Composition comprising a silylated polymer

Abstract

This application relates to a crosslinkable composition comprising: a polymer P comprising at least one polymer P1 comprising at least one functional group of the following formula (I): said polymer P1 comprising a main chain based on (meth)acrylate; - a polyurethane P' comprising at least one functional group of formula (II): carbon black having an oil absorption index (OAN) of at least 80 mL / 100 g. Figure: No

Description

Title of the invention: Composition comprising a silylated polymer. FIELD OF THE INVENTION

[0001] The present invention relates to a composition comprising a silylated polymer, and its use in particular for bonding and sealing. TECHNICAL BACKGROUND

[0002] In the automotive field, adhesive compositions are widely used, whether for fixing movable panels such as doors, hoods, etc., or for fixing windshields.

[0003] The adhesives used for windshields must fulfill several functions, namely: having sufficient adhesion to the seal / windshield interface, but also good sealing against external conditions (water, temperature, humidity...).

[0004] In the field of adhesives, silane-modified polymers (“SMPs”) are widely used. However, these adhesives can have the disadvantage of leading to adhesive joints that lose their adhesive properties under harsh climatic conditions.

[0005] There is therefore a need for new compositions leading to an adhesive joint exhibiting a compromise between good adhesion properties and good resistance to aging, particularly under demanding temperature and humidity conditions. DESCRIPTION OF THE INVENTION

[0006] The present invention relates to a crosslinkable composition comprising: - a polymer P comprising at least one polymer PI comprising at least one function of the following formula (I):

[0007] [Chem.l] -SiR3_pXp (I)

[0008] in which: - R represents a hydrocarbon group having from 1 to 20 carbon atoms, possibly substituted and / or comprising one or more heteroatoms; - X is a hydroxyl group or a hydrolyzable group; - p represents 1, 2 or 3;

[0009] said PI polymer comprising a main chain based on (meth)acrylate;

[0010] - a polyurethane P' comprising at least one function of formula (II):

[0011] [Chem.2]

[0012] in which: - R' ' represents a hydrocarbon group having from 1 to 20 carbon atoms, possibly substituted and / or comprising one or more heteroatoms; - X' is a hydroxyl group or a hydrolyzable group; - t represents 1, 2 or 3; - carbon black having an oil absorption index (OAN) of at least 80 mL / 100 g.

[0013] According to the invention, the composition comprises at least three different ingredients: the polymer P, the polyurethane P' and the aforementioned carbon black. Composition Polymer P

[0014] PI Polymer

[0015] The PI polymer comprises a main chain based on (meth)acrylate.

[0016] In the context of the invention, the term "(meth)acrylate" includes both acrylates and methacrylates.

[0017] In the PI polymer, the monomer unit constituting the main chain contains at least one (meth)acrylate monomer.

[0018] (Meth)acrylates can be diverse and varied.

[0019] The (meth)acrylate monomer can be chosen from methyl (meth)acrylate; ethyl (meth)acrylate; n-propyl (meth)acrylate; n-butyl (meth)acrylate; isobutyl (meth)acrylate; n-hexyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; n-octyl (meth)acrylate; isooctyl (meth)acrylate; n-Decyl (meth)acrylate; n-Dodecyl (meth)acrylate; tridecyl (meth)acrylate; tetradecyl (meth)acrylate; hexadecyl (meth)acrylate; 2-Hydroxyethyl (meth)acrylate; 2- and 3-Hydroxypropyl (meth)acrylate; 2-Methoxyethyl (meth)acrylate; 2-Ethoxyethyl (meth)acrylate; 2- and 3-Ethoxypropyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; alkoxylated tetrahydrofurfuryl (meth)acrylate; 2-(2-ethoxyethoxy)ethyl (meth)acrylate; cyclohexyl (meth)acrylate; glycidyl (meth)acrylate; isodecyl (meth)acrylate; lauryl (meth)acrylate; 2-Phenoxyethyl (meth)acrylate; 3-(dimethoxymethylsilyl)propyl (meth)acrylate; 2-(dimethoxymethylsilyl)ethyl (meth)acrylate; 2-(dimethoxymethylsilyl)methyl (meth)acrylate; 2-(diethoxymethylsilyl)methyl (meth)acrylate, and mixtures thereof.

[0020] Preferably, the monomer (meth)acrylate unit content relative to the PI polymer is greater than 50% by weight, preferably greater than or equal to 70% by weight relative to the total weight of said PL polymer

[0021] The monomer unit constituting the main chain may contain a unit composed of a monomer comprising a (meth)acryloyl group different from the aforementioned (meth)acrylate monomer. Examples of such monomers include (meth)acrylic acids, monomers containing an amido group (such as, for example, N-methylolacrylamide), monomers comprising an epoxy group (such as, for example, glycidyl acrylate), monomers comprising an amine group (such as diethylaminoethyl acrylate), and mixtures thereof.

[0022] The monomer unit constituting the main chain may contain a unit composed of a monomer copolymerizable with the aforementioned (meth)acrylate monomer. Examples of monomers that can be copolymerized with the aforementioned (meth)acrylate monomer include styrene monomers (such as vinyltoluene, alpha-methylstyrene, chlorostyrene), vinyl monomers containing a fluorine atom (such as para-fluoroethylene, perfluoropropylene), vinyl monomers containing a Si atom (such as vinyltrimethoxysilane, vinyltriethoxysilane); maleic anhydride, maleic acid, fumaric acid, maleimide monomers, vinyl monomers containing a nitrile group (such as acrylonitrile), vinyl ester monomers (such as vinyl acetate), vinyl chloride, allyl chloride, polyoxyethylene (meth)acrylate, and mixtures thereof.

[0023] Preferably, the PI polymer is: i. a polymer in which the monomer unit constituting the main chain is composed of an acrylate monomer and a methacrylate monomer; or ii. a polymer in which the monomer unit constituting the main chain is composed of an acrylate monomer.

[0024] The PI polymer comprises at least one function of formula (I) above, preferably at least two, and preferably in terminal position.

[0025] Preferably, in formula (I), R represents an alkyl group comprising from 1 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, or an aralkyl group comprising from 7 to 20 carbon atoms. Preferably, R represents an alkyl group comprising from 1 to 20 carbon atoms.

[0026] Preferably, in formula (I), the hydrolyzable group X is a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, an amino group, an amide group, or a mercapto group. Preferably, X is an alkoxy group.

[0027] The PI polymer preferably has at least one function of formula (LA):

[0028] [Chem.3]

[0029] in which: - R' and R each represent, independently of each other, an alkyl group having from 1 to 20 carbon atoms; - p represents 1, 2 or 3, preferably 2 or 3.

[0030] Preferably, the PI polymer comprises at least one function of formula (I) or (IA) selected from dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, more preferably trimethoxysilyl and dimethoxymethylsilyl.

[0031] Advantageously, the PI polymer has a number-average molar mass of between 500 g / mol and 70,000 g / mol, preferably between 4,000 g / mol and 60,000 g / mol, more preferably between 10,000 g / mol and 50,000 g / mol.

[0032] The molar mass of 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-type standards.

[0033] The PI polymer can be obtained by different polymerization methods.

[0034] Radical polymerization methods can be classified into "general radical polymerization" and "controlled radical polymerization." General radical polymerization is a polymerization method that typically involves simple polymerization using a polymerization initiator such as, for example, an azo compound or a peroxide. In contrast, "controlled radical polymerization" is notably a method capable of introducing a specific functional group into a controlled site such as an end. "Controlled radical polymerization" methods can be classified into "chain transfer agent polymerization" and "live radical polymerization." "Chain transfer agent polymerization" is characterized by polymerization using a chain transfer agent containing a specific functional group and produces a vinyl polymer containing the functional group at one end.In contrast, “live radical polymerization” is characterized by the fact that a growing polymer end develops without side reactions such as termination, and this method produces a polymer with a molecular weight almost as high as expected. In the present invention, one of these polymerization methods can be used.

[0035] Specific examples of “general radical polymerization” include solution polymerization and bulk polymerization, which typically involve the addition of a polymerization initiator, chain transfer agent, solvent, etc., followed by polymerization, for example, between 50°C and 150°C.

[0036] Examples of polymerization initiators include: azo compounds such as 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate) , 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], and l,l'-azobis(cyclohexane-l-carbonitrile); diacyl peroxides such as benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, and di(3,5,5-trimethylhexanoyl) peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-1-methyllieptyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate; peroxyesters such as tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl diperadipate, and cumyl perneodecanoate;Ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, and 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as cumene hydroperoxide and tert-butyl hydroperoxide; and peroxides such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane. One of these polymerization initiators may be used alone, or two or more of these initiators may be used in combination.

[0037] Examples of chain transfer agents include compounds containing a mercapto group such as n-dodecylmercaptan, tert-dodecylmercaptan, and laurylmercaptan.

[0038] The silylated group, in particular of formula (I) mentioned above, can be introduced into the PI polymer by different and varied methods. Examples include:

[0039] i) a method in which a monomer having a polymerizable double bond and a reactive silyl group (in particular of formula (I)) is copolymerized with monomers lacking a reactive silyl group;

[0040] ii) a method where the monomers copolymerize in the presence of a mercaptosilane compound (having in particular a silylated group of formula (I)) as a chain transfer agent;

[0041] iii) a method wherein a compound having a polymerizable double bond and a reactive silyl group (in particular of formula (I)) copolymerized with the monomers in the presence of a mercaptosilane as a transfer agent.

[0042] Examples of compounds having a polymerizable double bond and a reactive silyl group for method i) may be gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-acryloxypropyltriethoxysilane, vinyltriethoxysilane or vinyltrimethoxysilane.

[0043] Examples of mercaptosilane of the method ü) may be 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, 3-mercaptopropylchloromethyldimethoxysilane, 3-mercaptopropylmethoxymethyldimethoxysilane, 3-mercaptopropylaminomethyldimethoxysilane, and 3-mercaptopropyl-N,N-dimethylaminomethyldimethoxysilane.

[0044] Examples of solvents typically include: aromatic compounds such as toluene, xylene, styrene, ethylbenzene, p-dichlorobenzene, di-2-ethylhexyl phthalate, and di-n-butyl phthalate; hydrocarbon compounds such as hexane, heptane, octane, cyclohexane, and methylcyclohexane; carboxylate compounds such as butyl acetate, n-propyl acetate, and isopropyl acetate; ketones; dialkyl carbonates such as, for example, dimethyl carbonate; alcohols such as, for example, n-propanol or n-butanol.

[0045] Polymer P2

[0046] The polymer P may further also comprise at least one oxyalkylene polymer P2 comprising at least one function of formula (I) as defined above.

[0047] The oxyalkylene polymer P2 contains a repeating unit -R”-O- in which R' ' represents a linear or C2-C14 branched alkylene divalent radical.

[0048] Preferably, R represents -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH(C2H5)CH2-, -CH2 CH2CH2CH2-, and -C(CH3)2CH2-.

[0049] The polymer P2 may consist of a single repeating unit or several.

[0050] The polymer P2 can be linear or branched or a mixture.

[0051] The main chain of the P2 polymer can be obtained by ring-opening polymerization of a monoepoxide compound such as, for example, ethylene oxide or propylene oxide, in the presence of an initiator and a catalyst

[0052] Examples of initiators may be alcohols such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol.

[0053] Examples of catalysts may be KOH, NaOH, cobalt zinc cyanide complexes.

[0054] The main chain of the P2 polymer can also be obtained by a method in which the main chain is prepared by a chain extension reaction of a polyether polymer terminated by a hydroxy group with a bifunctional or polyfunctional alkyl halide such as CH2C12 and CH2Br2, in the presence of a basic compound such as KOH, NaOH, KOCH3, and NaOCH3.

[0055] Among these methods, the method which involves ring-opening polymerization of a monoepoxide in the presence of a metal cyanide complex catalyst double is preferred because the resulting polymer has a narrow molecular weight distribution and low viscosity.

[0056] The number of silylated groups of formula (I) in each oxyalkylene polymer P2 is preferably at least 0.8, preferably from 0.8 to 3, and preferably again from 0.8 to 2.0, on average.

[0057] The P2 polymer can have a number-average molecular weight (Mn) ranging from 10,000 to 100,000 g / mol, preferably from 10,000 to 45,000 g / mol.

[0058] The silylated groups of formula (I) can be introduced by any method known in this field.

[0059] For example, they can be introduced by one of the following methods: a. An organic polymer comprising a functional group such as a hydroxy group, an epoxy group, is reacted with a compound comprising a reactive group said functional group and a reactive silyl group (in particular of formula (I)); b. An organic polymer containing a functional group, such as a hydroxyl group, is reacted with an organic compound comprising a reactive group of said functional group and an unsaturation to prepare an organic polymer containing an unsaturation. Alternatively, in the polymerization reaction, the monomer containing an unsaturation (not involved in the polymerization reaction) is copolymerized to prepare an organic polymer containing an unsaturation. For example, in the case of ring-opening polymerization of a monoepoxide to prepare an organic polymer, a monoepoxide containing an unsaturation is copolymerized to prepare an organic polymer containing an unsaturation. The resulting polymer is then reacted with a hydrosilane containing a silyl group (in particular, of formula (I)). c. An organic polymer containing an unsaturation, prepared in the same way as method b)) is reacted with a mercaptosilane.

[0060] The hydrosilylation step of method b) can be carried out in the presence of an H2PtCl6.H2O type catalyst.

[0061] Hydrosilane can be selected from trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, trimethoxysilane, triethoxysilane, methyldimethoxysilane, methydiethoxysilane, phenyldimethoxysilane.

[0062] Hydrosilylation can be carried out at a temperature ranging from 50°C to 150°C, preferably from 70°C to 120°C.

[0063] Method c) can be carried out in the presence of a radical initiator. The mercaptosilanes can be 3-mercaptopropyltrimethoxysilane, 3- mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, 3-mercaptopropylchloromethyldimethoxysilane, 3-mercaptopropylmethoxymethyldimethoxysilane, 3-mercaptopropylaminomethyldimethoxysilane, and 3-mercaptopropyl-N,N-dimethylaminomethyldimethoxysilane.

[0064] There are also commercial products as P2 polymer such as, for example, MS 203H (methyldimethoxysilyl), MS303H (methyldimethoxysilyl), SAX510 (trimethoxysilyl) marketed by KANEKA.

[0065] The polymer P2 comprises at least one function of formula (I) above, preferably at least two, and preferably in a terminal position.

[0066] Preferably, in formula (I), R represents an alkyl group comprising from 1 to 20 carbon atoms, an aryl group comprising from 6 to 20 carbon atoms, or an aralkyl group comprising from 7 to 20 carbon atoms. Preferably, R represents an alkyl group comprising from 1 to 20 carbon atoms.

[0067] Preferably, in formula (I), the hydrolyzable group X is a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, an amino group, an amide group, or a mercapto group. Preferably, X is an alkoxy group.

[0068] The polymer P2 preferably has at least one function of formula (LA):

[0069] [Chem.4] -SiR^OR'îp (lA)

[0070] in which: - R' and R each represent, independently of each other, an alkyl group having from 1 to 20 carbon atoms; - p represents 1, 2 or 3, preferably 2 or 3.

[0071] Preferably, the polymer P2 comprises at least one function of formula (I) or (LA) chosen from dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, more preferably trimethoxysilyl and dimethoxymethylsilyl.

[0072] Polymer P

[0073] The polymer P according to the invention preferably has a Brookfield viscosity greater than or equal to 70 Pa.s at 23°C.

[0074] More preferably, the polymer P has a Brookfield viscosity greater than or equal to 100 Pa.s at 23°C.

[0075] Even more preferably, the polymer P has a Brookfield viscosity greater than or equal to 120 Pa.s at 23°C.

[0076] The Brookfield viscosity of polymer P can, for example, be measured at 23°C using a Brookfield model DV2T device with an S64 needle. Typically, the sample is placed at 23°C for a few minutes, the needle is chosen for testing between 2 and 15 rpm, and the viscosity value is recorded after 30 seconds of rotation.

[0077] Polymer P can be obtained by mixing polymers PI and P2 at a temperature ranging from 20°C to 60°C.

[0078] Polymer P can be obtained during the preparation of polymer PI as described above.

[0079] There are also commercial products as P polymer, such as for example MA480, MAX602 or MA490 marketed by KANEKA.

[0080] The mass content of polymer P is preferably from 5% to 60% by weight, more preferably from 10% to 50% by weight, and even more preferably from 10% to 40% by weight relative to the total weight of said composition. Polymer P'

[0081] The composition comprises a polyurethane P' comprising at least one function of formula (II):

[0082] [Chem.5] -SiRVXt (II)

[0083] in which: - R' ' represents a hydrocarbon group having from 1 to 20 carbon atoms, possibly substituted and / or comprising one or more heteroatoms; - X' is a hydroxyl group or a hydrolyzable group; - t represents 1, 2 or 3.

[0084] Polyurethane P' is preferably obtained by a process comprising the following steps:

[0085] - a-1) the polyaddition reaction between a composition of polyol(s) and a composition of polyisocyanate(s), in the presence of a catalyst to prepare a polyurethane with NCO terminations;

[0086] - a-2) the reaction of the NCO-terminated polymer obtained in step a-1) with a organosilane compound having at least one reactive function with the -NCO function of NCO-terminated polyurethane. Polyol

[0087] The aforementioned polyol(s) composition may consist of a polyol or a mixture of polyols.

[0088] The usable polyol(s) may be chosen from those having an average number molecular mass ranging from 200 g / mol to 20,000 g / mol, preferably from 400 g / mol to 18,000 g / mol.

[0089] The number-average molecular mass of polyols can be calculated from the hydroxyl number (HN) expressed in mg KOH / g and the functionality of the polyol or determined by methods well known to those skilled in the art, for example by size exclusion chromatography (or SEC) with PEG (polyethylene glycol) as a standard.

[0090] Polyols can have a hydroxyl functionality from 2 to 6, preferably 2 to 3. In the context of the invention, and unless otherwise stated, the hydroxyl functionality of a polyol is the average number of hydroxyl functions per mole of polyol.

[0091] The usable polyol(s) may be chosen from polyester polyols, polyether polyols, polydiene polyols, polycarbonate polyols, poly(ether-carbonate) polyols, -OH-terminated prepolymers, and mixtures thereof.

[0092] The usable polyol(s) may be chosen from aromatic polyols, aliphatic polyols, carbonate polyols and mixtures of these compounds.

[0093] According to the invention, the polyester polyol(s) can have a number average molecular mass ranging from 1,000 g / mol to 10,000 g / mol, preferably from 2,000 g / mol to 6,000 g / mol.

[0094] Examples of polyester polyols include:

[0095] - naturally derived polyol polyesters such as castor oil;

[0096] - polyester polyols resulting from condensation:

[0097] - of one or more aliphatic polyols (linear, branched or cyclic) or aromatics such as, for example, ethanediol, 1,2-propanediol, 1,3-propanediol, glycerol, trimethylolpropane, 1,6-hexanediol, 1,2,6-hexanetriol, butenediol, sucrose, glucose, sorbitol, pentaerythritol, mannitol, triethanolamine, N-methyldiethanolamine, and mixtures thereof, with

[0098] - one or more polycarboxylic acids or their ester or anhydride derivatives such as that 1,6-hexanedioic acid, dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, 1,18-octadecanedioic acid, phthalic acid, succinic acid and mixtures of these acids, an unsaturated anhydride such as maleic or phthalic anhydride, or a lactone such as caprolactone.

[0099] The aforementioned polyester polyols can be prepared conventionally, and are mostly commercially available.

[0100] Among polyester polyols, the following products with a hydroxyl functionality of 2 may be cited as examples:

[0101] - TONE® 0240 (marketed by UNION CARBIDE) which is a polycaprolactone with an average number molecular mass of approximately 2000 g / mol, and a melting point of approximately 50°C,

[0102] - DYNACOLL®7381 (marketed by EVONIK) with average molecular weight in a quantity of approximately 3500 g / mol, and having a melting point of approximately 65°C,

[0103] - DYNACOLL®7360 (marketed by EVONIK) which results from condensation of adipic acid with hexane diol, and has a number-average molecular mass of approximately 3500 g / mol, and a melting point of approximately 55°C,

[0104] - DYNACOLL®7330 (marketed by EVONIK) with a molecular mass average number density of approximately 3500 g / mol, and having a melting point of approximately 85°C,

[0105] - DYNACOLL®7363 (marketed by EVONIK) which also results from the condensation of adipic acid with hexane diol, and has a number-average molecular mass of approximately 5500 g / mol, and a melting point of approximately 57°C,

[0106] - DYNACOLL ® 7250 (marketed by EVONIK): polyester polyol having a viscosity of 180 Pa.s at 23°C, a number-average molecular mass (Mn) of 5500 g / mol, and a Tg of -50°C,

[0107] - KURARAY® P-6010 (marketed by KURARAY): polyester polyol having a viscosity of 68 Pa.s at 23°C, a number-average molecular mass of 6000 g / mol, and a Tg of -64°C,

[0108] - KURARAY® P-10010 (marketed by KURARAY): polyester polyol having a viscosity of 687 Pa.s at 23°C, and a number-average molecular mass of 10,000 g / mol.

[0109] According to a preferred embodiment, the polyester polyol is selected from: a polycaprolactone; castor oil; a polyester polyol resulting from the condensation of ethylene glycol, propylene glycol, 1,3-propanediol and / or 1,6-hexanediol with adipic acid and / or the various isomers of phthalic acid; and mixtures thereof.

[0110] According to the invention, the polyether polyol(s) may have a number average molecular mass ranging from 200 to 20,000 g / mol, preferably from 400 to 18,000 g / mol.

[0111] Preferably, the polyether polyol(s) has a hydroxyl functionality ranging from 2 to 3.

[0112] The polyether polyol(s) usable according to the invention is (are) preferably chosen from polyoxyalkylene-polyols, the alkylene part of which, linear or branched, comprises from 1 to 4 carbon atoms, preferably from 2 to 3 carbon atoms.

[0113] More preferably, the polyether polyol(s) usable according to the invention is / are preferably chosen from polyoxyalkylene diols or polyoxyalkylene triols, and even better from polyoxyalkylene diols, the alkylene portion of which is linear or branched, comprises 1 to 4 carbon atoms, preferably 2 to 3 carbon atoms.

[0114] By way of example of polyoxyalkylene diols or triols that can be used according to the invention, one may cite, for example:

[0115] - polyoxypropylene diol or triol (also referred to as polypropylene glycols (PPG) diol or triol) having a number-average molecular mass ranging from 400 g / mol to 18,000 g / mol and preferably ranging from 400 g / mol to 12,000 g / mol,

[0116] - polyethylene diol or triol (also referred to as polyethylene glycols (PEG) diol or triol) having a number-average molecular mass ranging from 400 g / mol to 18,000 g / mol and preferably ranging from 400 g / mol to 12,000 g / mol,

[0117] - polyoxybutylene glycols (also referred to as polybutylene glycols (PBG) diol or triol) having a number-average molecular mass ranging from 200 g / mol to 12,000 g / mol,

[0118] - copolymers or terpolymers of PPG / PEG / PBG diol or triol having a mass average molecular number ranging from 400 g / mol to 18,000 g / mol and preferably ranging from 400 g / mol to 12,000 g / mol,

[0119] - polytetrahydrofuran (PolyTHF) diol or triol having a molecular mass number average ranging from 250 g / mol to 12,000 g / mol,

[0120] - polytetramethylene glycols (PTMG) having an average molecular weight in numbers ranging from 200 g / mol to 12,000 g / mol,

[0121] - and their mixtures.

[0122] Preferably, the usable polyether polyol(s) is / are chosen from polyoxypropylene diols or triols. The polyether polyols mentioned above can be prepared conventionally and are widely available commercially. They can, for example, be obtained by polymerization of the corresponding alkylene oxide in the presence of a catalyst based on a metal-cyanide double complex.

[0123] Examples of polyether diols include polyoxypropylene diols marketed under the name "ACCLAIM®" by the company Covestro, such as "ACCLAIM® 12200" with a number-average molecular mass of approximately 11,335 g / mol, "ACCLAIM® 8200" with a number-average molecular mass of approximately 8,057 g / mol, and "ACCLAIM® 4200" with a number-average molecular mass of approximately 4,020 g / mol, or polyoxypropylene diol marketed under the name "VORANOL P2000" by the company DOW with a number-average molecular mass of approximately 2,004 g / mol.

[0124] Examples of polyether triols include polyoxypropylene triol marketed under the name "VORANOL CP3355" by DOW, with a number-average molecular mass of approximately 3,554 g / mol.

[0125] The polydiene polyol(s) usable according to the invention may preferably be chosen from among polydienes having terminal hydroxyl groups, and their corresponding hydrogenated or epoxidized derivatives.

[0126] Preferably, the polydiene polyol(s) usable according to the invention is / are selected from polybutadienes having terminal hydroxyl groups, optionally hydrogenated or epoxidized. Preferably, the polydiene polyol(s) usable according to the invention is / are selected from butadiene homopolymers and copolymers having terminal hydroxyl groups, optionally hydrogenated or epoxidized.

[0127] In the context of the invention, and unless otherwise stated, "terminal hydroxyl groups" of a polydiene polyol means the hydroxyl groups located at the ends of the main chain of the polydiene polyol.

[0128] The hydrogenated derivatives mentioned above can be obtained by total or partial hydrogenation of the double bonds of a polydiene having terminal hydroxyl groups, and are therefore saturated or unsaturated.

[0129] The epoxide derivatives mentioned above can be obtained by chemoselective epoxidation of the double bonds of the main chain of a polydiene having terminal hydroxyl groups, and therefore have at least one epoxy group in its main chain.

[0130] Examples of polybutadiene polyols include homopolymers of butadiene, saturated or unsaturated, comprising terminal hydroxyl groups, possibly epoxidized, such as for example those marketed under the name POLY BD® or KRASOL® by the company CRAY VALLEY.

[0131] As an example of polycarbonate diol, we can cite CONVERGE POLYOL 212-10 and CONVERGE POLYOL 212-20 marketed by the company NOVOMER with number molecular mass (Mn) of 1000 and 2000 g / mol respectively, whose hydroxyl numbers are 112 and 56 mg KOH / g respectively, DESMOPHEN® C XP 2716 marketed by COVESTRO with number molecular mass (Mn) of 326 g / mol and hydroxyl number of 344 mg KOH / g, POLYOL C-590, C1090, C-2090 and C-3090 marketed by KURARAY having a number molecular mass (Mn) ranging from 500 to 3000 g / mol and a hydroxyl number ranging from 224 to 37 mg KOH / g.

[0132] Preferably, the polyol composition(s) consists of one or more polyols selected from those mentioned above and mixtures thereof. In particular, the polyol composition(s) may consist of one or more polyols, including at least one polyether polyol. More specifically, the polyol composition(s) may consist of one or more polyether polyols. Polyisocyanate(s)

[0133] In the context of the invention, "polyisocyanate" means a compound comprising at least two isocyanate groups (NCO).

[0134] The aforementioned polyisocyanate(s) composition may consist of a polyisocyanate or a mixture of polyisocyanates.

[0135] The usable polyisocyanate(s) may be chosen from those typically used in the synthesis of an NCO-terminated polyurethane.

[0136] The usable polyisocyanate(s) may be aliphatic (linear or branched) or aromatic, and possibly substituted.

[0137] Preferably, the polyisocyanate(s) is / are chosen from among the diisocyanates, the triisocyanates, and their mixtures.

[0138] According to a preferred embodiment, the polyisocyanate(s) is / are selected from the group consisting of pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, isophorone diisocyanate (IPDI), norbornane diisocyanate, norbornene diisocyanate, 1,4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate, ethyl-cyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, cyclohexane dimethylene diisocyanate, and 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), toluene diisocyanate (TDI), diphenylemethylene diisocyanate (MDI), dicyclohexylemethylene diisocyanate (H12-MDI), xylylene diisocyanate (XDI) (in particular meta-xylylene diisocyanate (m-XDI)), and mixtures thereof.

[0139] MDI can be in the form of an isomer or a mixture of isomers, such as 4,4'-MDI and / or 2,4'-MDI.

[0140] TDI can be in the form of an isomer or a mixture of isomers, such as 2,4-TDI and / or 2,6-TDI.

[0141] Preferably, the polyisocyanate is MDI, and in particular 4,4'-MDI.

[0142] The polyisocyanate(s) that can be used to prepare the polyurethane used according to the invention are typically widely available commercially. For example, one can cite SCURANATE® TX, marketed by VENCOREX, corresponding to a 2,4-TDI with a purity of approximately 95%, SCURANATE® T100, also marketed by VENCOREX, corresponding to a 2,4-TDI with a purity greater than 99% by weight, and DESMODUR® I, marketed by the company COVESTRO, corresponding to an IPDI, or ISONATE ® M125 marketed by DOW, corresponding to an MDI containing at least 97% by weight of the 4,4'-MDI isomer.

[0143] Preferably, the polyisocyanate composition comprises IPDI.

[0144] In the context of the invention, the expressions "polyaddition reaction" and "polyaddition" are understood to be equivalent.

[0145] The polyaddition step can be carried out at a temperature below 95°C, preferably from 60°C to 90°C, more preferably from 65°C to 80°C.

[0146] The polyaddition step can be carried out under anhydrous conditions, for example under a nitrogen atmosphere.

[0147] The polyaddition step can be carried out in quantities of polyisocyanate(s) and polyol(s) such that the NCO / OH molar ratio is strictly greater than 1, for example between 1.1 and 2.5, preferably between 1.1 and 2.2, preferably between 1.2 and 2.0, for example between 1.20 and 1.80, advantageously between 1.20 and 1.50, in particular between 1.30 and 1.40, so as to advantageously obtain an NCO-terminated polyurethane.

[0148] In the context of the invention, and unless otherwise stated, the NCO / OH molar ratio corresponds to the molar ratio of the number of isocyanate groups (NCO) to the number of hydroxyl groups (OH) carried respectively by the polyisocyanates and polyols used.

[0149] The catalyst can be any catalyst known to a person skilled in the art of polyaddition reactions and the preparation of polyurethane. For example, it could be BORCHI® KAT 0761 (CAS number: 27253-29-8, zinc neodecanoate) available from BORCHERS, TIB KAT® 616 (zinc neodecanoate) available from TIB CHEMICALS, or K-KAT XK-664 (zinc carboxylate) marketed by KING INDUSTRIES.

[0150] The total content of catalyst used in the polyaddition reaction can range from 0.001% to 1% by weight, preferably from 0.01% to 0.8% by weight, preferably from 0.015% to 0.5% by weight relative to the total weight of the reactants used in the polyaddition reaction.

[0151] NCO-terminated polyurethane may have a number-average molecular weight ranging from 1,000 g / mol to 50,000 g / mol, preferably from 1,000 g / mol to 30,000 g / mol, preferably from 5,000 g / mol to 20,000 g / mol, advantageously from 15,000 g / mol to 25,000 g / mol.

[0152] The number-average molecular weight of NCO-terminated polyurethanes can be measured by methods well known to those skilled in the art, for example by size exclusion chromatography (or SEC) using polyethylene glycol-type standards.

[0153] NCO-terminated polyurethane may have a polymolecularity index ranging from 1.5 to 3.5, preferably from 2.0 to 3.3.

[0154] In the context of the invention, the polymolecularity index is defined as the ratio Mw (weight average molecular mass) / Mn (number average molecular mass) of polyurethane.

[0155] The polyurethane with NCO terminations may have a mass content of NCO groups ranging from 0.1% to 5% by weight, preferably from 0.1% to 1% by weight relative to the total weight of the polyurethane. Step a-2)

[0156] Step a-2) of the process according to the invention corresponds to the reaction of the NCO-terminated polyurethane obtained in step a-1) with an organosilane compound having at least one reactive function with the -NCO function of the NCO-terminated polymer.

[0157] The organosilane compound may be selected from mercaptosilanes and aminosilanes, preferably aminosilanes.

[0158] Aminosilanes contain an amine function as a reactive function with the -NCO function of the NCO-terminated polymer.

[0159] Aminosilane preferably has the following formula (III);

[0160] [Chem.6] (RaOMR')34S^^ (!!!)

[0161] in which:

[0162] - R” and Ra each represent, independently of each other, an alkyl group having from 1 to 20 carbon atoms;

[0163] -1 represents 1, 2 or 3, preferably 2 or 3;

[0164] - R3 represents a linear or branched divalent alkylene radical comprising 1 with 12 carbon atoms, preferably from 1 to 6 carbon atoms, R3 preferably representing methylene or n-propylene, and

[0165] - R6 represents H, a linear or branched alkyl radical, an arylalkyl radical, a cyclic radical comprising 1 to 20 carbon atoms.

[0166] According to a preferred embodiment, the aminosilane of formula (III) is that in which:

[0167] - R” and Ra each represent, independently of each other, an alkyl group having from 1 to 20 carbon atoms;

[0168] -1 represents 1, 2 or 3, preferably 2 or 3,

[0169] - R3 represents a linear or branched divalent alkylene radical comprising 1 with 12 carbon atoms, preferably from 1 to 6 carbon atoms, R1 preferably representing methylene or n-propylene, and

[0170] - R6 represents a linear or branched alkyl radical comprising from 1 to 10 atoms of carbon.

[0171] The aminosilanes of formula (III) above are preferably primary aminosilanes such as, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane; secondary aminosilanes such as, for example, N-butyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane.

[0172] Aminosilanes may be commercially available such as, for example, Dynasylan® 1189 marketed by Evonik. Terms

[0173] Step a-2) can be carried out under anhydrous conditions.

[0174] Step a-2) can be carried out at a temperature less than or equal to 95°C, preferably at a temperature ranging from 50°C to 80°C.

[0175] Step a-2) can be carried out in a time ranging from 5 to 30 min, preferably from 10 to 20 min.

[0176] According to one embodiment, step a-2) is carried out in quantities of NCO-terminated polyurethane and aminosilanes such that the NH / NCO molar ratio is between 0.90 and 1.00, preferably between 0.95 and 1.00.

[0177] In the context of the invention, and unless otherwise stated, the NH / NCO molar ratio corresponds to the molar ratio of the number of NH groups carried by the aminosilane to the number of isocyanate (NCO) groups carried by the NCO-terminated polymer.

[0178] The polymer P' preferably has at least one function of formula (ILA):

[0179] [Chem.7] -SiR'MOR3), (HA)

[0180] in which: - R” and Ra each represent, independently of each other, an alkyl group having from 1 to 20 carbon atoms; - t represents 1, 2 or 3, preferably 2 or 3.

[0181] Preferably, the polyurethane P' comprises one or more of the above formula groups (II) or (ILA) selected from the trimethoxysilyl groups, triethoxysilyl groups, methyldimethoxysilyl groups, methyldiethoxysilyl groups, dimethylmethoxysilyl groups, and dimethylethoxysilyl groups.

[0182] Even more preferably, polyurethane P' comprises trimethoxysilyl groups.

[0183] Polyurethane P' may have a number average molecular mass ranging from 500 to 100,000 g / mol, preferably still ranging from 700 to 50,000 g / mol, and preferably from 1,000 to 30,000 g / mol.

[0184] The number-average molecular mass of the polymers can be measured by methods well known to those skilled in the art, for example by size-exclusion chromatography using polyethylene glycol-type standards.

[0185] The polyurethane P' can have a viscosity at 23°C, less than or equal to 350,000 mPa.s, preferably less than or equal to 300,000 mPa.s, more preferably ranging from 10,000 mPa.s to 300,000 mPa.s, in particular from 20,000 mPa.s to 250,000 mPa.s, advantageously from 20,000 to 120,000 mPa.s.

[0186] The viscosity of polyurethane P' can be measured using a Brookfield viscometer according to ISO 2555 (2018). Typically, the measurement at 23°C can be carried out using a Brookfield RVT viscometer, a needle adapted to the viscosity range, and a rotation speed of 20 revolutions per minute.

[0187] Polyurethane P' preferably has the formula (IV) below:

[0188] [Chem.8] (IV)

[0189] in which:

[0190] - R1 represents a divalent hydrocarbon radical comprising 5 to 15 atoms of carbon, which can be aromatic, aliphatic, or cyclic.

[0191] - R3 represents a linear or branched divalent alkylene radical comprising 1 to 6 carbon atoms, preferably R3 representing methylene or n-propylene,

[0192] - R2 represents a linear or branched divalent alkylene radical comprising 2 to 4 carbon atoms,

[0193] - Ra and R are as defined above, preferably Ra and R, identical or different, each represent a linear or branched alkyl radical comprising 1 to 4 carbon atoms, more preferably Ra and R representing methyl,

[0194] - R6 is as defined above, preferably R6 represents an alkyl radical linear or branched comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms;

[0195] - m is a non-zero integer,

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202] - n and m are such that the number-average molecular mass of the polymer of formula (III) ranges from 500 g / mol to 50,000 g / mol, preferably from 700 g / mol to 22,000 g / mol, -1 is an integer equal to 1, 2 or 3. Preferably, the radical R1 is chosen from one of the following divalent radicals whose formulas below show the 2 free valences: - a) the divalent radical derived from isophorone diisocyanate (IPDI): [Chem.9] CH - b) the divalent radical derived from 4,4'- and 2,4'-dicyclohexylmethane diisocyanate (HMDI): [Chem. 10] [Chem. 10] H-----{

[0203]

[0204] Or - c) the radical derived from 2,4- and 2,6-toluene diisocyanate (TDI) [Chem. 11] [Chem. 11]

[0205] - d) the radical derived from 4,4'- and 2,4'-diphenylmethane diisocyanate (MDI)

[0206] [Chem. 12] —\^“ ch =-^7“ [Chem. 12] Or

[0207] - e) the radical derived from m-xylylene dusocyanate (m-XDI)

[0208] [Chem. 13]

[0209] - f) the radical derived from hexamethylene düsocyanate (HDI)

[0210] [Chem. 14]

[0211] Preferably, the radical R1 is the divalent radical derived from isophorone dusocyanate.

[0212] The mass content of polymer P' preferably ranges from 5% to 60% by weight, more preferably from 10% to 50% by weight, and even more preferably from 10% to 40% by weight relative to the total weight of said composition. Carbon black

[0213] The composition comprises carbon black having an oil absorption index (OAN) of at least 80 mL / 100 g. Thus, its content is strictly greater than 0% by weight relative to the total weight of said composition.

[0214] The mass content of carbon black in the composition is preferably less than or equal to 20% by weight relative to the total weight of said composition. More preferably, the mass content of said carbon black is less than or equal to 15% by weight, and even more preferably less than or equal to 10% by weight relative to the total weight of said composition.

[0215] Even more preferably, the carbon black content in the composition ranges from 2% to 8% by weight relative to the total weight of said composition.

[0216] The OAN of a carbon black corresponds to the volume in mL of dibutyl phthalate oil (DBP) absorbed by 100 g of carbon black

[0217] The OAN can for example be measured according to the ASTM D-2414 method and using DBP oil.

[0218] Unless otherwise indicated, the standards referred to throughout the application are those in force at the date of filing of the application.

[0219] Preferably, the OAN of carbon black is at least 90 mL / 100g, more preferably at least 100 mL / 100g.

[0220] The carbon black implemented in the present invention is generally called “structural” carbon black, and is distinguished from carbon blacks generally used as pigments, in particular by its high OAN.

[0221] Indeed, the carbon blacks used as pigments are of lower quality and have a lower OAN than the carbon black implemented in the present invention.

[0222] An example of carbon black used as a pigment is PRINTEX® 25 (marketed by Orion) which has an OAN of 45 mL / 100 g.

[0223] Examples of carbon black that can be used in the present invention are ELFTEX® S7100 and ELFTEX® S5100 (marketed by CABOT), having an OAN of approximately 117 and 108 mL / 100 g, respectively. Rheology agent

[0224] The rheology agent typically allows the rheological properties of a composition to be adjusted.

[0225] Preferably, the composition according to the invention comprises a rheology agent.

[0226] By way of example, one can cite any rheology agent commonly used in the field of adhesive or sealant compositions.

[0227] Advantageously, the rheology agent comprises one or more thixotropic agents, the thixotropic agents being, for example, solid at 23°C and / or having a viscosity at 23°C greater than 200 mPa·s according to ISO 12058-1, preferably solid at 23°C. A thixotropic agent generally influences the thixotropy of a composition. Thixotropy is the property of certain compositions to become less viscous when a constant force (e.g., constant stress shear) is applied and, after the loading is stopped, the viscosity returns to its initial state after an appropriate time. The higher the force, the greater the decrease in viscosity.

[0228] In particular, one or more rheological agents are used, selected from:

[0229] - PVC plastisols, corresponding to a suspension of PVC in an agent plasticizer miscible with PVC, obtained in situ by heating to temperatures ranging from 60°C to 80°C. These plastisols can, for example, be those described in particular in the book "Polyurethane Sealants", Robert M. Evans, ISBN 087762-998-6;

[0230] - fumed silica, such as HD K® N20 marketed by WACKER;

[0231] - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such that 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in application FR 1 591 172;

[0232] - waxes derived from castor oil, such as THIXCIN® R available from ELEMENTIS,

[0233] - amide waxes, preferably micronized, such as CRAYVALLAC® SLX, CRAYVALLAC® SLW or CRAYVALLAC® SUPER marketed by Arkema, or THIXATROL® AS8053 or THIXATROL® MAX (EC No. 432-430-3) which are available from ELEMENTIS, or RHEOBYK 7503 marketed by BYK.

[0234] These rheology agents are preferably thixotropic agents.

[0235] “Waxes derived from castor oil” means waxes obtained from castor oil, in particular hydrogenated castor oil. Waxes derived from castor oil are solid at 23 °C.

[0236] The term "amide waxes" means waxes comprising one or more compounds having at least one amide group. In particular, amide waxes can be obtained from fatty acid(s) (for example, ricinoleic acid) and (di)amine(s). Amide waxes are solid at 23°C.

[0237] Preferably, the rheology agent is an amide wax and / or a wax derived from castor oil, more preferably an amide wax.

[0238] The amide waxes are preferably micronized, that is to say, they have an average particle size of less than 1 mm. Advantageously, the amide waxes have an average particle size of less than 500 pm, preferably less than 100 pm, more preferably less than 10 pm.

[0239] The average particle size advantageously corresponds to the d50 particle size, i.e. the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN type device (for example according to standard NF ISO 13320).

[0240] Wax-amide type rheological agents can be heat-activated, meaning that a temperature above ambient temperature (23°C) may be required to activate them (in particular, to activate their rheological properties, especially thixotropic properties) during the preparation of the composition according to the invention. The activation temperature depends on the rheological agent. For example, THIXATROL® AS8053 is generally activated at a temperature between 50°C and 55°C, and CRAYVALLAC® SLX is generally activated at a temperature between 75°C and 80°C.

[0241] Preferably, the content of rheology agent in the composition ranges from 0.2% to 20% by weight relative to the total weight of the composition, preferably from 1% to 10% by weight. Membership promoter

[0242] The composition according to the invention may further comprise at least one adhesion promoter.

[0243] Advantageously, the adhesion promoter is chosen from among amino-, mercapto- and epoxy-alkoxysilanes, preferably chosen from among aminoalkoxysilanes, more preferably from among aminotrialkoxysilanes, even more preferably, from among aminotrimethoxysilanes.

[0244] As an example of an epoxy-alkoxysilane, we can cite (3-Glycidyloxypropyl)trimethoxysilane (also called GLYMO).

[0245] Advantageously, aminotrimethoxysilanes are formed by the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane (for example, SILQUEST A-LINK 600 marketed by MOMENTIVE), (3-aminopropyl)trimethoxysilane (for example, DYNASYLAN® AMMO marketed by EVONIK), and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (for example, DYNASYLAN® DAMO or DAMO-T marketed by EVONIK). Preferably, aminotrimethoxysilanes are formed by the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane and (3-aminopropyl)trimethoxysilane.

[0246] Advantageously, the composition according to the invention comprises at least one adhesion promoter.

[0247] According to this preferred embodiment, the adhesion promoters are chosen from among the aminoalkoxysilanes, preferably from among the aminotrimethoxysilanes, more preferably from among the aminotrimethoxysilanes.

[0248] The content of adhesion promoter(s) in the composition according to the invention can range from 0% to 8% by weight relative to the total weight of the composition, preferably from 0.5% to 5% by weight. Charge

[0249] Advantageously, the composition according to the invention further comprises a filler.

[0250] Preferably, the filler is chosen from mineral fillers, organic fillers and their mixtures, more preferably from mineral fillers.

[0251] Advantageously, the mineral fillers are chosen from the group consisting of clay, quartz, hollow mineral microspheres, carbonate fillers, kaolinite and quartz aggregates, and mixtures thereof.

[0252] Kaolinite and quartz aggregates may be natural or artificially produced. The kaolinite content in the aggregates may be less than or equal to 15% by weight. The aggregates may be surface-modified by a silane coupling agent such as, for example, vinyltrimethoxysilane, vinyltriethoxysilane, or gamma-acryloyloxypropylmethyltriethoxysilane.

[0253] Commercial examples may be the AKTISIL range from Hoffmann Minerai such as Aktisil PF216, or the AKTIFIT range from Hoffmann Minerai.

[0254] Among hollow mineral microspheres, we can mention hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate.

[0255] According to a preferred embodiment, the composition according to the invention further comprises a carbonate filler, advantageously the carbonate filler is chosen from alkali or alkaline-earth metal carbonates and their mixtures, preferably the carbonate filler comprises calcium carbonate, more preferably the carbonate filler is chalk or calcium carbonate coated with fatty acids, even more preferably precipitated calcium carbonate coated with fatty acids.

[0256] When calcium carbonate is coated with fatty acids, this imparts total or partial hydrophobicity to the calcium carbonate particles. Furthermore, the fatty acid coating acts as a hydrophobic coating that can prevent the calcium carbonate from absorbing the constituents of the composition and rendering them ineffective. The hydrophobic coating of the calcium carbonate can represent from 0.1% to 3.5% by weight, relative to the total weight of calcium carbonate.

[0257] Preferably, the fatty acids coating the calcium carbonate comprise or consist of more than 50% by weight of stearic acid relative to the total weight of fatty acids.

[0258] As an example of non-precipitated fatty acid coated calcium carbonate, we can cite OMYACARB 2T-AV or OMYA BLH (marketed by OMYA), or CALATEM C16T (marketed by Provençale).

[0259] Examples of precipitated calcium carbonate coated with fatty acids include HAKUENKA® CCR-S10 (marketed by OMYA) or CALOFORT® (marketed by Specialty Minerals).

[0260] Advantageously, the organic fillers are selected from the group consisting of polyvinyl chloride (PVC), polyolefins, rubber, ethylene vinyl acetate (EVA), expandable or non-expandable thermoplastic polymer hollow microspheres (such as vinylidene chloride / acrylonitrile hollow microspheres) and aramid fibers (such as Kevlar®), preferably PVC.

[0261] Advantageously, the average particle size of the charge is between 10 nm and 400 pm, preferably between 20 nm and 100 pm, more preferably between 30 nm and 1 pm, even more preferably between 40 nm and 300 nm.

[0262] The average particle size advantageously corresponds to the d50 particle size, i.e. the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN type device (for example according to standard NF ISO 13320).

[0263] Advantageously, the total filler content ranges from 5% to 50% by weight relative to the total weight of the composition, preferably from 10% to 40% by weight, more preferably from 20% to 40% by weight relative to the total weight of said composition. Crosslinking catalyst

[0264] The composition according to the invention may further comprise a crosslinking catalyst.

[0265] The crosslinking catalyst may be any catalyst known to those skilled in the art for the condensation of silanol. Examples of such catalysts include:

[0266] - organic derivatives of titanium such as titanium acetyl acetonate (for example the TYZOR® AA75 marketed by Dorf Ketal),

[0267] - of aluminium such as aluminium chelate (for example K-KAT® 5218 marketed by KING INDUSTRIES),

[0268] - amines such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5- diazabicyclo[4.3.0]non-5-ene (DBN), diethyl ether-2,2'-morpholine (DMDEE), l,4-diazabicyclo[2.2.2]octane (DABCO),

[0269] - zinc carboxylate and DBU-based catalysts (e.g. K-KAT® 670 marketed by KING INDUSTRIES),

[0270] - tin-based catalysts such as dioctyltin derivatives or of dibutyltin; in particular dioctyltin oxide, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dicarboxylate, dibutyltin diacetyl acetonate (DBTDAA), dibutyltin dilaurate (DBTDL), dibutyltin diacetate or dibutyltin oxide, preferably dioctyltin or dibutyltin oxide. Examples include NEOSTANN® Sl (marketed by KANEKA), or TIB KAT® 425 or TIB KAT® 423 (marketed by TIB CHEMICALS),

[0271] - guanidine derivatives such as l-(o-tolyl)biguanide (CAS No.: 93-69-6), by example RHENOCURE 1000 C (marketed by RheinChemie Additives).

[0272] Preferably, the crosslinking catalyst is a tin-based catalyst, preferably selected from compounds derived from dioctyltin and dibutyltin, more preferably from dioctyltin or dibutyltin oxide.

[0273] The content of crosslinking catalyst in the composition according to the invention can range from 0.01% to 5% by weight relative to the total weight of the composition, preferably from 0.02% to 2% by weight, more preferably from 0.05% to 1% by weight, even more preferably from 0.1% to 0.8% by weight.

[0274] The composition according to the invention may also further comprise a crosslinking cocatalyst. Advantageously, the crosslinking cocatalyst is an organic polyester derived from silicic acid, that is to say, an organic compound derived from silicic acid comprising at least two alkoxysilane groups. Examples include example tetraethoxysilane (for example WACKER® TES 28 or TES 40 WN) or l,2-bis(triethoxysilyl)ethane (for example Dynasylan® BTSE).

[0275] The content of crosslinking cocatalyst in the composition according to the invention can range from 0% to 5% by weight relative to the total weight of the composition, preferably from 0.05% to 3% by weight. Other additives

[0276] The composition according to the invention may further comprise at least one additive selected from plasticizers, moisture absorbers, solvents, UV stabilizers and mixtures thereof.

[0277] Advantageously, the composition according to the invention comprises a mixture of additives selected from plasticizers, moisture absorbers, solvents and UV stabilizers (or antioxidants).

[0278] The total content of additives in the composition according to the invention can range from 0.5% to 30% by weight relative to the total weight of the composition, preferably from 5% to 25% by weight, more preferably from 10% to 20% by weight.

[0279] Advantageously, the composition according to the invention comprises a plasticizer. A plasticizer differs from a rheology agent because the properties of a composition comprising a plasticizer will be identical under the application of stress (such as shear) or in the absence of stress. In contrast, the properties of a composition comprising a rheology agent will be different if stress is applied. A plasticizer can be used to adjust viscosity (like a solvent).

[0280] The plasticizer can be any plasticizer commonly used in the field of sealant compositions.

[0281] Preferably, the plasticizer is chosen from:

[0282] - diisodecyl phthalate (for example PALATINOL® DIDP marketed by BASF),

[0283] - diisononyl phthalate (DINP) (for example PALATINOL® N marketed by BASF),

[0284] - an ester of alkylsulfonic acid and phenol (for example MESAMOLL® marketed by LANXESS),

[0285] - the diisononyl ester of 1,2-cyclohexanedicarboxylic acid (for example the HEXAMOLL DINCH® (marketed by BASF), and

[0286] - pentaerythritol tetravalerate (for example PEVALEN™ marketed by PERSTORP).

[0287] More preferably, the plasticizer is the diisononyl ester of 1,2-cy clohexanedicarboxylic acid.

[0288] Advantageously, the plasticizer content ranges from 0% to 25% by weight relative to the total weight of the composition, preferably from 5% to 20% by weight, more preferably from 7% to 15% by weight.

[0289] The composition according to the invention may comprise from 0% to 5% by weight of a solvent relative to the total weight of the composition, preferably a solvent volatile at room temperature (approximately 23°C). The volatile solvent may, for example, be chosen from alcohols volatile at room temperature, such as ethanol or isopropanol. The volatile solvent makes it possible, for example, to reduce the viscosity of the composition and make it easier to apply. The volatile nature of the solvent allows the joint, obtained after the composition has hardened, to no longer contain any solvent. Thus, the solvent does not, for example, have a negative influence on the hardness of the joint.

[0290] Advantageously, the composition according to the invention comprises up to 3.5% by weight of a moisture absorber, relative to the total weight of the composition, which may be selected from vinyltrimethoxysilane (for example, DYNASYLAN® VTMO marketed by EVONIK), propyltrimethoxysilane (for example, DYNASYLAN® PTMO marketed by EVONIK), vinyltriethoxysilane (VTEO), alkoxyarylsilanes (for example, GENIOSIL® XL 70 marketed by WACKER), p-toluenesulfonyl isocyanate (PTSI) and calcium oxide.

[0291] Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, vinyltriethoxysilane and alkoxyarylsilanes, more preferably vinyltrimethoxysilane.

[0292] Advantageously, the composition according to the invention comprises up to 1% by weight of one or more UV stabilizers (or antioxidants) relative to the total weight of the composition. The UV stabilizers are typically introduced to protect the composition from degradation resulting from a reaction with oxygen that may be formed by the action of heat or light. These compounds may include antioxidants capable of scavenging free radicals.

[0293] Advantageously, the UV stabilizer(s) (or antioxidant(s)) are selected from among benzotriazoles, benzophenones, phenols, and so-called hindered amines such as bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate (CAS No. 41556-26-7), methyl l,2,2,6,6-pentamethyl-4-piperidyl sebacate (CAS No. 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, the 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, and mixtures thereof. Examples include IRGANOX 1076, TINUVIN® 292, TINUVIN® 765 or TINUVIN® 770 DF marketed by BASF, and RIASORB UV-123 marketed by RIANLON. AddWorks® IBC 760 marketed by CLARIANT and OKABEST CLX 50 marketed by OKA.

[0294] Preferably, the UV stabilizer(s) (or antioxidants) are chosen from among so-called hindered phenols and amines such as bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-bis(a,a-dimethylbenzyl)diphenylamine, and mixtures thereof.

[0295] According to one embodiment, the UV stabilizers (or antioxidants) are a mixture of bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)octadecyl propionate and 4,4'-bis(a,a-dimethylbenzyl)diphenylamine. Composition

[0296] The composition according to the invention preferably has a viscosity at 23°C ranging from 800 Pa.s to 2000

[0297] The viscosity of the composition is typically measured using a planar rheometer at a rotational speed of 5s-l.

[0298] The composition according to the invention advantageously offers at least one of the following advantages:

[0299] - it advantageously leads, after cross-linking, to an adhesive joint exhibiting good mechanical properties

[0300] - it advantageously leads, after cross-linking, to an adhesive joint exhibiting good resistance to aging, particularly under challenging temperature and humidity conditions (for example, after 7 days at 70°C, 100% RH, poultice type). Uses

[0301] The present invention also relates to a method for assembling two substrates by bonding, comprising:

[0302] - coating, on at least one of the two substrates to be assembled, with the composition according to the invention, as defined above; then

[0303] - the effective contacting of the two substrates.

[0304] The substrates concerned can be very varied, and preferably chosen from plastic, a metal such as aluminium and / or steel and glass.

[0305] According to a preferred embodiment, one of the substrates is steel (for example, part of the body of a vehicle) and the other substrate is glass (for example, a pane of glass such as a windshield or window).

[0306] The present invention also relates to an article that can be obtained according to the assembly process as defined above.

[0307] The present invention also relates to a vehicle comprising a composition as defined in this description, said composition being simultaneously in contact with a first substrate and a second substrate of said vehicle, preferably in contact with a part of the body of a vehicle and a glass such as a windshield or a window.

[0308] Furthermore, the present invention relates to the use of the composition according to the invention, as a sealant, in particular as a sealing gasket.

[0309] Finally, the present invention relates to the use of the composition according to the invention, for bonding and sealing particularly in the fields of building construction, transport, for example road, sea, rail or aerospace, and shipbuilding, preferably in the field of road, sea, rail or aerospace transport, particularly for fixing a glass (for example a windshield or a window) to the body of a vehicle, preferably for replacing the windshield or window of a vehicle.

[0310] All the embodiments described below can be combined with each other. In particular, the various aforementioned components of the composition, and especially the preferred embodiments, of the composition can be combined with each other.

[0311] In the context of the invention, "between x and y" or "ranging from x to y" means an interval in which the bounds x and y are included. For example, the range "between 0% and 25%" includes, in particular, the values ​​0% and 25%.

[0312] The invention is now described in the following embodiment examples which are given purely for illustrative purposes, and should not be interpreted to limit its scope. Examples

[0313] The following ingredients were used:

[0314] - PA: acrylate polymer with trimethoxysilane groups having a viscosity of 140 Pa.s at 23°C from KANEKA;

[0315] - MA452 acrylate polymer with trimethoxysilane groups having a viscosity at 23 °C is equivalent to 24 from KANEKA;

[0316] - DYNASYLAN® VTMO marketed by EVONIK: vinyltrimethoxysilane (No. CAS: 2768-02-7), moisture absorber;

[0317] - DYNASYLAN® AMMO marketed by EVONIK: (3-aminopropyl)trime thoxysilane (CAS No.: 13822-56-5), adhesion promoter;

[0318] - ACCLAIM® 12200: polyether polyol with number-average molecular weight close to 11,335 g / mol, marketed by COVESTRO;

[0319] - TI additive: (marketed by BORCHER): para-toluene sulfonyl isocyanate (dehydrating agent);

[0320] - IPDI: marketed by Evonik: isophorone diisocyanate;

[0321] - Dynasylan ® 1189: marketed by Evonik: N-butyl-3-aminopropyltrimet hoxysilane;

[0322] - HAKUENKA® CCR-S10 marketed by OMYA: calcium carbonate fatty acid-coated precipitate, having an average particle size of 80 nm;

[0323] - AKTIFIT VM marketed by HOFFMANN: calcined quartz / kaolinite mixture modified vinyl on the surface;

[0324] - ELFTEX® S7100 marketed by CABOT: carbon black having an OAN of 117 + 6 mL / 100 g measured according to ASTM D-2414 method;

[0325] - TIB KAT 425 marketed by TIB CHEMICALS: mixture TIB KAT 232 (dioctyltin oxide) / silane, crosslinking catalyst;

[0326] - TES 40WN: tetraethoxysilane marketed by WACKER;

[0327] - DINCH: 1,2-Cyclohexanedicarboxylic acid, diisononyl ester marketed by BASF

[0328] - SPUR SP1070: SPUR (silylated polyurethane) marketed by MOMENTIVE

[0329] - STPE-30: polypropylene glycol capped by an alpha silane function of type Methyl dimethoxy with a number-average molecular mass of approximately 14493 g / mol, marketed by WACKER. Measurement methods

[0330] The shear strength was measured according to the following method:

[0331] Two rectangular aluminum plates with dimensions: 100 mm x 25 mm x 2 mm are used. After cleaning both plates with isopropyl alcohol, a rectangular bonding area measuring 12.5 mm x 25 mm is defined, using adhesive tape, at the end of each plate.

[0332] On the bonding area of ​​a first substrate plate thus materialized, the silylated polymer composition is applied in an amount corresponding to a thickness of 2 mm. Then the bonding area of ​​the second substrate plate is superimposed on the area thus coated, so as to obtain an assembly in which the free ends of the 2 substrate plates are aligned on either side of the two areas joined by the sealant.

[0333] The resulting assembly specimen is held by clips for 14 days in a room with a controlled atmosphere at 23°C and 50% relative humidity, for crosslinking of the composition.

[0334] The two free ends of the specimen are pulled by means of a tensile machine at a constant speed of 50 mm / minute, until the assembly breaks, for which the applied stress is recorded.

[0335] The measurement is repeated for 3 assembly specimens, and the average of the shear stresses at failure (called shear strength) obtained is calculated.

[0336] It is also noted whether the break is of the cohesive type (break within the composition) or adhesive type (break at the composition / plate interface).

[0337] Poultice test:

[0338] The test is carried out according to the D47 1165-H7 standard used in the automotive industry.

[0339] This test consists of immersing the part to be tested in cotton soaked in demineralized water The entire assembly is then sealed in an airtight bag and placed in an oven at 70 ± 2°C for 7 days. Afterward, the parts are removed, the soaked cotton is removed, and they are placed at -20°C for 2 hours. Finally, after 2 hours at 23°C, the parts can be observed and mechanically or functionally tested to assess the effect of humidity on the system. This test is equivalent to several years of natural aging in a warm, humid environment.

[0340] Example 1: preparation of silylated polyurethane P'1

[0341] Polymer P' 1 was prepared according to the following procedure, under anhydrous conditions:

[0342] In a reactor, TAcclaim 12200 is introduced, followed by the Ti additive, and the mixture is heated to 60-65°C. Then, 1TPDI is added, the mixture is stirred for 10 minutes, and the catalyst is added. The mixture is then heated to 70°C for one hour with stirring. The NCO value is then checked; if the theoretical NCO value is not reached, the reaction time is extended by as many 15-minute periods as necessary. When the theoretical NCO value is reached, Dynasilane 1189 is added, and the mixture is stirred for 10 minutes. The reactor is then put into cooling mode, and VTMO and DINCH are added. The mixture is then stirred for 20 minutes.

[0343] The quantities indicated in the following table are expressed as mass percentages relative to the total weight of the polyurethane composition.

[0344] [Tables 1] Polyurethane P' 1 Acclaim 12 200 79.5 IPDI 3 Additive TI 0.21 DBTDL (dibutyltin dilaurate, cat) 0.09 Dynasilane 1189 3.0 VTMO 0.2 DINCH 14 NCO / OH molar ratio 1.96% by weight of final NCO 0.65 Viscosity of polymer P' 1 (23°C, Brookfield enmPa.s) ISO 2555 (2018) 35,200 mPa.s

[0345] Example 2: preparation of silylated polyurethane P'2

[0346] Polymer P'2 was prepared according to the following procedure, under anhydrous conditions:

[0347] In a reactor, Acclaim 8200 is introduced, followed by the Ti additive, and the mixture is heated to 60-65°C. IPDI is then added, the mixture is stirred for 10 minutes, and the catalyst is added. The mixture is then heated to 70°C for one hour with stirring. The NCO value is then checked; if the theoretical NCO value is not reached, the reaction time is extended by as many 15-minute periods as necessary. When the theoretical NCO value is reached, Dynasilane 1189 is added, and the mixture is stirred for 10 minutes. The reactor is then switched to cooling mode, and VTMO and DINCH are added. The mixture is then stirred for 20 minutes.

[0348] The quantities indicated in the following table are expressed as mass percentages relative to the total weight of the polyurethane composition.

[0349] [Tables2] Polyurethane P'2 Acclaim 8200 77 IPDI 2.78 TI Additive 0.24 DBTDL (cat) 0.04 Dynasilane 1189 1.6 VTMO 0.84 DINCH 17.5 NCO / OH molar ratio 1.34% by weight of final NCO 0.35% Polymer viscosity (23°C, Brookfield in mPa·s) - ISO 2555 (2018) 97535 mPa·s

[0350] Example 3: preparation of compositions Cl, C2 and C3 according to the invention and comparative C4

[0351] In a reactor maintained under agitation, the compositions Cl, C2 and C3 (invention) and the comparative composition C4 are prepared by mixing the ingredients in the proportions indicated in the Table below, in several steps according to the process described below.

[0352] The ingredients of step 1 are mixed at room temperature (approximately 23°C), at atmospheric pressure and at low stirring speed (sufficient to homogenize).

[0353] Next, the ingredients from step 2 are added to the reactor used for step 1, and mixed first at atmospheric pressure and high stirring speed (in order to shear and mix the solids), then the reactor is put under vacuum (16 kPa), the temperature is increased to 55-65°C and the mixing is carried out for 10 to 30 min.

[0354] Finally, the ingredients from step 3 are added under vacuum and the mixing is carried out at low stirring speed (sufficient to homogenize).

[0355] Table: Preparation of compositions

[0356] [Tables3] Step Ingredient Cl (invention) C2 (invention) C3 (invention) C4 (comparative) 1 Polymer PA 19 19 19 19 DYNASYLAN® VTMO 3 3 3 3 Polymer P' 1 - 19 - - Polymer P'2 19 - - - SPUR SP1070 - - 19 - STPE-30 - - - 19 2 Aktifit VM 16.25 16.25 16.25 16.25 Polyamide wax (Arkema) 6 6 6 6 Elftex S7100 6 6 6 6 Hakuenka CCR-S10 16.25 16.25 16.25 16.25 DINCH 10.95 10.95 10.95 10.95 3 TES 40 WN 2 2 2 2 DYNASYLAN® AMMO 1.4 1.4 1.4 1.4 TIB KAT 425 0.15 0.15 0.15 0.15

[0357] % by weight of the total weight of the composition

[0358] The mechanical properties of compositions Cl, C2, C3 and C4 (measured in accordance with the above-mentioned methods) are summarized in the table below.

[0359] [Tables4] Composition Cl invention C2 invention C3 invention C4 comparative Shear strength (MPa) 2.02 3.10 2.67 2.08 Fracture face cohesive cohesive cohesive cohesive Shear strength after wet poultice test 1.62 2.64 2.95 0.90 Fracture face cohesive cohesive cohesive adhesive

[0360] The adhesive compositions according to the invention (Cl, C2 and C3) advantageously lead to a cohesive fracture surface after the wet poultice test. Furthermore, compositions Cl, C2 and C3 advantageously result in a limited loss (less than 20%) of shear strength after being subjected to the wet poultice test, compared to the comparative composition C4, which lost more than 50% of its initial value.

Claims

Demands

1. Crosslinkable composition comprising: - a polymer P comprising at least one polymer PI comprising at least one function of the following formula (I): [Chem. 15] -SiR^pXp (!) in which: - R represents a hydrocarbon group having from 1 to 20 carbon atoms, optionally substituted and / or comprising one or more heteroatoms; - X is a hydroxyl group or a hydrolyzable group; - p represents 1, 2 or 3; said polymer PI comprising a main chain based on (meth)acrylate; - a polyurethane P' comprising at least one function of formula (II): [Chem.16] -SiRVsX't (1!) in which: - R” represents a hydrocarbon group having from 1 to 20 carbon atoms, possibly substituted and / or comprising one or more heteroatoms; - X' is a hydroxyl group or a hydrolyzable group; - t represents 1, 2 or 3; - carbon black having an oil absorption index (OAN) of at least 80 mL / 100 g.

2. Composition according to claim 1, characterized in that the monomer (meth)acrylate unit content relative to the PI polymer is greater than 50% by weight, preferably greater than or equal to 70% by weight relative to the total weight of said PI polymer.

3. Composition according to any one of claims 1 or 2, characterized in that the polymer PI has at least one function of formula (IA): [Chem. 17] -SiR^OR'Jp (lA) in which: - R' and R each represent, independently of each other, an alkyl group having from 1 to 20 carbon atoms; - p represents 1, 2 or 3, preferably 2 or 3.

4. Composition according to any one of claims 1 to 3, characterized in that the PI polymer comprises at least one function of formula (I) or (IA) selected from dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, preferably trimethoxysilyl and dimethoxymethylsilyl.

5. Composition according to any one of claims 1 to 4, characterized in that the polymer P further comprises at least one oxyalkylene polymer P2 comprising at least one function of formula (I) [Chem. 18] -SiRs-pXp (!) in which: - R represents a hydrocarbon group having from 1 to 20 carbon atoms, optionally substituted and / or comprising one or more heteroatoms; - X is a hydroxyl group or a hydrolyzable group; - p represents 1, 2 or 3.

6. Composition according to any one of claims 1 to 5, characterized in that polymer P has a Brookfield viscosity greater than or equal to 70 Pa.s at 23°C.

7. Composition according to any one of claims 1 to 6, characterized in that polymer P has a Brookfield viscosity greater than or equal to 100 Pa.s at 23°C.

8. Composition according to any one of claims 1 to 7, characterized in that the mass content of polymer P ranges from 5% to 60% by weight, preferably from 10% to 50% by weight, and preferably from 10% to 40% by weight relative to the total weight of said composition.

9. Composition according to any one of claims 1 to 8, characterized in that the polyurethane P' is obtained by a process comprising the following steps: - a-1) the polyaddition reaction between a composition of polyol(s) and a composition of polyisocyanate(s), in the presence of a catalyst to prepare an NCO-terminated polyurethane; - a-2) the reaction of the NCO-terminated polymer obtained in step a-1) with an organosilane compound having at least one reactive function with the -NCO function of the NCO-terminated polyurethane.

10. Composition according to claim 9, characterized in that the organosilane compound is selected from mercaptosilanes and aminosilanes, preferably aminosilanes.

11. Composition according to claim 9 or 10, characterized in that the organosilane compound is an aminosilane having the following formula (III); [Chem. 19] (RaO)t(R:)3-tS^ (III) in which: - R” and Ra each represent, independently of each other, an alkyl group having from 1 to 20 carbon atoms; -1 represents 1, 2 or 3, preferably 2 or 3; - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, R3 preferably representing methylene or n-propylene, and - R6 represents H, a linear or branched alkyl radical, an arylalkyl radical, a cyclic radical comprising from 1 to 20 carbon atoms.

12. Composition according to any one of claims 9 to 11, characterized in that the organosilane compound is an aminosilane selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane; N-butyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane.

13. Composition according to any one of claims 1 to 12, characterized in that the polyurethane P' has the formula (IV) below: [Chem.20] wbs ( w» - - s - $ - s? - « j ««. $ - jæù ■ o - ÿ - ss - • ç - s; - s*.sfs"} < c® ^'0 4 QC fV L (IV) wherein: - R1 represents a divalent hydrocarbon radical comprising from 5 to 15 carbon atoms which may be aromatic, aliphatic or cyclic, - R3 represents a linear or branched alkylene divalent radical comprising from 1 to 6 carbon atoms, preferably R3 representing methylene or n-propylene, - R2 represents a linear or branched alkylene divalent radical comprising from 2 to 4 carbon atoms, - Ra and R are as defined in claim 11, preferably Ra and R, identical or different, each represent a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, even more preferably Ra and R representing methyl, - R6 is as defined above, preferably R6 represents a linear or branched alkyl radical comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms; - m is a non-zero integer. - n and m are such that the average number molecular weight of the polymer of formula (IV) ranges from 500 g / mol to 50,000 g / mol, preferably from 700 g / mol to 22,000 g / mol, -1 is an integer equal to 1, 2 or 3.

14. Composition according to any one of claims 1 to 13, characterized in that the mass content of polymer P' ranges from 5% to 60% by weight, preferably from 10% to 50% by weight, and even more preferably from 10% to 40% by weight relative to the total weight of said composition.

15. Composition according to any one of claims 1 to 14, characterized in that the mass content of carbon black is less than or equal to 20% by weight, preferably less than or equal to 15% by weight relative to the total weight of said composition.

16. Composition according to any one of claims 1 to 15, characterized in that the carbon black content in the composition ranges from 2% to 8% by weight relative to the total weight of said composition.

17. Composition according to any one of claims 1 to 16, characterized in that the OAN of carbon black is at least 90 mL / 100g, preferably at least 100 mL / 100g.

18. Composition according to any one of claims 1 to 17, characterized in that it comprises a rheology agent.

19. Composition according to any one of claims 1 to 18, characterized in that it comprises a filler, preferably the filler being selected from mineral fillers, organic fillers and mixtures thereof, more preferably from mineral fillers.

20. Method of assembling two substrates by bonding, comprising: - coating, on at least one of the two substrates to be assembled, the composition according to any one of claims 1 to 19; then - bringing the two substrates into actual contact.