Ionic silylated copolyurethane

Abstract

The invention relates to an ionic silylated copolyurethane of formula (I): (I) The invention also relates to a process for preparing the ionic silylated copolyurethane of formula (I) according to the invention, to a composition comprising said ionic silylated copolyurethane and to the use of said composition.

Description

[0001] Ionic silylated copolymer urethane

[0002] Field of invention

[0003] The present invention relates to an ionic silylated copolyurethane and a process for its preparation. The invention also relates to a composition comprising said ionic silylated copolyurethane and the use of said composition.

[0004] Technical background

[0005] Silylated polymers are typically used as adhesives, sealants, coatings, for example in the aeronautics, automotive or construction industries. Such polymers generally comprise alkoxysilane type terminal groups linked, directly or indirectly, to a main chain, in particular of the polyurethane type. Among the industrially available silylated polymers, mention may be made of silylated polyurethanes which can be obtained from the reaction of a prepolymer with isocyanate terminations and a silylated compound comprising alkoxysilane functions.

[0006] Alkoxysilane-terminated polyurethane compositions (also known as silylated polyurethane) have the advantage of being free of free isocyanates (once the silylated polyurethane is formed). These compositions therefore constitute a toxicologically preferred alternative to isocyanate-terminated polyurethane compositions.

[0007] The crosslinking reaction of these silylated polyurethane-based compositions occurs, in the presence of humidity, by hydrolysis of the alkoxysilane groups carried by the polymer, then their condensation to form a siloxane bond (-Si- O-Si-) which unites the polymer chains into a solid three-dimensional network.

[0008] However, the crosslinking time of these silylated polyurethanes must be accelerated to meet user needs.

[0009] For this purpose, it is possible to add a crosslinking catalyst to the compositions comprising silylated polyurethanes.

[0010] Generally, the crosslinking catalyst used in adhesive and / or sealant compositions based on silylated polymers is a metal catalyst, particularly a tin-based one such as dibutyltin dilaurate (DBTDL), dibutyltin diacetate or dibutyltin or dioctyltin bis(acetylacetonate). However, the toxicity of these catalysts, particularly those based on tin, is increasingly highlighted, leading manufacturers to limit, and even avoid, their use, especially since these metal catalysts remain in the finished products.

[0011] An alternative to metal crosslinking catalysts can be organic crosslinking catalysts, notably 1,8-5 diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). However, these have the disadvantage of causing yellow discoloration in the finished products due to the migration of the catalyst to the surface of the adhesive and / or sealant.

[0012] There is therefore a need for new silylated polyurethanes which can crosslink rapidly, even without adding a metallic or organic crosslinking catalyst (DBU or TBD type) to the composition comprising it, in particular an adhesive and / or a sealant.

[0013] The present invention therefore aims to provide a silylated polyurethane which is self-catalyzed.

[0014] 15 Furthermore, the present invention aims to provide a self-catalyzed silylated polyurethane for an adhesive and / or sealant composition, especially a sealant, which leads to similar or improved mechanical properties compared to a (non-self-catalyzed) silylated polyurethane composition comprising a crosslinking catalyst.

[0015] 20

[0016] Summary of the invention

[0017] The present invention relates to an ionic silylated copolyurethane of formula (I):

[0018] The invention also relates to a process for preparing the ionic silylated copolyurethane of formula (I) according to the invention.

[0019] The invention also relates to a composition comprising the ionic silylated copolyurethane of formula (I) according to the invention.

[0020] 30 The invention also relates to the use of the composition according to the invention, as an adhesive and / or sealant, preferably as a sealant. In addition, the invention also relates to an article comprising the composition according to the invention, in airtight packaging, protected from air.

[0021] Furthermore, the invention relates to a method for assembling two substrates comprising: - coating the composition according to the invention on at least one of the two substrates to be assembled; then

[0022] - the effective contact of the two substrates.

[0023] The ionic silylated copolyurethane according to the invention, comprising a pendant cationic ammonium group, advantageously leads to compositions which have, without the addition of catalyst, in particular tin-based catalyst, a reduced crosslinking time compared to a silylated polyurethane not having this pendant cationic ammonium group (see Example 9 below).

[0024] Thus, the pendant cationic ammonium group of the ionic silylated copolyurethane according to the invention makes it possible to catalyze the crosslinking reaction when the ionic silylated copolyurethane comes into contact with moisture, for example air, or any other source of moisture or water. The ionic silylated copolyurethane according to the invention is therefore self-catalyzed.

[0025] Furthermore, the ionic silylated copolyurethane according to the invention makes it possible to obtain compositions with similar or improved mechanical properties compared to a silylated polyurethane composition (not self-catalyzed) comprising a crosslinking catalyst.

[0026] Description of the invention

[0027] Thus, the invention relates to an ionic silylated copolyurethane of formula (I): in which:

[0028] - R 1 represents a divalent hydrocarbon radical comprising from 5 to 45 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more optionally aromatic cycles, and optionally comprising at least one heteroatom chosen from O, S and N, - R 2 represents a saturated or unsaturated, linear or branched, divalent hydrocarbon radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon,

[0029] - A represents a nitrogen atom, or a carbon atom substituted by a hydrogen atom or a carbon atom substituted by an alkyl radical comprising from 1 to 10 carbon atoms,

[0030] - R and R', identical or different, represent:

[0031] - each a divalent hydrocarbon radical with a linear or branched open chain, optionally comprising at least one heteroatom chosen from O and S, or

[0032] - R represents a covalent bond and R' represents a divalent hydrocarbon radical with a linear or branched open chain, optionally comprising at least one heteroatom chosen from O and S, or

[0033] - R' represents a covalent bond and R represents a divalent hydrocarbon radical with a linear or branched open chain, optionally comprising at least one heteroatom chosen from O and S; preferably -OR- corresponds to the formula: -O-CH(R 0 )-CH2-[O-CH(R 0 )-CH2] x-, and / or -R'-O- has the formula: - [CH2-CH(R 0 )-O]y-CH2-CH(R 0 )-O-, in which R° is a hydrogen atom or an alkyl radical comprising one or two carbon atoms, and in which x and y, identical or different integers, are such that the molar mass or the number-average molecular mass Mn of the radical -ORA(R”-NHR 7 R 8 )-R'-O- ranges from 190 g / mol to 20000 g / mol, preferably from 190 g / mol to 5000 g / mol, in particular from 200 g / mol to 1000 g / mol; more preferably -OR- corresponds to the formula: -O- CH(R°)-CH2-[O-CH(R°)-CH2]X-, and -R'-O- corresponds to the formula: -[CH2-CH(R°)- O]y-CH2-CH(R°)-O-,

[0034] - R” represents a linear or branched, preferably linear, divalent alkylene radical comprising from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms,

[0035] - R 7 and R 8, identical or different, each represent a linear or branched alkyl radical, preferably linear, comprising from 1 to 4 carbon atoms, or R 7 and R 8 form a 5 or 6-membered heterocycle with the nitrogen atom to which they are attached, and R 7 and R 8 optionally include a heteroatom chosen from N, O and S,

[0036] - R 10 represents a saturated or unsaturated, linear or branched, divalent hydrocarbon radical optionally comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon, - G R 13 represents the conjugate base of an acid HR 13 , HR 13 which may be an organic or inorganic acid, preferably organic, which has a pKa at 25°C of less than 6, preferably less than or equal to 5, more preferably between -15 and 5.5, even more preferably between -3.0 and 5.0,

[0037] - m and n, identical or different, are each an integer greater than or equal to 1, such that the ratio n / m is within a range from 0.04 to 20, preferably from 0.06 to 13, more preferably from 0.08 to 5, and even more preferably from 0.10 to 1,

[0038] - 1 is an integer equal to 0 or 1, preferably equal to 0,

[0039] - u is an integer greater than or equal to 0, preferably equal to 0 or 1, more preferably equal to 0,

[0040] - m, n, t and u being further such that the number-average molecular mass Mn of the ionic silylated copolyurethane of formula (I) is within a range from 1500 to 50000 g / mol, preferably from 3000 g / mol to 30000 g / mol,

[0041] - f represents a radical of formula (II):

[0042] — XR 3 -If(R 4 ) p (GOLD 5 ) 3.p

[0043] (II) in which:

[0044] - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms,

[0045] - R 4 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, and when p is equal to 2, the radicals R 4 are the same or different,

[0046] - R 5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, an alkylcarbonyl radical comprising from 2 to 8 carbon atoms, or a dialkylimino radical comprising from 3 to 8 carbon atoms, and when p is equal to 0 or 1, the radicals R 5 are identical or different, two OR groups 5 which can be engaged in the same cycle, preferably R 5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms,

[0047] - X represents a divalent radical chosen from -NRS -, -NH- and -S-,

[0048] - R 6 represents a hydrocarbon radical comprising from 1 to 20 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more optionally aromatic cycles, and which may also comprise one or more heteroatoms, preferably R s represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms, and

[0049] - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

[0050] The main chain of the ionic silylated copolyurethane of formula (I) therefore comprises a repeating unit repeated m times and a repeating unit repeated n times. It is understood that the distribution of these two units on said main chain is statistical, and that the copolyurethane of formula (I) is therefore a statistical copolymer.

[0051] Additionally, for convenience, the interaction between the pendant tertiary amine and the HR acid 13 is described as being ionic. However, it is understood that formula (I) also covers silylated copolyurethanes whose interaction between the pendant tertiary amine and the HR acid 13 is not totally ionic, since there is an interaction between them (for example, a hydrogen bond).

[0052] The various groups, radicals and letters which are included in formula (I) and which are defined above, retain throughout this text, and, in the absence of any indication to the contrary, the same definition.

[0053] The number-average molecular mass Mn 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.

[0054] By "unsaturated" we mean one or more unsaturations. Unsaturations can be bonds (e.g. double or triple bonds) and / or rings.

[0055] The pKa of an acid is equal to -log(Ka), where Ka is the acidity constant of the acid in water. For polyprotic acids, the lowest pKa associated with that polyprotic acid is targeted.

[0056] In the context of the invention, by "between x and y", or "ranging from x to y", is meant an interval in which the limits x and y are included. For example, the range "between 1 and 5" includes in particular the values ​​1 and 5.

[0057] The following characteristics of the ionic silylated copolyurethane according to the invention are particularly preferred, taken individually or in combination with each other.

[0058] Advantageously, in the ionic silylated copolyurethane according to the invention, f represents a radical of formula (II) in which:

[0059] - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene;

[0060] - R 5 represents a methyl or ethyl radical, preferably methyl; - X represents a divalent radical -NR 6 -,

[0061] - R 6 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, preferably n-butyl, and

[0062] - p is equal to 0.

[0063] Advantageously, in the ionic silylated copolyurethane according to the invention, the radical R 1 is chosen from the following radicals whose formulas show the free valences:

[0064] - the divalent radical derived from isophorone diisocyanate (IPDI):

[0065] - divalent radicals derived from the isomers 4,4'- and 2,4'-dicyclohexylmethane diisocyanate (HMDI):

[0066] - divalent radicals derived from the 2,4- and 2,6- toluene diisocyanate (TDI) isomers:

[0067] - divalent radicals derived from the 4,4'- and 2,4'- isomers of diphenylmethane diisocyanate (MDI):

[0068] - the divalent radical derived from hexamethylene diisocyanate (RDI): - (CH2)e- - the divalent radical derived from m-xylylene diisocyanate (m-XDI):

[0069] - the divalent radical derived from a hexamethylene diisocyanate (HDI) allophanate of formula (III): in which:

[0070] - i is an integer ranging from 2 to 5;

[0071] - j is an integer ranging from 1 to 2;

[0072] - R 11 represents a hydrocarbon radical, saturated or unsaturated, cyclic, linear or branched, comprising from 6 to 14 carbon atoms;

[0073] - R 12 represents a divalent propylene group;

[0074] - i, j, R 11 and R 12 being such that the hexamethylene diisocyanate allophanate corresponding to formula (III) comprises an isocyanate group NCO content ranging from 12 to 14% by weight relative to the weight of said allophanate.

[0075] Preferably, the radical R 1 is the divalent radical derived from isophorone diisocyanate.

[0076] In the ionic silylated copolyurethane of formula (I), when the radical R 2 or the radical R 10 comprises one or more heteroatoms, said heteroatom(s) are not present at the end of the chain. In other words, the free valences of the divalent radical R 2 and the divalent radical R 10 linked to the neighboring oxygen atoms of the silylated polymer, each come from a carbon atom. Thus, the main chain of the radical R 2 and the divalent radical R 10is terminated by a carbon atom at each of the two ends, said carbon atom then having a free valence.

[0077] According to one embodiment, the ionic silylated copolyurethane of formula (I) is obtained from polyols chosen from polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols, polysiloxane polyols, polyolefin polyols and mixtures thereof, preferably from diols chosen from polyether diols, polyester diols, polycarbonate diols, polyacrylate diols, polysiloxane diols, polyolefin diols and mixtures thereof, more preferably from polyether diols. Such diols may be represented by the formula HO-R 2 -OH or HO-R 10 -OH, where R 2 and R 10 have the same meaning as in formula (I).

[0078] According to one embodiment, the radical R 2 and / or R 10can be chosen from the following divalent radicals whose formulas below show the two free valencies:

[0079] - derived from polyethylene glycol

[0080] - derived from a polypropylene glycol

[0081] - derived from a polyester diol

[0082] - derivative of a polybutadiene diol:

[0083] - derivative of a polyacrylate diol:

[0084] - derived from a polysiloxane diol: in which: - q represents an integer such as the number-average molar mass of the radical R 2 and / or R 10 ranges from 500 g / mol to 20000 g / mol, preferably from 3000 g / mol to 14000 g / mol,

[0085] - r and s represent zero or a non-zero integer such that the number-average molar mass of the radical R 2 and / or R 10ranges from 500 g / mol to 20000 g / mol, preferably from 3000 g / mol to 14000 g / mol, it being understood that the sum r+s is different from zero,

[0086] - Q 1 represents a linear or branched, saturated or unsaturated, aromatic or aliphatic divalent alkylene radical, preferably having from 1 to 18 carbon atoms, more preferably from 1 to 8 carbon atoms,

[0087] - Q 2 represents a linear or branched divalent alkylene radical preferably having from 2 to 36 carbon atoms, more preferably from 1 to 8 carbon atoms,

[0088] - Q 3 , Q 4 , Q 5 , Q 6 , Q 7 and Q 8 , represent, independently of one another, a hydrogen atom or an alkyl, alkenyl or aromatic radical, preferably having from 1 to 12 carbon atoms, preferably from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms.

[0089] Advantageously, the radical R 2 and / or R 10 represents a radical derived from a polyether, preferably from a polyethylene glycol or from a polypropylene glycol as described above, more preferably from a polypropylene glycol.

[0090] Preferably, the ionic silylated copolyurethane is of formula (I) in which:

[0091] - R 2 represents a radical derived from a polyethylene glycol of formula: of a polypropylene glycol of formula: , preferably of a polypropylene glycol , and

[0092] - q represents an integer such as the number-average molar mass of the radical R 2 ranges from 500 g / mol to 20000 g / mol, preferably from 3000 g / mol to 14000 g / mol.

[0093] According to one embodiment, the ionic silylated copolyurethane is of formula (I) in which:

[0094] - A represents a carbon atom substituted by a hydrogen atom, - R represents a covalent bond and R' represents the divalent radical -(CH2) Z - , or R represents the divalent radical -(CH2)z - and R' represents a covalent bond, z being an integer greater than or equal to 1, preferably between 2 and 15, more preferably equal to 10,

[0095] - R” represents the divalent radical -CH2-,

[0096] - R 7 and R 8 are identical and represent an ethyl radical, and

[0097] - 1 and u are equal to 0.

[0098] According to another embodiment, the ionic silylated copolyurethane is of formula (I) in which:

[0099] - A represents a carbon atom substituted by a hydrogen atom,

[0100] - R represents a covalent bond,

[0101] - R' represents the divalent radical -CH2-,

[0102] - R” represents the divalent radical -CH2-,

[0103] - R 7 and R 8 are identical and represent an ethyl radical,

[0104] - 1 and u are equal to 1, and

[0105] - R 10 represents a radical derived from a polypropylene glycol as described above.

[0106] Preferably, the ionic silylated copolyurethane is of formula (I) in which:

[0107] - A represents a nitrogen atom,

[0108] - -OR- has the formula: -O-CH(CH3)-CH2-[O-CH(CH3)-CH2] X -, and -R'- O- has the formula: -[CH2-CH(CH3)-O] y -CH2-CH(CH3)-O-, in which x and y are preferably equal to 0,

[0109] - R” represents a linear divalent alkylene radical comprising from 2 to 4 carbon atoms, preferably 3 carbon atoms,

[0110] - R 7 and R 8are identical and represent a methyl, ethyl, propyl or butyl radical, preferably methyl or ethyl, more preferably methyl, and

[0111] - 1 and u are equal to 0.

[0112] According to one embodiment, the ionic silylated copolyurethane is of formula (I) in which:

[0113] - A represents a nitrogen atom,

[0114] - -OR- has the formula: -O-CH(CH3)-CH2-[O-CH(CH3)-CH2] X -, and -R'- 0- has the formula: -[CH2-CH(CH3)-O] y -CH2-CH(CH3)-O-, in which x and y are such that the molar mass or the number-average molecular mass Mn of the radical -ORA(R”-NHR 7 R 8 )-R'-O- goes from 190 g / mol to 20000 g / mol,

[0115] - R” represents a linear divalent alkylene radical comprising 3 carbon atoms,

[0116] - R 7 and R 8 are identical and represent an ethyl radical, and

[0117] - 1 and u are equal to 0.

[0118] According to a preferred embodiment, the ionic silylated copolyurethane is of formula (I) in which:

[0119] - A represents a nitrogen atom,

[0120] — OR- has the formula: -O-CH(CH3)-CH2-, and -R'-O- has the formula: -CH2-CH(CH3)-O-,

[0121] - R” represents a linear divalent alkylene radical comprising 3 carbon atoms, and

[0122] - R 7 and R 8 are identical and represent a methyl radical, and

[0123] - 1 and u are equal to 0.

[0124] The n-fold repeating unit includes a pendant cationic ammonium group, the counterion of which is anionic and of formula: ®R 13 . The anionic counterion ®R 13 is derived from an acid of formula HR 13 , after reaction with the pendant amine(s) of the n-fold repeating unit.

[0125] By "organic acid" is meant an acid of formula HR 13 in which R 13 is a radical comprising at least one carbon atom.

[0126] By "inorganic acid" is meant an acid of formula HR 13 in which R 13 is a radical containing no carbon atoms.

[0127] Preferably, the acid of formula HR 13 is an organic acid. In particular, R 13 represents an OR radical 9 , in which R 9 represents an unsaturated hydrocarbon radical, with a linear or branched open chain, or comprising one or more optionally aromatic cycles, R 9 comprising at least one oxygen atom and optionally one or more heteroatoms chosen from N, F and S.

[0128] Advantageously, the ionic silylated copolyurethane is of formula (I) in which R 13 is such that the acid of formula HR 13is a carboxylic or sulfonic acid which has a pKa at 25°C between -15 and 5.5, preferably between -3.0 and 5.0.

[0129] By "carboxylic acid" is meant an organic acid comprising at least one -C(O)OH group. By "sulfonic acid" is meant an organic acid comprising at least one -S(O)2OH group.

[0130] According to one embodiment, the ionic silylated copolyurethane is of formula (I) in which R 13 is such that the acid of formula HR 13is selected from hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, sulfuric acid, perchloric acid, formic acid, acetic acid, trifluoroacetic acid, hydroxyacetic acid, oxalic acid, propanoic acid, 3-hydroxypropionic acid, malonic acid, methylmalonic acid, butanoic acid, isobutyric acid, succinic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, pentanoic acid, hexanoic acid, citric acid, sorbic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, acrylic acid, propiolic acid, crotonic acid, isocrotonic acid, methacrylic acid, benzoic acid, methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid and lactic acid, preferably from hydrochloric acid, phosphoric acid, formic acid, acetic acid,trifluoroacetic acid, propanoic acid, butanoic acid, iso-butyric acid, 2-methylbutanoic acid, 3-methylbutanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, acrylic acid, crotonic acid, isocrotonic acid, methacrylic acid, benzoic acid, methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid and p-toluenesulfonic acid, more preferably from formic acid, acetic acid, propanoic acid, acrylic acid, methacrylic acid, methanesulfonic acid and ethanesulfonic acid, even more preferably from acetic acid, acrylic acid and methanesulfonic acid.,

[0131] The viscosity at 23°C of the ionic silylated copolyurethane according to the invention can vary from 10 to 300 Pa.s, preferably from 20 to 100 Pa.s.

[0132] The viscosity of the ionic silylated copolyurethane according to the invention can, for example, be measured using a Brookfield-type method at 23°C and 50% relative humidity (S28 needle).

[0133] According to a particularly preferred embodiment, the ionic silylated copolyurethane is of formula (I) in which:

[0134] - R 1 represents the divalent radical derived from isophorone diisocyanate, - R 2 represents a radical derived from a polyethylene glycol or a polypropylene glycol as described above, preferably from a polypropylene glycol,

[0135] - q is an integer such that the number-average molecular mass of the radical R 2 ranges from 3000 to 14000 g / mol, - A represents a nitrogen atom,

[0136] — OR- has the formula: -O-CH(CH3)-CH2-, and -R'-O- has the formula: -CH2-CH(CH3)-O-,

[0137] - R” represents a linear divalent alkylene radical comprising 3 carbon atoms, and - R 7 and R 8 are identical and represent a methyl radical,

[0138] - R 13 is such that the acid of formula HR 13 is selected from acetic acid, acrylic acid and methanesulfonic acid,

[0139] - 1 and u are equal to 0,

[0140] - m and n are such that the ratio n / m is within a range from 0.10 to 1, - f represents a radical of formula (II) in which:

[0141] - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene;

[0142] - R 5 represents a methyl or ethyl radical, preferably methyl;

[0143] - X represents a divalent radical -NR S -, - R 6represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, preferably n-butyl, and

[0144] - p is equal to 0.

[0145] Process for the preparation of ionic silylated copolyurethane according to the invention

[0146] The invention also relates to a process for preparing the ionic silylated copolyurethane of formula (I) according to the invention, comprising the following steps:

[0147] (i) formation of a copolyurethane with -NCO ends of formula (IV): by implementing a polyaddition reaction between:

[0148] - a polyisocyanate of formula (IVa): OCN-R 1 -NCO, - a polyol polymer, preferably a diol polymer, of formula (IVb): H- OR 2 -OH, and

[0149] - a polyol, preferably a diol, branched with at least one tertiary amine of formula (IVc):

[0150] 5 Then

[0151] (ii) reaction of the copolyurethane from step (i) with an acid of formula HR 13 to form an ionic copolyurethane and

[0152] (iii) reaction of the copolyurethane resulting from step (i) with -NCO endings with a silylated compound of formula (IIa):

[0153] HX-R 3 -If(R 4 ) p (GOLD 5 ) 3.p

[0154] (lia). 5

[0155] R 1 , R 2 , m, n, t, u, R, R', R”, A, R 7 , R 8 , R 10 , R 13 , X, R 3 , R 4 , R 5 and p are as described above, including the embodiments.

[0156] By "copolyurethane resulting from step (i)" is meant the copolyurethane of formula (IV) or one of its derivatives (in particular an ionic derivative with -NCO endings obtained during step (ii) or a silylated derivative obtained during step (iii)).

[0157] Thus, in the process according to the invention, step (ii) can be carried out on the copolyurethane of formula (IV) and followed by step (iii), or step (iii) can be carried out on the copolyurethane of formula (IV) and followed by step (ii).

[0158] Preferably, the method according to the invention comprises the sequential steps 5:

[0159] (i) formation of a copolyurethane with -NCO ends of formula (IV): 0 by carrying out a polyaddition reaction between: - a polyisocyanate of formula (IVa): OCN-R 1 -NCO,

[0160] - a polyol polymer, preferably a diol polymer, of formula (IVb): H- OR 2 -OH, and

[0161] - a polyol, preferably a diol, branched with at least one tertiary amine of formula (IVc):

[0162] (ii) reaction of the copolyurethane of formula (IV) with an acid of formula HR 13to form an ionic copolyurethane with -NCO ends of formula (V):

[0163] (iii) reaction of the copolyurethane of formula (V) with a silylated compound of formula (IIa):

[0164] HX-R 3 -If(R 4 ) p (GOLD 5 ) 3.p

[0165] (lia).

[0166] Advantageously, the polymer polyol of formula (IVb) is a polyether diol, preferably a polypropylene glycol diol. Such polypropylene glycols are commercially available, in particular under the brand name ACCLAIM® from the company COVESTRO. Examples include:

[0167] - ACCLAIM® 4200 with a number-average molecular mass Mn equal to 4000 g / mol and an ion equal to 28 mg KOH / g,

[0168] - ACCLAIM® 8200 with a number-average molecular mass Mn equal to 8000 g / mol and an ion equal to 13.5 mg KOH / g,

[0169] - ACCLAIM® 12200 with a number-average molecular mass Mn equal to 12000 g / mole, and an ion equal to 10 mg KOH / g,

[0170] - ACCLAIM® 18200 with a number-average molecular mass Mn of 18000 g / mol and an ion of 6.5 mg KOH / g. The hydroxyl number IOH is the number of hydroxyl functions per gram of polyol, expressed as the equivalent number of milligrams of KOH used in the determination of hydroxyl functions. It can be determined by titrimetry according to ISO 14900:2017.

[0171] In the process according to the invention, step (i) is advantageously carried out with a molar ratio (branched polyol of formula (IVc) / polyol of formula (IVb)) corresponding to the n / m ratio as defined above. In particular, the molar ratio (branched polyol of formula (IVc) / polyol of formula (IVb)) is even more preferably between 0.10 and 1.

[0172] In the process according to the invention, step (i) is advantageously carried out with an excess of the equivalent number of -NCO groups of the polyisocyanate of formula (IVa) relative to the equivalent number of -OH groups provided by the polyols of formulas (IVb) and (IVc). Preferably, step (i) is carried out with an equivalent molar ratio -NCO / -OH of between 1.1 and 4.2, preferably between 1.3 and 3.8, more preferably between 1.5 and 2.

[0173] The molar equivalent ratio -NCO / -OH is defined as being equal to the molar equivalent number of -NCO groups of the polyisocyanate of formula (IVa), divided by the sum of the molar equivalent numbers of -OH groups provided by the polyols of formulas (IVb) and (IVc).

[0174] The molar equivalent number of -NCO groups in the polyisocyanate of formula (IVa) is equal to: f(-NCO)*(m ( iva) / M(i Va)), where f(-NCO) is the number of -NCO groups in the polyisocyanate of formula (IVa), m <iva) est la masse introduite en g de polyisocyanate de formule (IVa) et M<iva) est la masse molaire en g / mol du polyisocyanate de formule (IVa). De préférence, le polyisocyanate de formule (IVa) est un diisocyanate et f(-NCO) est donc égal à 2.

[0175] The molar equivalent number of -OH groups provided by the polyols of formulas (IVb) and (IVc) is equal to: [f(- OH)(ivb)*(m ( ivb) / M(ivb)) + f(-OH) (ivc)*(m (ivc) / M(ivc))], where f(—OH)(ivb) is the number of -OH groups in the polyol of formula (IVb), m ( ​ivb) and f(— OH)(ivo are therefore each equal to 2. Step (i) is generally carried out in the presence of a catalyst which may be any catalyst known to those skilled in the art for catalyzing the formation of polyurethane by reaction of a polyisocyanate and at least one polyol. Such a catalyst is for example chosen from carboxylates, in particular neodecanoate, of bismuth and / or zinc. As commercially available examples, mention may be made of BorchiOKat 315 from the company OMG Borchers which is a bismuth neodecanoate, or BorchiOKat 15 from the same company which is a zinc neodecanoate.

[0176] Step (i) is advantageously carried out under anhydrous conditions.

[0177] Step (i) is advantageously carried out at a temperature between 60°C and 120°C.

[0178] Step (i) is advantageously carried out at atmospheric pressure.

[0179] Step (ii) corresponds to the reaction of the -NR group 7 R 8 pendant which is included in the n-fold repeating unit of the copolyurethane of formula (IV) with the acid of formula HR 13 .

[0180] In step (ii) of the process according to the invention, the molar ratio (acid of formula HR 13 / branched polyol of formula (IVc) introduced in step (i)) can vary from 0.8 to 2.5, preferably from 1 to 2, more preferably equal to 1.

[0181] Step (ii) is advantageously carried out under anhydrous conditions.

[0182] Step (ii) is advantageously carried out at a temperature between 20°C and 80°C, preferably between 20°C and 453.

[0183] Step (ii) is advantageously carried out at atmospheric pressure.

[0184] In step (iii), the -NCO end groups of the copolyurethane (especially of formula (V)) react with the -XH group of the silylated compound of formula (IIa). Silylated compounds of formula (IIa) are widely available commercially. Examples include N-(3(trimethoxysilyl)propyl)butylamine available under the name Dynasylan® 1189 from Evonik.

[0185] In the process according to the invention, step (iii) can be carried out with an equivalent molar ratio -XH / -NCO equal to 1, preferably between 0.90 and 1.15.

[0186] The molar equivalent ratio -XH / -NCO is defined as being equal to the molar equivalent number of -XH groups of the silylated compound of formula (IIa) divided by the molar equivalent number of -NCO groups of the copolyurethane (in particular of formula (V)).

[0187] The molar equivalent number of -XH groups in the silylated compound of formula (IIa) is equal to: f(-XH)*(m(IIa) / M(Na)), where f(-XH) is the number of -XH groups in the silylated compound of formula (Ha), m ( (iia) is the mass introduced in g of silylated compound of formula (IIa) and M ( n a ) is the molar mass in g / mol of the silylated compound of formula (Ha).

[0188] The molar equivalent number of -NCO groups of the copolyurethane (in particular of formula (V)) corresponds to the molar equivalent number of -NCO groups of the polyisocyanate of formula (IVa) introduced in excess compared to the molar equivalent number of -OH groups provided by the polyols of formulas (IVb) and (IVc).

[0189] Step (iii) is advantageously carried out under anhydrous conditions.

[0190] Step (iii) is advantageously carried out at a temperature in the range from 20°C to 80°C, preferably from 20°C to 40°C.

[0191] Step (iii) is advantageously carried out at atmospheric pressure.

[0192] Advantageously, the process according to the invention is carried out in the absence of water as a solvent. Thus, the process according to the invention is carried out without adding free water, i.e. other than that inherently included in the ingredients used. In particular, the water content introduced into the process according to the invention is less than 5% by weight relative to the total weight of the ingredients used, preferably less than 3% by weight, in particular less than 1% by weight.

[0193] Composition comprising an ionic silylated copolyurethane according to the invention

[0194] The invention also relates to a composition comprising the ionic silylated copolyurethane of formula (I) according to the invention.

[0195] The content of ionic silylated copolyurethane is advantageously between 10% and 50% by weight relative to the total weight of the composition, preferably from 20% to 48% by weight, more preferably from 35% to 45% by weight.

[0196] Advantageously, the composition according to the invention further comprises a filler. The filler content is advantageously between 20% and 60% by weight relative to the total weight of the composition, preferably from 30% to 58% by weight, more preferably still from 40% to 55% by weight.

[0197] The filler that can be used in the composition according to the invention can be chosen from mineral fillers and mixtures of organic fillers and mineral fillers.

[0198] As an example of a mineral filler, we can cite any mineral filler usually used in the field of adhesive and / or sealant compositions. These fillers are in the form of particles of various geometry. They can be, for example, spherical, fibrous, or have an irregular shape.

[0199] Advantageously, the mineral fillers are formed by the group consisting of clay, quartz, hollow mineral microspheres and carbonate fillers.

[0200] Among the hollow mineral microspheres, we can cite hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate.

[0201] Preferably, the mineral fillers are formed by the group consisting of carbonate fillers.

[0202] Advantageously, the carbonated filler is chosen from alkali or alkaline earth metal carbonates and mixtures thereof. Preferably, the carbonated filler comprises calcium carbonate, more preferably the carbonated filler is chalk or calcium carbonate coated with fatty acids, even more preferably precipitated calcium carbonate coated with fatty acids.

[0203] When calcium carbonate is coated with fatty acids, this makes the calcium carbonate particles completely or partially hydrophobic. In addition, the fatty acid coating acts as a hydrophobic coating that can prevent the calcium carbonate from absorbing the composition's constituents and rendering them ineffective. The hydrophobic coating of the calcium carbonate can represent from 0.1% to 3.5% by weight, based on the total weight of calcium carbonate.

[0204] 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 the fatty acids. As an example of an organic filler, mention may be made of any organic filler, in particular polymeric, usually used in the field of adhesive and / or mastic compositions.

[0205] Advantageously, the organic fillers are formed by 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.

[0206] Advantageously, the average particle size of the filler 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.

[0207] The average particle size corresponds advantageously 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).

[0208] Unless otherwise indicated, the standards referred to throughout the application are those in effect on the date the application was filed.

[0209] According to a preferred embodiment, the composition according to the invention has an ionic silylated copolyurethane content of between 10% and 50% by weight and a filler content of between 20% and 60% by weight, the percentages by weight being relative to the total weight of the composition.

[0210] The composition according to the invention may further comprise at least one additive chosen from moisture absorbers, adhesion promoters, plasticizers, rheology agents, UV stabilizers and mixtures thereof.

[0211] Advantageously, the composition according to the invention comprises a mixture of additives chosen from moisture absorbers and adhesion promoters.

[0212] Suitable moisture absorbers (or drying agents) include alkoxysilanes such as trialkoxysilanes (particularly trimethoxysilanes). Such an agent advantageously prolongs the shelf life of the composition according to the invention during storage and transport, prior to its use.

[0213] Advantageously, the moisture absorber is chosen from vinyltrimethoxysilane, trimethoxymethylsilane, propyltrimethoxysilane, vinyltriethoxysilane, alkoxyarylsilanes (for example GENIOSIL® XL 70 marketed by WACKER) and mixtures thereof.

[0214] Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, vinyltriethoxysilane and their mixture, more preferably vinyltrimethoxysilane.

[0215] The moisture absorber content may be between 0.5% and 5% by weight relative to the total weight of the composition according to the invention, preferably between 1% and 3.5% by weight.

[0216] The adhesion promoter may be chosen from amino-, mercapto- and epoxy-alkoxysilanes, and mixtures thereof. Preferably, the adhesion promoter is chosen from aminoalkoxysilanes, more preferably from aminotrialkoxysilanes, even more preferably from aminotrimethoxysilanes, for example N-(3-

[0217] (trimethoxysilyl)propyl)ethylenediamine.

[0218] An example of an epoxy-alkoxysilane is (3-glycidyloxypropyl)trimethoxysilane (also known as GLYMO).

[0219] Advantageously, the 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-(3-(trimethoxysilyl)propyl)ethylenediamine (for example GENIOSIL® GF9 marketed by the company WACKER). Preferably, the aminotrimethoxysilanes are N-(3-(trimethoxysilyl)propyl)ethylenediamine.

[0220] The content of adhesion promoter may be between 0.1% and 5% by weight relative to the total weight of the composition according to the invention, preferably between 0.5% and 3% by weight, more preferably between 1.0% and 2.0% by weight.

[0221] The plasticizer may be any plasticizer commonly used in the field of adhesive and / or sealant compositions.

[0222] Preferably, the plasticizer is chosen from:

[0223] - diisodecyl phthalate (for example PALATINOL® DIDP marketed by BASF),

[0224] - diisononyl phthalate (DINP) (for example PALATINOL® N marketed by BASF), - an ester of alkylsulfonic acid and phenol (for example MESAMOLL® marketed by LANXESS),

[0225] - the diisononyl ester of 1,2-cyclohexanedicarboxylic acid (for example HEXAMOLL DINCH® marketed by BASF), and

[0226] - pentaerythritol tetravalerate (for example PEVALEN™ marketed by PERSTORP).

[0227] The plasticizer content may vary from 5% to 20% by weight relative to the total weight of the composition according to the invention, preferably from 10% to 15% by weight.

[0228] The rheology agent may be any rheology agent commonly used in the field of adhesive and / or sealant compositions.

[0229] Advantageously, the rheology agent is chosen from:

[0230] - PVC plastisols, corresponding to a suspension of PVC in a plasticizing agent miscible with PVC, obtained in situ by heating at temperatures ranging from 60°C to 80°C. These plastisols may be those described in particular in the work “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6,

[0231] - pyrogenic silica, such as HDK® N20 marketed by WACKER,

[0232] - 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, and

[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] By "amide waxes" is meant waxes comprising one or more compounds having at least one amide group. In particular, amide waxes can be obtained from fatty acid(s) (e.g. ricinoleic acid) and (di)amine(s).

[0235] By "micronized" is meant an average particle size of less than 1 mm, advantageously less than 500 pm, preferably less than 100 pm, more preferably less than 10 pm. 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).

[0236] The content of rheology agent may vary from 1% to 40% by weight relative to the total weight of the composition according to the invention, preferably from 5% to 30% by weight, more preferably from 10% to 25% by weight.

[0237] The composition according to the invention may comprise up to 1% by weight of one or more UV stabilizers (or antioxidants) relative to the total weight of the composition. UV stabilizers are typically introduced to protect the composition from degradation resulting from a reaction with oxygen which is likely to form by the action of heat or light. These compounds may include antioxidants capable of trapping free radicals.

[0238] Advantageously, the UV stabilizer(s) (or antioxidants) are chosen from benzotriazoles, benzophenones, 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-pentametiyl-4-piperidyl sebacate (CAS No.: 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-bis(a,a-dimethylbenzyl)diphenylamine, and mixtures thereof. Examples include IRGANOX 1076, TINUVIN® 292, TINUVIN® 765 or TINUVIN® 770 DF products marketed by BASF and RIASORB UV-123 marketed by RIANLON.

[0239] According to one embodiment, the composition according to the invention comprises:

[0240] - between 10% and 50% by weight of ionic silylated copolyurethane according to the invention,

[0241] - between 20% and 60% by weight of a load,

[0242] - between 0.5% and 5% by weight of moisture absorber, and

[0243] - between 0.1% and 5% by weight of adhesion promoter, the percentages by weight being relative to the total weight of the composition.

[0244] Preferably, the composition according to the invention consists essentially of the ingredients mentioned above. By "consisting essentially", it is meant that the composition according to the invention comprises less than 5% by weight of ingredients other than the aforementioned ingredients, relative to the total weight of the composition, preferably less than 2% by weight, even more preferably less than 1% by weight.

[0245] The ingredients of this embodiment and their particular contents are as described above, including the embodiments.

[0246] Advantageously, the composition according to the invention does not comprise a crosslinking catalyst.

[0247] Thus, no crosslinking catalyst is advantageously added to the ionic silylated copolyurethane according to the invention. Indeed, the ionic silylated copolyurethane according to the invention alone makes it possible to catalyze the crosslinking reaction.

[0248] By "crosslinking catalyst" is meant a catalyst known to those skilled in the art for the condensation of silanol.

[0249] Examples of such catalysts include:

[0250] - organic titanium derivatives such as titanium acetyl acetonate, titanium tetrapylate, titanium tetrabutylate,

[0251] - organic zirconium derivatives such as zirconium acetyl acetonate, zirconium tetrapropylate, zirconium tetrabutylate,

[0252] - 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-diazabicylo[2.2.2]octane (DABCO),

[0253] - catalysts based on zinc carboxylate and DBU (for example K-KAT® 670 marketed by KING INDUSTRIES),

[0254] - tin-based catalysts such as compounds derived from dioctyltin or dibutyltin.

[0255] Advantageously, the composition according to the invention does not comprise water as a solvent. Thus, the water content in the composition according to the invention is advantageously less than 5% by weight relative to the total weight of said composition, preferably less than 3% by weight, in particular less than 1% by weight.

[0256] The composition according to the invention is preferably stored in an anhydrous environment, for example in airtight packaging, where said composition is protected from humidity and preferably protected from light.

[0257] The composition according to the invention can be prepared by simply mixing its ingredients. Preferably, the composition according to the invention is prepared at atmospheric pressure and at a temperature between 10°C and 55°C, more preferably between 18°C ​​and 40°C.

[0258] An example of preparation of the composition according to the invention is described in Example 8.

[0259] Other objects of the invention

[0260] The invention also relates to the use of the composition according to the invention, as an adhesive and / or sealant, preferably as a sealant.

[0261] Furthermore, the invention also relates to an article comprising the composition according to the invention, in airtight packaging, protected from air.

[0262] Preferably, the airtight packaging is a polyethylene bag or a polyethylene cartridge fitted with a lid.

[0263] Furthermore, the invention relates to a method for assembling two substrates comprising:

[0264] - coating the composition according to the invention on at least one of the two substrates to be assembled; then

[0265] - the effective contact of the two substrates.

[0266] Preferably, the assembly method according to the invention is carried out at room temperature (approximately 23°C).

[0267] By "about X", we mean more or less 10% of the value of X.

[0268] Suitable substrates are, for example, inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminum, steel, non-ferrous metals, galvanized metals), or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins, or painted metal and composite substrates (for example, in the automotive sector).

[0269] All the embodiments described above can be combined with each other. In particular, the various aforementioned ingredients of the composition according to the invention, in particular the preferred embodiments, can be combined with each other.

[0270] The following examples are given purely for illustrative purposes of the invention and should not be interpreted as limiting its scope. Examples

[0271] 1 Ingredients and measurement methods

[0272] Ingredients used

[0273] The following ingredients were used:

[0274] - ACCLAIM® 4200 marketed by Covestro: poly(propylene oxide) with a number-average molar mass of approximately 4000 g / mol, having two -OH endings and a hydroxyl number IOH equal to 28.0 mg KOH / g;

[0275] - isophorone diisocyanate (IPDI) marketed by Covestro: molar mass equal to 222.3 g / mol (CAS No.: 4098-71-9);

[0276] - BorchiOKat 315 marketed by OMG Borchers: bismuth neodecanoate with a molar mass of 722.75 g / mol;

[0277] Dynasylan® 1189 marketed by Evonik: N-(3-

[0278] (trimethoxysilyl)propyl)butylamine with a molar mass equal to 235.4 g / mol;

[0279] - Jeffcat® DPA marketed by Huntsman: N-(3-dimethylaminopropyl)- N,N-diisopropanolamine with a molar mass equal to 218.34 g / mol;

[0280] - acetic acid marketed by Sigma Aldrich: molar mass equal to 60.05 g / mol and pKa equal to 4.8 at 25°C;

[0281] - acrylic acid marketed by Sigma Aldrich: molar mass equal to 72.06 g / mol and pKa equal to 4.25 at 25°C;

[0282] - methanesulfonic acid marketed by Sigma Aldrich: molar mass equal to 96.11 g / mol and pKa equal to -1.9 at 25°C;

[0283] - TIBKAT® 223 marketed by TIB Chemicals: dioctyltin bis(acetylacetonate) with a molar mass of 543.15 g / mol, crosslinking catalyst;

[0284] GENIOSIL® GF9 marketed by Wacker: N-(3-

[0285] (trimethoxysilyl)propyl)ethylenediamine with a molar mass equal to 222.36 g / mol, adhesion promoter;

[0286] - VTMO marketed by Sigma Aldrich: vinyltrimethoxysilane with a molar mass of 148.23 g / mol, moisture absorber

[0287] - CALOFORT® SV marketed by Specialty Minerals: precipitated calcium carbonate coated with stearic acid, with an average particle size of 70 nm.

[0288] Measurement methods

[0289] The %NCO is determined automatically using a T5 Excellence titrator (marketed by Mettler Toledo). A sample of the reaction medium is taken and introduced into the titrator, then a solution of dicyclohexylamine in DMF (N,N-dimethylformamide) is added automatically. The titration of the excess amine is also done automatically with hydrochloric acid.

[0290] The crosslinking time is measured by determining the skin formation time. To this end, a bead of sealant (approximately 10 cm long and approximately 1 cm in diameter) is first placed on a cardboard support. Then, using a low-density polyethylene (LDPE) pipette tip, the sealant surface is touched every minute for up to 2 hours to determine the exact time at which the surface skin forms. This test is carried out under controlled humidity and temperature conditions (23°C and 50% relative humidity).

[0291] Tensile strength and elongation at break were measured in accordance with ISO 37 (2012), at a constant speed of 100 mm / min.

[0292] In particular, the following conditions were applied:

[0293] A standard dumbbell-shaped specimen (H2), type 2, as illustrated in international standard ISO 37 (2012) is used. The narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 3 mm.

[0294] To prepare the dumbbell, the composition to be tested (previously packaged in a cartridge) is extruded into a Teflon mold and left to crosslink for 14 days under standard conditions (23°C and 50% relative humidity).

[0295] The principle of the measurement consists of stretching a standard test piece in a tensile machine (for example Zwick Roell 2.5KN), whose movable jaw moves at a constant speed equal to 100 mm / min, and recording:

[0296] - the elongation at break (expressed in %) which is the elongation of the test piece corresponding to the stretching observed at the time of break,

[0297] - Young's modulus (expressed in MPa) which is the slope of the tangent at the origin of the curve showing the tensile stress as a function of the elongation of the specimen, and

[0298] - the tensile strength (in MPa) which is the tensile stress at which the specimen ruptures (also called TS for Tensile Strength in English).

[0299] The measurement is repeated for 5 test pieces, and the corresponding average of the results obtained is calculated. The water content of the ingredients, including ACCLAIM® 4200 and Jeffcat® DPA, is measured using a Karl Fischer coulometric method using HYDRANAL™ as the titrant, with the equivalence point detected electrometrically.

[0300] The viscosity of the silylated polymers prepared in the examples below is measured using a Brookfield-type method at 23°C and 50% relative humidity (S28 needle).

[0301] Preparation of a reference silylated polyurethane (comparative)

[0302] In a 500 mL reactor, 304.81 g of ACCLAIM® 4200 are introduced (i.e. a molar equivalent number of -OH groups equal to 0.152 mol), then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate the ACCLAIM® 4200. The water content of the ACCLAIM® 4200 is then less than or equal to 0.02% by weight relative to the total weight of the ACCLAIM® 4200.

[0303] The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 32.6 g of IPDI (i.e. an equivalent molar number of -NCO groups equal to 0.293 mol) and 0.15 g of Borchi®Kat 315. The mixture is kept stirring until reaching a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the -OH groups (0.293-0.152=0.141 mol of excess -NCO groups, i.e. 0.141*42=5.9 g of -NCO groups).

[0304] 33.05 g of Dynasylan® 1189 are then introduced, corresponding to a molar ratio -NH / -NCO equal to 1 (the molar equivalent number of -NH groups being equal to 0.14 mol). The whole is heated to 70°C and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy (around 2260 cm' 1 ).

[0305] Approximately 375 g of silylated polyurethane are obtained and the silylated polyurethane is packaged in aluminum cartridges protected from humidity.

[0306] The viscosity of this silylated polyurethane is 35500 mPa.s at 23°C.

[0307] Preparation of an ionic silylated copolyurethane No. 1 (invention)

[0308] Ionic silylated copolyurethane No. 1 is prepared in a similar manner to the reference silylated polyurethane, except that 0.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is introduced into the reactor before the addition of IPDI, and that acetic acid is added, in a molar ratio of acetic acid to Jeffcat® DPA equal to 1, after the reaction with IPDI.

[0309] In a 500 mL reactor, 282.79 g of ACCLAIM® 4200 (i.e., a molar equivalent number of -OH groups equal to 0.141 mol) and 1.76 g of Jeffcat® DPA (i.e., a molar equivalent number of -OH groups equal to 0.016 mol) are introduced (i.e., a total molar equivalent number of -OH groups equal to 0.157 mol), then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate the ACCLAIM® 4200 and Jeffcat® DPA. The water content of the mixture of ACCLAIM® 4200 and Jeffcat® DPA is then less than or equal to 0.02% by weight relative to the total weight of said mixture.

[0310] The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 32.09 g of IPDI (i.e. an equivalent molar number of -NCO groups equal to 0.288 mol) and 0.15 g of Borchi®Kat 315. The mixture is kept stirring until reaching a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the -OH groups (0.288-0.157=0.131 mol of excess -NCO groups, i.e. 0.131 *42=5.5 g of -NCO groups).

[0311] 0.48 g of acetic acid is then added at 40° Q and stirring is left for 1 hour.

[0312] 30.67 g of Dynasylan® 1189 are then introduced, corresponding to a molar ratio -NH / -NCO equal to 1. The whole is heated to 40°C and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.

[0313] Approximately 350 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from moisture.

[0314] The viscosity of this ionic silylated copolyurethane is 36000 mPa.s at 23°C.

[0315] Example 4: Preparation of an ionic silylated copolyurethane no. 2 (invention)

[0316] Ionic silylated copolyurethane No. 2 is prepared in a similar manner to the reference silylated polyurethane, except that 1.3% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is introduced into the reactor before the addition of IPDI, and that acetic acid is added, in an acetic acid / Jeffcat® DPA molar ratio equal to 1, after the reaction with IPDI.

[0317] In a 500 mL reactor, 279.47 g of ACCLAIM® 4200 and 3.51 g of Jeffcat® DPA are introduced, then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate the ACCLAIM® 4200 and Jeffcat® DPA. The water content of the mixture of ACCLAIM® 4200 and Jeffcat® DPA is then less than or equal to 0.02% by weight relative to the total weight of said mixture.

[0318] The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 33.53 g of IPDI and 0.15 g of Borchi®Kat 315. The mixture is kept stirring until reaching a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the -OH groups.

[0319] 0.97 g of acetic acid is then added at 40° Q and stirring is left for 1 hour.

[0320] 30.31 g of Dynasylan® 1189 are then introduced, corresponding to a molar ratio -NH / -NCO equal to 1. The whole is heated to 40°C and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.

[0321] Approximately 350 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from moisture.

[0322] The viscosity of this ionic silylated copolyurethane is 40500 mPa.s at 23°C.

[0323] Example 5: Preparation of an ionic silylated copolyurethane no. 3 (invention)

[0324] Ionic silylated copolyurethane No. 3 is prepared in a similar manner to the reference silylated polyurethane, except that 2.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is introduced into the reactor before the addition of IPDI, and that acetic acid is added, in an acetic acid / Jeffcat® DPA molar ratio equal to 1, after the reaction with IPDI.

[0325] In a 500 mL reactor, 272.83 g of ACCLAIM® 4200 and 7.03 g of Jeffcat® DPA are introduced, then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate the ACOLAIM® 4200 and Jeffcat® DPA. The water content of the mixture of ACCLAIM® 4200 and Jeffcat® DPA is then less than or equal to 0.02% by weight relative to the total weight of said mixture.

[0326] The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 36.41 g of IPDI and 0.15 g of Borchi®Kat 315. The mixture is kept stirring until reaching a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the -OH groups. 1.93 g of acetic acid are then added at 40°C and stirring is left for 1 hour.

[0327] 29.59 g of Dynasylan® 1189 are then introduced, corresponding to a molar ratio -NH / -NCO equal to 1. The whole is heated to 40°C and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.

[0328] Approximately 350 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from moisture.

[0329] The viscosity of this ionic silylated copolyurethane is 59000 mPa.s at 23°C.

[0330] Example 6: Preparation of an ionic silylated copolyurethane no. 4 (invention)

[0331] Ionic silylated copolyurethane No. 4 is prepared in a similar manner to the reference silylated polyurethane, except that 2.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is introduced into the reactor before the addition of IPDI, and that acrylic acid is added, in a molar ratio of acrylic acid / Jeffcat® DPA equal to 1, after the reaction with IPDI.

[0332] In a 500 mL reactor, 300 g of ACCLAIM® 4200 and 7.82 g of Jeffcat® DPA are introduced, then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate the ACCLAIM® 4200 and the Jeffcat® DPA. The water content of the mixture of ACCLAIM® 4200 and Jeffcat® DPA is then less than or equal to 0.02% by weight relative to the total weight of said mixture.

[0333] The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 44.62 g of IPDI and 0.15 g of Borchi®Kat 315. The mixture is kept stirring until reaching a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the -OH groups.

[0334] 2.58 g of acrylic acid is then added at 40°C, and stirring is left for 1 hour.

[0335] 32.03 g of Dynasylan® 1189 are then introduced, corresponding to a molar ratio -NH / -NCO equal to 1. The whole is heated to 40°C and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.

[0336] Approximately 390 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from moisture. The viscosity of this ionic silylated copolyurethane is 36000 mPa.s at 23°C.

[0337] Example 7: Preparation of an ionic silylated copolyurethane No. 5 (invention)

[0338] Ionic silylated copolyurethane No. 5 is prepared in a similar manner to the reference silylated polyurethane, except that 2.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is introduced into the reactor before the addition of IPDI, and that methanesulfonic acid is added, in a molar ratio of methanesulfonic acid / Jeffcat® DPA equal to 1, after the reaction with IPDI.

[0339] In a 500 mL reactor, 299.3 g of ACCLAIM® 4200 and 7.82 g of Jeffcat® DPA are introduced, then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate the ACCLAIM® 4200 and the Jeffcat® DPA. The water content of the mixture of ACCLAIM® 4200 and Jeffcat® DPA is then less than or equal to 0.02% by weight relative to the total weight of said mixture.

[0340] The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 44.53 g of IPDI and 0.15 g of Borchi®Kat 315. The mixture is kept stirring until reaching a % NCO by weight of 1.7% relative to the total weight of the compounds introduced into the reactor, which corresponds to the excess of -NCO groups introduced relative to the -OH groups.

[0341] 3.44 g of methanesulfonic acid are then added at 40°C, and stirring is left for 1 hour.

[0342] 31.95 g of Dynasylan® 1189 are then introduced, corresponding to a molar ratio -NH / -NCO equal to 1. The whole is heated to 40°C and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.

[0343] Approximately 390 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from moisture.

[0344] The viscosity of this ionic silylated copolyurethane is 61500 mPa.s at 23°C.

[0345] Example 8: Preparation of an ionic silylated copolyurethane no. 6 (comparative)

[0346] Ionic silylated copolyurethane No. 6 is prepared similarly to ionic silylated copolyurethane No. 1, except that N-methyldiethanolamine is used instead of Jeffcat® DPA (i.e., 0.6% by weight of N-methyldiethanolamine relative to the weight of ACCLAIM® 4200, and an acetic acid / N-methyldiethanolamine molar ratio of 1).

[0347] The viscosity of this ionic silylated copolyurethane is 46390 mPa.s at 23°C. Example 9: Preparation of sealants

[0348] The polymers prepared in Examples 2 to 8 are used to prepare sealants, the composition of which is indicated in Table 1 below, the percentages being percentages by weight of the total weight of the sealant.

[0349] First, the ingredients from step 1 are added at room temperature (approximately 23°C) and atmospheric pressure in a high-speed mixer and then mixed for 2 min.

[0350] The ingredients from step 2 are then added and everything is mixed for 2 minutes.

[0351] The stirring speed is approximately 2000 rpm (rotations per minute).

[0352] The sealants obtained are packaged in polyethylene cartridges.

[0353] Table 1

[0354] Example 10: Properties of sealants 1 to 8

[0355] The properties of sealants 1 to 8 (measured according to Example 1) are summarized in Table 2 below.

[0356] \ID: Not determined

[0357] Table 2

[0358] Comparative sealant 1, prepared from the reference silylated polyurethane and without crosslinking catalyst, has a crosslinking time of 70 min.

[0359] This crosslinking time decreases by more than half when the sealant is prepared from an ionic silylated copolyurethane according to the invention (sealants 3 to 7).

[0360] This shows that the ionic silylated copolyurethane according to the invention makes it possible to accelerate crosslinking compared to the reference silylated polyurethane, without it being necessary to add a crosslinking catalyst to the sealant.

[0361] Furthermore, the crosslinking time can be reduced by increasing the amount of Jeffcat® DPA tertiary amine used during the preparation of the ionic silylated copolyurethane. Indeed, when 2.6% instead of 0.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is used, the crosslinking time decreases from 30 min to 22 min (comparison of sealants 3 and 5).

[0362] Furthermore, the crosslinking time varies depending on the acid used during the preparation of the ionic silylated copolyurethane. Indeed, the replacement of acetic acid with acrylic acid (mastic 6) or methanesulfonic acid (mastic 7) makes it possible to obtain a crosslinking time equal to, or even less than, that observed for a mastic obtained using a crosslinking catalyst and the reference silylated polyurethane (mastic 2).

[0363] However, the sealant based on comparative ionic silylated copolyurethane No. 6 (sealant 8) has a significantly longer crosslinking time than the ionic silylated copolyurethane according to the invention. Indeed, comparative copolyurethane No. 6 does not have a pendant tertiary amine, unlike the ionic silylated copolyurethane according to the invention. In addition, sealant 8 has a sticky appearance after 24 hours, which is not suitable for use as a sealant.

[0364] Furthermore, sealants 3 to 7 according to the invention have good tensile strength, generally higher than that of comparative sealant 1, as well as a Young's modulus higher than that of comparative sealant 1. The sealants according to the invention are therefore particularly suitable for rigid bonding (after crosslinking), preventing the bonded substrates from moving relative to each other.

[0365] In conclusion, the ionic silylated copolyurethane according to the invention is self-catalyzed, and can be used in a sealant without it being necessary to add a metallic or organic crosslinking catalyst. In addition, the ionic silylated copolyurethane according to the invention makes it possible to obtain sealants that are particularly suitable for rigid bonding.

Claims

Demands 1. Ionic silyl copolyurethane of formula (I): in which: - R 1 represents a divalent hydrocarbon radical comprising from 5 to 45 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more possibly aromatic rings, and possibly comprising at least one heteroatom selected from O, S and N, - R 2 represents a saturated or unsaturated, linear or branched divalent hydrocarbon radical possibly comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon, - A represents a nitrogen atom, or a carbon atom substituted by a hydrogen atom or a carbon atom substituted by an alkyl radical comprising from 1 to 10 carbon atoms, - R and R', whether identical or different, represent: - each a divalent hydrocarbon radical with a linear or branched open chain, possibly comprising at least one heteroatom chosen from O and S, OR - R represents a covalent bond and R' represents a linear or branched open-chain hydrocarbon divalent radical, possibly comprising at least one heteroatom selected from O and S, or - R' represents a covalent bond and R represents a linear or branched open-chain hydrocarbon divalent radical, possibly comprising at least one heteroatom selected from O and S; preferably -OR- corresponds to the formula: -O-CH(R 0 )-CH2-[O-CH(R°)-CH2] x- and / or -R'-O- corresponds to the formula: - [CH2-CH(R°)-O]y-CH2-CH(R°)-O-, where R° is a hydrogen atom or an alkyl radical comprising one or two carbon atoms, and where x and y, identical or different integers, are such that the molar mass or the number-average molecular mass of the radical -ORA(R”-NHR 7 R 8 )-R'-O- goes from 190 g / mol to 20000 g / mol, preferably from 190 g / mol to 5000 g / mol, in particular from 200 g / mol to 1000 g / mol; more preferably -OR- corresponds to the formula: -O- CH(R°)-CH2-[O-CH(R°)-CH2]X- and -R'-O- corresponds to the formula: -[CH2-CH(R°)- O]y-CH2-CH(R°)-O-, - R” represents a linear or branched divalent alkylene radical, preferably linear, comprising from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms, - R 7 and R 8, identical or different, each represent a linear or branched alkyl radical, preferably linear, comprising from 1 to 4 carbon atoms, or R 7 and R 8 form a heterocycle with 5 or 6 links with the nitrogen atom to which they are attached, and R 7 and R 8 possibly include a heteroatom chosen from N, O and S, - R 10 represents a saturated or unsaturated, linear or branched, divalent hydrocarbon radical possibly comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon, - Ô R 13 represents the conjugate base of an acid HR 13 HR 13 which may be an organic or inorganic acid, preferably organic, which has a pKa at 25°C less than 6, preferably less than or equal to 5, more preferably between -15 and 5.5, even more preferably between -3.0 and 5.0, - m and n, identical or different, are each an integer greater than or equal to 1, such that the ratio n / m is within a range from 0.04 to 20, preferably from 0.06 to 13, more preferably from 0.08 to 5, and even more preferably from 0.10 to 1, - 1 is an integer equal to 0 or 1, preferably equal to 0, - u is an integer greater than or equal to 0, preferably equal to 0 or 1, more preferably equal to 0, - m, n, t and u being further such that the number-average molecular mass Mn of the ionic silylated copolyurethane of formula (I) is within a range of 1500 to 50000 g / mol, preferably from 3000 g / mol to 30000 g / mol, - f represents a radical of formula (II): _ xR 3 -If(R 4 ) p (GOLD 5 ) 3.p (H) in which: - R 3represents a linear or branched alkylene divalent radical comprising 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, - R 4 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, and when p equals 2, the R radicals 4 are identical or different, - R 5 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, an alkylcarbonyl radical comprising 2 to 8 carbon atoms, or a dialkylimino radical comprising 3 to 8 carbon atoms, and when p is equal to 0 or 1, the R radicals 5 are identical or different, two OR groups 5 that can be engaged in the same cycle, preferably R 5 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, - X represents a divalent radical chosen from -NR 6 -, -NH- and -S-, - R 6represents a hydrocarbon radical comprising from 1 to 20 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more rings, possibly aromatic, and possibly also comprising one or more heteroatoms, preferably R 6 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms, and - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

2. Ionic silyl copolyurethane according to claim 1, wherein f represents a radical of formula (II) in which: - R 3 represents a linear or branched alkylene divalent radical comprising 1 to 3 carbon atoms, preferably n-propylene; - R 5 represents a methyl or ethyl radical, preferably methyl; - X represents a divalent radical -NR S -, - R 6represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, preferably n-butyl, and - p is equal to 0.

3. Ionic silyl copolyurethane according to claim 1 or 2, wherein the radical R 1 is chosen from the following radicals whose formulas show the free valences: - the divalent radical derived from isophorone diisocyanate (IPDI): - divalent radicals derived from the 4,4'- and 2,4'-dicyclohexylmethane diisocyanate (HMDI) isomers: - divalent radicals derived from the 2,4- and 2,6- toluene diisocyanate isomers (TDI): - divalent radicals derived from the 4,4'- and 2,4'- isomers of diphenylmethane diisocyanate (MDI): - the divalent radical derived from hexamethylene diisocyanate (HDI): - (CH2)B- - the divalent radical derived from m-xylylene diisocyanate (m-XDI): - the divalent radical derived from an allophanate of hexamethylene diisocyanate (HDI) of formula (III): in which: - i is an integer ranging from 2 to 5; - j is an integer ranging from 1 to 2; - R 11 represents a hydrocarbon radical, saturated or unsaturated, cyclic, linear or branched, comprising 6 to 14 carbon atoms; - R 12 represents a divalent propylene group; - i, j, R 11 and R 12 being such that the hexamethylene diisocyanate allophanate corresponding to formula (III) comprises an isocyanate group NCO content of 12 to 14% by weight relative to the weight of said allophanate.

4. Ionic silyl copolyurethane according to any one of claims 1 to 3, wherein: - R 2 represents a radical derived from polyethylene glycol with the formula: of a polypropylene glycol formula preference for polypropylene glycol, and - q represents an integer such that the number-average molar mass of the radical R 2 ranges from 500 g / mol to 20000 g / mol, preferably from 3000 g / mol to 14000 g / mol.

5. Ionic silyl copolyurethane according to any one of claims 1 to 4, wherein: - A represents a nitrogen atom, - -OR- corresponds to the formula: -O-CH(CH3)-CH2-[O-CH(CH3)-CH2] X -, and -R'- 0- corresponds to the formula: -[CH2-CH(CH3)-O] y -CH2-CH(CH3)-O-, in which x and y are preferably equal to 0, - R” represents a linear divalent alkylene radical comprising 2 to 4 carbon atoms, preferably 3 carbon atoms, - R 7 and R 8 are identical and represent a methyl, ethyl, propyl, or butyl radical, preferably methyl or ethyl, more preferably methyl, and - 1 and u are equal to 0.

6. Ionic silyl copolyurethane according to any one of claims 1 to 5, wherein R 13 is such that the acid of formula HR 13 is a carboxylic or sulfonic acid which has a pKa at 25 °C between -15 and 5.5, preferably between -3.0 and 5.

0.

7. A process for preparing ionic silylated copolyurethane as defined in any one of claims 1 to 6, comprising the following steps: (i) formation of a -NCO-terminated copolyurethane of formula (IV): by implementing a polyaddition reaction between: - a polyisocyanate of formula (IVa): OCN-R 1 -NCO, - a polyol polymer of formula (IVb): H-OR 2 -OH, and - a branched polyol with at least one tertiary amine of formula (IVc): Then (ii) reaction of the copolyurethane from step (i) with an acid of formula HR 13 to form an ionic copolyurethane and (iii) reaction of the copolyurethane from step (i) ending in -NCO with a silylated compound of formula (lia): HX— R 3 - If(R 4 ) p (GOLD 5 ) 3.p (Ha).

8. Composition comprising ionic silylated copolyurethane as defined in any one of claims 1 to 6.

9. Composition according to claim 8, further comprising a filler.

10. Composition according to claim 9, wherein the content of ionic silylated copolyurethane is between 10% and 50% by weight and the content of filler is between 20% and 60% by weight, the percentages by weight being relative to the total weight of the composition.

11. Use of the composition according to any one of claims 8 to 10, as an adhesive and / or sealant.

Images