Ionic polyurethane(ies), possibly silylated

Abstract

The present invention relates to a process for preparing an ionic polyurethane composition comprising: (i) an esterification step of a bio-based polyol (A) with a cyclic anhydride to form a polyol composition (B), then (ii) a reaction step of the polyol composition (B) with a polyisocyanate to form a terminal group polyurethane composition –NCO, then (iii) a reaction step of the terminal group polyurethane composition –NCO formed in step (ii) with a tertiary amine having a pKa at 25°C greater than 8, to form an ionic terminal group polyurethane composition –NCO (D). The present invention also relates to an ionic polyurethane composition with –NCO terminal groups, a silylated ionic polyurethane composition, an optionally silylated ionic polyurethane, and an adhesive and / or sealant composition. Figure for the abstract: none

Description

Title of the invention: Ionic polyurethane(ies), possibly silylated. Field of the invention

[0001] The present invention relates to a method for preparing an ionic polyurethane composition, possibly silylated, an ionic polyurethane composition with -NCO terminal groups, an ionic polyurethane composition, possibly silylated, and an adhesive and / or sealant composition. Technical background

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

[0003] The crosslinking reaction of these possibly silylated polyurethane-based compositions occurs in the presence of moisture: either through the formation of a urea bond between the isocyanate groups of the polyurethane molecules, or through the formation of a siloxane (-Si-O-Si-) bond following hydrolysis of the alkoxysilane groups of the silylated polyurethane molecules. These bonds unite the polymer chains into a solid three-dimensional network.

[0004] 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.

[0005] However, the crosslinking time of these silylated polyurethanes, and of polyurethanes in particular obtained from aliphatic polyisocyanate (not comprising aromatic structure) such as isophorone diisocyanate, must be accelerated to meet the needs of users.

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

[0007] Generally, the crosslinking catalyst used in adhesive and / or sealant compositions based on polyurethanes, possibly silylated, is a catalyst Metallic catalysts, particularly tin-based ones such as dibutyltin dilaurate (DBTDL), dibutyltin diacetate, or dibutyltin or dioctyltin bis(acetylacetonate), are increasingly being highlighted due to their toxicity. This has led manufacturers to limit, and even avoid, their use, especially since these metallic catalysts remain in finished products.

[0008] An alternative to metallic crosslinking catalysts may be organic crosslinking catalysts, in particular 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), or 1,4-diazabicyclo[2.2.2]octane (DABCO). 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] Moreover, the polyurethanes possibly silylated on the market are generally obtained from raw materials derived from petroleum resources.

[0010] However, this dependence on fossil resources risks limiting, or even preventing, the long-term production of monomers and consequently polymers. Furthermore, certain petroleum-based raw materials are criticized from both an environmental and economic standpoint, which increases regulatory restrictions concerning them.

[0011] At present, the possibly bio-based silylated polyurethanes available on the market have very low reactivity and it is difficult, if not impossible, to crosslink them without adding a large quantity of tin-based catalysts (or other metallic or organic catalysts).

[0012] There is therefore a need to manufacture new polyurethanes possibly silylated which are at least partially bio-based, and which can crosslink rapidly, even without adding metallic or organic crosslinking catalyst (type DBU, TBD or DABCO) in the composition comprising it.

[0013] The present invention therefore aims to provide a polyurethane possibly silylated which is self-catalyzed and at least partially bio-based. Summary of the invention

[0014] The present invention relates to a method for preparing an ionic polyurethane composition comprising:

[0015] (i) an esterification step of a bio-based polyol (A) with a cyclic anhydride to form a polyol(s) composition (B), then

[0016] (ii) a reaction step of the polyol composition(s) (B) with a polyisocyanate to form a polyurethane composition(s) with terminal -NCO groups, then

[0017] (iii) a reaction step of the -NCO terminal group polyurethane composition(s) formed in step (ii) with a tertiary amine having a pKa at 25°C greater than 8, to form an ionic -NCO terminal group polyurethane composition(s) (D).

[0018] The invention also relates to an ionic polyurethane(s) composition with terminal groups -NCO (D) capable of being obtained by the process according to the invention comprising steps (i) to (iii) as defined in this application.

[0019] The invention also relates to a silylated ionic polyurethane(s) composition (E) that can be obtained by the process according to the invention comprising steps (i) to (iv) as defined in this application.

[0020] The invention relates in particular to an ionic polyurethane, possibly silylated.

[0021] The invention also relates to an adhesive and / or sealant composition comprising the ionic polyurethane possibly silylated described in this application, or the ionic polyurethane(s) composition (D) or (E) according to the invention.

[0022] Surprisingly, it has been found that polyurethanes possibly silylated according to the invention can crosslink rapidly, even without the addition of a metallic or organic crosslinking catalyst, while being at least partially bio-based. Description of the invention

[0023] The present invention relates to a method for preparing an ionic polyurethane composition(s) comprising:

[0024] (i) an esterification step of a bio-based polyol (A) with a cyclic anhydride to form a polyol(s) composition (B), then

[0025] (ii) a step of reacting the polyol composition(s) (B) with a polyisocyanate to form a polyurethane composition(s) with terminal groups -NCO, then

[0026] (iii) a step of reacting the polyurethane composition(s) with terminal groups -NCO formed in step (ii) with a tertiary amine having a pKa at 25°C greater than 8, to form an ionic polyurethane composition(s) with terminal groups -NCO (D). Step (i) Polyol (A)

[0027] By "polyol (A)" is meant a polyol having a functionality f(OH) greater than or equal to 2, preferably greater than or equal to 2.0, more preferably greater than 2.0, for example between 2.5 and 3.0. The functionality f(OH) represents the average number of hydroxyl groups (-OH) per polyol molecule.

[0028] Said functionality f(OH) can be determined by measuring the hydroxyl number (denoted IqH) of the polyol, for example by titration according to ISO 14900:2017. Said functionality f(OH) can then be calculated as follows: f(OH)= (IOH*Mpoiyoi) / 56000, where Iqh is the hydroxyl number in mg KOH / g of the polyol and Mpoiyoi is The molar mass in g / mol of the polyol. When the polyol is a polymer, its mass molar is its average molar mass in number Mn.

[0029]

[0030] Within the framework of the present invention, the number-average molar mass Mn can be measured by methods well known to a person skilled in the art, for example by NMR or size exclusion chromatography using type standards polystyrene. The polyol (A) can be represented by the formula (!) : R 3 -Toh1 -Mid in which R2

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037] R2 is a plurivalent hydrocarbon radical possibly comprising one or more oxygen atoms, and n is a value corresponding to the f(OH) functionality as defined above. Thus, R2 does not include any heteroatoms other than oxygen, such as nitrogen. Furthermore, when the radical R2 includes one or more oxygen atoms, said oxygen atom(s) are not located at the end of the chain. In other words, the free valences of the radical R2, bonded to the oxygen atoms of the n hydroxyl groups, each originate from a carbon atom. The various groups, radicals and letters which are included in the formulas described in this application, retain throughout this text, and, in the absence of any indication to the contrary, the same definition. By "bio-based", we mean obtained from resources of biological origin, particularly plant-based, and which may have undergone chemical modifications. Chemical modifications can be the introduction of ether functions, for example by reaction of hydroxyl groups carried by a polyol (in particular lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or fatty acid glycerides) with propylene oxide or ethylene oxide. In a preferred embodiment, the polyol (A) is lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or a fatty acid glyceride, the fatty acid glyceride comprising several hydroxyl groups. It is understood that these compounds may have undergone chemical modifications. It is understood that the fatty acid glyceride mentioned in the present invention refers to a glyceride in which at least one of said fatty acids comprises one or more hydroxyl groups. Lignin is generally found in wood, but also in other plant resources. It is a polyphenolic macromolecule containing several hydroxyl groups. Sucrose is primarily extracted from sugar cane and sugar beets. It is a disaccharide composed of glucose and fructose.

[0038] Glucose can be obtained from various plants. It is a monosaccharide comprising six carbon atoms.

[0039] Fructose is found mainly in fruits and honey. It is also a monosaccharide comprising six carbon atoms.

[0040] Starch is found in many plants. It is a mixture of amylose and amylopectin, and its molecular formula is (C6HiO5)n where n is an integer generally between 500 and 1000.

[0041] Cellulose is generally found in the cell walls of plants. It is a linear polysaccharide made up of glucose units.

[0042] Hemicellulose is found mainly in the cell walls of plants and in wood. It is a linear or branched polysaccharide comprising sugar units that may be identical or different, but is not composed solely of glucose units.

[0043] By "fatty acid" is meant a molecule having an aliphatic chain, which may comprise one or more double bonds, and comprising a carboxylic acid group (-C(O)OH). In particular, the fatty acid comprises between 4 and 28 carbon atoms, preferably between 10 and 22 carbon atoms, more preferably between 16 and 20 carbon atoms, such as 18 carbon atoms.

[0044] In the context of the invention, the ranges of values ​​are understood to include the limits. For example, the range "between 4 and 28" includes, in particular, the values ​​4 and 28.

[0045] The term "glyceride" means an ester obtained from glycerol and fatty acids, which may be the same or different. In particular, the fatty acid glyceride may be a mixture of fatty acid monoglyceride(s), fatty acid diglyceride(s), and / or fatty acid triglyceride(s). Preferably, the fatty acid glyceride comprises at least one fatty acid triglyceride.

[0046] The fatty acid glyceride can be introduced directly in the form of a plant resource (for example, castor oil can be used in step (i)). The plant resource can also be pre-modified to obtain fatty acid glycerides not found directly in nature; for example, hydroxyl groups can be introduced onto the fatty acid chains (such as by double bond epoxidation) and / or ether functions can be introduced onto the fatty acid chains (such as by reaction of the hydroxyl groups on the fatty acids with propylene oxide or ethylene oxide).

[0047] Advantageously, the polyol (A) is lignin, sucrose, starch, hemicellulose, cellulose and / or a fatty acid glyceride.

[0048] Preferably, the polyol (A) is a fatty acid glyceride. In this case, the polyol (A) may be introduced in the form of castor oil and / or an oil Hydroxylated vegetable oils such as hydroxylated soybean oil, hydroxylated rapeseed oil, hydroxylated corn oil, hydroxylated cottonseed oil, hydroxylated linseed oil, hydroxylated olive oil, hydroxylated sesame oil, hydroxylated walnut oil, hydroxylated sunflower oil, hydroxylated safflower oil, hydroxylated grapeseed oil, etc. A vegetable oil is said to be "hydroxylated" when it has been modified to introduce hydroxyl groups onto the fatty acid chains of the glycerides.

[0049] More preferably, the polyol (A) is a glyceride, in particular a triglyceride, of ricinoleic acid. In this case, the polyol (A) is advantageously introduced in the form of castor oil.

[0050] Advantageously, at least 50% by weight of bio-based polyol(s) (A), in particular lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or fatty acid glycerides, is used in step (i) relative to the total weight of polyol(s) (A) used in step (i), preferably at least 70% by weight, more preferably at least 90% by weight. Thus, step (i) can be carried out with a mixture of polyols (A) that is predominantly bio-based, that is to say, obtained from resources of biological origin, particularly plant-based resources.

[0051] Advantageously, at least 50% by weight of fatty acid glyceride, in particular ricinoleic acid (tri)glyceride, is implemented in step (i) relative to the total weight of polyol(s) (A) implemented in step (i), preferably at least 70% by weight, more preferably at least 90% by weight. Cyclic anhydride

[0052] By "cyclic anhydride" is meant a molecule comprising an anhydride function (-C(O)-OC(O)-) involved in a ring. In particular, the cyclic anhydride has the formula (II): Q R7

[0053] (II)

[0054] wherein R7 is a saturated or unsaturated, optionally branched, divalent hydrocarbon radical, which may comprise one or more optionally aromatic rings, and which may comprise one or more heteroatoms selected from oxygen and sulfur, preferably one or more heteroatoms selected from oxygen. Thus, R7 does not comprise any heteroatom other than oxygen and / or sulfur, such as nitrogen.

[0055] The cyclic anhydride may have a molar mass between 86 g / mol and 1000 g / mol, preferably between 98 g / mol and 500 g / mol.

[0056] The cyclic anhydride may be selected from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, 2,3-dimethylsuccinic anhydride, tetrapropenylsuccinic anhydride (CAS: 26544-38-7, isomers having a branched olefin chain), n-dodecenylsuccinic anhydride (CAS: 19780-11-1), glutaric anhydride, 2,4-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride, 3-dimethylglutaric anhydride, adipic anhydride, glycolic anhydride, cis-aconitic anhydride, anhydride 2-(2'-carboxyethyl)maleic anhydride, l-methyl-2-(2'-carboxyethyl)maleic anhydride, octenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, trimellitic anhydride and mixtures thereof.

[0057] Advantageously, the cyclic anhydride is selected from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride, adipic anhydride, glycolic anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, l-methyl-2-(2'-carboxyethyl)maleic anhydride, octenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, 1,2-cis-cyclohexanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, trimellitic anhydride and their mixtures.

[0058] Preferably, the cyclic anhydride is selected from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride, adipic anhydride, glycolic anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, l-methyl-2-(2'-carboxyethyl)maleic anhydride, octenylsuccinic anhydride and mixtures thereof.

[0059] More preferably, the cyclic anhydride is chosen from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride and mixtures thereof, in particular maleic anhydride and / or tetrapropenylsuccinic anhydride. Composition of polyol(s) (B)

[0060] The polyol(s) composition (B) obtained at the end of step (i) comprises one or more polyols (B), said polyol (B) having one or more carboxylic acid groups (-C(O)OH). Indeed, during step (i), some of the groups hydroxyls of the polyol (A) reacts with the anhydride function of the cyclic anhydride to lead to the formation of a composition of polyol(s) (B) comprising at least one polyol (B) having one or more carboxylic acid groups (-C(O)OH).

[0061] By "polyol (B)", we mean a molecule having a functionality f(OH) greater than 1.0, f(OH) representing the average number of hydroxyl groups per polyol molecule.

[0062] Advantageously, the functionality f(OH) of the polyol(s) composition (B) is between 1.2 and 2.5, preferably between 1.3 and 2.2, more preferably between 1.7 and 2.0.

[0063] The functionality f(OH) of the polyol(s) composition (B) can be determined by measuring riOH of the polyol(s) composition (B), for example by titration according to ISO 14900:2017. Said functionality f(OH) can then be calculated as follows: f(OH)= (IoH*Mpoiyoi) / 56000, where IOH is the hydroxyl number in mg KOH / g of the polyol(s) composition (B) and Mpoiyoi is the theoretical molar mass in g / mol of the polyol (B) (said theoretical molar mass corresponding to the expected molar mass of the compound obtained following the esterification of the polyol (A) with the cyclic anhydride used in step (i)).

[0064] The f(OH) functionality of the polyol composition(s) (B) can vary depending on the cyclic anhydride / polyol molar ratio (A). Indeed, some of the hydroxyl groups of the polyol (A) react with the cyclic anhydride to form an ester bond, and a high cyclic anhydride / polyol molar ratio (A) leads to a polyol composition(s) (B) with a low f(OH) functionality.

[0065] Thus, the cyclic anhydride / polyol molar ratio (A) is advantageously chosen so as to obtain a composition of polyol(s) (B) having a functionality f(OH) as described above. Other characteristics of stage (i)

[0066] According to one embodiment, step (i) is implemented with at least: - a polyol (A) being lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or a fatty acid glyceride, at least one of said fatty acids comprising one or more hydroxyl groups, and - a cyclic anhydride chosen from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride, adipic anhydride, glycolic anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, l-methyl-2-(2'-carboxyethyl)maleic anhydride, octenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, isatoic anhydride, 1,2-cis-cyclohexanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, trimellitic anhydride and mixtures thereof.

[0067] Preferably, step (i) is implemented with at least: - a polyol (A) being a fatty acid glyceride, in particular a ricinoleic acid (tri)glyceride, and - a cyclic anhydride selected from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride and mixtures thereof, in particular maleic anhydride and / or tetrapropenylsuccinic anhydride.

[0068] More preferably, step (i) is implemented with at least: - a polyol (A) being a ricinoleic acid triglyceride introduced in the form of castor oil, and - a cyclic anhydride being maleic anhydride and / or tetrapropenylsuccinic anhydride.

[0069] The features of step (i) disclosed above apply to this embodiment. In particular, the cyclic anhydride / polyol molar ratio (A) is advantageously chosen so as to obtain a polyol(s) composition (B) having a functionality f(OH) as described above.

[0070] Step (i) is advantageously carried out under anhydrous conditions.

[0071] Step (i) is advantageously carried out at a temperature between 60°C and 120°C, preferably between 80°C and 100°C.

[0072] Step (i) can be carried out at atmospheric pressure. Step (ii) Polyisocyanate

[0073] By "polyisocyanate" is meant a compound comprising at least two isocyanate (-NCO) groups, preferably exactly two isocyanate groups (i.e., a diisocyanate). When the polyisocyanate is a diisocyanate, it can therefore be represented by the formula (III): OCN-R'-NCO in which R1 is a divalent hydrocarbon radical comprising from 4 to 45 carbon atoms, and optionally comprising one or more heteroatoms selected from oxygen, sulfur and nitrogen.

[0074] Polyisocyanate can be: - a polyisocyanate derived from vegetable oil comprising unsaturated fatty acids (such a polyisocyanate can be obtained by following the process described in G. Çayh et al., Biobased polyisocyanates from plant oil triglycerides Synthesis, polymerization, and characterization, J. Appl. Polym. Sci., 2008, 109, 2948-2955), in particular a polyisocyanate derived from soybean oil, and / Or

[0075] - a diisocyanate of formula (III): OCN-R'-NCO, R1 being such that the diisocyanate is chosen from: or a furan-derived diisocyanate such as 2,5-diisocyanatofuran, 2,5-bis(isocyanatomethyl)furan, 2,2'-(l-methylethylidene)bis[5-isocyanatofuran] (CAS 1008130-81-1), 2-isocyanato-5-[(5-isocyanatofuran-2-yl)methyl]furan (CAS 88768-51-8), 2-isocyanato-5-[l-(5-isocyanatofuran-2-yl)ethyl]furan (CAS 88768-52-9), [oxybis(methylene-5,2-furandiylmethylene)]diisocyanate (CAS 96732-82-0), the 2-(isocyanatomethyl)-5-[2-[5-(isocyanatomethyl)furan-2-yl]propan-2-yl]furan (CAS 88768-56-3),

[0076] o a diisocyanate derived from dianhydrohexitol with the formula:

[0077] o a methoxyphenyl-derived diisocyanate with the formula:

[0078]

[0079] in which R8 represents a hydrogen atom or a methoxy group and m is an integer between 1 and 3, o an allophanate of hexamethylene diisocyanate (HDI) of formula (Ilia):

[0080]

[0081]

[0082]

[0083]

[0084] (Ilia) 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;

[0085] - R12 represents a divalent propylene group;

[0086] - i, j, R11 and R12 being such that the hexamethylene diisocyanate allophanate corresponding to formula (Ilia) comprises an isocyanate group NCO content ranging from 12 to 14% by weight relative to the weight of said allophanate, • pentamethylene diisocyanate (PDI), • hexamethylene diisocyanate (HDI), • 1,7-diisocyanatoheptane, • 1,8-diisocyanatooctane, • 1,9-diisocyanatononane, • 1,16-diisocyanato-8-hexadecene, • L-isocyanato-10-[(isocyanatomethyl)thio]decane, • dimeryl diisocyanate (CAS 68239-06-5), • L-lysine diisocyanate methyl ester (CAS 34050-00-5), • L-lysine diisocyanate ethyl ester (CAS 45172-15-4), • 2,4-diisocyanato-l-pentadecylbenzene, • isophorone diisocyanate (IPDI), • 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate (HMDI), • 2,4- and / or 2,6-toluene diisocyanate (TDI), • 4,4'- and / or 2,4'-diphenylmethane diisocyanate (MDI), • m-xylylene diisocyanate (m-XDI), • m-hydrogenated xylylene diisocyanate (m-H6XDI), and • their mixtures.

[0087] Advantageously, the polyisocyanate is selected from pentamethylene diisocyanate, hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, dimeryl diisocyanate, L-lysine diisocyanate methyl ester, L-lysine diisocyanate ethyl ester, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 4,4'- and / or 2,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, m-hydrogenated xylylene diisocyanate and mixtures thereof.

[0088] Preferably, the polyisocyanate is selected from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 4,4'- and / or 2,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, m-hydrogenated xylylene diisocyanate and mixtures thereof.

[0089] More preferably, the polyisocyanate is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-Dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, m-hydrogenated xylylene diisocyanate and mixtures thereof, in particular isophorone diisocyanate.

[0090] Advantageously, step (ii) is carried out with an excess of the molar equivalent number of -NCO groups of the polyisocyanate relative to the molar equivalent number of -OH groups of the polyol composition(s) (B). Preferably, step (ii) is carried out with a molar equivalent ratio -NCO / -OH of between 1.1 and 4, preferably between 1.2 and 3, more preferably between 1.3 and 2.0.

[0091] The molar equivalent ratio -NCO / -OH is defined as being equal to the molar equivalent number of -NCO groups of the polyisocyanate divided by the sum of the molar equivalent number of -OH groups implemented during step (ii) (in particular the composition of polyol(s) (B) and the possible alcohol (C) described below).

[0092] The equivalent molar number of -NCO groups in the polyisocyanate is equal to: f(-NCO)*(mpoiyisocyanate / Mpoiyisocyanate), where f(-NCO) is the number of -NCO groups in the polyisocyanate, mpoiyisocyanate is the mass introduced in g of the polyisocyanate, and Mpoiyisocyanate is the molar mass in g / mol of the polyisocyanate. Preferably, the polyisocyanate is a diisocyanate, and f(-NCO) is therefore equal to 2.

[0093] The equivalent molar number of -OH groups in the polyol(s) composition (B) is equal to: (IOH*mB) / 56000, where IOH is the hydroxyl index in mg KOH / g of the polyol(s) composition (B) and where mB is the mass introduced in g of the polyol(s) composition (B).

[0094] The equivalent molar number of -OH groups of alcohol (C) is equal to: (IoH*mc) / 56000, where IoH is the hydroxyl index in mg KOH / g of alcohol (C) and where mc is the mass introduced in g of alcohol (C). Plasticizer

[0095] Advantageously, step (ii) is carried out in the presence of a plasticizer.

[0096] The presence of the plasticizer makes it possible to decrease the viscosity of the reaction medium of step (ii), and also the resulting polyurethane composition(s).

[0097] The plasticizer can be any plasticizer commonly used in the field of adhesive compositions and / or sealants.

[0098] Preferably, the plasticizer is chosen from:

[0099] - a mixture of fatty acid methyl esters, in particular fatty acids comprising 18 carbon atoms such as fatty acids from castor oil including ricinoleic acid (for example Esterol A marketed by ARKEMA),

[0100] - a mixture of alkylsulfonic acid and phenol esters, such as the mixture identified by CAS number 91082-17-6 (for example, MESAMOLL® marketed by LANXESS),

[0101] - diisodecyl phthalate (for example PALATINOL® DIDP marketed by BASF),

[0102] - diisononyl phthalate (DINP) (for example PALATINOL® N marketed by BASF),

[0103] - the diisononyl ester of 1,2-cyclohexanedicarboxylic acid (for example the HEXAMOLL DINCH® marketed by BASF),

[0104] - pentaerythritol tetravalerate (for example PEVALEN™ marketed by PERSTORP),

[0105] - a polysiloxane resin, in particular a silsesquioxane of average molar mass in Mn content ranging from 400 g / mol to 4000 g / mol, preferably from 500 g / mol to 2500 g / mol, such as DOW CORNING® 3074 marketed by DOW, whose Mn content is between 1300-1500 g / mol, and

[0106] - their mixtures.

[0107] More preferably, the plasticizer is chosen from:

[0108] - a mixture of fatty acid methyl esters, in particular fatty acids comprising 18 carbon atoms such as fatty acids from castor oil including ricinoleic acid (for example Esterol A marketed by ARKEMA), and / or

[0109] - a mixture of alkylsulfonic acid and phenol esters, such as the mixture identified by CAS number 91082-17-6 (for example, MESAMOLL® marketed by LANXESS).

[0110] According to one embodiment, the plasticizer consists of at least 50% by weight of a bio-based plasticizer, in particular a mixture of fatty acid methyl esters such as fatty acids derived from castor oil, relative to the total weight of plasticizer used in step (ii), preferably between 85% and 100% by weight. An example of a bio-based plasticizer is Esterol A, marketed by ARKEMA.

[0111] The quantity of plasticizer used in step (ii) may vary from 5% to 50% by weight relative to the total weight of the polyol(s) composition (B), preferably from 15% to 40% by weight, more preferably from 25% to 35% by weight. Alcohol (C)

[0112] An alcohol (C), preferably a polyol, can be added to carry out step (ii). The alcohol (C) differs from the polyol (B). Indeed, the alcohol (C) does not include a carboxylic acid group (-C(O)OH).

[0113] Alcohol (C) has a number-average molar mass Mn greater than or equal to 500 g / mol.

[0114] Alcohol (C) can have a functionality f(OH) between 1 and 6, preferably between 2 and 4, more preferably between 2 and 3, in particular equal to 2. The functionality f(OH) represents the average number of hydroxyl groups (-OH) per polyol molecule.

[0115] Said functionality f(OH) can be determined as indicated above for the polyol (A).

[0116] According to a preferred embodiment, the alcohol (C) is a polyol which may be the bio-based polyol (A) as described above, in particular of lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or a fatty acid glyceride, a poly(farnesene) diol, isosorbide, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyacrylate polyol, a polysiloxane polyol and / or a polyolefin polyol, preferably a polyether polyol such as polypropylene glycol or polyethylene glycol.

[0117] Poly(farnesene)diol can be obtained from a plant resource. Indeed, some plant resources, such as apples, contain farnesene. Krasol® F 3000, marketed by Total, is an example of a commercial poly(farnesene)diol.

[0118] Isosorbide can also be obtained from a plant resource, as it can be obtained from glucose, a sugar widely found in plants.

[0119] According to this embodiment, the alcohol (C) can have the formula HO-R9-OH in which the radical R9 is chosen from the following divalent radicals whose formulas below show the two free valences:

[0120] - derivative of a poly(farnesene) diol: ...... \ HAS /

[0121] - isosorbide derivative: O l

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133] - derived from polyethylene glycol - derived from polypropylene glycol ch3 oh3 CHâ - derived from a polyester diol - derived from a polybutadiene diol: - derived from a polyacrylate diol: q' q Q' - derived from a polysiloxane diol Q" —Q Si— u Q in which: - x and y are integers; preferably x and y are such that the number-average molar mass of poly(famesene)diol is between 500 g / mol and 8000 g / mol, more preferably between 1000 g / mol and 5000 g / mol, - q represents an integer such that the average molar mass in number Mn of the R9 radical 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 R9 radical 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,

[0134] - Q3, Q4, Q6, Q7 and Q8, represent, independently of each other, 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.

[0135] According to this embodiment, the radical R9 preferably represents a radical derived from a polyether, preferably from a polyethylene glycol or a polypropylene glycol as described above.

[0136] When an alcohol (C) is implemented in step (ii), the amount of alcohol (C) introduced in step (ii) can vary between 20% and 80% by weight relative to the weight of the polyol(s) composition (B). Additives

[0137] Step (ii) 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.

[0138] The amount of catalyst introduced in step (ii) may vary between 0.01% and 0.5% by weight relative to the weight of the polyol composition(s) (B), preferably between 0.01% and 0.3%, more preferably between 0.02% and 0.1%, even more preferably between 0.04% and 0.08%.

[0139] Step (ii) can be carried out in the presence of a UV stabilizer (or antioxidant). A UV stabilizer is typically introduced to prevent degradation resulting from a reaction with oxygen that is likely to form through the action of heat or light. UV stabilizers may include antioxidants capable of scavenging free radicals.

[0140] Advantageously, the UV stabilizer (or antioxidant) is selected from among benzotriazoles, benzophenones, so-called hindered phenols such as ethylenebis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], 2,2'-methylenebis(6-(tert-butyl)-4-methylphenol), 2,2'-methylenebis(6-(tert-butyl)-4-ethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4,6-di(tert-butyl)phenol), 4,4'-methylenebis(2,6-di(tert-butyl)phenol) and 2,6-di(tert-butyl)-4-methylphenol, 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 and 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, and mixtures thereof. Examples include Irganox® 245, Irganox® 1076, TINUVIN® 292, TINUVIN® 765 or TINUVIN® 770 DF marketed by BASF and RIASORB UV-123 marketed by RIANLON.

[0141] Preferably, the UV stabilizer (or antioxidant) is chosen from among the so-called hindered phenols, more preferably from ethylenebis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], 2,2'-methylenebis(6-(tert-butyl)-4-methylphenol), 2,2'-methylenebis(6-(tert-butyl)-4-ethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4,6-di(tert-butyl)phenol), 4,4'-methylenebis(2,6-di(tert-butyl)phenol), 2,6-di(tert-butyl)-4-methylphenol and mixtures thereof, in particular bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] of ethylenebis(oxyethylene).

[0142] The amount of UV stabilizer (or antioxidant) introduced in step (ii) may vary between 0.1% and 5% by weight relative to the weight of the polyol composition(s) (B), preferably between 0.2% and 3%, more preferably between 0.5% and 1.5%. Other features of step (ii)

[0143] Advantageously, no polyol comprising a carboxylic acid is implemented in step (ii) in addition to the polyol(s) composition (B).

[0144] The % NCO by weight of the terminal group -NCO polyurethane composition(s) obtained at the end of step (ii) may vary between 0.3% and 5% relative to the total weight of said composition, preferably between 0.4% and 3%.

[0145] The % NCO by weight of said polyurethane composition(s) can be determined by any method known to those skilled in the art, in particular by using an automatic titrator, for example as described in Example 1.

[0146] The % NCO by weight of said polyurethane composition(s) may vary according to the molar ratio of polyol(s) composition (B) / polyisocyanate.

[0147] According to one embodiment, step (ii) is carried out with, in addition to the polyol composition(s) (B), at least: - a polyisocyanate selected from pentamethylene diisocyanate, rhexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, dimeryl diisocyanate, L-lysine diisocyanate methyl ester, L-lysine diisocyanate ethyl ester, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 4,4'- and / or 2,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, m-hydrogenated xylylene diisocyanate and mixtures thereof, - a plasticizer, - a catalyst for the formation of polyurethane by reaction of a polyisocyanate and at least one polyol, and - optionally a UV stabilizer (or antioxidant).

[0148] Preferably, step (ii) is carried out with, in addition to the polyol(s) composition (B), at least: - a polyisocyanate selected from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, m-xylylene hydrogenated diisocyanate and mixtures thereof, in particular isophorone diisocyanate, - a plasticizer chosen from: • a mixture of fatty acid methyl esters, in particular fatty acids comprising 18 carbon atoms such as fatty acids from castor oil including, in particular, ricinoleic acid, • a mixture of alkylsulfonic acid and phenol esters, such as the mixture identified by CAS No. 91082-17-6, • diisodecyl phthalate, • diisononyl phthalate, • the diisononyl ester of 1,2-cyclohexanedicarboxylic acid, • pentaerythritol tetravalerate, • a polysiloxane resin, in particular a silsesquioxane with a number-average molar mass (Mn) ranging from 400 g / mol to 4000 g / mol, preferably from 500 g / mol to 2500 g / mol, and • their mixtures, - a catalyst chosen from among the carboxylates, in particular neodecanoate, of bismuth and / or zinc, and - optionally a UV stabilizer (or antioxidant) chosen from among the so-called hindered phenols.

[0149] More preferably, step (ii) is carried out with, in addition to the polyol(s) composition (B), at least: - a polyisocyanate being isophorone diisocyanate, - a plasticizer chosen from: • a mixture of fatty acid methyl esters, in particular fatty acids comprising 18 carbon atoms such as fatty acids from castor oil including ricinoleic acid, and / or • a mixture of alkylsulfonic acid and phenol esters, such as the mixture identified by CAS No. 91082-17-6, - a catalyst chosen from among the carboxylates, in particular neodecanoate, of bismuth and / or zinc, and - optionally a UV stabilizer (or antioxidant) selected from ethylenebis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], 2,2'-methylenebis(6-(tert-butyl)-4-methylphenol), 2,2'-methylenebis(6-(tert-butyl)-4-ethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4,6-di(tert-butyl)phenol), 4,4'-methylenebis(2,6-di(tert-butyl)phenol), 2,6-di(tert-butyl)-4-methylphenol and mixtures thereof, in particular ethylenebis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate].

[0150] The features of step (ii) disclosed above apply to this embodiment. In particular, the quantities implemented in this embodiment are advantageously as described above.

[0151] Step (ii) is advantageously carried out under anhydrous conditions.

[0152] Step (ii) is advantageously carried out at a temperature between 60°C and 120°C, preferably between 80°C and 100°C.

[0153] Step (ii) can be carried out at atmospheric pressure. Step (iii)

[0154] Step (iii) corresponds to the reaction of a tertiary amine with the carboxylic acid groups of the polyurethane composition(s) with terminal groups -NCO formed in step (ii).

[0155] The tertiary amine implemented in step (iii) has a pKa at 25°C greater than 8, preferably between 9 and 15, more preferably between 10 and 12.

[0156] Throughout the application, "pKa of the tertiary amine" means the pKa of its conjugate acid (i.e., of the protonated tertiary amine). The pKa of an acid is equal to -logio(Ka), where Ka is the acidity constant of the acid in water.

[0157] The tertiary amine may have formula (IV): N(R)(R')(R") in which R, R' and R", identical or different, each represent a saturated or unsaturated hydrocarbon radical, possibly comprising one or more heteroatoms chosen from N, O and S, and R and R' and / or R and R" and / or R' and R" which can form a heterocycle with the nitrogen atom to which they are attached.

[0158] According to one embodiment, the tertiary amine is chosen from the triethylamine (or TEA), l,8-diazabicyclo[5.4.0]undec-7-ene (or DBU), 1,4-diazabicyclo[2.2.2]octane (or DABCO), l,5-diazabicyclo[4.3.0]non-5-ene (or DBN), N,N-dicyclohexylmethylamine (or DCHMA), diethyl ether-2,2'-morpholine (or DMDEE), triazabicyclodecene (TBD), methyltriazabicyclodecene (MTBD), trihexylamine (or THA) and mixtures thereof.

[0159] When the process according to the invention further comprises a silylation step (iv), the tertiary amine is advantageously chosen from TEA, DBU, DABCO, DBN, DCHMA, TBD, MTBD, THA and mixtures thereof.

[0160] Preferably, the tertiary amine is chosen from DBU, DABCO, DBN, DCHMA and their mixtures, in particular DCHMA.

[0161] Tertiary amines are often incorporated as a crosslinking catalyst in a polyurethane (possibly silylated) sealant and / or adhesive composition. This has the disadvantage of leading to yellowing of the resulting adhesive joint, probably due to its migration onto the surface of said joint. Conversely, no yellowing of the adhesive joint resulting from a sealant and / or adhesive composition comprising the ionic polyurethane composition(s) according to the invention is observed. Such an effect is probably related to the interaction of the tertiary amine with the carboxylic acid groups.

[0162] In step (iii) of the process according to the invention, the molar ratio (tertiary amine / -C(O)OH) can vary from 0.5 to 2.5, preferably from 1 to 2, more preferably is equal to 1.

[0163] The tertiary amine / -C(O)OH molar ratio is defined as being equal to the number of moles of tertiary amine introduced in step (iii) divided by the equivalent molar number of -C(O)OH groups in the polyol(s) composition (B).

[0164] The equivalent molar number of -C(O)OH groups in the composition of polyol(s) (B) is equal to: f(-C(O)OH)*(manhydride / Manhydride), where f(-C(O)OH) is the sum of the number of anhydride functions and the number of -C(O)OH groups of the cyclic anhydride introduced in step (i), manhydride is the mass introduced in g of said anhydride and Manhydride is the molar mass in g / mol of said anhydride.

[0165] Step (iii) is advantageously carried out under anhydrous conditions.

[0166] Step (iii) is advantageously carried out at a temperature between 20°C and 80°C, preferably between 20°C and 50°C.

[0167] Step (iii) is advantageously carried out at atmospheric pressure. Step (iv)

[0168] Advantageously, the process according to the invention further comprises a step (iv) of silylating the ionic polyurethane composition(s) with terminal groups -NCO (D) with a silyl compound to form a silylated ionic polyurethane composition(s) (E), the silyl compound being of formula (V):

[0169] (V)

[0170] in which:

[0171] - R3 represents a linear or branched divalent alkylene radical comprising 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,

[0172] - 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,

[0173] - 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 able to be involved in the same ring, preferably R5 represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms,

[0174] - X represents a divalent radical chosen from -N(R6)-, -NH- and -S-,

[0175] - 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

[0176] - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

[0177] Advantageously, the silylated compound has formula (V) in which:

[0178] - R3 represents a linear or branched divalent alkylene radical comprising 1 to 3 carbon atoms, preferably n-propylene;

[0179] - R5 represents a methyl or ethyl radical, preferably methyl;

[0180] - X represents a divalent radical -N(R6)-,

[0181] - R6 represents a linear or branched alkyl radical comprising 1 to 4 atoms of carbon, preferably n-butyl, and

[0182] -pestégalàO.

[0183] Silylated compounds of formula (V) are widely available commercially. An example is N-(3(trimethoxysilyl)propyl)butylamine, available under the name Dynasylan® 1189 from Evonik.

[0184] In the process according to the invention, step (iv) can be carried out with an equivalent molar ratio -XH / -NCO equal to 1, preferably between 0.90 and 1.15.

[0185] 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 (V) divided by the molar equivalent number of -NCO groups of the ionic polyurethane composition(s) (D) obtained at the end of step (iii).

[0186] The molar equivalent number of -XH groups of the silylated compound of formula (V) is equal to the number of moles of the silylated compound of formula (V) introduced in step (iv).

[0187] The molar equivalent number of -NCO groups in the ionic polyurethane composition(s) (D) obtained at the end of step (iii) corresponds to the molar equivalent number of polyisocyanate -NCO groups introduced in excess relative to the molar equivalent number of -OH groups in the polyol composition(s) (B) in step (ii).

[0188] Step (iv) is advantageously carried out under anhydrous conditions.

[0189] Step (iv) is advantageously carried out at a temperature within a range from 20°C to 90°C, preferably from 30°C to 70°C.

[0190] Step (iv) is advantageously carried out at atmospheric pressure.

[0191] The viscosity at 23°C of the silylated ionic polyurethane composition(s) (E) obtained at the end of step (iv) can vary from 1 to 350 Pa.s, and is advantageously between 1 and 250 Pa.s, preferably between 5 and 100 Pa.s.

[0192] This viscosity can for example be measured according to a Brookfield type method at 23°C (needle S28).

[0193] Other features of the method according to the invention Preferred embodiment

[0194] According to a preferred embodiment, the method according to the invention comprises:

[0195] (i) an esterification step of a polyol (A) being a glyceride of acids fatty, in particular a (tri)glyceride of ricinoleic acid, with a cyclic anhydride selected from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride and mixtures thereof, in particular maleic anhydride and / or tetrapropenylsuccinic anhydride, to form a polyol(s) composition (B), then

[0196] (ii) a reaction step of the polyol composition(s) (B) with a polyisocyanate to form a polyurethane composition(s) with terminal -NCO groups, wherein: - the polyisocyanate is selected from pentamethylene diisocyanate, rhexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, m-xylylene hydrogenated diisocyanate and mixtures thereof, in particular isophorone diisocyanate, - a plasticizer is used, the plasticizer being chosen from: • a mixture of fatty acid methyl esters, in particular fatty acids comprising 18 carbon atoms such as fatty acids from castor oil including, in particular, ricinoleic acid, • a mixture of alkylsulfonic acid and phenol esters, such as the mixture identified by CAS No. 91082-17-6, • dusodecyl phthalate, • dusononyl phthalate, • the diisononyl ester of 1,2-cyclohexanedicarboxylic acid, • pentaerythritol tetravalerate, • a polysiloxane resin, in particular a silsesquioxane with a number-average molar mass (Mn) ranging from 400 g / mol to 4000 g / mol, preferably from 500 g / mol to 2500 g / mol, and • their mixtures, - a catalyst is used, the catalyst being chosen from among the carboxylates, in particular neodecanoate, of bismuth and / or zinc, and - Optionally, a UV stabilizer (or antioxidant) chosen from among the so-called hindered phenols is implemented,

[0197] then

[0198] (iii) a reaction step of the -NCO terminal group polyurethane composition(s) formed in step (ii) with a tertiary amine selected from TEA, DBU, DABCO, DBN, DCHMA, DMDEE, TBD, MTBD, THA and mixtures thereof, to form an ionic -NCO(D) terminal group polyurethane composition(s), then

[0199] (iv) optionally a step (iv) of silylating the -NCO-terminated ionic polyurethane composition(s) (D) with a silyl compound to form a silylized ionic polyurethane composition(s) (E), the silyl compound having formula (V) in which:

[0200] - R3 represents a linear or branched divalent alkylene radical comprising 1 to 3 carbon atoms, preferably n-propylene;

[0201] - R5 represents a methyl or ethyl radical, preferably methyl;

[0202] - X represents a divalent radical -N(R6)-,

[0203] - R6 represents a linear or branched alkyl radical comprising 1 to 4 atoms of carbon, preferably n-butyl, and

[0204] - p is equal to 0.

[0205] More preferably, the method according to the invention comprises:

[0206] (i) an esterification step of a polyol (A) being an acid triglyceride ricinoleic introduced in the form of castor oil, with a cyclic anhydride being maleic anhydride and / or tetrapropenylsuccinic anhydride, to form a polyol(s) composition (B), then

[0207] (ii) a reaction step of the polyol composition(s) (B) with a polyisocyanate to form a polyurethane composition(s) with terminal -NCO groups, wherein: - Polyisocyanate is isophorone diisocyanate, - a plasticizer is used, the plasticizer being chosen from: • a mixture of fatty acid methyl esters, in particular fatty acids comprising 18 carbon atoms such as fatty acids from castor oil including ricinoleic acid, and / or • a mixture of alkylsulfonic acid and phenol esters, such as the mixture identified by CAS No. 91082-17-6, - a catalyst is used, the catalyst being chosen from among the carboxylates, in particular neodecanoate, of bismuth and / or zinc, and - optionally a UV stabilizer (or antioxidant) is implemented, the UV stabilizer being chosen from ethylenebis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], 2,2'-methylenebis(6-(tert-butyl)-4-methylphenol), 2,2'-methylenebis(6-(tert-butyl)-4-ethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4,6-di(tert-butyl)phenol), 4,4'-methylenebis(2,6-di(tert-butyl)phenol), 2,6-di(tert-butyl)-4-methylphenol and their mixtures, in particular ethylenebis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate],

[0208] then

[0209] (iii) a reaction step of the -NCO terminal group polyurethane composition(s) formed in step (ii) with a tertiary amine selected from DBU, DABCO, DBN, DCHMA and mixtures thereof, in particular DCHMA, to form an ionic -NCO(D) terminal group polyurethane composition(s), then

[0210] (iv) optionally a step (iv) of silylating the -NCO-terminated ionic polyurethane composition(s) (D) with a silyl compound to form a silylized ionic polyurethane composition(s) (E), the silyl compound having formula (V) in which:

[0211] - R3 represents a linear or branched divalent alkylene radical comprising 1 to 3 carbon atoms, preferably n-propylene;

[0212] - R5 represents a methyl or ethyl radical, preferably methyl;

[0213] - X represents a divalent radical -N(R6)-,

[0214] - R6 represents a linear or branched alkyl radical comprising 1 to 4 atoms of carbon, preferably n-butyl, and

[0215] - p is equal to 0.

[0216] The characteristics of steps (i) to (iv) disclosed above apply to this embodiment. In particular, the quantities implemented in this embodiment are advantageously as described above. Solvent

[0217] The process according to the invention is advantageously implemented in the absence of solvent.

[0218] By “solvent”, we mean in particular a solvent used in the field of adhesives and / or sealants.

[0219] Solvents are well known to those skilled in the art and include, for example, water, ethanol, isopropanol, ethyl acetate, butyl acetate, acetone, butanone, methylisobutyl ketone, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, cyclohexane, benzene, toluene, xylene, etc.

[0220] Preferably, 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 the addition of free water, that is, water other than that inherently contained in the ingredients used. In particular, the water content introduced into the process according to the invention is less than 3% by weight relative to the total weight of the ingredients used, preferably less than 1% by weight. Furthermore, the polyol (A) is preferably dehydrated (for example, at about 100°C and under vacuum, in particular at less than 0.6 kPa) before its use in step (i) until it has a water content of less than 0.1% by weight, preferably less than 0.05% by weight, relative to the weight of the polyol (A). The other ingredients (in particular the plasticizers) can also be dehydrated in the same way.

[0221] The water content can be measured according to a Karl Fischer coulometric method, for example according to the method described in Example 1. Moisture absorber

[0222] A moisture absorber can be introduced at the end of step (iv) of the process according to the invention (once the silylation of the ionic polyurethane composition(s) with terminal groups -NCO (D) is complete).

[0223] A suitable moisture absorber (or desiccant) is, in particular, an alkoxysilane such as a trialkoxysilane (especially a trimethoxysilane). Such an agent advantageously prolongs the shelf life of the silylated ionic polyurethane composition(s) (E) during storage and transport, prior to use.

[0224] Advantageously, the moisture absorber is selected from vinyltrimethoxysilane, trimethoxymethylsilane, propyltrimethoxysilane, vinyltriethoxysilane, alkoxyarylsilanes (for example GENIOSIL® XL 70 marketed by WACKER) and mixtures thereof.

[0225] Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, vinyltriethoxysilane and their mixture, more preferably vinyltrimethoxysilane.

[0226] The moisture absorber content may be between 0.2% and 3% by weight relative to the total weight of the silylated ionic polyurethane composition(s) (E), preferably between 0.5% and 1.5% by weight. Bio-based ingredients

[0227] According to one embodiment, at least 50% by weight of the ingredients used in the process according to the invention are bio-based, relative to the total weight of the ingredients used in the process according to the invention, preferably at least 85% by weight.

[0228] Thus, the ionic polyurethane(s) compositions (D) and (E) are advantageously made up of at least 50% by weight of bio-based ingredients, respectively in relation to the total weight of the ionic polyurethane(s) compositions (D) and (E), preferably of at least 85% by weight.

[0229] Bio-based ingredients include polyol (A) and the possible plasticizer.

[0230] Composition of ionic polyurethane(s) with terminal groups -NCO (D) that can be obtained by the process according to the invention

[0231] The invention also relates to an ionic polyurethane composition(s) with terminal groups -NCO (D) capable of being obtained by the process according to the invention comprising steps (i) to (iii) as defined above.

[0232] Step (iv) of silylation is not carried out because the ionic polyurethane(s) of said composition (D) is (are) not silylated (but with terminal groups -NCO).

[0233] Thus, the composition of ionic polyurethane(s) (D) according to the invention comprises one or more ionic polyurethanes with terminal groups -NCO.

[0234] The content of ionic polyurethane(s) with terminal groups -NCO in said composition (D) may vary from 60% to 100% by weight relative to the total weight of the composition (D), preferably from 65% to 95% by weight, more preferably from 75% to 85% by weight.

[0235] Advantageously, the ionic polyurethane composition(s) (D) according to the invention comprises a plasticizer. The plasticizer is as described above. The plasticizer content in said composition (D) may vary from 3% to 30% by weight relative to the total weight of the composition (D), preferably from 7% to 25% by weight, more preferably from 10% to 20% by weight.

[0236] Advantageously, said ionic polyurethane composition (D) does not comprise a solvent, the solvent being as defined above. In particular, said composition (D) comprises less than 3% by weight of water relative to the total weight of said composition (D), preferably less than 1% by weight.

[0237] Furthermore, the characteristics mentioned above concerning the composition of ionic polyurethane(s) (D) obtained by the process according to the invention apply to the composition of ionic polyurethane(s) (D) that can be obtained by the process according to the invention.

[0238] In particular, the composition of ionic polyurethane(s) (D) is advantageously made up of at least 50% by weight of bio-based ingredients, relative to the total weight of said composition (D), preferably of at least 85% by weight.

[0239] Composition of silylated ionic polyurethane(s) (E) that can be obtained by the process according to the invention

[0240] The invention also relates to a silylated ionic polyurethane composition (E) that can be obtained by the process according to the invention comprising steps (i) to (iv) as defined above.

[0241] Thus, the composition of ionic polyurethane(s) (E) according to the invention comprises one or more silylated ionic polyurethanes.

[0242] The content of silylated ionic polyurethane(s) in said composition (E) may vary from 60% to 100% by weight relative to the total weight of the composition (E), preferably from 65% to 95% by weight, more preferably from 75% to 85% by weight.

[0243] Advantageously, the silylated ionic polyurethane composition(s) (E) according to the invention comprises a plasticizer. The plasticizer is as described above. The plasticizer content in said composition (E) may vary from 3% to 30% by weight relative to the total weight of the composition (E), preferably from 7% to 25% by weight, more preferably from 10% to 20% by weight.

[0244] Advantageously, said silylated ionic polyurethane composition (E) does not comprise a solvent, the solvent being as defined above. In particular, said composition (E) comprises less than 3% by weight of water relative to the total weight of said composition (E), preferably less than 1% by weight.

[0245] Furthermore, the characteristics mentioned above concerning the composition of silylated ionic polyurethane(s) (E) obtained by the process according to the invention apply to the composition of silylated ionic polyurethane(s) (E) that can be obtained by the process according to the invention.

[0246] In particular, the silylated ionic polyurethane composition (E) is advantageously made up of at least 50% by weight of bio-based ingredients, relative to the total weight of said composition (E), preferably of at least 85% by weight. Ionic polyurethane, possibly silylated

[0247] The invention relates in particular to an ionic polyurethane, possibly silylated.

[0248] The ionic polyurethane, optionally silylated according to the invention, comprises a motif (M) of the type:

[0249] in which: - R, R', R" are as described above, in particular R, R', R" are such that the tertiary amine of formula (IV): N(R)(R')(R") is chosen from among the tertiary amines described above, - R1 is as described above and is directly bonded to a nitrogen atom; in particular, R1 is such that the diisocyanate of formula (III): OCN-R'-NCO is chosen from among the diisocyanates described above. - R2 is as described above, and represents a radical with a valence greater than or equal to 3, in particular R2 is such that the polyol of formula (I), in which n is equal to the sum of t and u, is bio-based and preferably chosen from lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or a fatty acid glyceride, - R7 is as described above, in particular R7 is such that the anhydride cyclic of formula (II) is selected from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride, adipic anhydride, glycolic anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, l-methyl-2-(2'-carboxyethyl)maleic anhydride, octenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, 1,2-cis-cyclohexanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, trimellitic anhydride and their mixtures, - t and u are non-nuisable integers, u being greater than or equal to 2, preferably t is equal to 1 and u is equal to 2.

[0250] The radical R1 can be directly linked to the nitrogen of a carbamate group through which the polyurethane chain is extended or to the nitrogen of an isocyanate group (-NCO) or to the nitrogen of a silylated group of formula (VII): , in which X, R3, R4, R5 and p are such that defined above.

[0251] The radicals of this motif are as described above, including preferred features and embodiments.

[0252] Thus, according to a preferred embodiment, in the above motif: - R, R', R" are such that the tertiary amine of formula (IV): N(R)(R')(R") is chosen from TEA, DBU, DABCO, DBN, DCHMA, DMDEE, TBD, MTBD, THA and their mixtures, - R1 is such that the diisocyanate of formula (III): OCN-R'-NCO is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, m-xylylene hydrogenated diisocyanate and mixtures thereof, in particular isophorone diisocyanate, - R2 is such that the polyol of formula (I), in which n is equal to the sum of t and u, is chosen from lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or a fatty acid glyceride, in particular a fatty acid glyceride, for example a (tri)glyceride of ricinoleic acid, - R7 is such that the cyclic anhydride of formula (II) is chosen from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride and mixtures thereof, in particular maleic anhydride and / or tetrapropenylsuccinic anhydride, - t and u are non-nuisable integers, u being greater than or equal to 2, preferably t is equal to 1 and u is equal to 2.

[0253] When the radical R1 is linked to the nitrogen of a silylated group of formula (VII), R, R', R" are such that the tertiary amine of formula (IV): N(R)(R')(R") is advantageously chosen from TEA, DBU, DABCO, DBN, DCHMA, TBD, MTBD, THA and mixtures thereof.

[0254] Advantageously, the ionic polyurethane, possibly silylated according to the invention, has the formula (VI): IOO lh . h ff O „ n o LH o—f ! -- V

[0255] (VI)

[0256] in which:

[0257] - R, R', R” are as described above, in particular R, R', R” are such that The tertiary amine of formula (IV): N(R)(R')(R") is chosen from among the tertiary amines described above,

[0258] - R1 is as described above, in particular R1 is such that the diisocyanate of formula (III): OCN-R'-NCO is chosen from among the diisocyanates described above,

[0259] - R2 is as described above, and represents a higher valence radical or equal to 3, in particular R2 is such that the polyol of formula (I) is bio-based and preferably chosen from lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or a fatty acid glyceride,

[0260] - R7 is as described above, in particular R7 is such that the cyclic anhydride of formula (II) is selected from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride, adipic anhydride, glycolic anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, l-methyl-2-(2'-carboxyethyl)maleic anhydride, octenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, 1,2-cis-cyclohexanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, trimellitic anhydride and mixtures thereof,

[0261] - R9 is as described above and represents a divalent radical, in particular R9 is such that the alcohol of formula HO-R9-OH is chosen from a poly(famesene) diol, isosorbide, polyethylene glycol, polypropylene glycol, polyester diol, polybutadiene diol, polyacrylate diol and polysiloxane diol, preferably polyethylene glycol or polypropylene glycol,

[0262] - v is a non-zero integer,

[0263] -1 and u are non-null integers, u being greater than or equal to 2, preferably t is equal to 1 and u is equal to 2,

[0264] - c is an integer greater than or equal to 0, preferably equal to 0,

[0265] - Y represents f or a carbamate group through which the polyurethane chain prolongs, the nitrogen of said carbamate group being directly linked to R1,

[0266] - f represents an isocyanate group -NCO or a monovalent radical of formula (VII): O h — NH - C— X - OR ■ K p

[0267] in which X, R3, R4, R5 and p are as defined above, preferably f represents a monovalent radical of formula (VII).

[0268] The main chain of the optionally silylated ionic polyurethane of formula (VI) therefore comprises a repeating motif repeated v times and optionally a repeating motif repeated c times. It is understood that, when the motif comprising the R9 radical is present, the distribution of these two motifs on said main chain is statistical, and that said polyurethane of formula (VI) is therefore a statistical copolymer.

[0269] In addition, t represents the number of ionic groups carried by the radical R2 and can be an integer greater than 1 when the radical R2 is a radical with a valence greater than 3.

[0270] The radicals in formula (VI) are as described above, including preferred features and embodiments.

[0271] Thus, according to a preferred embodiment, the ionic polyurethane, optionally silylated according to the invention, has formula (VI) in which:

[0272] - R, R', R" are such that the tertiary amine of formula (IV): N(R)(R')(R") is chosen among TEA, DBU, DABCO, DBN, DCHMA, DMDEE, TBD, MTBD, THA and their mixtures, in particular DCHMA,

[0273] - R1 is such that the diisocyanate of formula (III): OCN-R'-NCO is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate and mixtures thereof, in particular isophorone diisocyanate,

[0274] - R2 is such that the polyol of formula (I), in which n is equal to the sum of t and u, is a fatty acid glyceride, in particular a (tri)glyceride of ricinoleic acid,

[0275] - R7 is such that the cyclic anhydride of formula (II) is chosen from the anhydride maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride and mixtures thereof, in particular maleic anhydride and / or tetrapropenylsuccinic anhydride,

[0276] - R9 is such that the alcohol of formula HO-R9-OH is chosen from a poly(farnesene) diol, isosorbide, polyethylene glycol, polypropylene glycol, polyester diol, polybutadiene diol, polyacrylate diol and polysiloxane diol, preferably polyethylene glycol or polypropylene glycol,

[0277] - v is a non-zero integer,

[0278] -1 is equal to 1 and u is equal to 2,

[0279] - c is an integer greater than or equal to 0, preferably equal to 0,

[0280] - f represents an isocyanate group -NCO or a monovalent radical of formula (VII): O — NH-C- X- R3-

[0281] in which X, R3, R4, R5 and p are as defined above, preferably f represents a monovalent radical of formula (VII).

[0282] Preferably, the ionic polyurethane of formula (VI) is silylated and f represents a monovalent radical of formula (VII). More preferably, f represents a monovalent radical of formula (VII) in which:

[0283] - R3 represents a linear or branched divalent alkylene radical comprising 1 to 3 carbon atoms, preferably n-propylene;

[0284] - R5 represents a methyl or ethyl radical, preferably methyl;

[0285] - X represents a divalent radical -N(R6)-,

[0286] - R6 represents a linear or branched alkyl radical comprising 1 to 4 atoms of carbon, preferably n-butyl, and

[0287] - p is equal to 0.

[0288] According to a preferred embodiment, the optionally silylated ionic polyurethane of the invention is derived from ricinoleic acid triglyceride. Ricinoleic acid triglyceride is a triol R2(OH)3 represented as follows:

[0289] In particular, the ionic polyurethane, possibly silylated according to the invention, has the formula (VIII): (VIII)

[0290] in which, among the radicals R13, R14 and R15:

[0291] - one of the radicals is a monovalent radical of formula (IX):

[0292] OO (IX), and U .. f A (9 —C— R ' ■ O "HNCRXR'XK)

[0293] - the other two radicals are monovalent radicals of formula (X): R™ Ô—07 '*N(HXRXH' XR ”) G" on § o ir 0 o “1 h. HU » J II H , — Q-.Ç-.^K^K'-NH-e—0-R' "OC M- R4'-NH-CO-ROC Ml-■ R] f Mr. J. jj i... ..j ,(

[0294] (X),

[0295] in which:

[0296] -R, R', R”, R1, R7 and f are as described above, including the characteristics preferred methods and implementations

[0297] - R2 represents the trivalent radical derived from ricinoleic acid triglyceride, the oxygens directly linked to R2 correspond to the oxygens of the hydroxyl groups carried by the ricinoleic acid chains,

[0298] - a and b are identical or different integers, preferably b is equal to 0.

[0299] Thus, in formula (X), the radical OJ\ can be represented as follows: : > £-OR*-O-|

[0300] It is understood that the values ​​of a and b may vary between the two radicals of formula (X). For example, one of the radicals of formula (X) could have a non-zero value of b, while the other radical of formula (X) would have a zero value of b (i.e., no motif including the R9 radical). Preferably, b is equal to 0 in both radicals of formula (X). In this case, a may be such that the number-average molar mass of the ionic polyurethane of formula (VIII) is between 1500 g / mol and 80000 g / mol, preferably between 2000 g / mol and 30000 g / mol.

[0301] Furthermore, when the motif comprising the radical R9 is present, the distribution of this motif and the motif comprising the radical R2 in the two radicals chosen from R13, R14 and R15 is statistical, and that said polyurethane of formula (VIII) is therefore a statistical copolymer.

[0302] Preferably, the ionic polyurethane, possibly silylated, is of formula (VIII) in which: - R, R', R" are such that the tertiary amine of formula (IV): N(R)(R')(R") is chosen from TEA, DBU, DABCO, DBN, DCHMA, DMDEE, TBD, MTBD, THA and their mixtures, - R1 is such that the diisocyanate of formula (III): OCN-R'-NCO is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, m-xylylene hydrogenated diisocyanate and mixtures thereof, in particular isophorone diisocyanate, - R7 is such that the cyclic anhydride of formula (II) is chosen from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride and mixtures thereof, in particular maleic anhydride and / or tetrapropenylsuccinic anhydride, and - preferably b is equal to zero in both radicals of formula (X).

[0303] More preferably, the ionic polyurethane, possibly silylated, has the formula (VIII) in which: - R, R', R" are such that the tertiary amine of formula (IV): N(R)(R')(R") is chosen from DBU, DABCO, DBN, DCHMA and their mixtures, in particular DCHMA, - R7 is such that the cyclic anhydride of formula (II) is maleic anhydride and / or tetrapropenylsuccinic anhydride, - R1 is such that the diisocyanate of formula (III): OCN-R'-NCO is the isophorone diisocyanate and - preferably b is equal to zero in both radicals of formula (X).

[0304] Preferably, the ionic polyurethane of formula (VIII) is silylated and f represents a monovalent radical of formula (VII), more preferably f represents a monovalent radical of formula (VII) in which:

[0305] - R3 represents a linear or branched divalent alkylene radical comprising 1 to 3 carbon atoms, preferably n-propylene;

[0306] - R5 represents a methyl or ethyl radical, preferably methyl;

[0307] - X represents a divalent radical -N(R6)-,

[0308] - R6 represents a linear or branched alkyl radical comprising 1 to 4 atoms of carbon, preferably n-butyl, and

[0309] - p is equal to 0.

[0310] According to a particularly preferred embodiment, the ionic polyurethane is silylated and of formula (VIII) in which: - R, R', R" are such that the tertiary amine of formula (IV): N(R)(R')(R") is chosen from DBU, DABCO, DBN, DCHMA and their mixtures, in particular DCHMA, - R7 is such that the cyclic anhydride of formula (II) is maleic anhydride and / or tetrapropenylsuccinic anhydride, - R1 is such that the diisocyanate of formula (III): OCN-R'-NCO is the isophorone diisocyanate, - b is equal to zero in both radicals of formula (X), and - f represents a monovalent radical of formula (VII) in which:

[0311] - R3 represents a linear or branched divalent alkylene radical comprising 1 to 3 carbon atoms, preferably n-propylene;

[0312] - R5 represents a methyl or ethyl radical, preferably methyl;

[0313] - X represents a divalent radical -N(R6)-,

[0314] - R6 represents a linear or branched alkyl radical comprising 1 to 4 atoms of carbon, preferably n-butyl, and

[0315] - p is equal to 0.

[0316] Ionic polyurethanes possibly silylated according to the invention can be obtained by following the process according to the invention as described above. Composition of adhesive and / or sealant

[0317] The invention also relates to an adhesive and / or sealant composition comprising the ionic polyurethane possibly silylated described above (comprising a motif (M), in particular of formula (VI), in particular of formula (VIII)), or the composition of ionic polyurethane(s) (D) or (E), preferably (E), according to the invention.

[0318] The content of ionic polyurethane possibly silylated of formula (VI), or of ionic polyurethane(s) included in the composition of ionic polyurethane(s) (D) or (E), is advantageously between 8% and 50% by weight relative to the total weight of the adhesive and / or sealant composition, preferably from 20% to 48% by weight, more preferably from 35% to 45% by weight.

[0319] Advantageously, the adhesive and / or sealant composition according to the invention further comprises a filler.

[0320] 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.

[0321] The filler usable in the adhesive and / or sealant composition according to the invention can be chosen from mineral fillers and mixtures of organic and mineral fillers.

[0322] 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.

[0323] Advantageously, the mineral fillers are formed by the group consisting of clay, quartz, hollow mineral microspheres and carbonate fillers.

[0324] Among hollow mineral microspheres, we can mention hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate.

[0325] Preferably, the mineral fillers are formed by the group consisting of the carbonate fillers.

[0326] 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.

[0327] 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.

[0328] 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.

[0329] 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.

[0330] 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.

[0331] 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.

[0332] 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).

[0333] Unless otherwise indicated, the standards referred to throughout the application are those in force at the date of filing of the application.

[0334] According to a preferred embodiment, the adhesive and / or sealant composition according to the invention comprises: - between 20% and 60% by weight when loaded, preferably between 30% and 58% by weight, more preferably between 40% and 55% by weight, and - between 8% and 50% by weight of ionic polyurethane, possibly silylated, of formula (VI) or of ionic polyurethane(s) included in the composition of ionic polyurethane(s) (D) or (E), preferably between 20% and 48% by weight, more preferably between 35% and 45% by weight,

[0335] the percentages by weight being in relation to the total weight of the adhesive and / or sealant composition.

[0336] The adhesive and / or sealant composition according to the invention may further comprise at least one additive selected from moisture absorbers, adhesion promoters, rheology agents, UV stabilizers and mixtures thereof.

[0337] Advantageously, the composition according to the invention comprises a mixture of additives selected from moisture absorbers and adhesion promoters.

[0338] The moisture absorber is advantageously as described above. Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, vinyltriethoxysilane and mixtures thereof, more preferably vinyltrimethoxysilane.

[0339] The total 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 2% and 4% by weight.

[0340] The adhesion promoter can be chosen from amino-, mercapto- and epoxy-alkoxysilanes, and mixtures thereof. Preferably, the adhesion promoter is chosen from aminoalkoxysilanes and mixtures thereof, more preferably from aminotrimethoxysilanes and mixtures thereof, and even more preferably from aminotrimethoxysilanes and mixtures thereof, for example N-(3-(trimethoxysilyl)propyl)ethylenediamine.

[0341] As an example of an epoxy-alkoxysilane, we can cite (3-glycidyloxypropyl)trimethoxysilane (also known as GLYMO).

[0342] 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), N-(3-(trimethoxysilyl)propyl)ethylenediamine (for example, GENIOSIL® GF9 marketed by WACKER) and mixtures thereof. Preferably, aminotrimethoxysilanes are N-(3-(trimethoxysilyl)propyl)ethylenediamine.

[0343] 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 0.2% and 3% by weight, more preferably between 0.5% and 1.5% by weight.

[0344] The rheology agent can be any rheology agent commonly used in the field of adhesive and / or sealant compositions.

[0345] Advantageously, the rheology agent is chosen from:

[0346] - 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,

[0347] - fumed silica, such as HD K® N20 marketed by WACKER,

[0348] - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such that 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in application FR 1 591 172, and

[0349] - 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.

[0350] 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).

[0351] 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.

[0352] 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).

[0353] 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.

[0354] The adhesive and / or sealant 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 said composition. The UV stabilizer (or antioxidant) is advantageously as described above.

[0355] Advantageously, the adhesive and / or sealant composition further comprises a plasticizer. When the adhesive and / or sealant composition comprises the ionic polyurethane composition(s) (D) or (E) according to the invention, the plasticizer may already be included in said composition (D) or (E). The plasticizer is preferably selected from among the plasticizers mentioned above, in particular from:

[0356] - a mixture of fatty acid methyl esters, in particular fatty acids comprising 18 carbon atoms such as fatty acids from castor oil including ricinoleic acid (for example Esterol A marketed by ARKEMA),

[0357] - a mixture of alkylsulfonic acid and phenol esters, such as the mixture identified by CAS number 91082-17-6 (for example, MESAMOLL® marketed by LANXESS), and

[0358] - their mixture.

[0359] The total plasticizer content in the adhesive and / or sealant composition may vary from 1% to 15% by weight relative to the total weight of said composition, preferably from 3% to 12% by weight, more preferably from 5% to 10% by weight.

[0360] According to one embodiment, the adhesive and / or sealant composition according to the invention comprises:

[0361] - between 8% and 50% by weight of ionic polyurethane, possibly silylated formula (VI), in particular formula (VIII), or ionic polyurethane(s) included in the composition of ionic polyurethane(s) (D) or (E),

[0362] - between 20% and 60% by weight of a charge,

[0363] - between 1% and 15% by weight of plasticizer,

[0364] - between 0.5% and 5% by weight of moisture absorber, and

[0365] - between 0.1% and 5% by weight of adhesion promoter,

[0366] the percentages by weight being in relation to the total weight of the adhesive and / or sealant composition.

[0367] 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.

[0368] The ingredients of this embodiment and their particular contents are as described above, including preferred characteristics and embodiments.

[0369] Advantageously, no crosslinking catalyst is added to the adhesive and / or sealant composition according to the invention.

[0370] Indeed, the ionic polyurethane, possibly silylated, of formula (VI) or included in the composition of ionic polyurethane(s) (D) or (E), is sufficient on its own to catalyze the crosslinking reaction. Thus, it is not necessary to add a crosslinking catalyst to said ionic polyurethane, possibly silylated.

[0371] As a result, the content of crosslinking catalyst is advantageously less than 0.05% by weight relative to the total weight of the adhesive and / or sealant composition, preferably less than 0.02% by weight, more preferably less than 0.015% by weight.

[0372] By “crosslinking catalyst” is meant a catalyst known to those skilled in the art for the condensation of silanol, or for the crosslinking of polyurethane.

[0373] Examples of crosslinking catalysts for silanol condensation include:

[0374] - organic derivatives of titanium such as titanium acetyl acetonate, the titanium tetrapropylate, titanium tetrabutylate,

[0375] - organic zirconium derivatives such as zirconium acetyl acetonate, the zirconium tetrapropylate, zirconium tetrabutylate,

[0376] - amines such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5- diazabicyclo[4.3.0]non-5-ene (DBN), diethyl ether-2,2'-morpholine (DMDEE), l,4-diazabicyclo[2.2.2]octane (DABCO), l,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD),

[0377] - zinc carboxylate-based catalysts (for example K-KAT® 670 marketed by KING INDUSTRIES),

[0378] - tin-based catalysts such as compounds derived from dioctyltin or dibutyltin.

[0379] Examples of crosslinking catalysts for the crosslinking of polyurethane include: - carboxylates, notably bismuth and / or zinc neodecanoate, - amines such as DABCO or DMDEE, - organic derivatives of titanium such as titanium acetyl acetonate, titanium tetrapropylate, titanium tetrabutylate, - organic zirconium derivatives such as zirconium acetyl acetonate, zirconium tetrapropylate, zirconium tetrabutylate, - tin-based catalysts such as compounds derived from dioctyltin or dibutyltin (in particular dibutyltin or dioctyltin dilaurate).

[0380] Advantageously, the adhesive and / or sealant composition according to the invention does not comprise a solvent, the solvent being as defined above. In particular, said composition comprises less than 3% by weight of water relative to the total weight of said composition, preferably less than 1% by weight.

[0381] The adhesive and / or sealant 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.

[0382] The adhesive and / or sealant composition according to the invention can be prepared by simply mixing its ingredients.

[0383] Preferably, the adhesive and / or sealant composition according to the invention is prepared at atmospheric pressure and at a temperature between 10°C and 80°C, more preferably between 18°C ​​and 60°C.

[0384] An example of preparing the adhesive and / or sealant composition according to the invention is described in Example 7. Other objects of the invention

[0385] The invention also relates to the use of the adhesive and / or sealant composition according to the invention, as an adhesive and / or sealant, preferably as a sealant.

[0386] In addition, the invention also relates to an article comprising the composition of adhesive and / or sealant according to the invention, in airtight packaging, protected from air.

[0387] Preferably, the airtight packaging is a polyethylene bag or a polyethylene cartridge with a lid.

[0388] Furthermore, the invention relates to a method for assembling two substrates comprising:

[0389] - the coating of the adhesive and / or sealant composition according to the invention, on the minus one of the two substrates to be assembled; then

[0390] - the effective contacting of the two substrates.

[0391] Preferably, the assembly process according to the invention is carried out at ambient temperature (in particular between 18°C ​​and 25°C, for example at about 23°C).

[0392] By "about X", we are aiming for plus or minus 10% of the value of X.

[0393] 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, the polyethylene, polypropylene, polyesters, epoxy resins, or even metal and composite substrates coated with paint (for example, in the automotive field).

[0394] All the embodiments described above can be combined with each other. In particular, the various aforementioned ingredients of the adhesive and / or sealant composition according to the invention, especially the preferred embodiments, can be combined with each other.

[0395] 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

[0396] The following ingredients were used:

[0397] - castor oil (CAS: 8001-79-4) marketed by ARKEMA: mixture of compounds comprising about 89% by weight, on the total weight of the mixture, of ricinoleic acid triglyceride having a molar mass of 933 g / mol, castor oil having a hydroxyl number IOH between 157 and 167 mg KOH / g, i.e. a functionality of about 2.7 (i.e. an average of 2.7 -OH groups per molecule of ricinoleic acid triglyceride);

[0398] - maleic anhydride marketed by Sigma Aldrich: molar mass equal to 98.06 g / mol;

[0399] - isophorone diisocyanate (IPDI) marketed by Covestro: molar mass equal to 222.3 g / mol (CAS number: 4098-71-9);

[0400] - Borchi®Kat 315 marketed by OMG Borchers: bismuth neodecanoate molar mass equal to 722.75 g / mol;

[0401] - Dynasylan® 1189 marketed by Evonik: N-(3- (trimethoxysilyl)propyl)butylamine with a molar mass of 235.4 g / mol;

[0402] - DCHMA marketed by ARKEMA: N,N-dicyclohexylmethylamine of mass molar equal to 195.34 g / mol;

[0403] - GENIOSIL® GF9 marketed by Wacker: N-(3- (trimethoxysilyl)propyl)ethylenediamine with a molar mass of 222.36 g / mol, adhesion promoter;

[0404] - Mesamoll® marketed by Lanxess: phenol alkylsulfonates (CAS: 91082-17-6);

[0405] - Esterai A marketed by ARKEMA: Cl6- fatty acid methyl esters C18 and C18 unsaturated fatty acids (CAS: 67762-38-3);

[0406] - VTMO marketed by Sigma Aldrich: vinyltrimethoxysilane with a molar mass equal to 148.23 g / mol, moisture absorber;

[0407] - CALOFORT® SV14 marketed by Specialty Minerals: calcium carbonate calcium stearate coated precipitate, having an average particle size of 70 nm;

[0408] - Irganox® 245 marketed by BASF: bis[3-(5-tert-butyl-4-hydroxy-m- tolyl)propionate] of ethylenebis(oxyethylene) (CAS: 36443-68-2) with a molar mass of 586.8 g / mol;

[0409] - PTSI marketed by Sigma Aldrich: p-toluenesulfonyl isocyanate (CAS: 4083-64-1) with a molar mass equal to 197.21 g / mol. Measurement methods

[0410] The water content of the ingredients, including castor oil (modified or unmodified), Mesamoll® and Esterol A, is measured according to a Karl Fischer coulometric method using HYDRANAL™ as a titrant, the equivalence point being detected electrometrically.

[0411] The hydroxyl number (denoted I0H) of modified castor oil, and more generally of a polyol, represents the number of hydroxyl functions per gram of polyol and is expressed as the equivalent number of milligrams of potassium hydroxide (KOH) used in the determination of hydroxyl functions, determined by titration according to ISO 14900:2017.

[0412] The equivalent molar number of -OH groups (in mol) of a mass m of polyol (in g) is equal to (IoH*m) / 56000, where IoH is the hydroxyl index in mg KOH / g of the polyol.

[0413] The viscosity of the silylated polymers prepared in the examples below is measured according to a Brookfield type method at 23°C (Brookfield rotational viscometer DV-I Prime, S28 needle).

[0414] 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 excess amine is also titrated automatically with hydrochloric acid.

[0415] 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 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).

[0416] Tensile strength and elongation at break were measured in accordance with ISO 37 (2012), at a constant speed of 100 mm / min.

[0417] In particular, the following conditions were applied:

[0418] 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.

[0419] 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).

[0420] 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:

[0421] - the elongation at break (expressed in %) which is the elongation of the test specimen corresponding to the stretch observed at the time of rupture, and

[0422] - the tensile strength (in MPa) which is the tensile stress at which the test specimen breaks (also called TS for Tensile Strength in English).

[0423] The measurement is repeated for 5 test tubes, and the corresponding average of the results obtained is calculated.

[0424] The curing depth is determined by filling a Teflon channel with sealant of increasing depth, ranging from 1 mm to 10 mm. The length-to-depth ratio of 20:1 is constant along the entire length of the channel. For example, at a length of 2 cm, the channel depth is 1 mm; at a length of 10 cm, the channel depth is 5 mm; and at a length of 20 cm, the channel depth is 10 mm. The channel has the following dimensions: - Block dimensions: 25 x 5 x 2 cm, - dimensions of the recess: 20 x 2 x 1 mm to 10 mm.

[0425] After filling with the sealant to be tested, the gutter is left in controlled humidity and temperature conditions (23°C and 50% relative humidity) for 10 days.

[0426] After these 10 days, the strip is pulled on the side of the thinnest part (i.e., 1 mm) until the non-crosslinked core is reached, i.e., a soft, non-cohesive part, which tends to remain in the groove. The corresponding fully crosslinked thickness is noted.

[0427] Example 2: Preparation of modified castor oil PTSI (comparative)

[0428] In a 250 mL reactor, 84.7 g of castor oil are introduced (corresponding to a molar equivalent of 0.245 mol of -OH groups), and then the reactor is left under vacuum (0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate the castor oil. The water content of the castor oil is then less than or equal to 0.02% by weight relative to the total weight of the castor oil.

[0429] The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 15.3 g of PTSI (i.e. a molar equivalent number of -NCO groups equal to 0.078 mol) and 0.03 g of Borchi®Kat 315. The mixture is kept under stirring until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy (around 2260 cm1).

[0430] The polyol obtained has an IOHd' of approximately 92 mg KOH / g.

[0431] Example 3: Preparation of modified castor oil with maleic anhydride (invention)

[0432] In a 250 mL reactor, 87.3 g of castor oil are introduced (corresponding to a molar equivalent of 0.253 mol of -OH groups), and the reactor is then left under vacuum (0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate the castor oil. The water content of the castor oil is then less than or equal to 0.02% by weight relative to the total weight of the castor oil.

[0433] The reactor is then cooled to 90°C in order to introduce, under nitrogen and at atmospheric pressure, 12.7 g of maleic anhydride (corresponding to a molar equivalent number of anhydride functions equal to 0.130 mol). The mixture is kept under stirring until the characteristic bands of the anhydride are no longer detectable by infrared spectroscopy (1849 cm⁻¹ and 1779 cm⁻¹).

[0434] The polyol obtained has an I0H of approximately 100 mg KOH / g.

[0435] Example 4: Preparation of a silylated polyurethane PO (comparative)

[0436] In a 250 mL reactor, 59.94 g of PTSI modified castor oil prepared in Example 2 (corresponding to a molar equivalent of 0.098 mol of -OH groups, determined by its I0H) and 14.91 g of Mesamoll® 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 these compounds. The water content of the mixture of these compounds is then less than or equal to 0.02% by weight relative to the total weight of said mixture.

[0437] The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 15.06 g of IPDI (i.e. a molar equivalent number of -NCO groups equal to 0.135 mol), 0.03 g of Borchi®Kat 315 and 0.5 g of Irganox® 245. 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, which corresponds to the excess of -NCO groups introduced relative to the -OH groups (0.135-0.098=0.037 mol of excess -NCO groups, i.e. 0.037*42=1.55 g of -NCO groups).

[0438] 8.56 g of Dynasylan® 1189 are then introduced, corresponding to a ratio The molar concentration of -NH / -NC0 is equal to 1 (the molar equivalent number of -NH groups being equal to 0.036 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).

[0439] Finally, 1 g of VTMO is added at approximately 40°C under stirring.

[0440] Approximately 100 g of silylated polyurethane PO are obtained and the silylated polyurethane PO is packaged in polyethylene cartridges protected from moisture.

[0441] Example 5: Preparation of an ionic silylated polyurethane P2 (invention)

[0442] Ionic silylized polyurethane P2 is prepared similarly to silylized polyurethane PO, except that maleic anhydride-modified castor oil (prepared in Example 3) is used instead of PTSI-modified castor oil. Furthermore, DCHMA is added, in a DCHMA / maleic anhydride-modified castor oil molar ratio of 1, after the reaction with IDPI.

[0443] In a 250 mL reactor, 52.23 g of maleic anhydride-modified castor oil (corresponding to a molar equivalent of 0.093 mol of -OH groups, determined by its IOH) and 15.07 g of Mesamoll® 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 these compounds. The water content of the mixture of these compounds is then less than or equal to 0.02% by weight relative to the total weight of said mixture.

[0444] The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 14.08 g of IPDI (i.e. a molar equivalent number of -NCO groups equal to 0.127 mol), 0.03 g of Borchi®Kat 315 and 0.5 g of Irganox® 245. 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, which corresponds to the excess of -NCO groups introduced relative to the -OH groups (0.127-0.093=0.034 mol of excess -NCO groups, i.e. 0.034*42=1.4 g of -NCO groups).

[0445] 9.28 g of DCHMA are then added at 40°C, and stirring is left for 30 min.

[0446] 7.81 g of Dynasylan® 1189 are then introduced, corresponding to a ratio molar -NH / -NCO 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.

[0447] Finally, 1 g of VTMO is added at approximately 40°C under stirring.

[0448] Approximately 100 g of ionic silylated polyurethane P2 are obtained and the ionic silylated polyurethane P2 is packaged in polyethylene cartridges protected from moisture.

[0449] Example 6: Characteristics of comparative silylated polyurethanes and ionic silylated polyurethanes according to the invention

[0450] A comparative silylated polyurethane PI is prepared in a similar manner to Example 4, using the compounds in the quantities indicated in Table 1 below.

[0451] Two ionic silylated polyurethanes P3 and P4 according to the invention are prepared in a manner similar to Example 5, using the compounds in the quantities indicated in Table 1 below. For the ionic silylated polyurethane P4, Esterol A is used instead of Mesamoll®.

[0452] [Tables 1] PO (comp.) PI (comp.) P2 (inv.) P3 (inv.) P4 (inv.) PTSI modified castor oil (g) 59.94 52.78 - - - Maleic anhydride modified castor oil (g) - - 52.23 46.84 52.23 Mesamoll® (g) 14.91 15 15.07 15.02 - Esterol A (g) - - - - 15.07 Irganox® 245 (g) 0.5 0.5 0.5 0.5 0.5 Borchi®Kat 315 (g) 0.03 0.03 0.03 0.03 0.03 IPDI (g) 15.06 16.44 14.08 15.02 14.08 DCHMA (g) - - 9.28 8.57 9.28 Dynasylan® 1189 (g) 8.56 14.25 7.81 13.02 7.81 VTMO (g) 1 1 1 1 1 TOTAL (g) 100 100 100 100 100 %NCO* 1.7 3 1.7 3 1.7 Viscosity at 23°C (Pa.s) 785 275 310 265 85

[0453] *Percentage by weight relative to the total weight of modified castor oil, Mesamoll® (or Esterol A), Irganox® 245, Borchi®Kat 315 and 1TDPI introduced into the reactor.

[0454] The viscosities of the ionic silylated polyurethanes according to the invention are lower than the corresponding comparative silylated polyurethanes (comparison of PO and P2, and of PI and P3).

[0455] Replacing Mesamoll® with Esterol A further reduces viscosity (comparison of P2 and P4).

[0456] Example 7: Preparation of sealants and characteristics

[0457] The PO to P4 polymers prepared previously are used to prepare sealants (respectively S0 to S4), the composition of which is as follows: - 46% of a PO, PI, P2, P3 or P4 polymer, 50% of CALOFORT® SV 14, 3% of VTMO, and 1% of GENIOSIL® GF9,

[0458] the percentages being percentages by weight on the total weight of the sealant.

[0459] Initially, all ingredients except GENIOSIL® GF9 are added at room temperature (approximately 23°C) and atmospheric pressure in a high-speed mixer and then mixed for 2 min.

[0460] GENIOSIL® GF9 is then added and everything is mixed for 2 min.

[0461] The stirring speed is approximately 2000 rpm (revolutions per minute).

[0462] The resulting sealants are packaged in polyethylene cartridges.

[0463] The properties of the S0 to S4 sealants (measured in accordance with Example 1) are summarized in Table 2 below.

[0464] [Tables2] Mastic SO (comp.) SI (comp.) S2 (inv.) S3 (inv.) S4 (inv.) Curing time (min) 105 85 25 5 45 Tensile strength (MPa) 2.0 1.5 3.0 4.5 3.5 Elongation at break (%) 25 50 50 25 50 Curing depth (mm) 3 3.5 10 10 10

[0465] Comparative S0 and SI sealants, prepared respectively from comparative silylated polyurethanes PO and PI (and without crosslinking catalyst), have crosslinking times of 105 min and 85 min respectively.

[0466] This crosslinking time decreases by more than half when the comparative silylated polyurethane is replaced by an ionic silylated polyurethane according to the invention (comparison of S0 and S2, and of SI and S3).

[0467] This shows that the ionic silylated polyurethane according to the invention makes it possible to accelerate crosslinking compared to the comparative silylated polyurethane, without it being necessary to add a crosslinking catalyst in the sealant.

[0468] In addition, the replacement of Mesamoll® with Esterol A during the preparation of ionic silylated polyurethane has an influence on the crosslinking time (comparison of S2 and S4).

[0469] Furthermore, the use of ionic silylated polyurethanes P2 to P4 according to the invention, in addition to the advantage of being obtained from a bio-based polyol, improves the tensile strength of the resulting sealants. Indeed, the S2 to S4 sealants according to the invention exhibit a higher tensile strength than the comparative S0 and SI sealants. 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.

[0470] Furthermore, the use of ionic silylated polyurethanes P2 to P4 according to the invention improves the crosslinking throughout the thickness of the resulting sealants. Indeed, the S2 to S4 sealants according to the invention are crosslinked throughout the entire depth of the joint (10 mm), unlike the comparative S0 and SI sealants, which are only partially crosslinked through their thickness (3 and 3.5 mm).

Claims

Demands

1. A process for preparing an ionic polyurethane composition comprising: (i) an esterification step of a bio-based polyol (A) with a cyclic anhydride to form a polyol composition (B) comprising at least one polyol (B) having one or more carboxylic acid groups, then (ii) a reaction step of the polyol composition (B) with a polyisocyanate to form a -NCO terminal group polyurethane composition, then (iii) a reaction step of the -NCO terminal group polyurethane composition formed in step (ii) with a tertiary amine having a pKa at 25 °C greater than 8, said pKa being the pKa of the conjugate acid of the tertiary amine, to form an ionic polyurethane composition (D).

2. A process according to claim 1, wherein the polyol (A) is lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or a fatty acid glyceride, the fatty acid glyceride comprising several hydroxyl groups.

3. A method according to claim 1 or 2, wherein the cyclic anhydride is selected from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride, adipic anhydride, glycolic anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, 1-methyl-2-(2'-carboxyethyl)maleic anhydride, octenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, 1,2-cis-cyclohexanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, trimellitic anhydride and their mixtures.

4. A process according to any one of claims 1 to 3, wherein the polyisocyanate is selected from pentamethylene diisocyanate, hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, dimeryl diisocyanate, L-lysine diisocyanate methyl ester, L-lysine diisocyanate ethyl ester, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 4,4'- and / or 2,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, m-hydrogenated xylylene diisocyanate and mixtures thereof.

5. A method according to any one of claims 1 to 4, wherein step (ii) is carried out in the presence of a plasticizer.

6. A method according to any one of claims 1 to 5, wherein the tertiary amine is selected from triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, l,4-diazabicyclo[2.2.2]octane, l,5-diazabicyclo[4.3.0]non-5-ene, N,N-dicyclohexylmethylamine, diethyl ether-2,2'-morpholine, triazabicyclodecene, methyltriazabicyclodecene, trihexylamine and mixtures thereof.

7. A process according to any one of claims 1 to 6, further comprising a step (iv) of silylating the -NCO-terminated ionic polyurethane composition(s) (D) with a silylated compound to form a silylated ionic polyurethane composition(s) (E), the silylated compound having formula (V): (V) wherein: - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms, - R4 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, and when p is equal to 2, the R4 radicals are either identical or different, - R5 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 carbon, and when p is equal to 0 or 1, the R5 radicals are either identical or different,two OR5 groups that can 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 -N(R6)-, -NH- and -S-, - R6 represents a hydrocarbon radical comprising 1 to 20 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more rings possibly aromatic,

8.

9.

10. and may also include 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. Composition of ionic polyurethane(s) with terminal groups -NCO (D) capable of being obtained by the process according to any one of claims 1 to 6. Composition of silylated ionic polyurethane(s) (E) that can be obtained by the process according to claim 7. Ionic polyurethane, possibly silylated, comprising a motif (M) of the type: in which: - R, R', R" identical or different, each represent a saturated or unsaturated hydrocarbon radical, possibly comprising one or more heteroatoms selected from N, O and S, and R and R' and / or R and R" and / or R' and R" capable of forming a heterocycle with the nitrogen atom to which they are attached, in particular R, R', R" are such that the tertiary amine of formula (IV): N(R)(R')(R") is selected from the tertiary amines described in claim 6, - R1 is directly bonded to a nitrogen atom and is a divalent hydrocarbon radical comprising from 4 to 45 carbon atoms, and optionally comprising one or more heteroatoms selected from oxygen, sulfur and nitrogen, in particular R1 is such that the diisocyanate of formula (III): OCN-R'-NCO is selected from the diisocyanates described in claim 4, - R2 is a plurivalent hydrocarbon radical possibly comprising one or more oxygen atoms, and represents a radical with a valence greater than or equal to 3, in particular R2 is such that the polyol of formula (I): R" ~[~QH I — n is bio-based and preferably chosen from the polyols described in claim 2,

11. - R7 is a saturated or unsaturated, possibly branched, divalent hydrocarbon radical, which may comprise one or more rings, possibly aromatic, and which may comprise one or more heteroatoms selected from oxygen and sulfur, preferably one or more heteroatoms selected from oxygen, in particular R7 is such that the cyclic anhydride of formula (II): HAS R7' is chosen from among the cyclic anhydrides described in claim 3, - t and u are non-nuisable integers, u being greater than or equal to 2, preferably t is equal to 1 and u is equal to 2. Ionic polyurethane, optionally silylated according to claim 10, being of formula (VI): ■“ OO „ lï fO-O-Qy-W soo: is i! i4-RL--NH----<4--o----^ 0 ■iH-CO- ? o !, if K'-OC--NH - R!-- -f - (VI) in which: - R, R', R” are as described in claim 10, - R1 is as described in claim 10, - R2 is as described in claim 10, and represents a radical with a valence greater than or equal to 3, - R7 is as described in claim 10, - R9 represents a divalent radical and is such that the alcohol of The formula HO-R9-OH is selected from a poly(famesene) diol, isosorbide, polyethylene glycol, polypropylene glycol, polyester diol, polybutadiene diol, polyacrylate diol, and polysiloxane diol, preferably polyethylene glycol or polypropylene glycol. - v is a non-zero integer, - t and u are non-null integers, u being greater than or equal to 2, preferably t is equal to 1 and u is equal to 2, - c is an integer greater than or equal to 0, preferably equal to 0, - Y represents f or a carbamate group through which the polyurethane chain is extended, the nitrogen of said carbamate group being directly linked to R1, - f represents an isocyanate group -NCO or a monovalent radical of formula (VII): O — NH— C™ X- R3- Si(R%(OR%p in which X, R3, R4, R5 and p are as defined above, preferably f represents a monovalent radical of formula (VII).

12. Ionic polyurethane optionally silylated according to claim 11, having formula (VIII): G OR13 (VIII) in which, among the radicals R13, R14 and R15: - one of the radicals is a monovalent radical of formula (IX): ü Q (IX), and H. H © © —C— RO HN(R)(R the other two radicals are monovalent radicals of formula (X): (X), in which:

13.

14. - R, R', R”, R1, R7 and f are as described in claim 11, - R2 represents the trivalent radical derived from the ricinoleic acid triglyceride, the oxygens directly linked to R2 corresponding to the oxygens of the hydroxyl groups carried by the ricinoleic acid chains, - a and b are identical or different integers, preferably b is equal to 0. Adhesive and / or sealant composition comprising ionic polyurethane optionally silylated according to any one of claims 10 to 12, or the composition of ionic polyurethane(s) (D) or (E) according to one of claims 8 or 9, preferably (E). Adhesive and / or sealant composition according to claim 13, further comprising a filler.