Ionic silylated copolyurethane

Abstract

The invention relates to an ionic silyl copolyurethane of formula (I): (I). The invention also relates to a method for preparing the ionic silyl copolyurethane of formula (I) according to the invention, a composition comprising said ionic silyl copolyurethane, and the use of said composition. Figure for the abstract: none

Description

Title of the invention: Ionic silyl copolyurethane Scope of the invention

[0001] The present invention relates to an ionic silyl copolyurethane and its preparation process. The invention also relates to a composition comprising said ionic silyl copolyurethane and the use of said composition. Technical background

[0002] Silylated polymers are typically used as adhesives, sealants, and coatings, for example in the aerospace, automotive, and construction industries. Such polymers generally comprise alkoxysilane-type terminal groups linked, directly or indirectly, to a main chain, particularly one of the polyurethane type. Among the industrially available silylated polymers are silylated polyurethanes, which can be obtained from the reaction of an isocyanate-terminated prepolymer and a silylated compound comprising alkoxysilane functional groups.

[0003] Compositions based on alkoxysilane-terminated polyurethane (also called 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.

[0004] The crosslinking reaction of these silylated polyurethane-based compositions occurs, in the presence of moisture, 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.

[0005] However, the crosslinking time of these silylated polyurethanes must be accelerated to meet user needs.

[0006] For this purpose, it is possible to add a crosslinking catalyst to compositions comprising silylated polyurethanes.

[0007] Generally, the crosslinking catalyst used in silylated polymer-based adhesive and / or sealant compositions is a metallic 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, especially tin-based ones, is increasingly being highlighted, leading manufacturers to limit, and even avoid, their use, especially since these metallic catalysts remain in the finished products.

[0008] An alternative to metal crosslinking catalysts may be constituted by the organic crosslinking catalysts, including 1,8-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 a yellow discoloration in the finished products due to the migration of the catalyst to the surface of the adhesive and / or sealant.

[0009] There is therefore a need for new silylated polyurethanes that can crosslink rapidly, even without adding a metallic or organic crosslinking catalyst (type DBU or TBD) to the composition comprising it.

[0010] The present invention therefore aims to provide a silylated polyurethane that is self-catalyzed. Summary of the invention

[0011] The present invention relates to an ionic silylated copolyurethane of formula (I): f—c-nh-rUnh-cvor2— oc- nh-r'^nh-co- ra-r'-o4r1"o4-Pr'— a—k-ô4c—nh-c—ï I! • il si UK 1 L- --!H ! O: OOJO R- i R" to -»PO —'JB. t | f [ — —n

[0012] (I).

[0013] The invention also relates to a process for preparing ionic silyl copolyurethane of formula (I) according to the invention

[0014] The invention also relates to a composition comprising ionic silylated copolyurethane of formula (I) according to the invention.

[0015] The invention also relates to the use of the composition according to the invention, as an adhesive and / or sealant.

[0016] Furthermore, the invention also relates to an article comprising the composition according to the invention, in airtight packaging, protected from air.

[0017] Furthermore, the invention relates to a method for assembling two substrates comprising:

[0018] - coating the composition according to the invention, on at least one of the two substrates to assemble; then

[0019] - the effective contacting of the two substrates.

[0020] The ionic silylated copolyurethane according to the invention, comprising a pendant ammonium cationic group, advantageously leads to compositions which, without the addition of a catalyst, in particular a tin-based catalyst, exhibit a reduced crosslinking time compared to a silylated polyurethane not exhibiting this pendant ammonium cationic group (see Example 9 below).

[0021] Thus, the ammonium cationic group pendant to the ionic silyl copolyurethane according to the invention makes it possible to catalyze the crosslinking reaction when the ionic silyl copolyurethane comes into contact with moisture, for example air, or any other source of moisture or water. The ionic silyl copolyurethane according to the invention is therefore self-catalyzed. Description of the invention

[0022] Thus, the invention relates to an ionic silylated copolyurethane of formula (I): NH-R'4 NH-C-0R- •O—C-NH'Rl-H-NH~CO—R—A—R'~04-R“bM-R'—A—R-O+C—NH-R'+NW-C—f R: ! fi 1 -h ! J. N: ! i: O ; >- OR" i R" JO ->n Ô i « IZ « i: ©NlWRMf1-' i |

[0023] (I)

[0024] in which:

[0025] - R1 represents a divalent hydrocarbon radical comprising from 5 to 45 atoms of carbon, saturated or unsaturated, with a linear or branched open chain, or comprising one or more rings, possibly aromatic, and possibly comprising at least one heteroatom selected from O, S and N,

[0026] - R2 represents a saturated or unsaturated, linear or divalent hydrocarbon radical branched, possibly comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon,

[0027] - A represents a nitrogen atom, or a carbon atom substituted by an atom hydrogen or a carbon atom substituted by an alkyl radical comprising 1 to 10 carbon atoms,

[0028] - R and R', whether identical or different, represent:

[0029] - each a divalent hydrocarbon radical with a linear or branched open chain, possibly including at least one heteroatom chosen from O and S, or

[0030] - R represents a covalent bond and R' represents a divalent radical hy open-chain or branched carbon atom, possibly comprising at least one heteroatom selected from O and S, or

[0031] - R' represents a covalent bond and R represents a divalent radical hy open-chain linear or branched carbon drocarbon, possibly comprising at least one heteroatom chosen from O and S; preferably -OR- corresponds to the formula: -O-CH(R°)-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 average molecular mass in number Mn of the radical -ORA(R”-NHR7R8)-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-,

[0032] - 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,

[0033] - R7 and R8, whether identical or different, each represent a linear alkyl radical or branched, preferably linear, comprising from 1 to 4 carbon atoms, or R7 and R8 form a heterocycle with 5 or 6 links with the nitrogen atom to which they are attached, and R7 and R8 possibly include a heteroatom chosen from N, O and S,

[0034] - R10 represents a saturated or unsaturated, linear or divalent hydrocarbon radical branched, possibly comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon,

[0035] - eR13 represents the conjugate base of an acid HR13, HR13 being able to be an acid organic or inorganic, 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,

[0036] - m and n, whether identical or different, are each an integer greater than or equal to 1, such that the n / m ratio is within a range of 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,

[0037] -1 is an integer equal to 0 or 1, preferably equal to 0,

[0038] - u is an integer greater than or equal to 0, preferably equal to 0 or 1, more preferably rentically equal to 0,

[0039] - 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,

[0040] - f represents a radical of formula (II): — X™ R3™

[0041] (II)

[0042] in which:

[0043] - R3 represents a linear or branched divalent alkylene radical comprising 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,

[0044] - R4 represents a linear or branched alkyl radical comprising 1 to 4 atoms of carbon, and when p equals 2, the R4 radicals are either identical or different,

[0045] - R5 represents a linear or branched alkyl radical comprising 1 to 4 atoms of carbon, 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 R5 radicals are identical or different, two OR5 groups being possible engaged in the same cycle, preferably R5 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms,

[0046] - X represents a divalent radical chosen from -NR6-, -NH- and -S-,

[0047] - R6 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 rings, possibly aromatic, and possibly also comprising one or more heteroatoms, preferably R6 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms, and

[0048] - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

[0049] The main chain of the ionic silylated copolyurethane of formula (I) therefore comprises a repeating motif repeated m times and a repeating motif repeated n times. It is understood that the distribution of these two motifs on said main chain is statistical, and that the copolyurethane of formula (I) is therefore a statistical copolymer.

[0050] 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.

[0051] 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.

[0052] By "unsaturated" we mean one or more unsaturations. The unsaturations may be bonding (for example double or triple bond) and / or ring unsaturations.

[0053] The pKa of an acid is equal to -logi0(Ka), where Ka is the acidity constant of the acid in water. For polyprotic acids, the lowest pKa associated with that polyprotic acid is sought.

[0054] 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 1 and 5" includes, in particular, the values ​​1 and 5.

[0055] The following characteristics of the ionic silylated copolyurethane according to the invention are particularly preferred, taken individually or in combination with each other.

[0056] Advantageously, in the ionic silylated copolyurethane according to the invention, f represents a radical of formula (II) in which:

[0057] - R3 represents a linear or branched divalent alkylene radical comprising 1 to 3 carbon atoms, preferably n-propylene;

[0058] - R5 represents a methyl or ethyl radical, preferably methyl;

[0059] - X represents a divalent radical -NR6-,

[0060] - R6 represents a linear or branched alkyl radical comprising 1 to 4 atoms of carbon, preferably n-butyl, and

[0061] - p is equal to 0.

[0062] Advantageously, in the ionic silylated copolyurethane according to the invention, the radical R1 is chosen from among the following radicals whose formulas show the free valences:

[0063] - the divalent radical derived from isophorone diisocyanate (IPDI): CH:

[0064] - the divalent radicals derived from the 4,4'- and 2,4'-dicyclohexylmethane diisomers socyanate (HMDI):

[0065] - divalent radicals derived from the 2,4- and 2,6- toluene diisocyanate (TDI) isomers:

[0066] - the divalent radicals derived from the 4,4'- and 2,4'- isomers of diphenylmethane di socyanate (MDI):

[0067] - the divalent radical derived from hexamethylene diisocyanate (HDI): - (CH2)6-

[0068] - the divalent radical derived from m-xylylene diisocyanate (m-XDI): /

[0069] - the divalent radical derived from an allophanate of hexamethylene diisocyanate (HDI) of formula (III): (HD 11 12 R—OR — m'Y O

[0070] in which:

[0071] - i is an integer from 2 to 5;

[0072] - j is an integer from 1 to 2;

[0073] - R11 represents a hydrocarbon radical, saturated or unsaturated, cyclic, linear or branched, comprising 6 to 14 carbon atoms;

[0074] - R12 represents a divalent propylene group;

[0075] - i, j, R11 and R12 being such that the hexamethylene diisocyanate allophanate cor corresponding to formula (III) comprises an isocyanate group NCO content ranging from 12 to 14% by weight relative to the weight of said allophanate.

[0076] Preferably, the radical R1 is the divalent radical derived from isophorone diisocyanate.

[0077] In the ionic silylated copolyurethane of formula (I), when the R2 radical or the R10 radical comprises one or more heteroatoms, said heteroatom(s) are not located at the end of the chain. In other words, the free valences of the divalent R2 radical and the divalent R10 radical, bonded to the oxygen atoms adjacent to the silylated polymer, each originate from a carbon atom. Thus, the main chain of the R2 radical and the divalent R10 radical terminates with a carbon atom at each of its two ends, said carbon atom then exhibiting a free valence.

[0078] According to one embodiment, the ionic silyl copolyurethane of formula (I) is obtained from polyols selected from polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols, polysiloxane polyols, polyolefin polyols and mixtures thereof, preferably from diols selected 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-R2-OH or HO-R10-OH, where R2 and R10 have the same meaning as in formula (I).

[0079] According to one embodiment, the radical R2 and / or R10 can be chosen from the following divalent radicals, the formulas below of which show the two free valences:

[0080] - derived from polyethylene glycol: , / 1

[0081] - derived from a polyester diol - derived from polypropylene glycol: S

[0082] - derived from a polybutadiene diol: QQ

[0083] - derived from a polyacrylate diol: —Q—

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090] - derived from a polysiloxane diol: in which: - q represents an integer such that the number-average molar mass of the radical R2 and / or R10 ranges from 500 g / mol to 20000 g / mol, preferably from 3000 g / mol to 14000 g / mol, - r and s represent zero or a non-zero integer such that the number-average molar mass of the radical R2 and / or R10 ranges 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 not zero, - Q1 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, - Q2 represents a linear or branched divalent alkylene radical preferably having from 2 to 36 carbon atoms, preferably from 1 to 8 carbon atoms, - Q3, Q4, Q5, Q6, Q7 and Q8, independently of each other, represent an atom hydrogen or an alkyl, alkenyl or aromatic radical, preferably having 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms, preferably still 2 to 8 carbon atoms.

[0091] Advantageously, the radical R2 and / or R10 represents a radical derived from a polyether, preferably from a polyethylene glycol or a polypropylene glycol as described above, more preferably from a polypropylene glycol.

[0092] Preferably, the ionic silyl copolyurethane has formula (I) in which:

[0093] - R2 represents a radical derived from a polyethylene glycol of formula: Or 0" ■p' 0" ™ q

[0094] of a polypropylene glycol of formula: CHo, of l I a I CHs CHj CH3 preferably a polypropylene glycol, and

[0095] - q represents an integer such that the number-average molar mass of the radical R2 will from 500 g / mol to 20,000 g / mol, preferably from 3000 g / mol to 14,000 g / mol.

[0096] According to one embodiment, the ionic silyl copolyurethane has the formula (I) in which:

[0097] - A represents a carbon atom substituted by a hydrogen atom,

[0098] - 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,

[0099] - R' ' represents the divalent radical -CH2 -,

[0100] - R7 and R8 are identical and represent an ethyl radical, and

[0101] -1 and u are equal to 0.

[0102] According to another embodiment, the ionic silyl copolyurethane has the formula (I) in which:

[0103] - A represents a carbon atom substituted by a hydrogen atom,

[0104] - R represents a covalent bond,

[0105] - R' represents the divalent radical -CH2-,

[0106] - R' ' represents the divalent radical -CH2 -,

[0107] - R7 and R8 are identical and represent an ethyl radical,

[0108] -1 and u are equal to 1, and

[0109] - R10 represents a radical derived from a polypropylene glycol as described above.

[0110] Preferably, the ionic silyl copolyurethane has formula (I) in which:

[0111] - A represents a nitrogen atom,

[0112] - -OR- corresponds to the formula: -O-CH(CH3)-CH2-[O-CH(CH3)-CH2]X-, and -R'-O- corresponds to the formula: -[CH2-CH(CH3)-O]y-CH2-CH(CH3)-O-, in which x and y are preferably equal to 0,

[0113] - R” represents a linear divalent alkylene radical comprising 2 to 4 atoms of carbon, preferably 3 carbon atoms,

[0114] - R7 and R8 are identical and represent a methyl, ethyl, propyl or radical butyl, preferably methyl or ethyl, more preferably methyl, and

[0115] -1 and u are equal to 0.

[0116] According to one embodiment, the ionic silyl copolyurethane has formula (I) in which:

[0117] - A represents a nitrogen atom,

[0118] - -OR- corresponds to the formula: -O-CH(CH3)-CH2-[O-CH(CH3)-CH2]X-, and -R'-O- corresponds to the formula: -[CH2-CH(CH3)-O]y-CH2-CH(CH3)-O-, in which x and y are such that the molar mass or the average molecular mass in number Mn of the radical -ORA(R”-NHR7R8)-R'-O- ranges from 190 g / mol to 20000 g / mol,

[0119] - R” represents a linear divalent alkylene radical comprising 3 atoms of carbon,

[0120] - R7 and R8 are identical and represent an ethyl radical, and

[0121] -1 and u are equal to 0.

[0122] According to a preferred embodiment, the ionic silyl copolyurethane has formula (I) in which:

[0123] - A represents a nitrogen atom,

[0124] - -OR- corresponds to the formula: -O-CH(CH3)-CH2-, and -R'-O- corresponds to the formula: -CH2-CH(CH3)-O-,

[0125] - R” represents a linear divalent alkylene radical comprising 3 atoms of carbon, and

[0126] - R7 and R8 are identical and represent a methyl radical, and

[0127] -1 and are equal to 0.

[0128] The motif repeated n times comprises a pendant ammonium cationic group, whose counter-ion is anionic and of formula: ®R13. The anionic counter-ion ®R13 is obtained from an acid of formula HR13, after reaction with the pendant amine(s) of the motif repeated n times.

[0129] By "organic acid" is meant an acid of formula HR13 in which R13 is a radical comprising at least one carbon atom.

[0130] By "inorganic acid" is meant an acid of formula HR13 in which R13 is a radical not comprising any carbon atoms.

[0131] Preferably, the acid of formula HR13 is an organic acid. In particular, R13 represents an OR9 radical, in which R9 represents an unsaturated hydrocarbon radical, open linear or branched chain, or comprising one or more rings possibly aromatic, R9 comprising at least one oxygen atom and possibly one or more heteroatoms selected from N, F and S.

[0132] Advantageously, the ionic silylated copolyurethane has formula (I) in which R 13 is such that the acid of formula HR13 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.

[0133] By "carboxylic acid" is meant an organic acid comprising at least one -C(O)OH group.

[0134] By "sulfonic acid" is meant an organic acid comprising at least one -S(O)2OH group.

[0135] According to one embodiment, the ionic silylated copolyurethane has formula (I) in which R13 is such that the acid of formula HR13 is 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, isobutyric 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, and even more preferentially among acetic acid, acrylic acid and methanesulfonic acid.

[0136] 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.

[0137] The viscosity of the ionic silylated copolyurethane according to the invention can for example be measured according to a Brookfield type method at 23°C and 50% relative humidity (S28 needle).

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

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[0160]

[0161] According to a particularly preferred embodiment, the ionic silyl copolyurethane has the formula (I) in which: - R1 represents the divalent radical derived from isophorone diisocyanate, - R2 represents a radical derived from a polyethylene glycol or a polypropylene glycol as described above, preferably from a polypropylene glycol, - q is an integer such that the number-average molecular mass of the R2 radical ranges from 3000 to 14000 g / mol, - A represents a nitrogen atom, - -OR- corresponds to the formula: -O-CH(CH3)-CH2-, and -R'-O- corresponds to the formula: -CH2-CH(CH3)-O-, - R' ' represents a linear divalent alkylene radical comprising 3 carbon atoms, and - R7 and R8 are identical and represent a methyl radical. - R13 is such that the acid of formula HR13 is chosen from acetic acid, acrylic acid and methanesulfonic acid, -1 and u are equal to 0, - 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: - R3 represents a linear or branched alkylene divalent radical comprising 1 to 3 carbon atoms, preferably n-propylene; - R5 represents a methyl or ethyl radical, preferably methyl; - X represents a divalent radical -NR6-, - R6 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, preferably n-butyl, and - p is equal to 0. Process for preparing ionic silylated copolvurethane according to the invention The invention also relates to a process for preparing ionic silylized copolyurethane of formula (I) according to the invention, comprising the following sequential steps: (i) formation of a copolyurethane with -NCO ends of formula (IV): NH-C-OR3—(>—C-NH-R44nH-€-O—R—A—PR!—A—R-GÎC—NH-Rsl 1: R ffi: | L_ _J < ti:■ i: [ b H !• f L 1 t • lfh} OOIUOR"! R- fo -5 — tn ( : : ! 1 -, « : s - „ ! NR'R1 ( NR'R* j (IV) by implementing a polyaddition reaction between: - a polyisocyanate of formula (IVa): OCN-R'-NCO, - a polyol polymer, preferably a diol polymer, of formula (IVb): H-OR2-OH, And

[0162]

[0163]

[0164] - a polyol, preferably a diol, branched with at least one tertiary amine of formula (IVc): HO— R— A— R - 4 RsoO-|-R—A—R-0¼ H R's 11 R" | —■ u (IVc) (ii) reaction of the copolyurethane of formula (IV) with an acid of formula HR13 to form an ionic copolyurethane with -NCO terminations of formula (V): OO-R1- NH-C-OR- 11 O ■ G--CN H - R 44 NH-0<>- R- A- R' - »4 R!"Ôl-U •: ! i ; I l__ ' t < R'—A E •CX:î K 11'

[0165]

[0166]

[0167]

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[0175]

[0176] (V) And (iii) reaction of the copolyurethane of formula (V) with a silylated compound of formula (lia): (lia). R1, R2, m, n, t, u, R, R', R”, A, R7, R8, R10, R13, X, R3, R4, R5 and p are as described above, including embodiments. Advantageously, the polyol polymer of formula (IVb) is a polyether diol, preferably a polypropylene glycol diol. Such polypropylene glycols are commercially available, notably under the brand name ACCLAIM® from the company COVESTRO. Examples include: - ACCLAIM® 4200 with an average molecular mass in number Mn equal to 4000 g / mol and an Ion equal to 28 mg KOH / g, - ACCLAIM® 8200 with an average molecular mass in number Mn equal to 8000 g / mol and an Ion equal to 13.5 mg KOH / g, - ACCLAIM® 12200 with an average molecular mass in number Mn equal to 12000 g / mol, and an IOH equal to 10 mg KOH / g, - ACCLAIM® 18200 with average molecular mass in number Mn equal to 18000 g / mol, and Ion equal to 6.5 mg KOH / g. The hydroxyl value (IOH) is the number of hydroxyl groups per gram of polyol, expressed as the equivalent number of milligrams of KOH used in the hydroxyl group determination. It can be determined by titration according to ISO 14900:2017. In the process according to the invention, step (i) is advantageously implemented with a molar ratio (branched polyol of formula (IVc) / polyol of formula (IVb)) corresponding to the n / m ratio as defined previously. In particular, the molar ratio (branched polyol of formula (IVc) / polyol of formula (IVb)) is even more preferably between 0.10 and 1.

[0177] In the process according to the invention, step (i) is advantageously carried out with an excess of the equivalent number of -NCO groups from the polyisocyanate of formula (IVa) compared 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 of -NCO / -OH between 1.1 and 4.2, preferably between 1.3 and 3.8, and more preferably between 1.5 and 2.

[0178] 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 contributed by the polyols of formulas (IVb) and (IVc).

[0179] The molar equivalent number of -NCO groups in the polyisocyanate of formula (IVa) is equal to: f(-NCO)*(m(1va) / M(1va)), where f(-NCO) is the number of -NCO groups in the polyisocyanate of formula (IVa), m(1Va) is the mass introduced in g of polyisocyanate of formula (IVa), and M(1Va) is the molar mass in g / mol of the polyisocyanate of formula (IVa). Preferably, the polyisocyanate of formula (IVa) is a diisocyanate, and f(-NCO) is therefore equal to 2.

[0180] The equivalent molar 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)(lvb) is the number of -OH groups of the polyol of formula (IVb), m(lvb) is the mass introduced in g of polyol of formula (IVb), M(lvb) is the molar mass in g / mol of the polyol of formula (IVb), f(-OH)(lvc) is the number of -OH groups of the polyol of formula (IVc), m(lvc) is the mass introduced in g of polyol of formula (IVc) and M(lvc) is the molar mass in g / mol of the polyol of formula (IVc). Preferably, polyols of formulas (IVb) and (IVc) are diols, and f(-OH)(lvb) and f(-OH)(1Vc) are therefore each equal to 2.

[0181] 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 the reaction of a polyisocyanate and at least one polyol. Such a catalyst is, for example, chosen from among the carboxylates, in particular bismuth and / or zinc neodecanoates. Commercially available examples include Borchi®Kat 315 from OMG Borchers, which is a bismuth neodecanoate, and Borchi®Kat 15 from the same company, which is a zinc neodecanoate.

[0182] Step (i) is advantageously carried out under anhydrous conditions.

[0183] Step (i) is advantageously carried out at a temperature between 60°C and 120°C.

[0184] Step (i) is advantageously carried out at atmospheric pressure.

[0185] Step (ii) corresponds to the reaction of the -NR7R8 group during which is included in the n-times repeated motif of the copolyurethane of formula (IV) with the acid of formula HR13.

[0186] In step (ii) of the process according to the invention, the molar ratio (acid of formula HR13 / 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.

[0187] Step (ii) is advantageously carried out under anhydrous conditions.

[0188] Step (ii) is advantageously carried out at a temperature between 20°C and 80°C, preferably between 20°C and 45°C.

[0189] Step (ii) is advantageously carried out at atmospheric pressure.

[0190] In step (iii), the terminal -NCO groups of the copolyurethane of formula (V) react with the -XH group of the silylated compound of formula (Ha). Silylated compounds of formula (lia) are widely available commercially. An example is N-(3(trimethoxysilyl)propyl)butylamine, available under the name Dynasylan® 1189 from Evonik.

[0191] 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.

[0192] 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 (lia) divided by the molar equivalent number of -NCO groups of the copolyurethane of formula (V).

[0193] The equivalent molar number of -XH groups of the silylated compound of formula (lia) is equal to: f(-XH)*(m(lla) / M(lla)), where f(-XH) is the number of -XH groups of the silylated compound of formula (Ha), m(lla) is the mass introduced in g of the silylated compound of formula (lia) and M(1Ia) is the molar mass in g / mol of the silylated compound of formula (lia).

[0194] The equivalent molar number of -NCO groups of the copolyurethane of formula (V) corresponds to the equivalent molar number of -NCO groups of the polyisocyanate of formula (IVa) introduced in excess with respect to the equivalent molar number of -OH groups provided by the polyols of formulas (IVb) and (IVc).

[0195] Step (iii) is advantageously carried out under anhydrous conditions.

[0196] Step (iii) is advantageously carried out at a temperature within a range from 20°C to 80°C, preferably from 20°C to 40°C.

[0197] Step (iii) is advantageously carried out at atmospheric pressure.

[0198] Composition comprising an ionic silylated copolyurethane according to the invention

[0199] The invention also relates to a composition comprising ionic silylated copolyurethane of formula (I) according to the invention.

[0200] 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.

[0201] Advantageously, the composition according to the invention further comprises a filler.

[0202] 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 from 40% to 55% by weight.

[0203] The filler usable in the composition according to the invention can be chosen from mineral fillers and mixtures of organic and mineral fillers.

[0204] As an example of a mineral filler, any mineral filler commonly used in adhesive and / or sealant compositions may be cited. These fillers are in the form of particles of various geometries. They may, for example, be spherical, fibrous, or have an irregular shape.

[0205] Advantageously, the mineral fillers are formed by the group consisting of clay, quartz, hollow mineral microspheres and carbonate fillers.

[0206] Among hollow mineral microspheres, we can mention hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or of alu-minosilicate.

[0207] Preferably, the mineral fillers are formed by the group consisting of carbonate fillers.

[0208] Advantageously, the carbonate filler is selected from alkali or alkaline earth metal carbonates and mixtures thereof. Preferably, the carbonate filler comprises calcium carbonate, more preferably chalk or calcium carbonate coated with fatty acids, and even more preferably precipitated calcium carbonate coated with fatty acids.

[0209] When calcium carbonate is coated with fatty acids, this imparts total or partial hydrophobicity to the calcium carbonate particles. Furthermore, the fatty acid coating acts as a hydrophobic coating that can prevent the calcium carbonate from absorbing the constituents of the composition and rendering them ineffective. The hydrophobic coating of the calcium carbonate can represent from 0.1% to 3.5% by weight, relative to the total weight of calcium carbonate.

[0210] 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.

[0211] As an example of an organic filler, any organic filler, in particular polymeric, commonly used in the field of adhesive compositions and / or sealants may be cited.

[0212] 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.

[0213] 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.

[0214] 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).

[0215] Unless otherwise indicated, the standards referred to throughout the application are those in force at the date of filing of the application.

[0216] 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 weight percentages being relative to the total weight of the composition.

[0217] The composition according to the invention may further comprise at least one additive selected from moisture absorbers, adhesion promoters, plasticizers, rheology agents, UV stabilizers and mixtures thereof.

[0218] Advantageously, the composition according to the invention comprises a mixture of additives selected from moisture absorbers and adhesion promoters.

[0219] Suitable moisture absorbers (or desiccants) 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.

[0220] Advantageously, the moisture absorber is selected from vinyltrimethoxysilane, trimethoxymethylsilane, propyltrimethoxysilane, vinyltriethoxysilane, al-koxyarylsilanes (for example GENIOSIL® XL 70 marketed by WACKER) and mixtures thereof.

[0221] Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, vinyltriethoxysilane and their mixture, more preferably vinyltrimethoxysilane.

[0222] 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.

[0223] The adhesion promoter may be selected from amino-, mercapto-, and epoxy-alkoxysilanes, and mixtures thereof. Preferably, the adhesion promoter is selected from aminoalkoxysilanes, more preferably from aminotrimethoxysilanes, and even more preferably from aminotrimethoxysilanes, for example N- (3-(trimethoxysilyl)propyl)ethylenediamine.

[0224] As an example of an epoxy-alkoxysilane, we can cite (3-glycidyloxypropyl)trimethoxysilane (also known as GLYMO).

[0225] Advantageously, aminotrimethoxysilanes are formed by the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane (for example, SILQUEST A-LINK 600 marketed by MOMENTIVE), (3-aminopropyl)trimethoxysilane (for example, DYNASYLAN® AMMO marketed by EVONIK) and N-(3-(trimethoxysilyl)propyl)ethylenediamine (for example, GENIOSIL® GF9 marketed by WACKER). Preferably, aminotrimethoxysilanes are N-(3-(trimethoxysilyl)propyl)ethylenediamine.

[0226] 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.

[0227] The plasticizer can be any plasticizer commonly used in the field of adhesive compositions and / or sealants.

[0228] Preferably, the plasticizer is chosen from:

[0229] - diisodecyl phthalate (for example PALATINOL® DIDP marketed by BASF),

[0230] - diisononyl phthalate (DINP) (for example PALATINOL® N marketed by BASF),

[0231] - an ester of alkylsulfonic acid and phenol (for example MESAMOLL® marketed by LANXESS),

[0232] - the diisononyl ester of 1,2-cyclohexanedicarboxylic acid (for example the HEXAMOLL DINCH® (marketed by BASF), and

[0233] - pentaerythritol tetravalerate (for example PEVALEN™ marketed by PERSTORP).

[0234] The plasticizer content can 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.

[0235] The rheology agent may be any rheology agent commonly used in the field of adhesive compositions and / or sealants.

[0236] Advantageously, the rheology agent is chosen from:

[0237] - PVC plastisols, corresponding to a suspension of PVC in an agent Plasticizer 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 book "Polyurethane Sealants", Robert M. Evans, ISBN 087762-998-6,

[0238] - fumed silica, such as HDK® N20 marketed by WACKER,

[0239] - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such than 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives are described in particular in application FR 1 591 172, and

[0240] - 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.

[0241] 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) (for example ricinoleic acid) and (di)amine(s).

[0242] 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.

[0243] 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).

[0244] The content of rheology agent can 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.

[0245] 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. 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.

[0246] Advantageously, the UV stabilizer(s) (or antioxidant(s)) are selected from among benzotriazoles, benzophenones, so-called hindered amines such as bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate (CAS No. 41556-26-7), methyl l,2,2,6,6-pentamethyl-4-piperidyl sebacate (CAS No. 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, the 4,4'-bis(a,a-dimethylbenzyl)diphenylamine, and mixtures thereof. Examples include IRGANOX 1076, TINUVIN® 292, TINUVIN® 765 or TINUVIN® 770 DF marketed by BASF and RIASORB UV-123 marketed by RIANLON.

[0247] According to one embodiment, the composition according to the invention comprises:

[0248] - between 10% and 50% by weight of ionic silylated copolyurethane according to the invention,

[0249] - between 20% and 60% by weight of a load,

[0250] - between 0.5% and 5% by weight of moisture absorber, and

[0251] - between 0.1% and 5% by weight of adhesion promoter,

[0252] the percentages by weight being in relation to the total weight of the composition.

[0253] Preferably, the composition according to the invention consists essentially of the ingredients mentioned above. By "consists essentially of" means 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, and even more preferably less than 1% by weight.

[0254] The ingredients of this embodiment and their particular contents are as described above, including the embodiments.

[0255] Advantageously, the composition according to the invention does not include a crosslinking catalyst.

[0256] Thus, no crosslinking catalyst is advantageously added to the ionic silyl copolyurethane according to the invention. Indeed, the ionic silyl copolyurethane according to the invention alone catalyzes the crosslinking reaction.

[0257] By "crosslinking catalyst" is meant a catalyst known to those skilled in the art for the condensation of silanol.

[0258] Examples of such catalysts include:

[0259] - organic derivatives of titanium such as titanium acetyl acetonate, tetra- titanium propylate, titanium tetrabutylate,

[0260] - organic zirconium derivatives such as zirconium acetyl acetonate, te- zirconium tetrapropylate, zirconium tetrabutylate,

[0261] - amines such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or the 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), diethyl ether-2,2'-morpholine (DMDEE), 1,4-diazabicyclo[2.2.2]octane (DABCO),

[0262] - zinc carboxylate and DBU-based catalysts (e.g. K-KAT®) 670 marketed by KING INDUSTRIES),

[0263] - tin-based catalysts such as compounds derived from dioctyltin or di- butyltin.

[0264] The composition according to the invention is preferably stored in an anhydrous environment, for example in airtight packaging, where said composition is protected from moisture and preferably from light.

[0265] The composition according to the invention can be prepared by simply mixing its ingredients.

[0266] Preferably, the composition according to the invention is prepared at atmospheric pressure spherical and at a temperature between 10°C and 55°C, more preferably between 18°C ​​and 40°C.

[0267] An example of preparing the composition according to the invention is described in Example 8. Other objects of the invention

[0268] The invention also relates to the use of the composition according to the invention, as an adhesive and / or sealant.

[0269] In addition, the invention also relates to an article comprising the composition according to the invention, in airtight packaging, protected from air.

[0270] Preferably, the airtight packaging is a polyethylene bag or a polyethylene cartridge with a lid.

[0271] Furthermore, the invention relates to a method for assembling two substrates comprising:

[0272] - coating the composition according to the invention, on at least one of the two substrates to assemble; then

[0273] - the effective contacting of the two substrates.

[0274] Preferably, the assembly process according to the invention is carried out at room temperature (approximately 23°C).

[0275] By "about X", we mean plus or minus 10% of the value of X.

[0276] Suitable substrates include, for example, inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminium, steel, non-ferrous metals, galvanized metals), or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins, or metal and composite substrates coated with paint (for example, in the automotive field).

[0277] All the embodiments described above can be combined with each other. In particular, the various aforementioned ingredients of the composition according to the invention, especially the preferred embodiments, can be combined with each other.

[0278] The following examples are given purely for illustrative purposes of the invention and should not be interpreted as limiting its scope. Examples Example 1: Ingredients and measurement methods Ingredients used

[0279] The following ingredients were used:

[0280] - ACCLAIM® 4200 marketed by Covestro: poly(propylene oxide) of number average molar mass of about 4000 g / mol, having two -OH endings and a hydroxyl number IOH of 28.0 mg KOH / g;

[0281] - isophorone diisocyanate (IPDI) marketed by Covestro: molar mass equal to 222.3 g / mol (CAS number: 4098-71-9);

[0282] - Borchi®Kat 315 marketed by OMG Borchers: bismuth neodecanoate molar mass equal to 722.75 g / mol;

[0283] - Dynasylan® 1189 marketed by Evonik: N- (3-(trimethoxysilyl)propyl)butylamine with a molar mass of 235.4 g / mol;

[0284] - Jeffcat® DPA marketed by Huntsman: N- (3-dimethylaminopropyl)-N,N-diisopropanolamine with a molar mass of 218.34 g / mol;

[0285] - acetic acid marketed by Sigma Aldrich: molar mass equal to 60.05 g / mol and pKa equal to 4.8 at 25°C;

[0286] - acrylic acid marketed by Sigma Aldrich: molar mass equal to 72.06 g / mol and pKa equal to 4.25 at 25 °C;

[0287] - methanesulfonic acid marketed by Sigma Aldrich: molar mass equal to 96.11 g / mol and pKa equal to -1.9 at 25°C;

[0288] - TIBKAT® 223 marketed by TIB Chemicals: dioccylacetonate bis(acetylacetonate) tyletin with a molar mass of 543.15 g / mol, crosslinking catalyst;

[0289] - GENIOSIL® GF9 marketed by Wacker: N- (3-(trimethoxysilyl)propyl)ethylenediamine with a molar mass of 222.36 g / mol, adhesion promoter;

[0290] - VTMO marketed by Sigma Aldrich: vinyltrimethoxysilane with molar mass equal to 148.23 g / mol, moisture absorber

[0291] - CALOFORT® SV marketed by Specialty Minerals: calcium carbonate Stearic acid-coated precipitate with an average particle size of 70 nm. Measurement methods

[0292] 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, and then a solution of dicyclohexylamine in DMF (N,N-dimethylformamide) is automatically added. The titration of excess amine is also carried out automatically with hydrochloric acid.

[0293] The curing time is measured by determining the skin formation time. For this purpose, a bead of sealant (approximately 10 cm long and approximately 1 cm in diameter) is first deposited on a cardboard support. Then, using a low-density polyethylene (LDPE) pipette tip, the surface of the sealant is touched every minute for up to 2 hours in order to determine the exact time at which the surface skin forms. This test is carried out under conditions controlled humidity and temperature (23°C and 50% relative humidity).

[0294] Tensile strength and elongation at break were measured in accordance with ISO 37 (2012), at a constant speed of 100 mm / min.

[0295] In particular, the following conditions were applied:

[0296] A standard dumbbell-shaped test 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.

[0297] To prepare the dumbbell, the composition to be tested (previously conditioned in a cartridge) is extruded into a Teflon mold, and is left to crosslink for 14 days under standard conditions (23°C and 50% relative humidity).

[0298] The principle of the measurement consists of stretching a standard test specimen in a tensile testing machine (for example, Zwick Roell 2.5KN), whose moving jaw travels at a constant speed of 100 mm / min, and recording:

[0299] - the elongation at break (expressed in %) which is the elongation of the specimen cor responding to the stretching observed at the time of rupture,

[0300] - 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

[0301] - the tensile strength (in MPa) which is the tensile stress at which produces the rupture of the test specimen (also called TS for Tensile Strength in English).

[0302] The measurement is repeated for 5 test tubes, and the corresponding average of the results obtained is calculated.

[0303] The water content of the ingredients, including ACCLAIM® 4200 and Jeffcat® DPA, is measured using a Karl Fischer coulometric method with HYDRANAL™ as the titrant, the equivalence point being detected electrometrically.

[0304] The viscosity of the silylated polymers prepared in the examples below is measured according to a Brookfield type method at 23°C and 50% relative humidity (needle S28).

[0305] Example 2: Preparation of a reference silylated polyurethane (comparative)

[0306] In a 500 mL reactor, 304.81 g of ACCLAIM® 4200 are introduced (corresponding to 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.

[0307] 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 under stirring until a % NCO by weight of 1.7% is reached 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).

[0308] 33.05 g of Dynasylan® 1189 are then introduced, corresponding to a ratio The molar concentration of -NH / -NCO is equal to 1 (the molar equivalent number of -NH groups being equal to 0.14 mol). The mixture is heated to 70°C and stirred until the characteristic band of the -NCO groups is no longer detectable by infrared spectroscopy (around 2260 cm1).

[0309] Approximately 375 g of silylated polyurethane are obtained and the silylated polyurethane is packaged in aluminum cartridges protected from moisture.

[0310] The viscosity of this silylated polyurethane is 35500 mPa.s at 23°C.

[0311] Example 3: Preparation of an ionic silylated copolyurethane no. 1 (invention)

[0312] Ionic silylated copolyurethane No. 1 is prepared in a manner similar to the reference silylated polyurethane, except that 0.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 are introduced into the reactor before the addition of the PDI, and acetic acid is added, in a molar ratio acetic acid / Jeffcat® DPA equal to 1, after the reaction with the IPDI.

[0313] In a 500 mL reactor, 282.79 g of ACCLAIM® 4200 (corresponding to a molar equivalent of -OH groups equal to 0.141 mol) and 1.76 g of Jeffcat® DPA (corresponding to a molar equivalent of -OH groups equal to 0.016 mol) are introduced (corresponding to a total molar equivalent of -OH groups equal to 0.157 mol). The reactor is then 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.

[0314] 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. a molar equivalent number of -NCO groups equal to 0.288 mol) and 0.15 g of Borchi®Kat 315. The mixture is kept under stirring until a % NCO by weight of 1.7% is reached 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).

[0315] 0.48 g of acetic acid are then added at 40°C, and stirring is left for 1 hour.

[0316] 30.67 g of Dynasylan® 1189 are then introduced, corresponding to a ratio molar -NH / -NCO equals 1. The mixture is heated to 40°C and stirred until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.

[0317] Approximately 350 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from moisture.

[0318] The viscosity of this ionic silylated copolyurethane is 36000 mPa.s at 23°C.

[0319] Example 4: Preparation of an ionic silylated copolyurethane No. 2 (invention)

[0320] 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 are introduced into the reactor before the addition of IPDI, and that acetic acid is added, in a molar ratio acetic acid / Jeffcat® DPA equal to 1, after the reaction with IPDI.

[0321] In a 500 mL reactor, 279.47 g of ACCLAIM® 4200 and 3.51 g of Jeffcat® DPA are introduced, and the reactor is then left under vacuum (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.

[0322] 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 under stirring until a % NCO by weight of 1.7% is reached 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.

[0323] 0.97 g of acetic acid are then added at 40°C, and stirring is left for 1 hour.

[0324] 30.31 g of Dynasylan® 1189 are then introduced, corresponding to a ratio molar -NH / -NC0 equals 1. The mixture is heated to 40°C and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.

[0325] Approximately 350 g of ionic silyl copolyurethane are obtained and the ionic silyl copolyurethane is packaged in aluminum cartridges protected from moisture.

[0326] The viscosity of this ionic silylated copolyurethane is 40500 mPa.s at 23°C.

[0327] Example 5: Preparation of an ionic silylated copolyurethane No. 3 (invention)

[0328] 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 are introduced into the reactor before the addition of IPDI, and acetic acid is added, in an acetic acid / Jeffcat® DPA molar ratio of 1, after the reaction with IPDI.

[0329] In a 500 mL reactor, 272.83 g of ACCLAIM® 4200 and 7.03 g of Jeffcat® DPA are introduced, and then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for Dehydrate ACCLAIM® 4200 and Jeffcat® DPA for 2 hours at 110°C. The water content of the ACCLAIM® 4200 and Jeffcat® DPA mixture is then less than or equal to 0.02% by weight relative to the total weight of said mixture.

[0330] 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 under stirring until a % NCO by weight of 1.7% is reached 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.

[0331] 1.93 g of acetic acid are then added at 40°C, and stirring is left for 1 hour.

[0332] 29.59 g of Dynasylan® 1189 are then introduced, corresponding to a ratio molar -NH / -NC0 equals 1. The mixture is heated to 40°C and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.

[0333] Approximately 350 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from moisture.

[0334] The viscosity of this ionic silylated copolyurethane is 59000 mPa.s at 23°C.

[0335] Example 6: Preparation of an ionic silylated copolyurethane No. 4 (invention)

[0336] 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 are introduced into the reactor before the addition of IPDI, and that acrylic acid is added, in an acrylic acid / Jeffcat® DPA molar ratio of 1, after the reaction with IPDI.

[0337] In a 500 mL reactor, 300 g of ACCLAIM® 4200 and 7.82 g of Jeffcat® DPA are introduced, and the reactor is then left under vacuum (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.

[0338] 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 under stirring until a % NCO by weight of 1.7% is reached 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.

[0339] 2.58 g of acrylic acid are then added at 40°C, and stirring is left for 1 hour.

[0340] 32.03 g of Dynasylan® 1189 are then introduced, corresponding to a ratio The molar concentration of -NH / -NC0 is equal to 1. The mixture is heated to 40°C and mixed until the characteristic band of the -NCO groups is no longer detectable by spectroscopy. infrared.

[0341] Approximately 390 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from moisture.

[0342] The viscosity of this ionic silylated copolyurethane is 36000 mPa.s at 23°C.

[0343] Example 7: Preparation of an ionic silylated copolyurethane No. 5 (invention)

[0344] 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 are introduced into the reactor before the addition of IPDI, and that methanesulfonic acid is added, in a methanesulfonic acid / Jeffcat® DPA molar ratio of 1, after the reaction with IPDI.

[0345] In a 500 mL reactor, 299.3 g of ACCLAIM® 4200 and 7.82 g of Jeffcat® DPA are introduced, and the reactor is then left under vacuum (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.

[0346] 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 under stirring until a % NCO by weight of 1.7% is reached 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.

[0347] 3.44 g of methanesulfonic acid are then added at 40°C, and stirring is left for 1 hour.

[0348] 31.95 g of Dynasylan® 1189 are then introduced, corresponding to a ratio molar -NH / -NC0 equals 1. The mixture is heated to 40°C and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy.

[0349] Approximately 390 g of ionic silylated copolyurethane are obtained and the ionic silylated copolyurethane is packaged in aluminum cartridges protected from moisture.

[0350] The viscosity of this ionic silylated copolyurethane is 61500 mPa.s at 23°C. Example 8: Preparation of sealants

[0351] The polymers prepared in Examples 2 to 7 are used to prepare sealants, the composition of which is indicated in Table 1 below, the percentages being percentages by weight over the total weight of the sealant.

[0352] Initially, the ingredients of step 1 are added at room temperature (approximately 23°C) and atmospheric pressure in a high-speed mixer and then mixed for 2 min.

[0353] The ingredients from step 2 are then added and the mixture is blended for 2 min.

[0354] The stirring speed is approximately 2000 rpm (revolutions per minute).

[0355] The resulting sealants are packaged in polyethylene cartridges.

[0356] [Tables] Step e Ingredient Mastic 1 (comp.) Mastic 2 (comp.) Mastic 3 (inv.) Mastic 4 (inv.) Mastic 5 (inv.) Mastic 6 (inv.) Mastic 7 (inv.) 1 Reference polyurethane 41.8% 41.5% - - - - - Polyurethane copolymer (in°1) - - 41.8% - - - - Polyurethane copolymer (in°2) - - - 41.8% - - - Polyurethane copolymer (in°3) - - - - 41.8% - - Polyurethane copolymer (in°4) - - - - - 41.8% - Polyurethane copolymer (in°5) - - - - - - 41.8% VTMO 3% 3% 3% 3% 3% 3% 3% CALOFORT® SV 53.8% 53.5% 53.8% 53.8% 53.8% 53.8% 53.8% 2 GF9 1.4% 1.4% 1.4% 1.4% 1.4% 1.4% 1.4% TIBKAT® 223 - 0.6% - - - - -

[0357] Table 1 Example 9: Properties of sealants 1 to 7

[0358] The properties of sealants 1 to 7 (measured in accordance with Example 1) are summarized in Table 2 below.

[0359] [Tables2] Mastic 1 (comp.) 2 (comp.) 3 (invert.) 4 (invert.) 5 (invert.) 6 (invert.) 7 (invert.) Curing time (min) 70 15 30 28 22 12 15 Tensile strength (MPa) 3.8 3.4 4.5 4.5 4.0 4.0 3.1 Elongation at break (%) 60 30 60 52 45 30 35 Young's modulus (MPa) 13 20 16 15 17 21 17

[0360] Table 2

[0361] Comparative sealant 1, prepared from the reference silylated polyurethane and without a crosslinking catalyst, has a crosslinking time of 70 min.

[0362] 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).

[0363] This shows that ionic silylated copolyurethane accelerates crosslinking compared to the reference silylated polyurethane, without the need to add a crosslinking catalyst to the sealant.

[0364] Furthermore, the curing time can be reduced by increasing the amount of Jeffcat® DPA tertiary amine used in the preparation of the ionic silylated copolyurethane. Specifically, when 2.6% instead of 0.6% by weight of Jeffcat® DPA relative to the weight of ACCLAIM® 4200 is used, the curing time is reduced from 30 min to 22 min (comparison of sealants 3 and 5).

[0365] Furthermore, the crosslinking time varies depending on the acid used in the preparation of the ionic silylized copolyurethane. Indeed, replacing acetic acid with acrylic acid (sealant 6) or methanesulfonic acid (sealant 7) makes it possible to obtain a crosslinking time equal to, or even shorter than, that observed for a sealant obtained using a crosslinking catalyst and the reference silylized polyurethane (sealant 2).

[0366] Furthermore, sealants 3 to 7 according to the invention exhibit good tensile strength, generally superior to that of comparative sealant 1, as well as a higher Young's modulus than comparative sealant 1. The sealants according to the invention are therefore particularly suitable for rigid bonding (after curing), preventing the bonded substrates from moving relative to each other.

Claims

Demands

1. Ionic silylated copolyurethane of formula (I): (I) in which: - R1 represents a divalent hydrocarbon radical comprising 5 to 45 carbon atoms, saturated or unsaturated, with a linear open chain or branched, or comprising one or more rings possibly aromatic, and possibly comprising at least one heteroatom selected from O, S and N, - R2 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 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 divalent hydrocarbon radical, possibly comprising at least one heteroatom chosen from O and S, or - R' represents a covalent bond and R represents a divalent hydrocarbon radical with a linear or branched open chain, possibly comprising at least one heteroatom chosen from O and S; preferably -OR- corresponds to the formula: -O-CH(R°)-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”-NHR7R8)-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-, - 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, - R7 and R8, identical or different, each represent a linear or branched alkyl radical, preferably linear, comprising from 1 to 4 carbon atoms, or R7 and R8 form a heterocycle with 5 or 6 links with the nitrogen atom to which they are attached, and R7 and R8 possibly include a heteroatom chosen from N, O and S, - R10 represents a saturated or unsaturated, linear or branched, divalent hydrocarbon radical possibly comprising one or more heteroatoms, such as oxygen, nitrogen, sulfur, silicon, - ® R13 represents the conjugate base of an acid HR13, HR13 being 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): (II) in which: - R3 represents a linear or branched alkylene divalent radical comprising 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, - R4 represents a linear or branched alkyl radical comprising 1 to 4

2.

3. carbon atony, and when p equals 2, the R4 radicals are either identical or different, - R5 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 R5 radicals are identical or different, two OR5 groups being able to be involved in the same ring, preferably R5 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, - X represents a divalent radical chosen from -NR6-, -NH- and -S-, - R6 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 rings, possibly aromatic, and possibly also comprising one or more heteroatoms, preferably R6 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. Ionic silyl copolyurethane according to claim 1, wherein f represents a radical of formula (II) in which: - R3 represents a linear or branched alkylene divalent radical comprising 1 to 3 carbon atoms, preferably n-propylene; - R5 represents a methyl or ethyl radical, preferably methyl; - X represents a -NR6- divalent radical, - R6 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, preferably n-butyl, and - p is equal to 0. Ionic silylated copolyurethane according to claim 1 or 2, wherein the radical R1 is selected from the following radicals whose formulas show the free valences: - the divalent radical derived from isophorone diisocyanate (IPDI): GL: i - divalent radicals derived from 4,4'- isomers and 2,4'-dicyclohexylmethane diisocyanate (HMDI): - divalent radicals derived from the 2,4- and 2,6- toluene dii-socyanate (TDI) isomers: CH, - divalent radicals derived from the 4,4'- and 2,4'- isomers of diphenylmethane diisocyanate (MDI): - the divalent radical derived from hexamethylene diisocyanate (HDI): -(CH2)6- - the divalent radical derived from m-xylylene diisocyanate (m-XDI): - the divalent radical derived from an allophanate of hexamethylene diisocyanate (HDI) of formula (III): (III) (CH^__ in which: - i is an integer ranging from 2 to 5; - j is an integer ranging from 1 to 2; - R11 represents a hydrocarbon radical, saturated or unsaturated, cyclic, linear or branched, comprising 6 to 14 carbon atoms; - R12 represents a divalent propylene group; - i, j, R11 and R12 being such that the hexamethylene diisocyanate allophanate corresponding to formula (III) comprises a content of group isocyanate NCO ranging from 12 to 14% by weight relative to the weight of said allophanate.

4. Ionic silylated copolyurethane according to any one of claims 1 to 3, wherein: - R2 represents a radical derived from a polyethylene glycol of formula: x ~ „or '0' '(■'' of a polypropylene glycol of formula: CH 1 la 1 CHS CHa CH2 , preferably from a polypropylene glycol, and - q represents an integer such that the number-average molar mass of the radical R2 ranges from 500 g / mol to 20000 g / mol, preferably from 3000 g / mol to 14000 g / mol.

5. Ionic silylated 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'-O- 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 from 2 to 4 carbon atoms, preferably 3 carbon atoms, - R7 and R8 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 silylated copolyurethane according to any one of claims 1 to 5, wherein R13 is such that the acid of formula HR13 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 sequential steps: (i) of forming a -NCO-terminated copolyurethane of formula (IV): CT Wf-C-œ O— O NM' R '-H-NH R— A— R'-O-Tk OJ—t— R'— A— R-04-C— NM—RM NCO |:; H; ; ü | -M ; ; ; |-: O 0 i !- QR"': R' EO *— — IU । ;: J NR';R' i NR'r8 [ — — u (IV) by carrying out a polyaddition reaction between: - a polyisocyanate of formula (IVa): OCN-R'-NCO, - a polymer polyol of formula (IVb): H-0R2-0H,and - a branched polyol with at least one tertiary amine of formula (IVc): HO—R— A — R - 04 H4—A— R- (fj-H t | R" R” | nrV 1 nrV 1 (IVc) (ii) reaction of the copolyurethane of formula (IV) with an acid of formula HR13 to form an ionic copolyurethane with -NCO terminations of formula (V): OCN-R'InW-C-OR-'—C^f-SK-R'l-jN.UCOR—A-R'-oTr^'oU+^-R'—A—R—OfC—NH—R^NCO p U ' ! ! " 1 L- -0 : ! : |: : OO ' >- 0. R-' : 1V : ü « ...

1. - i / E -U ÿ (V) and (iii) reaction of the copolyurethane of formula (V) with a silylated compound of formula (lia): (Ha).,

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

9.

10. Composition according to claim 8, further comprising a filler. Composition according to claim 9, wherein the content of ionic silyl 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.