Composition comprising a silylated polymer

Abstract

The present 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): -SiR3-pXp (I) said polymer P1 comprising a main chain based on (meth)acrylate; - a polyurethane P' comprising at least one functional group of formula (II): -SiR''3-tX't (II) - carbon black having an oil absorption number (OAN) of at least 80 mL / 100g.

Description

[0001] Composition comprising a silylated polymer

[0002] FIELD OF INVENTION

[0003] The present invention relates to a composition comprising a silylated polymer, and its use in particular for bonding and sealing.

[0004] TECHNICAL BACKGROUND

[0005] In the automotive field, adhesive compositions are widely used, whether for fixing movable panels such as doors, hoods, etc., or for fixing windshields.

[0006] 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...).

[0007] In the field of adhesives, silane-modified polymers ("SMPs") are widely used. However, these adhesives can have the disadvantage of resulting in adhesive joints that lose their adhesive properties under harsh climatic conditions.

[0008] There is therefore a need for new compositions leading to an adhesive joint that offers a compromise between good adhesion properties and good resistance to aging, particularly under demanding temperature and humidity conditions.

[0009] DESCRIPTION OF THE INVENTION

[0010] The present invention 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):

[0011] -SiR3-pX p (I) in which:

[0012] R represents a hydrocarbon group having from 1 to 20 carbon atoms, possibly substituted and / or comprising one or more heteroatoms;

[0013] X is a hydroxyl group or a hydrolyzable group; p represents 1, 2 or 3; said polymer P1 comprising a main chain based on (meth)acrylate; a polyurethane P' comprising at least one function of formula (II):

[0014] -SiR”3-tX't (II) in which:

[0015] R” represents a hydrocarbon group having from 1 to 20 carbon atoms, possibly substituted and / or comprising one or more heteroatoms;

[0016] 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-

[0017] According to the invention, the composition comprises at least three different ingredients: polymer P, polyurethane P' and the aforementioned carbon black.

[0018] P1 Polymer

[0019] The P1 polymer comprises a main chain based on (meth)acrylate.

[0020] In the context of the invention, the term "(meth)acrylate" includes both acrylates and methacrylates.

[0021] In polymer P1, the monomer unit constituting the main chain contains at least one (meth)acrylate monomer.

[0022] (Meth)acrylates can be diverse and varied.

[0023] The monomer (meth)acrylate can be selected 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. Preferably, the monomer (meth)acrylate unit content relative to polymer P1 is greater than 50% by weight, preferably greater than or equal to 70% by weight relative to the total weight of said polymer P1.

[0024] 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 N-methylolacrylamide), monomers comprising an epoxy group (such as glycidyl acrylate), monomers comprising an amine group (such as diethylaminoethyl acrylate), and mixtures thereof.

[0025] 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.

[0026] Preferably, polymer P1 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.

[0027] The polymer P1 comprises at least one function of formula (I) above, preferably at least two, and preferably in a terminal position.

[0028] 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.

[0029] 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.

[0030] The polymer P1 preferably has at least one function of formula (lA):

[0031] -SiR3-p(OR') p (lA) in which:

[0032] 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.

[0033] Preferably, the polymer P1 comprises at least one function of formula (I) or (lA) selected from dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, more preferably trimethoxysilyl and dimethoxymethylsilyl.

[0034] Advantageously, polymer P1 has a number-average molar mass 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.

[0035] 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.

[0036] The P1 polymer can be obtained by different polymerization methods.

[0037] 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 an azo compound or a peroxide. In contrast, "controlled radical polymerization" is a method capable of introducing a specific functional group into a controlled site such as an end. Controlled radical polymerization methods can be further 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, producing a vinyl polymer with 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.

[0038] 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. 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 1,1'-azobis(cyclohexane-1-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-methylheptyl 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 can be used alone, or two or more of these initiators can be used in combination.

[0039] Examples of chain transfer agents include compounds containing a mercapto group such as n-dodecylmercaptan, tert-dodecylmercaptan, and laurylmercaptan.

[0040] The silyl group, in particular of formula (I) mentioned above, can be introduced into the P1 polymer by different and varied methods. Examples include: 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; ii) a method in which the monomers copolymerize in the presence of a mercaptosilane compound (in particular having a silyl group of formula (I)) as a chain transfer agent; iii) a method in which a compound having a polymerizable double bond and a reactive silyl group (in particular of formula (I)) is copolymerized with the monomers in the presence of a mercaptosilane as a transfer agent.

[0041] Examples of compounds having a polymerizable double bond and a silyl group reactive for method i) may be gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-acryloxypropyltriethoxysilane, vinyltriethoxysilane or vinyltrimethoxysilane.

[0042] Examples of mercaptosilane from method 11) may be 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, 3-mercaptopropylchloromethyldimethoxysilane, 3-mercaptopropylmethoxymethyldimethoxysilane, 3-mercaptopropylaminomethyldimethoxysilane, and 3-mercaptopropyl-N,N-dimethylaminomethyldimethoxysilane.

[0043] 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.

[0044] P2 Polymer

[0045] The polymer P may further also comprise at least one oxyalkylene polymer P2 comprising at least one function of formula (I) as defined above.

[0046] The P2 polymer oxyalkylene contains a repeating unit -R”-O- in which R” represents a linear or C2-C14 branched alkylene divalent radical.

[0047] Preferably, R represents -CH2-, -CH2CH2-, -CH(CH3)CH2-, -CH(C2H5)CH2-, -CH2CH2CH2CH2-, and -C(CH3)2CH2-.

[0048] The P2 polymer can consist of a single repeating unit or several.

[0049] The P2 polymer can be linear, branched, or a mixture.

[0050] 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.

[0051] Examples of initiators can be alcohols such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol.

[0052] Examples of catalysts include KOH, NaOH, and cobalt-zinc-cyanide complexes.

[0053] 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 CH2Cl2 and CH2Br2, in the presence of a basic compound such as KOH, NaOH, KOCH3, and NaOCH3.

[0054] Among these methods, the method involving ring-opening polymerization of a monoepoxide in the presence of a complex double metal cyanide catalyst is preferred because the resulting polymer has a narrow molecular weight distribution and low viscosity.

[0055] The number of silylated groups of formula (I) in each oxyalkylene P2 polymer is preferably at least 0.8, preferably from 0.8 to 3, and preferably again from 0.8 to 2.0, on average.

[0056] 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.

[0057] Silyl groups of formula (I) can be introduced by any method known in this field.

[0058] For example, they can be introduced by one of the following methods: a) An organic polymer comprising a functional group such as a hydroxyl group or an epoxy group is reacted with a compound comprising a reactive group of 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 in the molecule is reacted with an organic compound comprising a reactive group of said functional group and an unsaturation to prepare an organic polymer comprising an unsaturation. Or alternatively, in the polymerization reaction, the monomer containing an unsaturation (not involved in the polymerization reaction) is copolymerized to prepare an organic polymer comprising 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 in method b)), is reacted with a mercaptosilane.

[0059] The hydrosilylation step of method b) can be carried out in the presence of a catalyst of type F PtCle.h O.

[0060] The hydrosilane can be selected from trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, and phenyldimethoxysilane. Hydrosilylation can be carried out at a temperature ranging from 50°C to 150°C, preferably from 70°C to 120°C.

[0061] 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.

[0062] There are also commercial products as P2 polymers such as MS 203H (methyldimethoxysilyl), MS303H (methyldimethoxysilyl), SAX510 (trimethoxysilyl) marketed by KANEKA.

[0063] The polymer P2 comprises at least one function of formula (I) above, preferably at least two, and preferably in a terminal position.

[0064] 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.

[0065] 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.

[0066] The polymer P2 preferably has at least one function of formula (lA): -SiR3-p(OR') p (lA) in which:

[0067] 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.

[0068] Preferably, the P2 polymer comprises at least one function of formula (I) or (lA) selected from dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, more preferably trimethoxysilyl and dimethoxymethylsilyl.

[0069] Polymer P

[0070] The polymer P according to the invention preferably has a Brookfield viscosity greater than or equal to 70 Pa.s at 23°C. More preferably, the polymer P has a Brookfield viscosity greater than or equal to 100 Pa.s at 23°C.

[0071] Even more preferentially, polymer P has a Brookfield viscosity greater than or equal to 120 Pa.s at 23°C.

[0072] 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.

[0073] Polymer P can be obtained by mixing polymers P1 and P2 at a temperature ranging from 20°C to 60°C.

[0074] Polymer P can be obtained during the preparation of polymer P1 as described previously.

[0075] There are also commercial products as P polymers, such as MA480, MAX602 or MA490 marketed by KANEKA.

[0076] 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.

[0077] Polymer P'

[0078] The composition comprises a polyurethane P' comprising at least one function of formula (II):

[0079] -SiR”3-tX't (II) in which:

[0080] R” represents a hydrocarbon group having from 1 to 20 carbon atoms, possibly substituted and / or comprising one or more heteroatoms;

[0081] X' is a hydroxyl group or a hydrolyzable group; t represents 1, 2 or 3.

[0082] Polyurethane P' is preferably obtained by a process comprising the following steps:

[0083] - 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.

[0084] Polyol

[0085] The aforementioned polyol composition(s) may consist of a single polyol or a mixture of polyols.

[0086] 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.

[0087] The number-average molecular weight 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.

[0088] Polyols can have a hydroxyl functionality ranging 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.

[0089] The usable polyol(s) may be chosen from polyester polyols, polyether polyols, polydiene polyols, polycarbonate polyols, poly(ether-carbonate) polyols, -OH-terminated prepolymers, and their mixtures.

[0090] The usable polyol(s) may be chosen from aromatic polyols, aliphatic polyols, carbonate polyols and mixtures of these compounds.

[0091] 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.

[0092] Examples of polyester polyols include:

[0093] - naturally derived polyol polyesters such as castor oil;

[0094] - polyester polyols resulting from condensation:

[0095] - of one or more aliphatic (linear, branched or cyclic) or aromatic polyols 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

[0096] - one or more polycarboxylic acids or their ester or anhydride derivatives such as 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, for example, maleic or phthalic anhydride, or a lactone such as, for example, caprolactone.

[0097] The aforementioned polyester polyols can be prepared conventionally, and are mostly commercially available.

[0098] Examples of polyester polyols include the following products with a hydroxyl functionality of 2:

[0099] - 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,

[0100] - DYNACOLL® 7381 (marketed by EVONIK) with an average molecular mass by number of approximately 3500 g / mol, and a melting point of approximately 65°C,

[0101] - DYNACOLL® 7360 (marketed by EVONIK) which results from the condensation of adipic acid with hexane diol, and has an average molecular mass by number of approximately 3500 g / mol, and a melting point of approximately 55°C,

[0102] - DYNACOLL®7330 (marketed by EVONIK) with an average molecular mass by number of approximately 3500 g / mol, and a melting point of approximately 85°C,

[0103] - DYNACOLL® 7363 (marketed by EVONIK), which also results from the condensation of adipic acid with hexane diol, and has an average number molecular mass of approximately 5500 g / mol, and a melting point of approximately 57°C,

[0104] - DYNACOLL® 7250 (marketed by EVONIK): polyester polyol with a viscosity of 180 Pa.s at 23°C, a number-average molecular weight (Mn) of 5,500 g / mol, and a T g equal to -50°C,

[0105] - KURARAY® P-6010 (marketed by KURARAY): polyester polyol with a viscosity of 68 Pa.s at 23°C, a number-average molecular weight of 6,000 g / mol, and a T g equal to -64°C,

[0106] - KURARAY® P-10010 (marketed by KURARAY): polyester polyol with a viscosity of 687 Pa.s at 23°C, and a number average molecular mass of 10,000 g / mol.

[0107] 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.

[0108] According to the invention, the polyether polyol(s) can have a number-average molecular mass ranging from 200 to 20,000 g / mol, preferably from 400 to 18,000 g / mol.

[0109] Preferably, the polyether polyol(s) has a hydroxyl functionality ranging from

[0110] 2 to 3. 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.

[0111] 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 part of which, linear or branched, comprises from 1 to 4 carbon atoms, preferably from 2 to 3 carbon atoms.

[0112] Examples of polyoxyalkylene diols or triols that can be used according to the invention include:

[0113] - polyoxypropylene diol or triol (also designated 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,

[0114] - polyethylene diol or triol (also designated 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,

[0115] - 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,

[0116] - copolymers or terpolymers of PPG / PEG / PBG 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] - polytetrahydrofuran (PolyTHF) diol or triol having a number-average molecular mass ranging from 250 g / mol to 12,000 g / mol,

[0118] - polytetramethylene glycols (PTMG) having a number-average molecular mass ranging from 200 g / mol to 12,000 g / mol,

[0119] - and their mixtures.

[0120] Preferably, the usable polyether polyol(s) is / are chosen from among the 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] The hydrogenated derivatives mentioned above can be obtained by total or partial hydrogenation of the double bonds of a polydiene containing terminal hydroxyl groups, and are therefore saturated or unsaturated.

[0127] 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.

[0128] Examples of polybutadiene polyols include homopolymers of butadiene, saturated or unsaturated, comprising terminal hydroxyl groups, possibly epoxidized, such as those marketed under the name POLY BD® or KRASOL® by the company CRAY VALLEY.

[0129] Examples of polycarbonate diols include CONVERGE POLYOL 212-10 and CONVERGE POLYOL 212-20 marketed by NOVOMER, with number molecular weights (Mn) of 1000 and 2000 g / mol respectively, and hydroxyl values ​​of 112 and 56 mg KOH / g respectively; DESMOPHEN® C XP 2716 marketed by COVESTRO, with number molecular weights (Mn) of 326 g / mol and hydroxyl values ​​of 344 mg KOH / g; and POLYOL C-590, C1090, C-2090 and C-3090 marketed by KURARAY, with number molecular weights (Mn) ranging from 500 to 3000 g / mol and hydroxyl values ​​ranging from 224 to 37 mg KOH / g. Preferably, the polyol composition consists of one or more polyols selected from those mentioned above and their mixtures. In particular, the polyol composition may consist of one or more polyols, including at least one polyether polyol.More specifically, the composition of polyol(s) can consist of one or more polyether polyols.

[0130] Polyisocyanate(s)

[0131] In the context of the invention, "polyisocyanate" means a compound comprising at least two isocyanate groups (NCO).

[0132] The aforementioned polyisocyanate composition(s) may consist of a polyisocyanate or a mixture of polyisocyanates.

[0133] The usable polyisocyanate(s) can be chosen from those typically used in the synthesis of an NCO-terminated polyurethane.

[0134] The usable polyisocyanate(s) may be aliphatic (linear or branched) or aromatic, and possibly substituted.

[0135] Preferably, the polyisocyanate(s) is / are chosen from among the diisocyanates, triisocyanates, and mixtures thereof.

[0136] 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, ethylcyclohexane 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.

[0137] MDI can exist as a single isomer or a mixture of isomers, such as 4,4'-MDI and / or 2,4'-MDL

[0138] TDI can be present as an isomer or a mixture of isomers, such as 2,4-TDI and / or 2,6-TDL. Preferably, the polyisocyanate is MDI, and in particular 4,4'-MDL.

[0139] The polyisocyanate(s) usable for preparing 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 exceeding 99% by weight; DESMODUR® I, marketed by 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'-MDL isomer.

[0140] Preferably, the polyisocyanate composition includes IPDI.

[0141] In the context of the invention, the expressions "polyaddition reaction" and "polyaddition" are understood to be equivalent.

[0142] 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.

[0143] The polyaddition step can be carried out under anhydrous conditions, for example under a nitrogen atmosphere.

[0144] 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.

[0145] Within the framework 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.

[0146] The catalyst can be any catalyst known to a person skilled in the art of polyaddition reactions and polyurethane preparation. Examples include BORCHI® KAT 0761 (CAS number: 27253-29-8, zinc neodecanoate) available from BORCHERS, TIB KAT® 616 (zinc neodecanoate) available from TIB CHEMICALS, and K-KAT XK-664 (zinc carboxylate) marketed by KING INDUSTRIES.

[0147] The total catalyst content 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 reactants used in the polyaddition reaction.

[0148] 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.

[0149] 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.

[0150] NCO-terminated polyurethane can have a polymolecularity index ranging from 1.5 to 3.5, preferably from 2.0 to 3.3.

[0151] In the context of the invention, the polymolecularity index is defined as the ratio M w (average molecular mass by weight) / M n (number average molecular mass) of polyurethane.

[0152] NCO-terminated polyurethane 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 polyurethane.

[0153] Step a-2)

[0154] 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.

[0155] The organosilane compound can be chosen from among mercaptosilanes and aminosilanes, preferably aminosilanes.

[0156] Aminosilanes contain an amine function as a reactive function with the -NCO function of the NCO-terminated polymer.

[0157] Aminosilane preferably has the following formula (III);

[0158] (R a O)t(R”)3-tSi-R 3 -NH-R 6 (III) in which:

[0159] - R” and R a each represents, independently of each other, an alkyl group having from 1 to 20 carbon atoms;

[0160] - t represents 1, 2 or 3, preferably 2 or 3;

[0161] - R 3 represents a linear or branched alkylene divalent radical comprising from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, R 3 preferentially representing methylene or n-propylene, and

[0162] - R 6represents H, a linear or branched alkyl radical, an arylalkyl radical, or a cyclic radical comprising 1 to 20 carbon atoms. According to a preferred embodiment, aminosilane of formula (III) is that in which:

[0163] - R” and R a each represents, independently of each other, an alkyl group having from 1 to 20 carbon atoms;

[0164] - 1 represents 1, 2 or 3, preferably 2 or 3,

[0165] - R 3 represents a linear or branched alkylene divalent radical comprising from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, R 1 preferentially representing methylene or n-propylene, and

[0166] - R 6 represents a linear or branched alkyl radical comprising 1 to 10 carbon atoms.

[0167] 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.

[0168] Aminosilanes may be commercially available, such as Dynasylan® 1189 marketed by Evonik.

[0169] Terms

[0170] Step a-2) can be carried out under anhydrous conditions.

[0171] 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.

[0172] Step a-2) can be completed in a time ranging from 5 to 30 min, preferably from 10 to 20 min.

[0173] 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.

[0174] Within the framework 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.

[0175] The polymer P' preferably has at least one function of formula (I lA): -SiR”3-t(OR a )t (ll-A) in which:

[0176] R” and R aeach represents, independently of each other, an alkyl group having from 1 to 20 carbon atoms; t represents 1, 2 or 3, preferably 2 or 3. Preferably, polyurethane P' comprises one or more groups of formula (II) or (II-A) above selected from the trimethoxysilyl groups, triethoxysilyl groups, methyldimethoxysilyl groups, methyldiethoxysilyl groups, dimethylmethoxysilyl groups, and dimethylethoxysilyl groups.

[0177] Even more preferably, polyurethane P' includes trimethoxysilyl groups.

[0178] Polyurethane P' can 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.

[0179] The number-average molecular weight of 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.

[0180] Polyurethane P' may have a viscosity at 23°C of 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.

[0181] 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 performed using a Brookfield RVT viscometer, a needle adapted to the viscosity range, and a rotation speed of 20 revolutions per minute.

[0182] Polyurethane P' preferably has the formula (IV) below:

[0183] (IV) in which:

[0184] - R 1 represents a divalent hydrocarbon radical comprising 5 to 15 carbon atoms which can be aromatic, aliphatic or cyclic,

[0185] - R 3 represents a linear or branched alkylene divalent radical comprising 1 to 6 carbon atoms, preferably R 3 representing methylene or n-propylene,

[0186] - R 2 represents a linear or branched divalent alkylene radical comprising 2 to 4 carbon atoms, -R a and R” are as defined previously, preferably R a and R”, identical or different, each represent a linear or branched alkyl radical comprising 1 to 4 carbon atoms, even more preferably R a and R” representing methyl,

[0187] - R 6 is such as defined previously, preferably R 6represents a linear or branched alkyl radical comprising 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms;

[0188] - m is a non-zero integer,

[0189] - 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,

[0190] - 1 is an integer equal to 1, 2 or 3.

[0191] Preferably, the radical R 1 is chosen from one of the following divalent radicals, whose formulas below show the 2 free valences:

[0192] - a) the divalent radical derived from isophorone diisocyanate (I PDI):

[0193] - b) the divalent radical derived from 4,4'- and 2,4'-dicyclohexylmethane diisocyanate (HMDI):

[0194] - c) the radical derived from 2,4- and 2,6-toluene diisocyanate (TDI)

[0195] - d) the radical derived from 4,4'- and 2,4'-diphenylmethane diisocyanate (MDI)

[0196] - e) the radical derived from m-xylylene diisocyanate (m-XDI)

[0197] - f) the radical derived from hexamethylene diisocyanate (HDI)

[0198] -(CHsJs-

[0199] Preferably, the radical R 1 is the divalent radical derived from isophorone diisocyanate.

[0200] 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.

[0201] Carbon black

[0202] The composition includes 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.

[0203] 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. Even 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.

[0204] 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.

[0205] The OAN of a carbon black corresponds to the volume in mL of dibutyl phthalate (DBP) oil absorbed by 100 g of carbon black.

[0206] For example, the OAN can be measured according to the ASTM D-2414 method and using DBP oil.

[0207] Unless otherwise stated, the standards mentioned throughout the application are those in effect on the date the application was filed.

[0208] Preferably, the OAN of carbon black is at least 90 mL / 100g, more preferably at least 100 mL / 100g.

[0209] The carbon black used in the present invention is generally called "structural" carbon black, and differs from carbon blacks commonly used as pigments, particularly in its high OAN (Oxygen-Attenuating Net Carbonate). Indeed, carbon blacks used as pigments are of lower quality and have a lower OAN than the carbon black used in the present invention.

[0210] An example of carbon black used as a pigment is PRINTEX® 25 (marketed by Orion) which has an OAN of 45 mL / 100 g.

[0211] Examples of carbon black that can be implemented in the present invention are ELFTEX® S7100 and ELFTEX® S5100 (marketed by CABOT), having respectively an OAN of approximately 117 and 108 mL / 100 g.

[0212] A rheology agent typically allows the rheological properties of a composition to be adjusted.

[0213] Preferably, the composition according to the invention comprises a rheology agent.

[0214] As an example, one can cite any rheology agent commonly used in the field of adhesive or sealant compositions.

[0215] 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 period. The greater the force, the greater the decrease in viscosity.

[0216] In particular, one or more rheological agents are used, chosen from among:

[0217] - PVC plastisols, corresponding to a suspension of PVC in a plasticizing agent 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;

[0218] - fumed silica, such as H DK® N20 marketed by WACKER;

[0219] - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as 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;

[0220] - waxes derived from castor oil, such as THIXCIN® R available from ELEMENTIS,

[0221] - 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.

[0222] These rheology agents are preferably thixotropic agents.

[0223] "Waxes derived from castor oil" refers to waxes obtained from castor oil, particularly hydrogenated castor oil. Castor oil-derived waxes are solid at 23°C.

[0224] The term "amide waxes" refers to waxes comprising one or more compounds containing at least one amide group. In particular, amide waxes can be obtained from fatty acid(s) (e.g., ricinoleic acid) and (di)amine(s). Amide waxes are solid at 23°C.

[0225] Preferably, the rheology agent is an amide wax and / or a wax derived from castor oil, more preferably an amide wax.

[0226] 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.

[0227] 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 the NF ISO 13320 standard).

[0228] Wax-like amide 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.

[0229] 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.

[0230] Membership promoter

[0231] The composition according to the invention may further comprise at least one adhesion promoter.

[0232] Advantageously, the adhesion promoter is chosen from among amino-, mercapto- and epoxy-alkoxysilanes, preferably chosen from aminoalkoxysilanes, more preferably from aminotrialkoxysilanes, and even more preferably from aminotrimethoxysilanes.

[0233] An example of an epoxy-alkoxysilane is (3-Glycidyloxypropyl)trimethoxysilane (also known as GLYMO).

[0234] Advantageously, aminotrimethoxysilanes are formed by the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane (e.g., SILQUEST A-LINK 600 marketed by MOMENTIVE), (3-aminopropyl)trimethoxysilane (e.g., DYNASYLAN® AMMO marketed by EVONIK), and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (e.g., 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.

[0235] Advantageously, the composition according to the invention comprises at least one adhesion promoter.

[0236] 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.

[0237] 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.

[0238] Advantageously, the composition according to the invention further comprises a filler.

[0239] Preferably, the filler is chosen from mineral fillers, organic fillers and their mixtures, more preferably from mineral fillers.

[0240] 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.

[0241] Kaolinite and quartz aggregates can be natural or artificially produced. The kaolinite content in the aggregates can be less than or equal to 15% by weight. The aggregates can be surface-modified with a silane coupling agent such as vinyltrimethoxysilane, vinyltriethoxysilane, or gamma-acryloyloxypropylmethyltriethoxysilane.

[0242] Commercial examples include Hoffmann Minerals' AKTISIL range, such as Aktisil PF216, or Hoffmann Minerals' AKTIFIT range. Among hollow mineral microspheres, one can cite hollow glass microspheres, and more specifically those made of sodium and calcium borosilicate or aluminosilicate.

[0243] 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.

[0244] When calcium carbonate is coated with fatty acids, it imparts total or partial hydrophobicity to the calcium carbonate particles. Furthermore, the fatty acid coating acts as a hydrophobic layer that can prevent the calcium carbonate from absorbing the constituents of the composition and rendering them ineffective. The hydrophobic coating of calcium carbonate can represent from 0.1% to 3.5% by weight, relative to the total weight of calcium carbonate.

[0245] 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.

[0246] Examples of non-precipitated fatty acid coated calcium carbonate include OMYACARB 2T-AV or OMYA BLH (marketed by OMYA), or CALATEM C16T (marketed by Provençale).

[0247] Examples of precipitated calcium carbonate coated with fatty acids include HAKUENKA® CCR-S10 (marketed by OMYA) or CALOFORT® (marketed by Specialty Minerals).

[0248] Advantageously, the organic fillers are chosen 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.

[0249] 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.

[0250] The average particle size advantageously corresponds to the d50 particle size distribution, i.e., the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, particularly by laser diffraction on a MALVERN-type instrument (for example, according to standard NF ISO 13320). 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, and more preferably from 20% to 40% by weight relative to the total weight of said composition. Crosslinking

[0251] The composition according to the invention may further comprise a crosslinking catalyst.

[0252] The crosslinking catalyst can be any catalyst known to those skilled in the art for the condensation of silanol. Examples of such catalysts include:

[0253] - organic derivatives of titanium such as titanium acetyl acetonate (for example TYZOR® AA75 marketed by Dorf Ketal),

[0254] - aluminum such as aluminum chelate (for example K-KAT® 5218 marketed by KING INDUSTRIES),

[0255] - 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), 1,4-diazabicyclo[2.2.2]octane (DABCO),

[0256] - catalysts based on zinc carboxylate and DBU (for example K-KAT® 670 marketed by KING INDUSTRIES),

[0257] - Tin-based catalysts such as compounds derived from dioctyltin or 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® S-1 (marketed by KANEKA), or TIB KAT® 425 or TIB KAT® 423 (marketed by TIB CHEMICALS),

[0258] - Guanidine derivatives such as 1-(o-tolyl)biguanide (CAS No.: 93-69-6), for example RHENOCURE 1000 C (marketed by RheinChemie Additives).

[0259] Preferably, the crosslinking catalyst is a tin-based catalyst, preferably chosen from compounds derived from dioctyltin and dibutyltin, more preferably from dioctyltin or dibutyltin oxide.

[0260] The crosslinking catalyst content in the composition according to the invention may 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, and even more preferably from 0.1% to 0.8% by weight. 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, an organic compound derived from silicic acid comprising at least two alkoxysilane groups. Examples include tetraethoxysilane (e.g., WACKER® TES 28 or TES 40 WN) or 1,2-bis(triethoxysilyl)ethane (e.g., Dynasylan® BTSE).

[0261] 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.

[0262] Other additives

[0263] The composition according to the invention may further comprise at least one additive selected from plasticizers, moisture absorbers, solvents, UV stabilizers and mixtures thereof.

[0264] Advantageously, the composition according to the invention comprises a mixture of additives selected from plasticizers, moisture absorbers, solvents and UV stabilizers (or antioxidants).

[0265] 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.

[0266] 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).

[0267] The plasticizer can be any plasticizer commonly used in the field of sealant compositions.

[0268] Preferably, the plasticizer is chosen from:

[0269] - diisodecyl phthalate (for example PALATINOL® DI DP marketed by BASF),

[0270] - diisononyl phthalate (DINP) (for example PALATINOL® N marketed by BASF),

[0271] - an ester of alkylsulfonic acid and phenol (for example MESAMOLL® marketed by LANXESS),

[0272] - the diisononyl ester of 1,2-cyclohexanedicarboxylic acid (for example HEXAMOLL DINCH® marketed by BASF), and - pentaerythritol tetravalerate (for example PEVALEN™ marketed by PERSTORP).

[0273] Preferably, the plasticizer is the diisononyl ester of 1,2-cyclohexanedicarboxylic acid.

[0274] 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.

[0275] 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 allows, for example, a reduction in the viscosity of the composition and makes it easier to apply. The volatile nature of the solvent ensures that the joint, obtained after the composition has hardened, no longer contains any solvent. Thus, the solvent does not, for example, have a negative influence on the hardness of the joint.

[0276] 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 (e.g. DYNASYLAN® VTMO marketed by EVONIK), propyltrimethoxysilane (e.g. DYNASYLAN® PTMO marketed by EVONIK), vinyltriethoxysilane (VTEO), alkoxyarylsilanes (e.g. GENIOSIL® XL 70 marketed by WACKER), p-toluenesulfonyl isocyanate (PTSI) and calcium oxide.

[0277] Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, vinyltriethoxysilane and alkoxyarylsilanes, more preferably vinyltrimethoxysilane.

[0278] 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.

[0279] Advantageously, the UV stabilizer(s) (or antioxidant(s)) are chosen from among benzotriazoles, benzophenones, phenols, and so-called 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-piperidylsebacate (CAS No. 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, the 4,4'-bis(a,a-dimethylbenzyl)diphenylamine, and their mixtures. Examples include IRGANOX 1076, TINUVIN® 292, TINUVIN® 765 or TINUVIN® 770 DF marketed by BASF, RIASORB UV-123 marketed by RIANLON, AddWorks® IBC 760 marketed by CLARIANT and OKABEST CLX 50 marketed by OKA.

[0280] Preferably, the LIV stabilizer(s) (or antioxidants) are chosen from among so-called hindered phenols and amines such as bis(1-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.

[0281] According to one embodiment, the LIV stabilizers (or antioxidants) are a mixture of bis(1-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.

[0282] Composition

[0283] The composition according to the invention preferably has a viscosity at 23°C ranging from 800 Pa.s to 2000

[0284] The viscosity of the composition is typically measured using a planar rheometer at a rotation speed of 5s-1.

[0285] The composition according to the invention advantageously offers at least one of the following advantages:

[0286] - it advantageously leads, after cross-linking, to an adhesive joint exhibiting good mechanical properties

[0287] - it advantageously leads, after cross-linking, to an adhesive joint exhibiting good resistance to aging, particularly under demanding temperature and humidity conditions (for example, after 7 days at 70°C, 100% RH, poultice type).

[0288] Uses

[0289] The present invention also relates to a method for assembling two substrates by bonding, comprising:

[0290] - the coating, on at least one of the two substrates to be assembled, of the composition according to the invention, as defined above; then

[0291] - the effective contact of the two substrates. The substrates concerned can be very varied, and preferably chosen from among plastic, a metal such as aluminium and / or steel and glass.

[0292] According to a preferred embodiment, one of the substrates is steel (for example, part of a vehicle body) and the other substrate is glass (for example, a pane of glass such as a windshield or window).

[0293] The present invention also relates to an article that can be obtained according to the assembly process as defined above.

[0294] 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.

[0295] Furthermore, the present invention relates to the use of the composition according to the invention, as a sealant, in particular as a sealing gasket.

[0296] 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 window) to the body of a vehicle, preferably for replacing the windshield or window of a vehicle.

[0297] All the embodiments described below can be combined with one another. In particular, the various aforementioned components of the composition, and especially the preferred embodiments, can be combined with one another.

[0298] 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%.

[0299] The invention is now described in the following embodiment examples which are given for illustrative purposes only, and should not be interpreted to limit its scope.

[0300] The following ingredients were used:

[0301] - PA: acrylate polymer with trimethoxysilane groups having a viscosity of 140 Pa.s at 23°C from KANEKA;

[0302] - DYNASYLAN® VTMO marketed by EVONIK: vinyltrimethoxysilane (CAS No.: 2768-02-7), moisture absorber; - DYNASYLAN® AMMO marketed by EVONIK: (3-aminopropyl)trimethoxysilane (CAS No.: 13822-56-5), adhesion promoter;

[0303] - ACCLAIM® 12200: polyether polyol with a number average molecular mass of approximately 11,335 g / mol, marketed by COVESTRO;

[0304] -Additive Tl: (marketed by BORCHER): para-toluene sulfonyl isocyanate (dehydrating agent);

[0305] - IPDI: marketed by Evonik: isophorone diisocyanate;

[0306] - Dynasylan ® 1189: marketed by Evonik: N-butyl-3-aminopropyltrimethoxysilane;

[0307] - HAKUENKA® CCR-S10 marketed by OMYA: precipitated calcium carbonate coated with fatty acids, having an average particle size of 80 nm;

[0308] - AKTIFIT VM marketed by HOFFMANN: calcined quartz / kaolinite mixture with vinyl surface modification;

[0309] - ELFTEX® S7100 marketed by CABOT: carbon black having an OAN of 117 ± 6 mL / 100 g measured according to the ASTM D-2414 method;

[0310] - Printex 25: marketed by ORION: carbon black with an OAN of 45 mL / 100 g measured according to the ASTM D-2414 method

[0311] - TIB KAT 425 marketed by TIB CHEMICALS: mixture TIB KAT 232 (dioctyltin oxide) / silane, crosslinking catalyst;

[0312] - TES 40WN: tetraethoxysilane marketed by WACKER;

[0313] - DINCH: 1,2-Cyclohexanedicarboxylic acid, diisononyl ester marketed by BASF

[0314] - SPUR SP1070: SPUR (silylated polyurethane) marketed by MOMENTIVE

[0315] - STPE-30: polypropylene glycol capped with an alpha-silane methyl dimethoxy group with a number-average molecular weight of approximately 14493 g / mol, marketed by WACKER

[0316] Measurement methods

[0317] Shear strength was measured using the following method:

[0318] Two rectangular aluminum plates measuring 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.

[0319] On the bonding area of ​​a 1 ère Once the substrate plate is thus formed, the silylated polymer composition is applied in an amount corresponding to a thickness of 2 mm. Then, the bonding area of ​​the 2nd layer is superimposed on this coated area. èmeThe substrate plate is assembled to obtain a joint in which the free ends of the two substrate plates are aligned on either side of the two areas joined by the sealant. The resulting assembly specimen is held in place by clips for 14 days in a room with a controlled atmosphere at 23°C and 50% relative humidity to allow the composition to cross-link. The two free ends of the specimen are then pulled using a tensile testing machine at a constant speed of 50 mm / minute until the joint breaks, at which point the applied stress is recorded.

[0320] The measurement is repeated for 3 assembly specimens, and the average of the shear stresses at failure (called shear strength) obtained is calculated.

[0321] 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).

[0322] Poultice test:

[0323] The test is carried out according to the D47 1165-H7 standard used in the automotive industry.

[0324] This test involves immersing the part to be tested in cotton soaked in demineralized water and sealing it in an airtight bag. The bag is then placed in an oven at 70 ± 2°C for 7 days. Afterward, the parts are removed, the cotton soaked, and placed at -20°C for 2 hours. Finally, the parts can be observed and mechanically or functionally tested after 2 hours at 23°C to assess the effect of humidity on the system. This test is equivalent to several years of natural aging in a warm, humid environment.

[0325] Example 1: Preparation of silylated polyurethane P'1

[0326] Polymer P'1 was prepared according to the following procedure, under anhydrous conditions:

[0327] In a reactor, Acclaim 12200 is introduced, followed by the Ti additive, and the mixture is heated to 60-65°C. Next, IPDI is added, the mixture is stirred for 10 minutes, and then 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 target NCO value is not reached, the reaction time is extended by as many 15-minute periods as necessary. When the target 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.

[0328] The quantities indicated in the following table are expressed as mass percentages relative to the total weight of the polyurethane composition.

[0329] Example 2: Preparation of silylated polyurethane P'2

[0330] The P'2 polymer was prepared according to the following procedure under anhydrous conditions: In a reactor, Acclaim 8200 is introduced, followed by the Ti additive, and the mixture is heated to 60-65°C. Next, IPDI is added, the mixture is stirred for 10 minutes, and then 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.

[0331] The quantities indicated in the following table are expressed as mass percentages relative to the total weight of the polyurethane composition.

[0332] Example 3: Preparation of compositions C1, C2 and C3 according to the invention and comparative C4, C5 and C6

[0333] In a reactor maintained under agitation, compositions C1, C2 and C3 (invention) and comparative compositions C4, C5 and C6 are prepared by mixing the ingredients in the proportions indicated in the Table below, in several steps according to the process described below.

[0334] The ingredients in step 1 are mixed at room temperature (approximately 23°C), at atmospheric pressure and at low stirring speed (enough to homogenize).

[0335] Next, the ingredients from step 2 are added to the reactor used for step 1 and initially mixed at atmospheric pressure and high stirring speed (to shear and mix the solids). Then, the reactor is placed under vacuum (16 kPa), the temperature is increased to 55-65°C, and mixing is carried out for 10 to 30 minutes. Finally, the ingredients for step 3 are added under vacuum and mixed at low stirring speed (sufficient for homogenization).

[0336] Table: Preparation of compositions

[0337]

[0338] % by weight of the total weight of the composition

[0339] The mechanical properties of compositions C1, C2, C3, C4, C5 and C6 (measured according to the aforementioned methods) are summarized in the table below.

[0340] The adhesive compositions according to the invention (C1, C2 and C3) advantageously lead to a cohesive fracture surface after the wet poultice test. Furthermore, the compositions

[0341] C1, C2 and C3 advantageously lead to 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.

[0342] Furthermore, composition C1 according to the invention advantageously leads to a limited loss of shear strength after being subjected to the wet poultice test, compared to the comparative compositions C5 and C6. Moreover, the final shear strength value is advantageously higher after wet poultice.

Claims

DEMANDS 1. Crosslinkable composition comprising: a polymer P comprising at least one polymer P1 comprising at least one functional group of the following formula (I): -SiR3-pX p (I) 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; said polymer P1 comprising a main chain based on (meth)acrylate; a polyurethane P' comprising at least one function of formula (II): -SiR”3-tX't (II) 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 content in monomer (meth)acrylate units relative to polymer P1 is greater than 50% by weight, preferably greater than or equal to 70% by weight relative to the total weight of said polymer P1.

3. Composition according to any one of claims 1 or 2, characterized in that the polymer P1 has at least one function of formula (lA): -SiR3-p(OR') p (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 polymer P1 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) -SiR3-pX p (I) 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.

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 a polyurethane with NCO terminations; - 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); (R a O)t(R”)3-tSi-R 3 -NH-R 6 (III) in which: - R” and R a each represents, independently of each other, an alkyl group having from 1 to 20 carbon atoms; - t represents 1, 2 or 3, preferably 2 or 3; - R 3 represents a linear or branched alkylene divalent radical comprising from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, R 3 preferentially representing methylene or n-propylene, and - R 6 represents H, a linear or branched alkyl radical, an arylalkyl radical, a cyclic radical comprising 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, the 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: in which: - R 1 represents a divalent hydrocarbon radical comprising 5 to 15 carbon atoms which can be aromatic, aliphatic or cyclic, - R 3 represents a linear or branched alkylene divalent radical comprising 1 to 6 carbon atoms, preferably R 3 representing methylene or n-propylene, - R 2 represents a linear or branched alkylene divalent radical comprising 2 to 4 carbon atoms, - R a and R” are as defined in claim 11, preferably R a and R”, identical or different, each represent a linear or branched alkyl radical comprising 1 to 4 carbon atoms, even more preferably R a and R” representing methyl, - R6 is such as defined previously, preferably R 6 represents a linear or branched alkyl radical comprising 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms; - m is a non-zero integer, - n and m are such that the number-average molecular mass 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. A method for joining two substrates by bonding, comprising: - coating, on at least one of the two substrates to be assembled, with the composition according to any one of claims 1 to 19; then - the effective contacting of the two substrates.

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