evonik): isophorone diisocyanate;

[0263] - Omya BL (Omya): calcium carbonate;

[0264] - Ti02(Kronos): rutile titanium dioxide;

[0265] - Silane A187 (Evonik): ([3-(2,3-epoxypropoxy)propyl]trimethoxysilane);

[0266] - Desmodur L75 (Covestro): aromatic polyisocyanate (about 75% in ethyl acetate);

[0267] - Incozol BH (Incorez): aldimine (N,N-dibenzylidene) polyoxypropylenediamine);

[0268] - DPK in 10% solution of salicylic acid, Disflamoll;

[0269] - Catex E70 (Tib Chemicals): dibutyltin dilaurate;

[0270] - MTMO (Evonik): mercaptosilane (3-trimethoxysilylpropane-1-thiol);

[0271] - Voranol 2000 sold by Dow TM P2000 is a polypropylene glycol (PPG) with functionality F = 2, with an OHN of 55 mg KOH / g, i.e. a number average molecular weight (Mn) of about 2040 g / mol;

[0272] - Polyol P: polyether polyol with functionality 3, with an OHN ranging from 45 to 50 mg KOH / g;

[0273] - Polyisocyanate T: 80 / 20 mixture of 2,4- and 2,6-TDI;

[0274] - 1076: antioxidant sold by BASF;

[0275] - 765: Hindered liquid amine sold by BASF;

[0276] - DINP: Diisononyl phthalate, sold by Sigma Aldrich.

[0277] Example 1 Preparation of NCO-terminated polyurethane

[0278] The ingredients were placed in a reactor maintained under constant stirring and under nitrogen, at a temperature of 70°C.

[0279] The whole was kept under stirring at this temperature until the hydroxyl functions of the polyol had been completely consumed.

[0280] The reaction was monitored by measuring the content of NCO groups by back-titration of dibutylamine with hydrochloric acid, according to the standard NF T52-132. The reaction was stopped when the measured content of NCO groups was approximately equal to the desired content of NCO groups (1.8%).

[0281] The proportions of the ingredients used to prepare the polyurethane are indicated in Table 1 below (weight %):

[0282] [Table 1]:

[0283]

[0284] The percentages are weight percentages relative to the total weight of the composition.

[0285] Example 2 Preparation of the bis-urea (rheological agent)

[0286] Two solutions were prepared:

[0287] - Solution A of n-butylamine in diisodecyl phthalate (DIDP), consisting of 17.17% by weight of n-butylamine and 82.83% by weight of DIDP, the percentages being relative to the total weight of solution A, then - Solution B of -4,4'-MDI in DIDP, consisting of 29.46% by weight of 4,4'-MDI in 70.54% by weight of DIDP, the percentages being relative to the total weight of solution B.

[0288] The two solutions A and B were heated to 100°C and then introduced into a reactor under a pressure of 100 bars, where they were sprayed one after the other in a weight ratio A / B = 50.1 / 49.9, which corresponds to a n-butylamine / MDI molar ratio equal to 2. The reaction was instantaneous and the temperature of the reactor reached 140°C at the end of production.

[0289] At the reactor outlet, a stable dispersion of 23.3 wt% (relative to the total weight of the dispersion) of the bis-urea in DIDP was obtained, the bis-urea having the following formula:

[0290]

[0291] The Brookfield viscosity of the suspension measured at 23 °C was 15 Pa-s.

[0292] Example 3: Preparation of a moisture-crosslinkable composition

[0293] The following composition was prepared according to the following procedure:

[0294] DINP and the polyurethane of Example 1 were added to the reactor and mixed at 23 °C for 30 minutes. MTMO was added and the reaction mixture was stirred at 23 °C for 15 minutes to form a mixture comprising DINP, unreacted polyurethane of Example 1 and a hybrid polyurethane comprising isocyanate end groups and silane end groups formed from the reaction of MTMO with the NCO functional groups of the polyurethane of Example 1. IR monitoring was used to show that the MTMO had been consumed. The polyurethane of Example 1 : isocyanate- and silane-terminated polyurethane mass ratio was greater than 94:6. The hybrid polyurethane was synthesised in situ in this example and did not need to be isolated.

[0295] Omya BL, PVC powder and titanium dioxide were then added to the reaction mixture which was then stirred for 10 minutes. IPDI was then added, followed by stirring of all under vacuum (-0.8 bar) for 10 minutes. Next, the bis-urea in Example 2 was added under vacuum (-0.8 bar) for 5 minutes and also stirred under vacuum for 10 minutes before the other ingredients were added.

[0296] The mixture was stirred under vacuum (-0.8 bar) for 10 to 20 minutes.

[0297]

[0298]

[0299] The ingredients in the table are expressed in wt% relative to the total weight of the composition.

[0300] Example 4: Properties of the composition C1

[0301] The skinning time was measured in a controlled atmosphere at a temperature of 23 °C and a relative humidity of about 50%.

[0302] The composition is applied in the form of a bead with a thickness of 2 or 3 millimetres using a doctor blade. The stopwatch is started immediately after the application of the bead and the film is checked every 5 minutes by gently pressing with a spatula to see if it is dry or if there is a residue of composition transferred onto the spatula. The skinning time is the time at which the bead of composition is dry and there is no longer any residue of product transferred onto the spatula. The result is expressed in minutes.

[0303] The determination of the tensile strength and the elongation at break by tensile test is carried out according to the following method. The same applies to the Young's modulus.

[0304] The principle of the measurement consists in pulling a standard test specimen consisting of the crosslinked composition in a tensile testing device whose movable jaws move at a constant speed equal to 500 mm / min and in recording the tensile stress applied (in MPa) and the elongation of the specimen (in %) at the time of rupture of the specimen. The standard test specimen is dumbbell-shaped as described in the international standard ISO 37.

[0305] To prepare the dumbbell, the composition to be tested (previously packaged in a cartridge) is extruded into a Teflon mould and left to cure under standard conditions (23°C and 50% relative humidity) for 14 days. The narrow part of the dumbbell has a length of 20 mm (+ / - 0.5 mm), a width of 4 mm and a thickness of 2 mm.

[0306] The modulus at 100% elongation is measured according to the test appearing in the standard ISO 11600 of 2002, which refers to the standard ISO 8339 of 2005: tensile stress corresponding to the elongation of the specimen of 100%.

[0307] The elastic recovery rate is determined according to the test appearing in the standard ISO 11600 of 2002, which refers to the standard ISO 7389 of 2002.

[0308] The slump is measured according to the ASTM D2202 standard.

[0309] The results are shown in the following table:

[0310] Composition C1 Skin formation time (min) 90 Extrusion rate (g / min) 105.1 Deep crosslinking (24h - mm) 3.9 Elongation at break (%) 720±0.76 Modulus at 100% elongation (MPa) 0.86±0.04 Elastic recovery rate (%) (ISO 7389 - conditioning A) 90.9±1.3

[0311] The composition C1 advantageously leads to an adhesive joint which, after crosslinking, exhibits good mechanical performance qualities, including:

[0312] - an elongation at break greater than or equal to 400%, preferably greater than or equal to 600%;

[0313] - an elastic recovery rate greater than or equal to 70%;

[0314] - a modulus at 100% elongation less than or equal to 1 MPa.

[0315] The extrusion rate of composition C1 was 105.1 g / min, which is convenient for end user use, for example by spray gun.

[0316] Example 5: Preparation of a moisture-curable composition

[0317] The following compositions C2 and C3 were prepared according to the following procedure:

[0318] DINCH and polyurethane from Example 1 were added to the reactor and mixed at 23 °C for 30 minutes. Silane A1110 (C2) or silane 1189 (C3) and the reaction mixture was stirred at 23 °C for 15 minutes to form a mixture comprising DINCH, unreacted polyurethane from Example 1 and a mixture of isocyanate-terminated and silane-terminated hybrid polyurethane generated from the reaction of the NCO functional groups of silane A1110 or 1189 with the polyurethane from Example 1. IR monitoring showed that all silane was consumed. The mass ratio of polyurethane from Example 1 to isocyanate-terminated and silane-terminated polyurethane was greater than 94:6. The hybrid polyurethane was synthesised in situ in this example and did not need to be isolated.

[0319] Omya BL, PVC powder and titanium dioxide were subsequently added to the reaction mixture and mixed for 10 minutes. IPDI was then added, followed by mixing of all under vacuum (-0.8 bar) for 10 minutes. Next, the diurea from Example 2 was added under vacuum (-0.8 bar) for 5 minutes and mixed under vacuum for a further 10 minutes, before the other ingredients were added.

[0320] The mixture was stirred under vacuum (-0.8 bar) for 10 to 20 minutes.

[0321]

[0322] The ingredients in the table are expressed in weight % relative to the total weight of the composition.

[0323] Example 6: Properties of the compositions C2 and C3

[0324] The procedure and tests were similar to those in Example 4.

[0325] The results are shown in the following table:

[0326]

[0327]

[0328] Compositions C2 and C3 advantageously resulted in adhesive joints which exhibited good mechanical properties after curing, including:

[0329] • an elongation at break greater than or equal to 400%, preferably greater than or equal to 600%;

[0330] • an elastic recovery greater than or equal to 70%;

[0331] • a modulus at 100% elongation less than or equal to 1 MPa.

[0332] Example 7: Preparation of a moisture-curable composition C4

[0333] Composition C4 was prepared following the steps: in a rapid mixing reactor, Dynasilan MTMO was added to the polyurethane from example 1 and the reaction mixture was stirred at 30°C, atmospheric pressure for 10 minutes, forming a mixture comprising unreacted polyurethane from example 1 and hybrid polyurethane with isocyanate and silane endcapping resulting from the reaction of MTMO silane with the NCO functional groups of the polyurethane from example 1. IR monitoring showed that all silanes were consumed.

[0334] Next, the obtained hybrid polyurethane was added to the same mixture comprising polyurethane from example 1, Omya BL, PVC powder and titanium dioxide. The reaction mixture was stirred at 23°C for 10 minutes. Then, IPDI was added, followed by mixing all under vacuum (-0.9 bar) for 15 minutes. Next, the bis-urea from example 2 was added under vacuum (-0.9 bar) and the reaction mixture was stirred under vacuum for another 10 minutes, before the other ingredients were added.

[0335] The mixture was stirred under vacuum (-0.9 bar) for 10 to 20 minutes.

[0336] In the formulation C4, the mass ratio of polyurethane from example 1 to hybrid polyurethane from the first step was greater than 94:6.

[0337]

[0338]

[0339] The ingredients in the table are expressed in weight % relative to the total weight of the composition.

[0340] Example 8: Properties of the composition C4

[0341] The results are shown in the following table:

[0342] Composition C4 Skin formation time (min) 80 Extrusion rate (g / min) 104 Elastic recovery rate (%) (ISO 7389 - conditioning A) 85

[0343] Composition C4 advantageously leads to a glued joint exhibiting good mechanical properties after curing, including an elastic recovery greater than or equal to 70%.

[0344] Example 9: Preparation of the composition C5

[0345] The following composition was prepared by adding DINCH and polyurethane from Example 1 in a reactor and mixing for 30 minutes at 23 °C. MTMO was added and the reaction mixture was stirred for 15 minutes at 23 °C to form a mixture comprising DINCH, unreacted polyurethane from Example 1 and isocyanate- and silane-terminated hybrid polyurethane formed from the reaction of MTMO with the NCO functional groups of the polyurethane from Example 1. IR monitoring showed that all of the MTMO had been consumed. The mass ratio of polyurethane from Example 1 to isocyanate- and silane-terminated polyurethane was greater than 94:6. The hybrid polyurethane was synthesized in situ and did not require isolation.

[0346] Omya BL, PVC powder and titanium dioxide were added to the reaction mixture and mixed for 10 minutes. IPDI was then added, followed by mixing of all under vacuum (-0.8 bar) for 10 minutes, followed by addition of the other ingredients.

[0347] The mixture was stirred under vacuum (-0.8 bar) for 10 to 20 minutes.

[0348]

[0349]

[0350] The ingredients in the table are expressed in weight % relative to the total weight of the composition.

[0351] Example 10: Properties of the composition C5

[0352] The procedure and tests performed were the same as those performed for Composition C1.

[0353] The results are shown in the following table:

[0354] Composition C5 Skin formation time (min) 85 Extrusion rate (g / min) 167 Elastic recovery rate (%) (ISO 7389 - conditioning A) Example 9: Preparation of the composition C5 Example 10: Properties of the composition C5 Composition C5 Skin formation time (min) Extrusion rate (g / min) Elastic recovery rate (%) (ISO 7389 - conditioning A) Example 9: Preparation of the composition C5 Example 10: Properties of the composition C5 Composition C5 Skin formation time (min) Extrusion rate (g / min) Elastic recovery rate (%) (ISO 7389 - conditioning A) Example 9: Preparation of the composition C5 Example 10: Properties of the composition C5 Composition C5 Skin formation time (min) Extrusion rate (g / min) Elastic recovery rate (%) (ISO 7389 - conditioning A) Example 9: Preparation of the composition C5 Example 10: Properties of the composition C5 Composition C5 Skin formation time (min) Extrusion rate (g / min) Elastic recovery rate (%) (ISO 7389 - conditioning A) Example 9: Preparation of the composition C5 Example 10: Properties of the composition C5 Composition C5 Skin formation time (min) Extrusion rate (g / min) Elastic recovery rate (%) (ISO 7389 - conditioning A) Example 9: Preparation of the composition C5 Example 10: Properties of the composition C5 Composition C5 Skin formation time (min) Extrusion rate (g / min) Elastic recovery rate (%) (ISO 7389 - conditioning A) Example 9: Preparation of the composition C5 Example 10: Properties of the composition C5 Composition C5 Skin formation time (min) Extrusion rate (g 91

[0355] Composition C5 advantageously resulted in an adhesive joint that exhibited good mechanical properties after curing, including an elastic recovery of greater than or equal to 70%.

Claims

1. Moisture-crosslinkable composition comprising: o a polyurethane P1 comprising at least two isocyanate groups; o a polyurethane P2 comprising at least one isocyanate group and one group having the following formula (I): [Chem 14] -N(H)-C(=O)-X-R 1 -Si(R 2 ) p (OR 3 ) 3-p (I) wherein: - X represents S or NR 4 , R 4 represents H, alkyl, aryl or cycloalkyl; - R 1 represents a divalent hydrocarbon group comprising from 1 to 12 carbon atoms; - p is an integer equal to 0, 1 or 2, preferably 0 or 1 ; - each R 2 , which can be identical or different, represent a linear or branched alkyl group comprising from 1 to 4 carbon atoms; - each R 3 , which can be identical or different, represent a linear or branched alkyl group comprising from 1 to 4 carbon atoms; the composition is characterized by a polyurethane P1 : polyurethane P2 mass ratio ranging from 50:50 to 99:1, preferably from 70:30 to 99:1, still more preferably from 80:20 to 99:

1.

2. The composition of claim 1, wherein The polyurethane P1 is obtained by a process comprising a step E1 of polyaddition reaction: i) a composition comprising a polyether diol and a polyether triol; ii) a composition comprising a diisocyanate selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate.

3. The composition according to any one of claims 1 and 2, characterized in that The polyurethane P1 has a NCO groups content ranging from 0.5% to 10%, more preferably from 1 % to 8%.

4. The composition according to any one of claims 1 to 3, characterized in that The composition comprises from 5% to 60% by weight of polyurethane P1, preferably from 10% to 50% by weight, relative to the total weight of the composition.

5. The composition according to any one of claims 1 to 4, characterized in that The polyurethane P2 comprises terminal isocyanate groups and end groups having formula (I): [Chem 15] -N(H)-C(=O)-X-R 1 -Si(R 2 ) p (OR 3 ) 3-p (I).。 6. The composition according to any one of claims 1 to 5, characterized in that The polyurethane P2 comprises a group of formula (I) wherein: - X represents S; and / or - R 1 represents a linear or branched alkylene radical comprising from 1 to 6 carbon atoms; and / or - p represents 0; and / or -R 3 may be the same or different and represent a methyl or ethyl group.

7. The composition according to any one of claims 1 to 6, characterized in that The polyurethane P2 comprises a group of formula (I) wherein: - X represents S; and - R 1 represents a linear or branched alkylene group comprising from 1 to 6 carbon atoms; and - p represents 0; and -R 3 may be the same or different and represent a methyl or ethyl group.

8. The composition according to any one of claims 1 to 7, characterized in that The polyurethane P2 is obtained by a process comprising a step E2 of reacting a composition comprising a polyurethane P1 with at least one organosilane of the following formula (II) in an amount such that the NCO / XH molar ratio (r2) ranges from 70 to 200, preferably from 90 to 140: [Chem 16] H-X-R 1 -Si(R 2 ) p (OR 3 ) 3-p (II).

9. The composition according to any one of claims 1 to 8, characterized in that The composition comprises polyurethane P2 in an amount less than or equal to 4% by weight, preferably less than or equal to 3% by weight, relative to the total weight of the composition.

10. The composition according to any one of claims 1 to 9, characterized in that The polyurethane P2 has a weight average molecular weight (Mw) ranging from 5000 g / mol to 100000 g / mol, preferably from 8000 g / mol to 60000 g / mol, and still more preferably from 10000 g / mol to 40000 g / mol.

11. The composition according to any one of claims 1 to 10, characterized in that The composition comprises at least one rheological agent.

12. The composition according to any one of claims 1 to 11, characterized in that The composition comprises from 1 % to 45% by weight of rheological agent, more preferably from 5% to 40% by weight, and more preferably from 10% to 35% by weight, relative to the total weight of the composition.

13. The composition according to any one of claims 11 and 12, characterized in that The rheological agent is a thixotropic agent selected from amide waxes, suspensions of biuret in plasticizer obtained from the reaction of a diisocyanate with a primary aliphatic amine, and mixtures thereof.

14. The composition of claim 13, wherein The suspension of biuret in plasticizer consists of: - from 1 % to 40% by weight of biuret obtained from the reaction of a diisocyanate with a primary aliphatic amine having a molar mass less than 500 g / mol, relative to the total weight of the suspension, and - from 60% to 99% by weight of plasticizer, relative to the total weight of the suspension. - from 60 to 99% by weight of plasticizer, relative to the total weight of the suspension, chosen from alkyl phthalates, pentaerythritol tetrapentanoate, esters of alkyl sulfonic acids and phenols, diisononyl 1,2-cyclohexane dicarbonate, 3,3'-[methylenebis(oxy-methylene)]bis[heptane], dioctyl carbonate and mixtures thereof, the suspension is a suspension of solid particles of bisurea in a continuous phase of plasticizer.

15. The composition according to any one of claims 1 to 14, characterized in that The composition comprises from 5 to 60% by weight of a mixture of polyurethanes P1 and P2, relative to the total weight of the composition.

16. The composition of any one of claims 1 to 15, characterized in that The composition comprises from 5 to 50% by weight of filler, preferably from 5 to 40% by weight, relative to the total weight of the composition.

17. The composition of any one of claims 1 to 16, characterized in that The composition comprises at least a carbonate filler and a PVC filler.

18. The composition of any one of claims 1 to 17, characterized in that The composition does not comprise any aminosilane.

19. Use of the composition according to any one of claims 1 to 18 as an adhesive, in particular as a semi-structural adhesive, as a sealant or as a coating.

20. Method of assembling substrates, comprising: - applying the composition as defined in any one of claims 1 to 19 to at least one surface of the substrates to be assembled, then - bringing the substrates into contact.

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