Optionally silylated ionic polyurethane(s)

Abstract

The present invention relates to a method for preparing a composition of ionic polyurethane(s), comprising: (i) a step of esterifying a bio-based polyol (A) with a cyclic anhydride to form a composition of polyol(s) (B) comprising at least one polyol (B) having one or more carboxylic acid groups, followed by (ii) a step of reacting the composition of polyol(s) (B) with a polyisocyanate to form a composition of polyurethane(s) having –NCO end groups, followed by (iii) a step of reacting the composition of polyurethane(s) from step (ii) with a tertiary amine having a pKa greater than 8 at 25°C, this pKa being the pKa of the conjugate acid of the tertiary amine, to form a composition of ionic polyurethane(s). The present invention further relates to a composition of ionic polyurethane(s) having –NCO end groups, a composition of silylated ionic polyurethane(s), an optionally silylated ionic polyurethane, and an adhesive and / or mastic composition.

Description

[0001] Ionic polyurethane(s) possibly silylated

[0002] Field of invention

[0003] The present invention relates to a process for preparing a composition of optionally silylated ionic polyurethane(s), a composition of ionic polyurethane(s) with -NCO end groups, a composition of silylated ionic polyurethane(s), an optionally silylated ionic polyurethane and an adhesive and / or sealant composition.

[0004] Technical background

[0005] Optionally silylated polyurethanes are generally used as adhesives, sealants, coatings, for example in the aeronautics, automotive or construction industries. When polyurethanes are silylated, they generally comprise alkoxysilane terminal groups linked, directly or indirectly, to a polyurethane main chain. Industrially, they can be obtained from the reaction of a prepolymer with isocyanate terminations and a silylated compound comprising alkoxysilane functions.

[0006] The crosslinking reaction of these compositions based on possibly silylated polyurethane occurs in the presence of humidity: by formation of a urea bond between the isocyanate groups of the polyurethane molecules, or by formation of a siloxane bond (—Si— O— Si— ) occurring after hydrolysis of the alkoxysilane groups of the silylated polyurethane molecules. These bonds unite the polymer chains into a solid three-dimensional network.

[0007] Alkoxysilane-terminated polyurethane compositions (also known as silylated polyurethane) have the advantage of being free of free isocyanates (once the silylated polyurethane is formed). These compositions therefore constitute a toxicologically preferred alternative to isocyanate-terminated polyurethane compositions.

[0008] However, the crosslinking time of these silylated polyurethanes, and of polyurethanes in particular obtained from aliphatic polyisocyanate (not comprising an aromatic structure) such as isophorone diisocyanate, must be accelerated to meet the needs of users.

[0009] For this purpose, it is possible to add a crosslinking catalyst to the compositions comprising optionally silylated polyurethanes. Generally, the crosslinking catalyst used in adhesive and / or sealant compositions based on optionally silylated polyurethanes is a metal catalyst, in particular based on tin such as dibutyltin dilaurate (DBTDL), dibutyltin diacetate or dibutyltin or dioctyltin bis(acetylacetonate). However, the toxicity of these catalysts, in particular those based on tin, is increasingly highlighted, leading manufacturers to limit, and even avoid their use, especially since these metal catalysts remain in the finished products.

[0010] An alternative to metal crosslinking catalysts can be organic crosslinking catalysts, including 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 yellow discoloration in the finished products due to the migration of the catalyst to the surface of the adhesive and / or sealant.

[0011] Furthermore, the polyurethanes that may be silylated on the market are generally obtained from raw materials derived from petroleum resources.

[0012] However, this dependence on fossil resources risks limiting, or even preventing, the production of monomers and therefore polymers in the long term. In addition, some petroleum-based raw materials are criticized from an ecological and economic perspective, which increases the regulatory restrictions concerning them.

[0013] Currently, the bio-sourced possibly silylated polyurethanes 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).

[0014] There is therefore a need to manufacture new polyurethanes, possibly silylated, which are at least partially bio-sourced, and which can crosslink quickly, even without adding a metallic or organic crosslinking catalyst (DBU, TBD or DABCO type) to the composition comprising it.

[0015] The present invention therefore aims to provide an optionally silylated polyurethane which is self-catalyzed and at least partially biosourced.

[0016] Summary of the invention

[0017] The present invention relates to a process for preparing a composition of ionic polyurethane(s) comprising: (i) a step of esterifying a biosourced polyol (A) with a cyclic anhydride to form a composition of polyol(s) (B) comprising at least one polyol (B) having one or more carboxylic acid groups, then

[0018] (ii) a step of reacting the polyol composition(s) (B) with a polyisocyanate to form a polyurethane composition(s) with -NCO end groups, then

[0019] (iii) a step of reacting the polyurethane composition(s) resulting from 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(s).

[0020] The invention also relates to a composition of ionic polyurethane(s) with -NCO (D) end groups capable of being obtained by the process according to the invention comprising steps (i) to (iii) as defined in the present application.

[0021] The invention also relates to a composition of silylated ionic polyurethane(s) (E) capable of being obtained by the process according to the invention comprising steps (i) to (iv) as defined in the present application.

[0022] The invention relates in particular to an optionally silylated ionic polyurethane.

[0023] The invention also relates to an adhesive and / or sealant composition comprising the optionally silylated ionic polyurethane described in the present application, or the composition of ionic polyurethane(s) (D) or (E) according to the invention.

[0024] Surprisingly, it was found that the optionally silylated polyurethanes according to the invention can crosslink rapidly, even without adding a metallic or organic crosslinking catalyst, while being at least partially bio-sourced.

[0025] Description of the invention

[0026] The present invention relates to a process for preparing a composition of ionic polyurethane(s) comprising:

[0027] (i) a step of esterification of a biosourced polyol (A) with a cyclic anhydride to form a composition of polyol(s) (B) comprising at least one polyol (B) having one or more carboxylic acid groups, then

[0028] (ii) a step of reacting the polyol composition(s) (B) with a polyisocyanate to form a polyurethane composition(s) with -NCO end groups, then (iii) a step of reacting the polyurethane composition(s) resulting from 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 a composition of ionic polyurethane(s).

[0029] This process does not exclude the presence of additional steps (before, after and / or between the steps described above). For example, step (iii) can be carried out after the polyurethane composition(s) resulting from step (ii) has been formulated in the form of an adhesive and / or sealant (i.e. after adding one or more additives usually used in the field of adhesive and / or sealant compositions such as fillers).

[0030] By "polyurethane composition(s) resulting from step (ii)" is meant the polyurethane composition(s) with -NCO end groups obtained directly at the end of step (ii) or a derived composition (in particular a composition of ionic polyurethane(s) obtained during step (iii) or a composition of silylated polyurethane(s) obtained during step (iv) described below).

[0031] Thus, when the process according to the invention comprises a silylation step (iv), step (iii) can be carried out on the polyurethane composition(s) obtained directly at the end of step (ii) and followed by the silylation step (iv), or the silylation step (iv) can be carried out on the polyurethane composition(s) obtained directly at the end of step (ii) and followed by step (iii). It is preferable that the silylation step (iv) is carried out before the polyurethane composition(s) resulting from step (ii) has been formulated in the form of a putty, while step (iii) can be carried out before or after the polyurethane composition(s) resulting from step (ii) has been formulated in the form of a putty.

[0032] In particular, the process for preparing a composition of ionic polyurethane(s) comprises:

[0033] (i) a step of esterification of a biosourced polyol (A) with a cyclic anhydride to form a composition of polyol(s) (B), then

[0034] (ii) a step of reacting the polyol composition(s) (B) with a polyisocyanate to form a polyurethane composition(s) with -NCO end groups, then

[0035] (iii) a step of reacting the polyurethane composition(s) with -NCO end groups 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 -NCO end groups (D).

[0036] 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.

[0037] Said functionality f(OH) can be determined by measuring the hydroxyl number (denoted IOH) of the polyol, for example by titrimetry according to ISO 14900:2017. Said functionality f(OH) can then be calculated as follows: f(OH)= (10H*M P oiyoi) / 56000, where IOH is the hydroxyl number in mg KOH / g of the polyol and M po iyoi is the molar mass in g / mol of the polyol. When the polyol is a polymer, its molar mass is its number-average molar mass Mn.

[0038] In the context of the present invention, the number-average molar mass Mn can be measured by methods well known to those skilled in the art, for example by NMR or by size exclusion chromatography using polystyrene-type standards.

[0039] R 2 -TOH~|

[0040] The polyol (A) can be represented by the formula (I): n in which

[0041] R 2is a multivalent hydrocarbon radical optionally comprising one or more oxygen atoms, and n is a value corresponding to the functionality f(OH) as defined above. Thus, R 2 does not include a heteroatom other than oxygen, such as nitrogen. Furthermore, when the radical R 2 comprises one or more oxygen atoms, said oxygen atom(s) are not present at the end of the chain. In other words, the free valences of the radical R 2 linked to the oxygen atoms of the n hydroxyl groups, each come from a carbon atom.

[0042] 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 contrary indication, the same definition.

[0043] By "bio-sourced" we mean obtained from resources of biological origin, in particular plants, and which may have undergone chemical modifications.

[0044] The chemical modifications may 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 glyceride) with propylene oxide or ethylene oxide. According to 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.

[0045] It is understood that the fatty acid glyceride mentioned in the present invention relates to a glyceride of which at least one of said fatty acids comprises one or more hydroxyl groups.

[0046] Lignin is commonly found in wood, but also in other plant resources. It is a polyphenolic macromolecule containing several hydroxyl groups.

[0047] Sucrose is mainly extracted from sugar cane and sugar beet. It is a disaccharide of glucose and fructose.

[0048] Glucose can be obtained from various plants. It is a monosaccharide consisting of six carbon atoms.

[0049] Fructose is found primarily in fruits and honey. It is also a monosaccharide with six carbon atoms.

[0050] Starch is found in many plants. It is a mixture of amylose and amylopectin, and its molecular formula is (C6Hio05)n where n is an integer usually between 500 and 1000.

[0051] Cellulose is usually found in the wall of plant cells. It is a linear polysaccharide made up of glucose units.

[0052] Hemicellulose is found primarily in plant cell walls and wood. It is a linear or branched polysaccharide consisting of sugar units that may be the same or different, but not composed solely of glucose units.

[0053] 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.

[0054] In the context of the invention, the ranges of values ​​are understood to be inclusive. For example, the range "between 4 and 28" includes in particular the values ​​4 and 28. By "glyceride" is meant an ester obtained from glycerol and fatty acids, which may be identical 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.

[0055] The fatty acid glyceride may be introduced directly in the form of a plant resource (for example, castor oil may be used in step (i)). The plant resource may also be previously modified so as to obtain fatty acid glycerides not found directly in nature; for example, hydroxyl groups may be introduced onto the fatty acid chains (such as by double bond epoxidation) and / or ether functions may be introduced onto the fatty acid chains (such as by reaction of the hydroxyl groups carried by the fatty acids with propylene oxide or ethylene oxide).

[0056] Advantageously, the polyol (A) is lignin, sucrose, starch, hemicellulose, cellulose and / or a fatty acid glyceride.

[0057] 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 a hydroxylated vegetable oil 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 grape oil, etc. A vegetable oil is said to be "hydroxylated" when it has been modified so as to introduce hydroxyl groups onto the fatty acid chains of the glycerides. The hydroxyl group may be directly or indirectly, preferably directly, bonded to a carbon atom of the fatty acid chain. For example, when the hydroxyl group is indirectly bonded, it may have been introduced by hydroformylation / hydrogenation of a double bond.

[0058] 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.

[0059] Advantageously, at least 50% by weight of bio-sourced polyol(s) (A), in particular lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or fatty acid glyceride, 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) which is predominantly bio-sourced, i.e. obtained from resources of biological origin, in particular plant-based.

[0060] Advantageously, at least 50% by weight of fatty acid glyceride, in particular ricinoleic acid (tri)glyceride, 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.

[0061] By "cyclic anhydride" is meant a molecule comprising an anhydride function (-C(O)-OC(O)-) engaged in a cycle. In particular, the cyclic anhydride is of formula (II):

[0062] (H) in which R 7 is a saturated or unsaturated, optionally branched, divalent hydrocarbon radical, which may comprise one or more optionally aromatic cycles, and optionally comprising one or more heteroatoms chosen from oxygen and sulfur, preferably optionally one or more heteroatoms chosen from oxygen. Thus, R 7does not include a heteroatom other than oxygen and / or sulfur, such as nitrogen.

[0063] 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.

[0064] 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 olefinic 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, 2-(2'-carboxyethyl)maleic anhydride, 1-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.

[0065] Advantageously, the cyclic anhydride is 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, 1-methyl-2-(2'-carboxyethyl)maleic anhydride, octenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, 1,2-cis-cyclohexanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, trimellitic and their mixtures.

[0066] 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, 1-methyl-2-(2'-carboxyethyl)maleic anhydride, octenylsuccinic anhydride and mixtures thereof.

[0067] 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.

[0068] The polyol 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), a portion of the hydroxyl groups of the polyol (A) reacts with the anhydride function of the cyclic anhydride to lead to the formation of a polyol composition (B) comprising at least one polyol (B) having one or more carboxylic acid groups (-C(O)OH).

[0069] By "polyol (B)" is meant a molecule having a functionality f(OH) greater than 1.0, f(OH) representing the average number of hydroxyl groups per polyol molecule. 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.

[0070] The functionality f(OH) of the polyol(s) composition (B) can be determined by measuring the IOH of the polyol(s) composition (B), for example by titrimetry according to ISO 14900:2017. Said functionality f(OH) can then be calculated as follows: f(OH)= (10H*M P oiyoi) / 56000, where IOH is the hydroxyl number in mg KOH / g of the polyol(s) composition (B) and M po iyoi 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)).

[0071] The f(OH) functionality of the polyol(s) composition (B) may vary depending on the cyclic anhydride / polyol (A) molar ratio. Indeed, a portion of the hydroxyl groups of the polyol (A) react with the cyclic anhydride to form an ester bond, and a high cyclic anhydride / polyol (A) molar ratio leads to a polyol(s) composition (B) having a low f(OH) functionality.

[0072] 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.

[0073] Other features of step (i)

[0074] According to one embodiment, step (i) is implemented with at least:

[0075] - 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

[0076] - a cyclic anhydride 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, isatoic anhydride, 1,2-cis-cyclohexanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, trimellitic anhydride and mixtures thereof. Preferably, step (i) is carried out with at least:

[0077] - a polyol (A) being a glyceride of fatty acids, in particular a (tri)glyceride of ricinoleic acid, and

[0078] - a cyclic anhydride 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.

[0079] More preferably, step (i) is implemented with at least:

[0080] - a polyol (A) being a triglyceride of ricinoleic acid introduced in the form of castor oil, and

[0081] - a cyclic anhydride being maleic anhydride and / or tetrapropenylsuccinic anhydride.

[0082] The characteristics of step (i) disclosed above apply to this embodiment. In particular, the cyclic anhydride / polyol (A) molar ratio is advantageously chosen so as to obtain a composition of polyol(s) (B) having a f(OH) functionality as described above.

[0083] Step (i) is advantageously carried out under anhydrous conditions.

[0084] Step (i) is advantageously carried out at a temperature between 60°C and 120°C, preferably between 80°C and 10°C.

[0085] Step (i) can be carried out at atmospheric pressure.

[0086] The term "polyisocyanate" means a compound comprising at least two isocyanate groups (-NCO), 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 1-NCO in which R 1 is a divalent hydrocarbon radical comprising from 4 to 45 carbon atoms, and optionally comprising one or more heteroatoms chosen from oxygen, sulfur and nitrogen.

[0087] The polyisocyanate can be:

[0088] - a polyisocyanate derived from vegetable oil comprising unsaturated fatty acids (such a polyisocyanate can be obtained by following the method described in G. Çayli 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

[0089] - a diisocyanate of formula (III): OCN-R 1 -NCO, R 1being such that the diisocyanate is chosen from: o a diisocyanate derived from furan such as 2,5-diisocyanatofuran, 2,5-bis(isocyanatomethyl)furan, 2,2'-(1-methylethylidene)bis[5-isocyanatofuran] (CAS 1008130-81-1), 2-isocyanato-5-[(5-isocyanatofuran-2-yl)methyl]furan (CAS 88768-51-8), 2-isocyanato-5-[1-(5-isocyanatofuran-2-yl)ethyl]furan (CAS 88768-52-9), [oxybis(methylene-5,2- furandiylmethylene)]diisocyanate (CAS 96732-82-0), 2- (isocyanatomethyl)-5-[2-[5-(isocyanatomethyl)furan-2-yl]propan-2-yl]furan (CAS 88768-56-3), or a diisocyanate derived from dianhydrohexitol of formula: o a diisocyanate derived from methoxyphenyl of formula: in which R 8 represents a hydrogen atom or a methoxy group and m is an integer between 1 and 3, o a hexamethylene diisocyanate (HDI) allophanate of formula (Ilia): in which:

[0090] - i is an integer ranging from 2 to 5;

[0091] - j is an integer ranging from 1 to 2; - R 11 represents a hydrocarbon radical, saturated or unsaturated, cyclic, linear or branched, comprising from 6 to 14 carbon atoms;

[0092] - R 12 represents a divalent propylene group;

[0093] - i, j, R 11 and R 12being 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, o pentamethylene diisocyanate (PDI), o hexamethylene diisocyanate (RDI), o 1,7-diisocyanatoheptane, o 1,8-diisocyanatooctane, o 1,9-diisocyanatononane, o 1,16-diisocyanato-8-hexadecene, o 1-isocyanato-10-[(isocyanatomethyl)thio]decane, o dimeryl diisocyanate (CAS 68239-06-5), o L-lysine diisocyanate methyl ester (CAS 34050-00-5), o ester ethyl L-lysine diisocyanate (CAS 45172-15-4), o 2,4-diisocyanato-1-pentadecylbenzene, o isophorone diisocyanate (IPDI), o 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate (HMDI), o 2,4- and / or 2,6-toluene diisocyanate (TDI), o 4,4'- and / or 2,4'-diphenylmethane diisocyanate (MDI), o m-xylylene diisocyanate (m-XDI), o hydrogenated m-xylylene diisocyanate (m-H6XDI),and their mixtures.,

[0094] Advantageously, the polyisocyanate is chosen 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, hydrogenated m-xylylene diisocyanate and mixtures thereof.

[0095] 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, hydrogenated m-xylylene diisocyanate and mixtures thereof.

[0096] More preferably, the polyisocyanate 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.

[0097] 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(s) composition (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.

[0098] 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 used during step (ii) (in particular of the composition of polyol(s) (B) and of the possible alcohol (C) described below).

[0099] The molar equivalent number of -NCO groups in the polyisocyanate is equal to: f(— NCO)*(m P polyisocyanate / Mpoiyisocyanate), where f(-NCO) is the number of -NCO groups in the polyisocyanate, m P oiyi SO cyanate 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.

[0100] The molar equivalent number of -OH groups in the polyol(s) composition (B) is equal to: (10H*m B) / 56000, where IOH is the hydroxyl number in mg KOH / g of the polyol(s) composition (B) and where m B is the mass introduced in g of the polyol(s) composition (B).

[0101] The molar equivalent number of -OH groups of the alcohol (C) is equal to: (10H*mc) / 56000, where IOH is the hydroxyl number in mg KOH / g of the alcohol (C) and where m c is the mass introduced in g of alcohol (C).

[0102] Plasticizer

[0103] Advantageously, step (ii) is carried out in the presence of a plasticizer.

[0104] The presence of the plasticizer makes it possible to reduce the viscosity of the reaction medium of step (ii), and also of the resulting polyurethane composition(s).

[0105] The plasticizer may be any plasticizer commonly used in the field of adhesive and / or sealant compositions.

[0106] Preferably, the plasticizer is chosen from: - a mixture of methyl esters of fatty acids, in particular of fatty acids comprising 18 carbon atoms such as fatty acids derived from castor oil including in particular ricinoleic acid (for example Esterol A marketed by ARKEMA),

[0107] - a mixture of esters of alkylsulfonic acids and phenol, such as the mixture identified by CAS No. 91082-17-6 (for example MESAMOLL® marketed by LANXESS),

[0108] - diisodecyl phthalate (for example PALATINOL® DIDP marketed by BASF),

[0109] - diisononyl phthalate (DINP) (for example PALATINOL® N marketed by BASF),

[0110] - the diisononyl ester of 1,2-cyclohexanedicarboxylic acid (for example HEXAMOLL DINCH® marketed by BASF),

[0111] - pentaerythritol tetravalerate (for example PEVALEN™ marketed by PERSTORP),

[0112] - 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, such as DOW CORNING® 3074 marketed by DOW, the Mn of which is between 1300-1500 g / mol, and

[0113] - their mixtures.

[0114] More preferably, the plasticizer is chosen from:

[0115] - a mixture of methyl esters of fatty acids, in particular fatty acids comprising 18 carbon atoms such as fatty acids derived from castor oil, including in particular ricinoleic acid (for example Esterol A marketed by ARKEMA), and / or

[0116] - a mixture of alkylsulfonic acid esters and phenol, such as the mixture identified by CAS No. 91082-17-6 (for example MESAMOLL® marketed by LANXESS).

[0117] According to one embodiment, the plasticizer consists of at least 50% by weight of bio-sourced plasticizer, in particular a mixture of methyl esters of fatty acids 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-sourced plasticizer is Esterol A marketed by ARKEMA.

[0118] The amount 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

[0119] An alcohol (C), preferably a polyol, may be added to carry out step (ii). The alcohol (C) is different from the polyol (B). Indeed, the alcohol (C) does not comprise a carboxylic acid group (-C(O)OH).

[0120] Alcohol (C) has a number-average molar mass Mn greater than or equal to 500 g / mol.

[0121] The alcohol (C) may have a functionality f(OH) of 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.

[0122] Said functionality f(OH) can be determined as indicated above for the polyol (A).

[0123] According to a preferred embodiment, the alcohol (C) is a polyol which may be the bio-sourced polyol (A) as described above, in particular 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.

[0124] Poly(farnesene) diol can be obtained from a plant resource. Indeed, some plant resources such as apples contain farnesene. An example of a commercial poly(farnesene) diol is Krasol® F 3000 marketed by Total.

[0125] Isosorbide can also be obtained from a plant resource, as it can be obtained from glucose, a sugar that is very common in plants.

[0126] According to this embodiment, the alcohol (C) may be of formula HO-R 9 -OH in which the radical R 9 is chosen from the following divalent radicals whose formulas below show the two free valencies:

[0127] - derivative of a poly(farnesene) diol:

[0128]

[0129] - derived from polyethylene glycol

[0130] - derived from a polypropylene glycol

[0131] - derived from a polyester diol

[0132] - derivative of a polybutadiene diol:

[0133] - derivative of a polyacrylate diol:

[0134] - derivative of a polysiloxane diol in which: - x and y are integers; preferably x and y are such that the number-average molar mass Mn of the poly(farnesene) diol is between 500 g / mol and 8000 g / mol, more preferably between 1000 g / mol and 5000 g / mol,

[0135] - q represents an integer such as the number-average molar mass Mn of the radical R 9 ranges from 500 g / mol to 20000 g / mol, preferably from 3000 g / mol to 14000 g / mol,

[0136] - r and s represent zero or a non-zero integer such that the number-average molar mass of the radical R 9 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 different from zero,

[0137] - Q 1 represents a linear or branched, saturated or unsaturated, aromatic or aliphatic divalent alkylene radical, preferably having from 1 to 18 carbon atoms, more preferably from 1 to 8 carbon atoms,

[0138] - Q 2 represents a linear or branched divalent alkylene radical preferably having from 2 to 36 carbon atoms, more preferably from 1 to 8 carbon atoms,

[0139] - Q 3 , Q 4 , Q 5 , Q 6 , Q 7 and Q 8 , represent, independently of one another, a hydrogen atom or an alkyl, alkenyl or aromatic radical, preferably having from 1 to 12 carbon atoms, preferably from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms.

[0140] According to this embodiment, the radical R 9 preferably represents a radical derived from a polyether, preferably from a polyethylene glycol or a polypropylene glycol as described above.

[0141] When an alcohol (C) is used in step (ii), the quantity of alcohol (C) introduced during step (ii) can vary between 20% and 80% by weight relative to the weight of the polyol composition(s) (B).

[0142] Additives

[0143] 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 reaction of a polyisocyanate and at least one polyol. Such a catalyst is for example chosen from carboxylates, in particular neodecanoate, of bismuth and / or zinc. As commercially available examples, mention may be made of BorchiOKat 315 from the company OMG Borchers which is a bismuth neodecanoate, or BorchiOKat 15 from the same company which is a zinc neodecanoate. The quantity of catalyst introduced during step (ii) may vary between 0.01% and 0.5% by weight relative to the weight of the polyol(s) composition (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%.

[0144] Step (ii) may 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 by the action of heat or light. UV stabilizers may include antioxidants capable of scavenging free radicals.

[0145] Advantageously, the UV stabilizer (or antioxidant) is chosen from 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( 1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (CAS No. 41556-26-7), methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (CAS No. 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 4,4'-bis(o,a-dimethylbenzyl)diphenylamine, and mixtures thereof.Examples include the products Irganox® 245, Irganox® 1076, TINUVIN® 292, TINUVIN® 765 or TINUVIN® 770 DF marketed by BASF and RIASORB UV-123 marketed by RIANLON.

[0146] Preferably, the UV stabilizer (or antioxidant) is chosen from 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).

[0147] The amount of UV stabilizer (or antioxidant) introduced during step (ii) may vary between 0.1% and 5% by weight relative to the weight of the polyol(s) composition (B), preferably between 0.2% and 3%, more preferably between 0.5% and 1.5%. Other characteristics of step (ii)

[0148] Advantageously, no polyol comprising a carboxylic acid is used in step (ii) in addition to the polyol composition(s) (B).

[0149] The % NCO by weight of the polyurethane composition(s) with -NCO end groups obtained at the end of step (ii) can vary between 0.3% and 5% relative to the total weight of said composition, preferably between 0.4% and 3%.

[0150] 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.

[0151] The % NCO by weight of said polyurethane composition(s) may vary depending on the molar ratio of polyol(s) composition (B)Zpolyisocyanate.

[0152] According to one embodiment, step (ii) is carried out with, in addition to the polyol(s) composition (B), at least:

[0153] - a polyisocyanate 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, hydrogenated m-xylylene diisocyanate and mixtures thereof,

[0154] - a plasticizer,

[0155] - a catalyst for the formation of polyurethane by reaction of a polyisocyanate and at least one polyol, and

[0156] - optionally a UV stabilizer (or antioxidant).

[0157] Preferably, step (ii) is carried out with, in addition to the polyol(s) composition (B), at least:

[0158] - a polyisocyanate 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,

[0159] - a plasticizer chosen from: o a mixture of methyl esters of fatty acids, in particular fatty acids comprising 18 carbon atoms such as fatty acids derived from castor oil including in particular ricinoleic acid, o a mixture of esters of alkylsulfonic acids and phenol, such as the mixture identified by CAS No. 91082-17-6, o diisodecyl phthalate, o diisononyl phthalate, o diisononyl ester of 1,2-cyclohexanedicarboxylic acid, o pentaerythritol tetravalerate, o 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 o mixtures thereof,

[0160] - a catalyst chosen from carboxylates, in particular neodecanoate, of bismuth and / or zinc, and

[0161] - optionally a UV stabilizer (or antioxidant) chosen from so-called hindered phenols.

[0162] More preferably, step (ii) is carried out with, in addition to the composition of polyol(s) (B), at least:

[0163] - a polyisocyanate being isophorone diisocyanate,

[0164] - a plasticizer chosen from: o a mixture of methyl esters of fatty acids, in particular fatty acids comprising 18 carbon atoms such as fatty acids derived from castor oil including in particular ricinoleic acid, and / or o a mixture of esters of alkylsulfonic acids and phenol, such as the mixture identified by CAS No. 91082-17-6,

[0165] - a catalyst chosen from carboxylates, in particular neodecanoate, of bismuth and / or zinc, and

[0166] - optionally a UV stabilizer (or antioxidant) 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 mixtures thereof, in particular ethylenebis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate].

[0167] The characteristics of step (ii) disclosed above apply to this embodiment. In particular, the quantities used in this embodiment are advantageously as described above. Step (ii) is advantageously carried out under anhydrous conditions.

[0168] Step (ii) is advantageously carried out at a temperature between 60°C and 120°C, preferably between 80°C and 10°C.

[0169] Step (ii) can be carried out at atmospheric pressure.

[0170] Step (iii)

[0171] Step (iii) corresponds to the reaction of a tertiary amine with the carboxylic acid groups of the polyurethane composition(s) resulting from step (ii), in particular the polyurethane composition(s) with -NCO end groups formed in step (ii) (to form an ionic polyurethane composition(s) with -NCO end groups (D)) or the non-ionic silylated polyurethane composition(s)^) formed in step (iv) (to form an ionic silylated polyurethane composition(s) (E)). For convenience, the interaction between tertiary amine and carboxylic acid group is described as being ionic. However, it is understood that this interaction is not necessarily totally ionic, and may be, for example, a hydrogen bond. It is likely that this interaction explains the absence of yellowing of the compositions obtained from the ionic polyurethane composition(s) according to the invention.

[0172] The tertiary amine used in step (iii) has a pKa at 25°C greater than 8, preferably between 9 and 15, more preferably between 10 and 12.

[0173] Throughout the application, "pKa of the tertiary amine" means the pKa of its conjugate acid (i.e., the protonated tertiary amine). The pKa of an acid is equal to — logi o (Ka), where Ka is the acidity constant of the acid in water.

[0174] The tertiary amine may be of formula (IV): N(R)(R')(R") in which R, R' and R", identical or different, each represent a saturated or unsaturated hydrocarbon radical, optionally 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" being able to form a heterocycle with the nitrogen atom to which they are attached.

[0175] According to one embodiment, the tertiary amine is selected from triethylamine (or TEA), 1,8-diazabicyclo[5.4.0]undec-7-ene (or DBU), 1,4-diazabicyclo[2.2.2]octane (or DABCO), 1,5-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. 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.

[0176] Preferably, the tertiary amine is selected from DBU, DABCO, DBN, DCHMA and mixtures thereof, in particular DCHMA.

[0177] Tertiary amines are often incorporated as a crosslinking catalyst in a polyurethane-based sealant and / or adhesive composition (optionally silylated). This then has the disadvantage of leading to yellowing of the resulting adhesive joint, probably linked to its migration to the surface of said joint. On the contrary, 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 linked to the interaction of the tertiary amine with the carboxylic acid groups.

[0178] 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.

[0179] 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 molar equivalent number of -C(O)OH groups in the polyol composition(s) (B).

[0180] The molar equivalent number of -C(O)OH groups in the polyol(s) composition (B) is equal to: f(-C(O)OH)*(m an hybrid / M an hydride), 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), m a nhydride is the mass introduced in g of said anhydride and Manhydride is the molar mass in g / mol of said anhydride.

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

[0182] Step (iii) is advantageously carried out at a temperature between 20°C and 80°C, preferably between 20°C and 50°C.

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

[0184] Advantageously, the process according to the invention further comprises a step (iv) of silylation of the polyurethane composition(s) resulting from step (ii) with a silylated compound to form a silylated polyurethane composition(s), the silylated compound being of formula (V):

[0185] HX—R 3 - If(R 4 ) p (GOLD 5 ) 3.p (V) in which:

[0186] - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms,

[0187] - R 4 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, and when p is equal to 2, the radicals R 4 are the same or different,

[0188] - R 5represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, an alkylcarbonyl radical comprising from 2 to 8 carbon atoms, or a dialkylimino radical comprising from 3 to 8 carbon atoms, and when p is equal to 0 or 1, the radicals R 5 are identical or different, two OR groups 5 which can be engaged in the same cycle, preferably R 5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms,

[0189] - X represents a divalent radical chosen from -N(R 6 )-, -NH- and -S-,

[0190] - R 6 represents a hydrocarbon radical comprising from 1 to 20 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more optionally aromatic cycles, and which may also comprise one or more heteroatoms, preferably R 6represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms, and

[0191] - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

[0192] Advantageously, the silylated compound is of formula (V) in which:

[0193] - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene;

[0194] - R 5 represents a methyl or ethyl radical, preferably methyl;

[0195] - X represents a divalent radical -N(R 6 )-,

[0196] - R 6 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, preferably n-butyl, and

[0197] - p is equal to 0.

[0198] Silylated compounds of formula (V) are widely available commercially. Examples include N-(3(trimethoxysilyl)propyl)butylamine available under the name Dynasylan® 1189 from Evonik.

[0199] Step (iv) corresponds to the reaction of a silylated compound with the NCO groups of the polyurethane composition(s) resulting from step (ii), in particular the polyurethane composition(s) with -NCO end groups formed at the end of step (ii) (to form a non-ionic silylated polyurethane composition(s)) or the ionic polyurethane composition(s) with -NCO end groups (D) (to form a silylated ionic polyurethane composition(s) (E)).

[0200] 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.

[0201] 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 polyurethane composition(s) with -NCO end groups formed at the end of step (ii) or of the ionic polyurethane composition(s) (D) obtained at the end of step (iii).

[0202] 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).

[0203] The molar equivalent number of -NCO groups of the polyurethane composition(s) with -NCO end groups formed at the end of step (ii) or of the ionic polyurethane composition(s) (D) obtained at the end of step (iii) corresponds to the molar equivalent number of -NCO groups of polyisocyanate introduced in excess relative to the molar equivalent number of -OH groups of the polyol composition(s) (B) during step (ii).

[0204] Step (iv) is advantageously carried out under anhydrous conditions.

[0205] Step (iv) is advantageously carried out at a temperature in the range from 20°C to 90°C, preferably from 30°C to 70°C.

[0206] Step (iv) is advantageously carried out at atmospheric pressure.

[0207] 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.

[0208] This viscosity can for example be measured using a Brookfield type method at 23°C (S28 needle).

[0209] Other characteristics of the method according to the invention

[0210] Preferred embodiment

[0211] According to a preferred embodiment, the method according to the invention comprises:

[0212] (i) a step of esterifying a polyol (A) being a fatty acid glyceride, in particular a ricinoleic acid (tri)glyceride, with a cyclic anhydride 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, to form a composition of polyol(s) (B), then

[0213] (ii) a step of reacting the polyol(s) composition (B) with a polyisocyanate to form a polyurethane(s) composition with -NCO end groups, in which:

[0214] - the polyisocyanate 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,

[0215] - a plasticizer is used, the plasticizer being chosen from: o a mixture of methyl esters of fatty acids, in particular fatty acids comprising 18 carbon atoms such as fatty acids derived from castor oil including in particular ricinoleic acid, o a mixture of esters of alkylsulfonic acids and phenol, such as the mixture identified by CAS No. 91082-17-6, o diisodecyl phthalate, o diisononyl phthalate, o diisononyl ester of 1,2-cyclohexanedicarboxylic acid, o pentaerythritol tetravalerate, o 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 o their mixtures,

[0216] - a catalyst is used, the catalyst being chosen from carboxylates, in particular neodecanoate, of bismuth and / or zinc, and

[0217] - optionally a UV stabilizer (or antioxidant) chosen from so-called hindered phenols is used, then

[0218] (iii) a step of reacting the polyurethane composition(s) resulting from step (ii) (in particular the polyurethane composition(s) with -NCO end groups formed in step (ii)) with a tertiary amine chosen from TEA, DBU, DABCO, DBN, DCHMA, DMDEE, TBD, MTBD, THA and mixtures thereof, to form an ionic polyurethane composition(s) (in particular an ionic polyurethane composition(s) with -NCO end groups (D)), and

[0219] (iv) optionally a step (iv) of silylation of the polyurethane composition(s) resulting from step (ii) (in particular the composition of ionic polyurethane(s) with -NCO end groups (D)) with a silylated compound to form a composition of silylated polyurethane(s) (in particular a composition of silylated ionic polyurethane(s) (E)), the silylated compound being of formula (V) in which:

[0220] - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene;

[0221] - R 5 represents a methyl or ethyl radical, preferably methyl;

[0222] - X represents a divalent radical -N(R 6 )-,

[0223] - R 6 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, preferably n-butyl, and

[0224] - p is equal to 0.

[0225] More preferably, the method according to the invention comprises:

[0226] (i) a step of esterifying a polyol (A) being a ricinoleic acid triglyceride introduced in the form of castor oil, with a cyclic anhydride being maleic anhydride and / or tetrapropenylsuccinic anhydride, to form a composition of polyol(s) (B), then

[0227] (ii) a step of reacting the polyol(s) composition (B) with a polyisocyanate to form a polyurethane(s) composition with -NCO end groups, in which:

[0228] - the polyisocyanate is isophorone diisocyanate,

[0229] - a plasticizer is used, the plasticizer being chosen from: o a mixture of methyl esters of fatty acids, in particular fatty acids comprising 18 carbon atoms such as fatty acids derived from castor oil including in particular ricinoleic acid, and / or o a mixture of esters of alkylsulfonic acids and phenol, such as the mixture identified by CAS No. 91082-17-6,

[0230] - a catalyst is used, the catalyst being chosen from carboxylates, in particular neodecanoate, of bismuth and / or zinc, and

[0231] - optionally a UV stabilizer (or antioxidant) is used, 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 mixtures thereof, in particular bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] of ethylenebis(oxyethylene), then

[0232] (iii) a step of reacting the polyurethane composition(s) resulting from step (ii) (in particular the polyurethane composition(s) with -NCO end groups formed in step (ii)) with a tertiary amine chosen from DBU, DABCO, DBN, DCHMA and mixtures thereof, in particular DCHMA, to form an ionic polyurethane composition(s) (in particular an ionic polyurethane composition(s) with -NCO end groups (D)), and

[0233] (iv) optionally a step (iv) of silylation of the polyurethane composition(s) resulting from step (ii) (in particular the composition of ionic polyurethane(s) with -NCO end groups (D)) with a silylated compound to form a composition of silylated polyurethane(s) (in particular a composition of silylated ionic polyurethane(s) (E)), the silylated compound being of formula (V) in which:

[0234] - R 3represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene;

[0235] - R 5 represents a methyl or ethyl radical, preferably methyl;

[0236] - X represents a divalent radical -N(R 6 )-,

[0237] - R 6 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, preferably n-butyl, and

[0238] - p is equal to 0.

[0239] The characteristics of steps (i) to (iv) disclosed above apply to this embodiment. In particular, the quantities used in this embodiment are advantageously as described above.

[0240] Solvent

[0241] The method according to the invention is advantageously implemented in the absence of solvent.

[0242] By "solvent" we mean in particular a solvent used in the field of adhesives and / or sealants.

[0243] Solvents are well known to those skilled in the art and include, for example, water, ethanol, isopropanol, ethyl acetate, butyl acetate, acetone, butanone, methyl isobutyl ketone, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, cyclohexane, benzene, toluene, xylene, etc.

[0244] 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 adding free water, i.e. other than that inherently included in the ingredients used. In particular, the water content introduced into the process according to the invention is less than 3% by weight relative to the total weight of the ingredients used, preferably less than 1% by weight. In addition, the polyol (A) is preferably dehydrated (for example at approximately 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) may also be dehydrated in the same manner.

[0245] The water content can be measured by a Karl Fischer coulometric method, for example by the method described in Example 1.

[0246] Moisture absorber

[0247] A moisture absorber may be introduced at the end of step (iv) of the process according to the invention (once the silylation of the composition of ionic polyurethane(s) with -NCO (D) end groups is complete).

[0248] A suitable moisture absorber (or desiccant) is, in particular, an alkoxysilane such as a trialkoxysilane (particularly a trimethoxysilane). Such an agent advantageously prolongs the shelf life of the silylated ionic polyurethane composition (E) during storage and transport, prior to its use.

[0249] Advantageously, the moisture absorber is chosen from vinyltrimethoxysilane, trimethoxymethylsilane, propyltrimethoxysilane, vinyltriethoxysilane, alkoxyarylsilanes (for example GENIOSIL® XL 70 marketed by WACKER) and mixtures thereof.

[0250] Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, vinyltriethoxysilane and their mixture, more preferably vinyltrimethoxysilane.

[0251] 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-sourced ingredients

[0252] According to one embodiment, at least 50% by weight of the ingredients used in the process according to the invention are biosourced, relative to the total weight of the ingredients used in the process according to the invention, preferably at least 85% by weight.

[0253] Thus, the ionic polyurethane compositions (D) and (E) advantageously consist of at least 50% by weight of bio-sourced ingredients, respectively relative to the total weight of the ionic polyurethane compositions (D) and (E), preferably at least 85% by weight.

[0254] The bio-sourced ingredients include polyol (A) and any plasticizer.

[0255] Composition of ionic polyurethane(s) with -NCO terminal atoms (D) capable of being obtained by the process according to the invention

[0256] The invention also relates to a composition of ionic polyurethane(s) with -NCO (D) end groups capable of being obtained by the process according to the invention comprising steps (i) to (iii) as defined above.

[0257] The silylation step (iv) is not carried out because the ionic polyurethane(s) of said composition (D) is (are) not silylated (but has -NCO end groups).

[0258] Thus, the composition of ionic polyurethane(s) (D) according to the invention comprises one or more ionic polyurethanes with -NCO end groups.

[0259] The content of ionic polyurethane(s) with -NCO end groups 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.

[0260] 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 10% to 20% by weight.

[0261] Advantageously, said ionic polyurethane composition(s) (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. In addition, the characteristics mentioned above concerning the ionic polyurethane composition(s) (D) obtained by the process according to the invention apply to the ionic polyurethane composition(s) (D) capable of being obtained by the process according to the invention.

[0262] In particular, the composition of ionic polyurethane(s) (D) advantageously consists of at least 50% by weight of bio-sourced ingredients, relative to the total weight of said composition (D), preferably at least 85% by weight.

[0263] Composition of ionic silvered polyurethane(s) (E) capable of being obtained by the process according to the invention

[0264] The invention also relates to a composition of silylated ionic polyurethane(s) (E) capable of being obtained by the process according to the invention comprising steps (i) to (iv) as defined above.

[0265] Thus, the composition of ionic polyurethane(s) (E) according to the invention comprises one or more silylated ionic polyurethanes.

[0266] 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.

[0267] Advantageously, the composition of silylated ionic polyurethane(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 10% to 20% by weight.

[0268] Advantageously, said composition of silylated ionic polyurethane(s) (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.

[0269] 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) capable of being obtained by the process according to the invention.

[0270] In particular, the composition of silylated ionic polyurethane(s) (E) advantageously consists of at least 50% by weight of bio-sourced ingredients, relative to the total weight of said composition (E), preferably at least 85% by weight.

[0271] The invention relates in particular to an optionally silylated ionic polyurethane.

[0272] The optionally silylated ionic polyurethane according to the invention comprises a unit (M) of type: in which:

[0273] 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 the tertiary amines described above,

[0274] R 1 is as described above and is directly bonded to a nitrogen atom, in particular R 1 is such that the diisocyanate of formula (III): OCN-R 1 -NCO is chosen from the diisocyanates described above,

[0275] R 2 is as described above, and represents a radical with a valence greater than or equal to 3, in particular R 2is such that the polyol of formula (I), in which n is equal to the sum of t and u, is biosourced and preferably chosen from lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or a fatty acid glyceride, R 7 is as described above, in particular R 7 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, 1-methyl-2-(2'-carboxyethyl)maleic anhydride, octenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, 1,2-cis-cyclohexanedicarboxylic anhydride, phthalic anhydride, homophthalic, trimellitic anhydride and their mixtures,

[0276] - 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. The radical R 1 can be directly linked to the nitrogen of a carbamate group by which the polyurethane chain is extended or to the nitrogen of an isocyanate group (-NCO) or to the nitrogen of a silyl group of formula (VII): are as defined above.

[0277] The radicals of this motif are as described above, including preferred features and embodiments.

[0278] Thus, according to a preferred embodiment, in the above pattern:

[0279] 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 mixtures thereof,

[0280] R 1 is such that the diisocyanate of formula (III): OCN-R 1-NCO is selected 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, R 2 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,

[0281] R 7is 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,

[0282] - 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.

[0283] When the radical R 1 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. Advantageously, the optionally silylated ionic polyurethane according to the invention is of formula (VI): in which:

[0284] 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 the tertiary amines described above,

[0285] R 1 is as described above, in particular R 1 is such that the diisocyanate of formula (III): OCN-R 1 -NCO is chosen from the diisocyanates described above,

[0286] R 2 is as described above, and represents a radical with a valence greater than or equal to 3, in particular R 2 is such that the polyol of formula (I) is biosourced and preferably chosen from lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or a fatty acid glyceride,

[0287] R 7 is as described above, in particular R 7is 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, 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, R 9 is as described above and represents a divalent radical, in particular R 9 is such that the alcohol of formula HO-R 9-OH is selected from poly(farnesene) 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,

[0288] - 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,

[0289] - c is an integer greater than or equal to 0, preferably equal to 0,

[0290] - Y represents f or a carbamate group by which the polyurethane chain extends, the nitrogen of said carbamate group being directly linked to R 1 ,

[0291] - f represents an isocyanate group -NCO or a monovalent radical

[0292] O of formula (VII): — NH-CX- R3 -IF( R4 ) P (O R5 ) 3.P DANS | AQUE || E X R 3 , R 4 , R5 and p are as defined above, preferably f represents a monovalent radical of formula (VII).

[0293] The main chain of the optionally silylated ionic polyurethane of formula (VI) therefore comprises a repeating unit repeated v times and optionally a repeating unit repeated c times. It is understood that, when the unit comprising the radical R 9 is present, the distribution of these two units on said main chain is statistical, and that said polyurethane of formula (VI) is therefore a statistical copolymer.

[0294] In addition, t represents the number of ionic groups carried by the radical R 2 and can be an integer greater than 1 when the radical R 2 is a radical with a valence greater than 3.

[0295] Furthermore, for convenience, the interaction between tertiary amine and carboxylic acid group is described as ionic. However, it is understood that this interaction is not necessarily fully ionic, and may be, for example, a hydrogen bond. Thus, it is understood that the formulae in this text showing an ionic interaction between tertiary amine and carboxylic acid group also cover compounds whose tertiary amine-carboxylic acid interaction is not fully ionic, provided that there is an interaction between them.

[0296] The radicals in formula (VI) are as described above, including preferred features and embodiments.

[0297] Thus, according to a preferred embodiment, the optionally silylated ionic polyurethane according to the invention is of formula (VI) 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 mixtures thereof, in particular DCHMA, R 1 is such that the diisocyanate of formula (III): OCN-R 1 -NCO is selected 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, R 2 is such that the polyol of formula (I), in which n is equal to the sum of t and u, is a glyceride of fatty acids, in particular a (tri)glyceride of ricinoleic acid,

[0298] R 7is 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,

[0299] R 9 is such that the alcohol of formula HO-R 9 -OH is selected from poly(farnesene) 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,

[0300] - t is equal to 1 and u is equal to 2,

[0301] - c is an integer greater than or equal to 0, preferably equal to 0,

[0302] - f represents an isocyanate group -NCO or a monovalent radical

[0303] O of formula (VII): — NH-CX- R3 -IF( R4 ) P (O R5 ) 3.P DANS | AQUE || E X R 3 , R 4 , R 5 and p are as defined above, preferably f represents a monovalent radical of formula (VII).

[0304] 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:

[0305] - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene; - R 5 represents a methyl or ethyl radical, preferably methyl;

[0306] - X represents a divalent radical -N(R 6 )-,

[0307] - R 6represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, preferably n-butyl, and - p is equal to 0.

[0308] According to a preferred embodiment, the optionally silylated ionic polyurethane according to the invention is derived from ricinoleic acid triglyceride. Ricinoleic acid triglyceride is a triol R 2 (OH)3 represented as follows: In particular, the optionally silylated ionic polyurethane according to the invention is of formula (VIII):

[0309] - one of the radicals is a monovalent radical of formula (IX):

[0310] OO H7H e ©

[0311] — C— R 7 — C— O HN(R)(R')(R") ( | X)j et

[0312] - the other two radicals are monovalent radicals of formula (X):

[0313] (X), in which: R, R', R”, R 1 , R 7and f are as described above, including preferred features and embodiments,

[0314] R 2 represents the trivalent radical derived from ricinoleic acid triglyceride, the oxygens directly linked to R 2 corresponding to the oxygens of the hydroxyl groups carried by the ricinoleic acid chains,

[0315] - a and b are identical or different integers, preferably b is equal to 0. oX can be represented as follows:

[0316] It is understood that the values ​​of a and b can vary between the two radicals of formula (X). For example, one of the radicals of formula (X) could have a non-zero b value, while the other radical of formula (X) would have a zero b value (i.e. no motif comprising the radical R 9). 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 Mn 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.

[0317] Furthermore, when the motif comprising the radical R 9 is present, the distribution of this motif and of the motif comprising the radical R 2 in the two radicals chosen from R 13 , R 14 and R 15 is statistical, and that said polyurethane of formula (VIII) is therefore a statistical copolymer.

[0318] Preferably, the optionally silylated ionic polyurethane is of formula (VIII) in which:

[0319] 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 mixtures thereof,

[0320] R1 is such that the diisocyanate of formula (III): OCN-R 1 -NCO is selected 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, R 7 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

[0321] - preferably b is equal to zero in both radicals of formula (X).

[0322] More preferably, the optionally silylated ionic polyurethane is of formula (VIII) in which:

[0323] R, R', R” are such that the tertiary amine of formula (IV): N(R)(R')(R") is chosen from DBU, DABCO, DBN, DCHMA and mixtures thereof, in particular DCHMA,

[0324] R 7 is such that the cyclic anhydride of formula (II) is maleic anhydride and / or tetrapropenylsuccinic anhydride,

[0325] R 1 is such that the diisocyanate of formula (III): OCN-R 1 -NCO is isophorone diisocyanate and

[0326] - preferably b is equal to zero in both radicals of formula (X).

[0327] 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:

[0328] - R 3represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene;

[0329] - R 5 represents a methyl or ethyl radical, preferably methyl;

[0330] - X represents a divalent radical -N(R 6 )-,

[0331] - R 6 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, preferably n-butyl, and

[0332] - p is equal to 0.

[0333] According to a particularly preferred embodiment, the ionic polyurethane is silylated and of formula (VIII) in which:

[0334] R, R', R” are such that the tertiary amine of formula (IV): N(R)(R')(R") is chosen from DBU, DABCO, DBN, DCHMA and mixtures thereof, in particular DCHMA,

[0335] R 7is such that the cyclic anhydride of formula (II) is maleic anhydride and / or tetrapropenylsuccinic anhydride, R 1 is such that the diisocyanate of formula (III): OCN-R 1 -NCO is isophorone diisocyanate,

[0336] - b is equal to zero in both radicals of formula (X), and

[0337] - f represents a monovalent radical of formula (VII) in which:

[0338] - R 3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene;

[0339] - R 5 represents a methyl or ethyl radical, preferably methyl;

[0340] - X represents a divalent radical -N(R 6 )-,

[0341] - R 6 represents a linear or branched alkyl radical comprising from 1 to

[0342] 4 carbon atoms, preferably n-butyl, and

[0343] - p is equal to 0.

[0344] The optionally silylated ionic polyurethanes according to the invention can be obtained by following the process according to the invention as described above.

[0345] Adhesive and / or sealant composition

[0346] The invention also relates to an adhesive and / or sealant composition comprising the optionally silylated ionic polyurethane described above (comprising a unit (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. Said optionally silylated ionic polyurethane and said composition (D) or (E) can be obtained during the preparation of the adhesive and / or sealant composition; in particular, step (iii) can be carried out at the end of the preparation of the adhesive and / or sealant composition.

[0347] The content of optionally silylated ionic polyurethane 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.

[0348] Advantageously, the adhesive and / or sealant composition according to the invention further comprises a filler.

[0349] 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.

[0350] The filler that can be used in the adhesive and / or sealant composition according to the invention can be chosen from mineral fillers and mixtures of organic fillers and mineral fillers. As an example of a mineral filler, mention may be made of any mineral filler usually used in the field of adhesive and / or sealant compositions. These fillers are in the form of particles of various geometry. They can be, for example, spherical, fibrous, or have an irregular shape.

[0351] Advantageously, the mineral fillers are formed by the group consisting of clay, quartz, hollow mineral microspheres and carbonate fillers.

[0352] Among the hollow mineral microspheres, we can cite hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate.

[0353] Preferably, the mineral fillers are formed by the group consisting of carbonate fillers.

[0354] Advantageously, the carbonated filler is chosen from alkali or alkaline earth metal carbonates and mixtures thereof. Preferably, the carbonated filler comprises calcium carbonate, more preferably the carbonated filler is chalk or calcium carbonate coated with fatty acids, even more preferably precipitated calcium carbonate coated with fatty acids.

[0355] When calcium carbonate is coated with fatty acids, this makes the calcium carbonate particles completely or partially hydrophobic. In addition, the fatty acid coating acts as a hydrophobic coating that can prevent the calcium carbonate from absorbing the composition's constituents and rendering them ineffective. The hydrophobic coating of the calcium carbonate can represent from 0.1% to 3.5% by weight, based on the total weight of calcium carbonate.

[0356] Preferably, the fatty acids coating the calcium carbonate comprise or consist of more than 50% by weight of stearic acid relative to the total weight of the fatty acids.

[0357] As an example of an organic filler, we can cite any organic filler, in particular polymeric, usually used in the field of adhesive and / or mastic compositions.

[0358] 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.

[0359] Advantageously, the average particle size of the filler is between 10 nm and 400 pm, preferably between 20 nm and 100 pm, more preferably between 30 nm and 1 pm, even more preferably between 40 nm and 300 nm.

[0360] The average particle size corresponds advantageously to the d50 particle size, i.e. the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN type device (for example according to standard NF ISO 13320).

[0361] Unless otherwise indicated, the standards referred to throughout the application are those in effect on the date the application was filed.

[0362] According to a preferred embodiment, the adhesive and / or sealant composition according to the invention comprises:

[0363] - between 20% and 60% by weight of filler, preferably between 30% and 58% by weight, more preferably between 40% and 55% by weight, and

[0364] - between 8% and 50% by weight of optionally silylated ionic polyurethane 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, the percentages by weight being relative to the total weight of the adhesive and / or sealant composition.

[0365] The adhesive and / or sealant composition according to the invention may further comprise at least one additive chosen from moisture absorbers, adhesion promoters, rheology agents, UV stabilizers and mixtures thereof.

[0366] Advantageously, the composition according to the invention comprises a mixture of additives chosen from moisture absorbers and adhesion promoters.

[0367] The moisture absorber is advantageously as described above. Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, vinyltriethoxysilane and their mixture, more preferably vinyltrimethoxysilane.

[0368] 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.

[0369] The adhesion promoter may 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 aminotrialkoxysilanes and mixtures thereof, even more preferably from aminotrimethoxysilanes and mixtures thereof, for example N-(3-(trimethoxysilyl)propyl)ethylenediamine.

[0370] An example of an epoxy-alkoxysilane is (3-glycidyloxypropyl)trimethoxysilane (also known as GLYMO).

[0371] Advantageously, the aminotrimethoxysilanes are formed by the group consisting of 4-amino-3,3-dimethylbutyltrimethoxysilane (for example SILQUEST A-LINK 600 marketed by MOMENTIVE), (3-aminopropyl)trimethoxysilane (for example DYNASYLAN® AMMO marketed by EVONIK), N-(3-(trimethoxysilyl)propyl)ethylenediamine (for example GENIOSIL® GF9 marketed by the company WACKER) and mixtures thereof. Preferably, the aminotrimethoxysilanes are N-(3-(trimethoxysilyl)propyl)ethylenediamine.

[0372] 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.

[0373] The rheology agent may be any rheology agent commonly used in the field of adhesive and / or sealant compositions.

[0374] Advantageously, the rheology agent is chosen from:

[0375] - PVC plastisols, corresponding to a suspension of PVC in a plasticizing agent miscible with PVC, obtained in situ by heating at temperatures ranging from 60°C to 80°C. These plastisols may be those described in particular in the work “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6,

[0376] - pyrogenic silica, such as HDK® N20 marketed by WACKER,

[0377] - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in application FR 1 591 172, and

[0378] - 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.

[0379] By "amide waxes" is meant waxes comprising one or more compounds having at least one amide group. In particular, amide waxes can be obtained from fatty acid(s) (e.g. ricinoleic acid) and (di)amine(s).

[0380] 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.

[0381] The average particle size corresponds advantageously to the d50 particle size, i.e. the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN type device (for example according to standard NF ISO 13320).

[0382] The content of rheology agent may vary from 1% to 40% by weight relative to the total weight of the composition according to the invention, preferably from 5% to 30% by weight, more preferably from 10% to 25% by weight.

[0383] 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.

[0384] 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 chosen from the plasticizers mentioned above, in particular from:

[0385] - a mixture of methyl esters of fatty acids, in particular fatty acids comprising 18 carbon atoms such as fatty acids derived from castor oil, including in particular ricinoleic acid (for example Esterol A marketed by ARKEMA),

[0386] - a mixture of alkylsulfonic acid esters and phenol, such as the mixture identified by CAS No. 91082-17-6 (for example MESAMOLL® marketed by LANXESS), and

[0387] - their mixture.

[0388] 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 5% to 10% by weight.

[0389] According to one embodiment, the adhesive and / or sealant composition according to the invention comprises: - between 8% and 50% by weight of optionally silylated ionic polyurethane of formula (VI), in particular of formula (VIII), or of ionic polyurethane(s) included in the composition of ionic polyurethane(s) (D) or (E),

[0390] - between 20% and 60% by weight of a load,

[0391] - between 1% and 15% by weight of plasticizer,

[0392] - between 0.5% and 5% by weight of moisture absorber, and

[0393] - between 0.1% and 5% by weight of adhesion promoter, the percentages by weight being relative to the total weight of the adhesive and / or sealant composition.

[0394] Preferably, the composition according to the invention consists essentially of the ingredients mentioned above. By "consisting essentially", it is meant that the composition according to the invention comprises less than 5% by weight of ingredients other than the aforementioned ingredients, relative to the total weight of the composition, preferably less than 2% by weight, even more preferably less than 1% by weight.

[0395] The ingredients of this embodiment and their particular contents are as described above, including preferred features and embodiments.

[0396] Advantageously, no crosslinking catalyst is added to the adhesive and / or sealant composition according to the invention.

[0397] Indeed, the optionally silylated ionic polyurethane of formula (VI) or included in the composition of ionic polyurethane(s) (D) or (E) alone allows the crosslinking reaction to be catalyzed. Thus, it is not necessary to add a crosslinking catalyst to said optionally silylated ionic polyurethane.

[0398] Therefore, 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.

[0399] 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.

[0400] Examples of crosslinking catalysts for silanol condensation include:

[0401] - organic titanium derivatives such as titanium acetyl acetonate, titanium tetrapropylate, titanium tetrabutylate,

[0402] - organic zirconium derivatives such as zirconium acetyl acetonate, zirconium tetrapropylate, zirconium tetrabutylate, - 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), 1,4-diazabicylo[2.2.2]octane (DABCO), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD),

[0403] - zinc carboxylate catalysts (for example K-KAT® 670 marketed by KING INDUSTRIES),

[0404] - tin-based catalysts such as compounds derived from dioctyltin or dibutyltin.

[0405] Examples of crosslinking catalysts for polyurethane crosslinking include:

[0406] - carboxylates, in particular neodecanoate, of bismuth and / or zinc, amines such as DABCO or DMDEE,

[0407] - organic titanium derivatives such as titanium acetyl acetonate, titanium tetrapropylate, titanium tetrabutylate,

[0408] - organic zirconium derivatives such as zirconium acetyl acetonate, zirconium tetrapropylate, zirconium tetrabutylate,

[0409] - tin-based catalysts such as compounds derived from dioctyltin or dibutyltin (in particular dibutyltin or dioctyltin dilaurate).

[0410] 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.

[0411] 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 humidity and preferably protected from light.

[0412] The adhesive and / or sealant composition according to the invention can be prepared by simply mixing its ingredients.

[0413] 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.

[0414] When the preparation of the adhesive and / or sealant composition according to the invention involves heating to a temperature above 55°C, the optionally silylated ionic polyurethane or the ionic polyurethane composition(s) (D) or (E) is advantageously introduced in the form of non-ionic derivative(s), and step (iii) is carried out once the temperature of the adhesive and / or sealant composition has dropped to approximately 20°C-35°C.

[0415] An example of preparation of the adhesive and / or sealant composition according to the invention is described in Example 7.

[0416] Other objects of the invention

[0417] 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.

[0418] Furthermore, the invention also relates to an article comprising the adhesive and / or sealant composition according to the invention, in airtight packaging, protected from air.

[0419] Preferably, the airtight packaging is a polyethylene bag or a polyethylene cartridge fitted with a lid.

[0420] Furthermore, the invention relates to a method for assembling two substrates comprising:

[0421] - coating the adhesive and / or mastic composition according to the invention on at least one of the two substrates to be assembled; then

[0422] - the effective contact of the two substrates.

[0423] Preferably, the assembly method according to the invention is carried out at room temperature (in particular between 18°C ​​and 25°C, for example at approximately 23°C).

[0424] By "about X", we mean more or less 10% of the value of X.

[0425] Suitable substrates are, for example, inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminum, steel, non-ferrous metals, galvanized metals), or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins, or painted metal and composite substrates (for example, in the automotive sector).

[0426] 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, in particular the preferred embodiments, can be combined with each other.

[0427] The following examples are given purely for illustrative purposes of the invention and should not be interpreted as limiting its scope. Examples

[0428] 1 Ingredients and measurement methods

[0429] Ingredients used

[0430] The following ingredients were used:

[0431] - castor oil (CAS: 8001-79-4) marketed by ARKEMA: mixture of compounds comprising approximately 89% by weight, based on the total weight of the mixture, of ricinoleic acid triglyceride having a molar mass equal to 933 g / mol, the castor oil having a hydroxyl number IOH of between 157 and 167 mg KOH / g, i.e. a functionality equal to approximately 2.7 (i.e. an average of 2.7 -OH groups per molecule of ricinoleic acid triglyceride);

[0432] - maleic anhydride marketed by Sigma Aldrich: molar mass equal to 98.06 g / mol;

[0433] - isophorone diisocyanate (IPDI) marketed by Covestro: molar mass equal to 222.3 g / mol (CAS No.: 4098-71-9);

[0434] - BorchiOKat 315 marketed by OMG Borchers: bismuth neodecanoate with a molar mass of 722.75 g / mol;

[0435] Dynasylan® 1 189 marketed by Evonik: N-(3-

[0436] (trimethoxysilyl)propyl)butylamine with a molar mass equal to 235.4 g / mol;

[0437] - DCHMA marketed by ARKEMA: N,N-dicyclohexylmethylamine with a molar mass equal to 195.34 g / mol;

[0438] GENIOSIL® GF9 marketed by Wacker: N-(3-

[0439] (trimethoxysilyl)propyl)ethylenediamine with a molar mass equal to 222.36 g / mol, adhesion promoter;

[0440] - Mesamoll® marketed by Lanxess: phenol alkylsulfonates (CAS: 91082-17-6);

[0441] - Esterol A marketed by ARKEMA: methyl esters of C16-C18 fatty acids and C18 unsaturated fatty acids (CAS: 67762-38-3);

[0442] - VTMO marketed by Sigma Aldrich: vinyltrimethoxysilane with a molar mass equal to 148.23 g / mol, moisture absorber;

[0443] - CALOFORT® SV14 marketed by Specialty Minerals: precipitated calcium carbonate coated with calcium stearate, with an average particle size of 70 nm;

[0444] - Irganox® 245 marketed by BASF: ethylenebis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (CAS: 36443-68-2) with a molar mass of 586.8 g / mol; - PTSI marketed by Sigma Aldrich: p-toluenesulfonyl isocyanate (CAS: 4083-64-1) with a molar mass of 197.21 g / mol.

[0445] Measurement methods

[0446] The water content of ingredients, including castor oil (modified or unmodified), Mesamoll® and Esterol A, is measured using a Karl Fischer coulometric method using HYDRANAL™ as the titrant, with the equivalence point detected electrometrically.

[0447] The hydroxyl number (denoted IOH) of modified castor oil, and more generally of a polyol, represents the number of hydroxyl functions per gram of polyol and is expressed in the form of the equivalent number of milligrams of potash (KOH) used in the determination of hydroxyl functions, determined by titrimetry according to the ISO 14900:2017 standard.

[0448] The molar equivalent number of -OH groups (in mol) of a mass m of polyol (in g) is equal to (10H*m) / 56000, where IOH is the hydroxyl number in mg KOH / g of the polyol.

[0449] 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, needle S28).

[0450] The %NCO is determined automatically using a T5 Excellence titrator (marketed by Mettler Toledo). A sample of the reaction medium is taken and introduced into the titrator, then a solution of dicyclohexylamine in DMF (N,N-dimethylformamide) is added automatically. The titration of the excess amine is also done automatically with hydrochloric acid.

[0451] The crosslinking time is measured by determining the skin formation time. To this end, a bead of sealant (approximately 10 cm long and approximately 1 cm in diameter) is first placed on a cardboard support. Then, using a low-density polyethylene (LDPE) pipette tip, the sealant surface is touched every minute for up to 2 hours to determine the exact time at which the surface skin forms. This test is carried out under controlled humidity and temperature conditions (23°C and 50% relative humidity).

[0452] Tensile strength and elongation at break were measured in accordance with ISO 37 (2012), at a constant speed of 100 mm / min.

[0453] In particular, the following conditions were applied: A standard dumbbell-shaped specimen (H2), type 2, as illustrated in the 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.

[0454] To prepare the dumbbell, the composition to be tested (previously packaged in a cartridge) is extruded into a Teflon mold, and left to crosslink for 14 days under standard conditions (23°C, 50% relative humidity).

[0455] The principle of the measurement consists of stretching a standard test piece in a tensile machine (for example Zwick Roell 2.5KN), whose movable jaw moves at a constant speed equal to 100 mm / min, and recording:

[0456] - the elongation at break (expressed in %) which is the elongation of the specimen corresponding to the stretching observed at the time of break, and

[0457] - the tensile strength (in MPa) which is the tensile stress at which the specimen ruptures (also called TS for Tensile Strength in English).

[0458] The measurement is repeated for 5 test pieces, and the corresponding average of the results obtained is calculated.

[0459] The crosslinking depth is determined by filling a Teflon gutter with sealant of increasing depth from 1 mm to 10 mm. The length to depth ratio of 20:1 is constant along the entire length of the gutter. For example, at 2 cm in length, the gutter depth is 1 mm, at 10 cm in length, the gutter depth is 5 mm, and at 20 cm in length, the gutter depth is 10 mm. The gutter has the following dimensions: block dimensions: 25 x 5 x 2 cm, recess dimensions: 20 x 2 x 1 mm to 10 mm.

[0460] After filling with the sealant to be tested, the gutter is left under controlled humidity and temperature conditions (23°C and 50% relative humidity) for 10 days.

[0461] After these 10 days, the strip is pulled on the thinnest part (i.e. 1 mm) until it reaches the non-crosslinked part at the core, i.e. a soft, non-cohesive part, which tends to remain in the gutter. The corresponding fully crosslinked thickness is noted. PTSI Modified Castor Oil Preparation (Comparison)

[0462] In a 250 mL reactor, 84.7 g of castor oil are introduced (i.e., a molar equivalent number of -OH groups equal to 0.245 mol), then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate the 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.

[0463] 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. an equivalent molar number of -NCO groups equal to 0.078 mol) and 0.03 g of BorchiOKat 315. The mixture is kept stirring until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy (around 2260 cm -1 ).

[0464] The resulting polyol has a l OH of approximately 92 mg KOH / g. Preparation of modified castor oil maleic anhydride

[0465] (invention)

[0466] In a 250 mL reactor, 87.3 g of castor oil are introduced (i.e., a molar equivalent number of -OH groups equal to 0.253 mol), then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate the 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.

[0467] The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 12.7 g of maleic anhydride (i.e. a molar equivalent number of anhydride functions equal to 0.130 mol). The mixture is kept stirring until the characteristic bands of the anhydride are no longer detectable by infrared spectroscopy (1849 cm -1 and 1779 cm -1 ).

[0468] The resulting polyol has an I O H of about 100 mg KOH / g. Preparation of a silylated polyurethane PO (comparative)

[0469] In a 250 mL reactor, 59.94 g of PTSI modified castor oil prepared in Example 2 (i.e. a molar equivalent number of -OH groups equal to 0.098 mol, determined using its I O H) and 14.91 g of Mesamoll® are introduced, then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate 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.

[0470] 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. an equivalent molar 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 stirring until reaching a % NCO by weight of 1.7% 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).

[0471] 8.56 g of Dynasylan® 1 189 are then introduced, corresponding to a molar ratio -NH / -NCO equal to 1 (the molar equivalent number of -NH groups being equal to 0.036 mol). The whole is heated to 70°C and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy (around 2260 cm' 1 ).

[0472] Finally, 1 g of VTMO is added at approximately 40°C with stirring.

[0473] Approximately 100 g of silylated polyurethane PO are obtained and the silylated polyurethane PO is packaged in polyethylene cartridges protected from humidity.

[0474] Example 5: Preparation of an ionic silylated polyurethane P2 (invention)

[0475] The ionic silylated polyurethane P2 is prepared similarly to the silylated polyurethane PO, except that maleic anhydride modified castor oil (prepared in Example 3) is used instead of the PTSI modified castor oil. In addition, DCHMA is added, in a DCHMA / maleic anhydride modified castor oil molar ratio of 1, after the reaction with IDPI.

[0476] In a 250 mL reactor, 52.23 g of maleic anhydride modified castor oil (i.e. a molar equivalent number of -OH groups equal to 0.093 mol, determined using its I OH) and 15.07 g of Mesamoll® are introduced, then the reactor is left under vacuum (from 0.1 kPa to 0.5 kPa) for 2 hours at 110°C to dehydrate 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.

[0477] 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. an equivalent molar 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 stirring until reaching a % NCO by weight of 1.7% 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).

[0478] 9.28 g of DCHMA are then added at 40 °C, and stirring is left for 30 min.

[0479] 7.81 g of Dynasylan® 1 189 are then introduced, corresponding to a molar ratio -NH / -NCO equal to 1. The whole is heated to 40°C and mixed until the characteristic band of the -NCO functions is no longer detectable by infrared spectroscopy. Finally, 1 g of VTMO is added at approximately 40°C with stirring.

[0480] Approximately 100 g of ionic silylated polyurethane P2 are obtained and the ionic silylated polyurethane P2 is packaged in polyethylene cartridges protected from moisture.

[0481] 5

[0482] Example 6: Characteristics of comparative silylated polyurethanes and ionic silylated polyurethanes according to the invention

[0483] A comparative silylated polyurethane P1 is prepared in a similar manner to Example 4, using the compounds in the amounts indicated in Table 10 1 below.

[0484] Two ionic silylated polyurethanes P3 and P4 according to the invention are prepared in a similar manner to Example 5, using the compounds in the amounts indicated in Table 1 below. For ionic silylated polyurethane P4, Esterol A is used instead of Mesamoll®.

[0485] 15 The non-ionic silylated polyurethane P'5 is prepared in a similar manner to the ionic silylated polyurethane P2 of Example 5, except that DCHMA is not used. The corresponding ionic silylated polyurethane P5 will be generated in situ in the sealant composition S5 described below.

[0486] [Table 1]

[0487] 20 Percentage by weight relative to the total weight of modified castor oil, Mesamoll® (or Esterai A), Irganox® 245, Borchi®Kat 315 and IDPI introduced into the reactor. 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 P1 and P3).

[0488] Replacing Mesamoll® with Esterol A further reduces viscosity (comparison of P2 and P4).

[0489] Example 7: Preparation of sealants and characteristics

[0490] The previously prepared polymers PO to P'5 are used to prepare mastics (respectively SO to S5), the composition of which is as follows:

[0491] 46 g of a polymer PO, P1, P2, P3, P4 or P'5,

[0492] - 50 g of CALOFORT® SV14,

[0493] - 3 g of VTMO,

[0494] - 1 g of GENIOSIL® GF9, and

[0495] - 4.27 g of DCHMA in S5 putty only (obtained from P'5).

[0496] The amount of DCHMA in S2 and S5 sealants is therefore identical.

[0497] First, all ingredients except GENIOSIL® GF9, and DCHMA for S5, are added at room temperature (approximately 23°C) and atmospheric pressure in a high-speed mixer and then mixed for 2 min.

[0498] GENIOSIL® GF9 is then added and everything is mixed for 2 minutes.

[0499] The stirring speed is approximately 2000 rpm (rotations per minute).

[0500] For S5 sealant only, the DCHMA is added once the composition has returned to room temperature and the whole thing is mixed for approximately 10 min.

[0501] The sealants obtained are packaged in polyethylene cartridges.

[0502] The properties of sealants S0 to S5 (measured according to Example 1) are summarized in Table 2 below.

[0503] [Table 2] Comparative sealants SO and S1, prepared respectively from comparative silylated polyurethanes PO and P1 (and without crosslinking catalyst), have a crosslinking time of 105 min and 85 min respectively.

[0504] 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 S1 and S3).

[0505] 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 to the sealant.

[0506] Furthermore, 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).

[0507] Furthermore, the use of ionic silylated polyurethanes P2 to P5 according to the invention, in addition to the advantage of being obtained from a biosourced polyol, makes it possible to improve the tensile strength of the resulting sealants. Indeed, sealants S2 to S5 according to the invention have a tensile strength greater than that of comparative sealants S0 and S1. The sealants according to the invention are therefore particularly suitable for rigid bonding (after crosslinking), preventing the bonded substrates from moving relative to each other.

[0508] In addition, the use of ionic silylated polyurethanes P2 to P5 according to the invention makes it possible to improve crosslinking in the thickness of the resulting sealants. Indeed, sealants S2 to S5 according to the invention are crosslinked throughout the entire depth of the joint (10 mm), unlike comparative sealants S0 and S1 which are only partially crosslinked in the thickness (3 and 3.5 mm).

[0509] It is worth noting that the ionic silylated polyurethane P5 was indeed obtained in situ from the silylated polyurethane P'5, since no yellowing of the sealant S5 was observed (confirming that an interaction between DCHMA and the carboxylic acid groups of P'5 did indeed occur in the sealant). Furthermore, the properties of S2 and S5 are similar. The tertiary amine can therefore be implemented during the preparation of the polyurethane or in the final composition.

Claims

Claims 1. Process for preparing a composition of ionic polyurethane(s) comprising: (i) a step of esterification of a biosourced polyol (A) with a cyclic anhydride to form a composition of polyol(s) (B) comprising at least one polyol (B) having one or more carboxylic acid groups, then (ii) a step of reacting the polyol composition(s) (B) with a polyisocyanate to form a polyurethane composition(s) with -NCO end groups, then (iii) a step of reacting the polyurethane composition(s) resulting from 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(s).

2. Method according to claim 1, in which 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. The method of 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 mixtures thereof.

4. A method 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, hydrogenated m-xylylene diisocyanate and mixtures thereof.

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

6. A process 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, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, N,N-dicyclohexylmethylamine, diethyl ether-2,2'-morpholine, triazabicyclodecene, methyltriazabicyclodecene, trihexylamine and mixtures thereof.

7. Method according to any one of claims 1 to 6, further comprising a step (iv) of silylation of the polyurethane composition(s) resulting from step (ii) with a silylated compound to form a silylated polyurethane composition(s), the silylated compound being of formula (V): HX—R 3 - If(R 4 ) p (GOLD 5 )3. p (V) in which: - R 3 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 radicals R 4 are the same or different, - R 5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, an alkylcarbonyl radical comprising from 2 to 8 carbon atoms, or a dialkylimino radical comprising from 3 to 8 carbon atoms, and when p is equal to 0 or 1, the radicals R 5 are identical or different, two OR groups 5 which can be engaged in the same cycle, preferably R 5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, - X represents a divalent radical chosen from -N(R 6 )-, -NH- and -S-, - R 6represents a hydrocarbon radical comprising from 1 to 20 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more optionally aromatic cycles, and which may also comprise one or more heteroatoms, preferably R 6 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms, and - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1. Composition of ionic polyurethane(s) with -NCO end groups (D) capable of being obtained by the process according to any one of claims 1 to 6. Composition of silylated ionic polyurethane(s) (E) capable of being obtained by the process according to claim 7. Optionally silylated ionic polyurethane comprising a unit (M) of type: in which: R, R', R” which may be identical or different, each represent a saturated or unsaturated hydrocarbon radical, optionally 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" being able to form 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 chosen from the tertiary amines described in claim 6, R 1 is directly linked to a nitrogen atom and is a divalent hydrocarbon radical comprising from 4 to 45 carbon atoms, and optionally comprising one or more heteroatoms chosen from oxygen, sulfur and nitrogen, in particular R 1 is such that the diisocyanate of formula (III): OCN-R 1 -NCO is chosen from the diisocyanates described in claim 4, R 2is a multivalent hydrocarbon radical optionally comprising one or more oxygen atoms, and represents a radical with a valence greater than or equal to 3, in particular R 2 is such that the polyol of formula R 2 -TOH~| (I) n is biosourced and preferably chosen from the polyols described in claim 2, R 7 is a saturated or unsaturated, optionally branched, divalent hydrocarbon radical, which may comprise one or more optionally aromatic cycles, and optionally comprising one or more heteroatoms chosen from oxygen and sulfur, preferably optionally one or more heteroatoms chosen from oxygen, in particular R 7 is such that 0=0=0 n / the cyclic anhydride of formula (II) is chosen from the cyclic anhydrides described in claim 3, - 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.

11. Optionally silylated ionic polyurethane according to claim 10, being of formula (VI): in which: R, R', R” are as described in claim 10, R 1 is as described in claim 10, R 2 is as described in claim 10, and represents a radical of valence greater than or equal to 3, R 7 is as described in claim 10, R 9 represents a divalent radical and is such that the alcohol of formula HO-R 9 - OH is selected from poly(farnesene) 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 by which the polyurethane chain extends, the nitrogen of said carbamate group being directly linked to R 1 , - f represents an isocyanate group -NCO or a monovalent radical of formula R 3 , R 4 , R 5 and p are as defined above, preferably f represents a monovalent radical of formula (VII). Optionally silylated ionic polyurethane according to claim 11, being of formula (VIII): - one of the radicals is a monovalent radical of formula (IX): OO Il7H 0 © — C— R 7 — C— O HN(R)(R')(R") ( | X)j et - the other two radicals are monovalent radicals of formula (X): (X), in which: R, R', R”, R 1 , R 7 and f are as described in claim 11, R 2 represents the trivalent radical derived from ricinoleic acid triglyceride, the oxygens directly linked to R 2 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 the optionally silylated ionic polyurethane according to any one of claims 10 to 12, or the ionic polyurethane(s) composition (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.

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