WO2024069084A1

WO2024069084A1 - Optionally silylated ionic polyurethane(s)

Info

Publication number: WO2024069084A1
Application number: PCT/FR2023/051467
Authority: WO
Inventors: Boris COLIN; Colombine POIVRET
Original assignee: Bostik Sa
Priority date: 2022-09-28
Filing date: 2023-09-25
Publication date: 2024-04-04
Also published as: FR3140086A1

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

Ionic polyurethane(s) optionally silylated

Field of the invention

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 terminal groups, a composition of polyurethane(s) ) silylated ionic(s), an optionally silylated ionic polyurethane and an adhesive and/or sealant composition.

Technical background

Optionally silylated polyurethanes are generally used as adhesives, sealants and coatings, for example in the aeronautical, automobile or construction industries. When polyurethanes are silylated, they generally include alkoxysilane type terminal groups linked, directly or indirectly, to a polyurethane type main chain. Industrially, they can be obtained from the reaction of a prepolymer with isocyanate endings and a silylated compound comprising alkoxysilane functions.

The crosslinking reaction of these compositions based on optionally 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 silylated polyurethane molecules. These bonds unite the polymer chains into a strong three-dimensional network.

Compositions based on polyurethane with alkoxysilane terminations (also called silylated polyurethane) have the advantage of being free of free isocyanates (once the silylated polyurethane is formed). These compositions therefore constitute an alternative, preferred from a toxicological point of view, to compositions based on polyurethane with isocyanate terminations.

However, the crosslinking time of these silylated polyurethanes, and 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.

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 putty 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, particularly those based on tin, is increasingly highlighted, leading manufacturers to limit, and even avoid their use, especially since these metal catalysts remain in the finished products. .

An alternative to metallic crosslinking catalysts can be organic crosslinking catalysts, in particular 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5,7-triazabicyclo[4.4.0 ]dec-5-ene (TBD) or 1,4-diazabicyclo[2.2.2]octane (DABCO). However, the latter have the disadvantage of causing a yellow color in the finished products due to the migration of the catalyst to the surface of the adhesive and/or putty.

Furthermore, any silylated polyurethanes on the market are generally obtained from raw materials derived from petroleum resources.

However, this dependence on fossil resources risks in the long term limiting, or even preventing, the manufacture of monomers and therefore polymers. In addition, certain raw materials of petroleum origin are criticized on an ecological and economic level, which increases the regulatory limitations concerning them.

At present, the possibly silylated biosourced polyurethanes present on the market have a 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).

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

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

Summary of the invention

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

(ii) a step of reacting the polyol(s) composition (B) with a polyisocyanate to form a polyurethane(s) composition 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(s) composition.

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

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 this request.

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

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. .

Surprisingly, it has been found that the optionally silylated polyurethanes according to the invention can crosslink quickly, even without adding a metallic or organic crosslinking catalyst, while being at least partially biosourced.

Description of the invention

The present invention relates to a process for preparing an ionic polyurethane(s) composition comprising:

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

(ii) a step of reacting the polyol(s) composition (B) with a polyisocyanate to form a polyurethane(s) composition 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(s) composition.

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 implemented after the polyurethane composition(s) resulting from step (ii) has been formulated in the form of adhesive and/or sealant (i.e. say after adding one or more additives usually used in the field of adhesive and/or mastic compositions such as fillers).

By “polyurethane(s) composition resulting from step (ii)”, we mean the polyurethane(s) composition with -NCO terminal 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).

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

In particular, the process for preparing an ionic polyurethane(s) composition comprises:

(i) a step of esterifying a biosourced polyol (A) with a cyclic anhydride to form a polyol(s) composition (B), then

(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 a cb polyurethane composition ( s) ionic(s) with terminal groups -NCO (D).

By “polyol (A)”, we mean 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 f(OH) functionality represents the average number of hydroxyl groups (-OH) per polyol molecule.

Said functionality f(OH) can be determined by measuring the hydroxyl index (denoted IOH) of the polyol, for example by titrimetry according to standard ISO 14900:2017. Said functionality f(OH) can then be calculated as follows: f(OH)= (loH*M _P oiyoi)/56000, where IOH is the hydroxyl index 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.

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 steric exclusion chromatography using polystyrene type standards.

R ² -TOH~|

The polyol (A) can be represented by formula (I): ⁿ in which

R ² is a plurivalent 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 any 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 valencies of the R ² radical linked to the oxygen atoms of the n hydroxyl groups each come from a carbon atom.

The various groups, radicals and letters which are included in the formulas described in this application, retain throughout this text, and, in the absence of contrary indication, the same definition.

By “biosourced”, we mean obtained from resources of biological origin, particularly plant-based, and which may have undergone chemical modifications.

The chemical modifications can be the introduction of ether functions, for example by reaction of hydroxyl groups carried by a polyol (in particular lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and/or glyceride of fatty acids) 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 glyceride of fatty acids, the glyceride of fatty acids comprising several hydroxyl groups. It is understood that these compounds may have undergone chemical modifications.

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

Lignin is generally found in wood, but also in other plant resources. It is a polyphenolic macromolecule comprising several hydroxyl groups.

Sucrose is mainly extracted from sugar cane and sugar beets. It is a disaccharide of glucose and fructose.

Glucose can be obtained from different plants. It is a monosaccharide comprising six carbon atoms.

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

Starch is found in many plants. It is a mixture of amylose and amylopectin, and its crude formula is (C ₆ Hio0 ₅ )n where n is an integer generally between 500 and 1000.

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

Hemicellulose is found mainly in plant cell walls and in wood. It is a linear or branched polysaccharide comprising sugar units which may be the same or different, but not consisting solely of glucose units.

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.

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.

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

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

Preferably, the polyol (A) is a fatty acid glyceride. In this case, the polyol (A) can 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 flaxseed 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 into the fatty acid chains of the glycerides. The hydroxyl group may be directly or indirectly, preferably directly, linked to a carbon atom of the fatty acid chain. For example, when the hydroxyl group is indirectly linked, it may have been introduced by double bond hydroformylation/hydrogenation.

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.

Advantageously at least 50% by weight of biosourced polyol(s) (A), in particular lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and/or glyceride. fatty acids, 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 implemented with a mixture of polyols (A) which is mainly biosourced, that is to say obtained from resources of biological origin, in particular plant-based.

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.

By “cyclic anhydride” is meant a molecule comprising an anhydride function (-C(O)-OC(O)-) engaged in a cycle. In particular, the cyclic anhydride has formula (II):

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

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

The cyclic anhydride can be chosen from maleic anhydride, itaconic anhydride, citracononic anhydride, dimethylmaleic anhydride, succinic anhydride, 2,3-dimethylsuccinic anhydride, tetrapropenylsuccinic anhydride (CAS: 26544 -38-7, isomers having a branched olefin chain), n-dodecenylsuccinic anhydride (CAS: 19780-1 1 -1), glutaric anhydride, 2,4-dimethylglutaric anhydride, 3,3 anhydride -dimethylglutaric anhydride, 3-dimethylglutaric anhydride, adipic anhydride, glycolic anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, 1 -methyl-2-( 2'- carboxyethyl) maleic, 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.

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 anhydride and mixtures thereof.

Preferably, 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, l octenylsuccinic anhydride and mixtures thereof.

More preferably, the cyclic anhydride is chosen from maleic anhydride, itaconic anhydride, citracononic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric acid and their mixtures, in particular maleic anhydride and/or tetrapropenylsuccinic anhydride.

The polyol(s) composition (B) obtained at the end of step (i) comprises one or more polyols (B), said polyol (B) having one or more carboxylic acid groups (-C(O)OH ). Indeed, during step (i), part 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(s) composition (B) comprising at least one polyol (B) having one or more carboxylic acid groups (-C(O)OH).

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.

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)= (loH*M _P oiyoi)/56000, where IOH is the hydroxyl index 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 put into work in step (i)).

The f(OH) functionality of the polyol(s) composition (B) can vary depending on the cyclic anhydride/polyol molar ratio (A). Indeed, part 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 composition of polyol(s) (B) having a weak functionality f(OH).

Thus, the cyclic anhydride/polyol molar ratio (A) is advantageously chosen so as to obtain a polyol(s) composition (B) having an f(OH) functionality as described above.

Other characteristics of step (i)

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

- a polyol (A) being lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and/or a fatty acid glyceride, at least one of said fatty acids comprising one or more hydroxyl groups, and

- a cyclic anhydride chosen from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride, adipic anhydride, glycolic anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, 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 implemented with at least:

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

- a cyclic anhydride chosen from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride and their mixtures , in particular maleic anhydride and/or tetrapropenylsuccinic anhydride.

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

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

- a cyclic anhydride being maleic anhydride and/or tetrapropenylsuccinic anhydride.

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

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

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

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

By “polyisocyanate” is meant a compound comprising at least two isocyanate groups (-NCO), preferably exactly two isocyanate groups (that is to say a diisocyanate). When the polyisocyanate is a diisocyanate, it can therefore be represented by 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.

The polyisocyanate can be:

- a polyisocyanate derived from vegetable oil comprising unsaturated fatty acids (such a polyisocyanate can be obtained by following the process described in G. 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

- a diisocyanate of formula (III): OCN-R ¹ -NCO, R ¹ being 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 ), o 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 allophanate (HDI) of formula (Ilia):

in which :

- i is an integer ranging from 2 to 5;

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

- R ¹² represents a divalent propylene group;

- i, j, R ¹¹ and R ¹² being such that the hexamethylene diisocyanate allophanate corresponding to formula (Ilia) comprises an NCO isocyanate group 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 methyl ester of L-lysine diisocyanate (CAS 34050-00-5), o ethyl ester of 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 o their mixtures.

Advantageously, the polyisocyanate is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, dimeryl diisocyanate, methyl ester of L-lysine diisocyanate, ethyl ester of L -lysine 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.

Preferably, the polyisocyanate is chosen 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.

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

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 implemented with an -NCO/-OH molar equivalent ratio of between 1.1 and 4, preferably between 1.2 and 3, more preferably between 1.3 and 2.0. .

The -NCO/-OH molar equivalent ratio 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 the composition of polyol(s) (B) and the possible alcohol (C) described below).

The molar equivalent number of -NCO groups of the polyisocyanate is equal to: f(— NCO)*(m _P oiyisocyanate/Mpoiyisocyanate), where f(-NCO) is the number of -NCO groups of 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.

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

The molar equivalent number of -OH groups of the alcohol (C) is equal to: (loH*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 the alcohol (C).

Plasticizer

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

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(s) composition.

The plasticizer can be any plasticizer usually used in the field of adhesive and/or putty compositions.

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

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

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

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

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

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

- 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 whose Mn is between 1300-1500 g/mole, and

- their mixtures.

More preferably, the plasticizer is chosen from:

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

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

According to one embodiment, the plasticizer consists of at least 50% by weight of biosourced plasticizer, in particular a mixture of methyl esters of fatty acids such as fatty acids 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 biosourced plasticizer is Esterol A marketed by ARKEMA.

The quantity of plasticizer used in step (ii) can 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. weight, more preferably from 25% to 35% by weight. Alcohol

An alcohol (C), preferably a polyol, can be added to carry out step (il). Alcohol (C) is different from polyol (B). Indeed, alcohol (C) does not include a carboxylic acid group (-C(O)OH).

The alcohol (C) has a number average molar mass Mn greater than or equal to 500 g/mol.

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.

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

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

Poly(farnesene) diol can be obtained from a plant resource. Indeed, some plant resources like apples include farnesene. As an example of a commercial poly(farnesene) diol, we can cite Krasol® F 3000 marketed by Total.

Isosorbide can also be obtained from a plant resource, as it can be obtained from glucose, a sugar very common in plants.

According to this embodiment, the alcohol (C) can 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 valences:

- derived from a poly(farnesene) diol:

- derived from a polyethylene glycol

- derived from a polypropylene glycol

- derived from a polyester diol

- derived from a polybutadiene diol:

- derived from a polyacrylate diol:

- derived from 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,

- q represents an integer such that 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,

- 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,

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

- 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,

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

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.

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(s) composition (B).

Additives

Step (ii) is generally carried out in the presence of a catalyst which can be any catalyst known to those skilled in the art to catalyze 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, we can cite BorchiOKat 315 from the company OMG Borchers which is a bismuth neodecanoate, or even BorchiOKat 15 from this same company which is a zinc neodecanoate. The quantity of catalyst introduced during step (ii) can 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%.

Step (ii) can be carried out in the presence of a UV stabilizer (or antioxidant). A UV stabilizer is typically introduced to prevent degradation resulting from a reaction with oxygen which is likely to be formed by the action of heat or light. UV stabilizers may include antioxidants that can scavenge free radicals.

Advantageously, the UV stabilizer (or antioxidant) is chosen from benzotriazoles, benzophenones, so-called hindered phenols such as bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] of ethylenebis( oxyethylene), 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), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl and 4,4'-bis(o,a-dimethylbenzyl)diphenylamine, and mixtures thereof. We can for example cite the products Irganox® 245, Irganox® 1076, TINUVIN® 292, TINUVIN® 765 or TINUVIN® 770 DF marketed by BASF and RIASORB UV-123 marketed by RIANLON.

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 ethylene bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]bis(oxyethylene) .

The quantity of UV stabilizer (or antioxidant) introduced during step (ii) can 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 features of step (ii)

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

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

The % NCO by weight of said polyurethane(s) composition 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.

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

According to one embodiment, step (ii) is implemented with, in addition to the polyol(s) composition (B), at least:

- a polyisocyanate chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, dimeryl diisocyanate, methyl ester of L-lysine diisocyanate, ethyl ester of L-lysine 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 their mixtures,

- a plasticizer,

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

- optionally a UV stabilizer (or antioxidant).

Preferably, step (ii) is implemented with, in addition to the polyol(s) composition (B), at least:

- 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 their mixtures, in particular isophorone diisocyanate,

- a plasticizer chosen from: o a mixture of methyl esters of fatty acids, in particular of fatty acids comprising 18 carbon atoms such as fatty acids from castor oil including in particular ricinoleic acid, o a mixture of esters of alkylsulphonic acids and phenol, such as the mixture identified by CAS No. 91082-17-6, o diisodecyl phthalate, o diisononyl phthalate, o diisononyl ester of acid 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,

- a catalyst chosen from carboxylates, in particular neodecanoate, bismuth and/or zinc, and

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

More preferably, step (ii) is implemented with, in addition to the polyol(s) composition (B), at least:

- a polyisocyanate being isophorone diisocyanate,

- 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 from castor oil including in particular ricinoleic acid, and/ or o a mixture of alkylsulphonic acid esters and phenol, such as the mixture identified by CAS No. 91082-17-6,

- 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 ethylene bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate]bis(oxyethylene).

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.

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

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

Step (iii)

Step (iii) corresponds to the reaction of a tertiary amine with the carboxylic acid groups of the polyurethane(s) composition resulting from step (ii), in particular the polyurethane(s) composition with -NCO terminal groups formed in step (ii) (to form an ionic polyurethane(s) composition with -NCO (D) end groups) or the non-ionic silylated polyurethane(s) composition^) formed at step (iv) (to form a silylated ionic polyurethane(s) composition (E)). 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 totally ionic, and can be for example a hydrogen bond. It is probable that this interaction explains the absence of yellowing of the compositions obtained from the ionic polyurethane(s) composition according to the invention.

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.

Throughout the application, “pKa of the tertiary amine” means the pKa of its conjugated acid (i.e. of the protonated tertiary amine). The pKa of an acid is equal to — logi o (Ka), Ka being the acidity constant of the acid in water.

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 a or several heteroatoms chosen from N, O and S, and R and R' and/or R and R” and/or R' and R" capable of forming a heterocycle with the nitrogen atom to which they are attached.

According to one embodiment, the tertiary amine is chosen 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-2,2'-ether morpholine (or DMDEE), triazabicyclodecene (TBD), methyltriazabicyclodecene (MTBD), trihexylamine (or THA) and their mixtures. 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 their mixtures.

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

Tertiary amines are often incorporated as a crosslinking catalyst in a polyurethane (optionally silylated) sealant and/or adhesive composition. 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 putty and/or adhesive composition comprising the ionic polyurethane(s) composition according to the invention is observed. Such an effect is probably linked to the interaction of the tertiary amine with the carboxylic acid groups.

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 equal to 1.

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

The molar equivalent number of groups - C(O)OH of the polyol(s) composition (B) is equal to: f(-C(O)OH)*(m _an hydride/M _an hydride), where f( -C(O)OH) is the sum of the number of anhydride functions and the number of groups - C(O)OH 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.

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

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

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

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

HX— R ³ - Si(R ⁴ ) _p (OR 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,

- R ⁴ represents a linear or branched alkyl radical comprising 1 to 4 carbon atoms, and when p is equal to 2, the R ⁴ radicals are identical 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 ⁵ groups 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 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 rings, 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.

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

- 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;

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

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

- p is equal to 0.

Silylated compounds of formula (V) are widely available commercially. We can cite for example N-(3(trimethoxysilyl)propyl)butylamine available under the name Dynasylan® 1 189 from Evonik.

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

In the process according to the invention, step (iv) can be implemented with a molar equivalent ratio -XH/-NCO equal to 1, preferably between 0.90 and 1.15.

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

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).

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

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

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

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

The viscosity at 23°C of the composition of silylated ionic polyurethane(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.

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

Other characteristics of the process according to the invention

Preferred embodiment

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

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

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

- the polyisocyanate is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and/or 2,4'-dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, m-hydrogenated xylylene diisocyanate and their mixtures, in particular isophorone diisocyanate,

- a plasticizer is used, the plasticizer being chosen from: o a mixture of methyl esters of fatty acids, in particular of fatty acids comprising 18 carbon atoms such as fatty acids from castor oil comprising in particular ricinoleic acid, o a mixture of esters of alkylsulphonic acids and phenol, such as the mixture identified by CAS No. 91082-17-6, o diisodecyl phthalate, o diisononyl phthalate, o the ester diisononyl acid 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 500 g/mol mol to 2500 g/mol, and o their mixtures,

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

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

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

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

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

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

- p is equal to 0.

More preferably, the method according to the invention comprises:

(i) a step of esterification of 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, for form a polyol(s) composition (B), then

- the polyisocyanate is isophorone diisocyanate,

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

- optionally a UV stabilizer (or antioxidant) is used, the UV stabilizer being chosen from bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] of ethylenebis(oxyethylene), 2,2'-methylenebis(6-(tert-butyl)-4-methylphenol), 2,2'-methylenebis(6-(tert-butyl)-4-ethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4,6-di(tert-butyl)phenol), 4,4'-methylenebis(2,6- di(tert-butyl)phenol), 2,6-di(tert-butyl)-4-methylphenol and their mixtures, in particular bis[3-(5-tert-butyl-4-hydroxy-m-tolyl) propionate] of ethylenebis(oxyethylene), then

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

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

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

- p is equal to 0.

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.

Solvent

The process according to the invention is advantageously carried out in the absence of solvent.

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

The 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.

Preferably, the process according to the invention is carried out in the absence of water as solvent. Thus, the process according to the invention is implemented without adding free water, that is to say other than that included inherently 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 implementation in step (i) until it has a water content less than 0.1% by weight, preferably less than 0.05% by weight, relative to the weight of the polyol (A). Other ingredients (especially plasticizers) can also be dehydrated in the same way.

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

Moisture absorber

A moisture absorber can 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 terminal groups -NCO (D) has been completed ).

A suitable moisture absorber (or drying agent) is in particular an alkoxysilane such as a trialkoxysilane (particularly a trimethoxysilane). Such an agent advantageously extends the shelf life of the silylated ionic polyurethane(s) composition (E) during storage and transport, before its use.

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

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

The moisture absorber content may be between 0.2% and 3% by weight relative to the total weight of the silylated ionic polyurethane(s) composition (E), preferably between 0. 5% and 1.5% by weight. Biosourced ingredients

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 % in weight.

Thus, the ionic polyurethane(s) compositions (D) and (E) are advantageously made up of at least 50% by weight of biosourced ingredients, respectively relative to the total weight of the ionic polyurethane(s) compositions. (s) (D) and (E), preferably at least 85% by weight.

The biosourced ingredients include polyol (A) and possible plasticizer.

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

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

Silylation step (iv) is not implemented because the ionic polyurethane(s) of said composition (D) is (are) not silylated (but with groups -NCO terminals).

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

The content of ionic polyurethane(s) with -NCO terminal groups in said composition (D) can 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.

Advantageously, the ionic polyurethane(s) composition (D) according to the invention comprises a plasticizer. The plasticizer is as described above. The plasticizer content in said composition (D) can 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%. in weight.

Advantageously, said composition of ionic polyurethane(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 composition of ionic polyurethane(s) (D) obtained by the process according to the invention apply to the composition of ionic polyurethane(s) (D) capable of being obtained by the process according to the invention.

In particular, the ionic polyurethane(s) composition (D) advantageously consists of at least 50% by weight of biosourced ingredients, relative to the total weight of said composition (D), preferably at least less 85% by weight.

Composition of ionic polyurethane(s) silvlé(s) (E) capable of being obtained by the process according to the invention

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 below. Before.

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

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.

Advantageously, the silylated ionic polyurethane(s) composition (E) according to the invention comprises a plasticizer. The plasticizer is as described above. The plasticizer content in said composition (E) can 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%. in weight.

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.

In addition, 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 ionic polyurethane(s). ) silylated(s) (E) capable of being obtained by the process according to the invention.

In particular, the composition of silylated ionic polyurethane(s) (E) advantageously consists of at least 50% by weight of biosourced ingredients, for example relative to the total weight of said composition (E), preferably at least 85% by weight.

The optionally silylated ionic polyurethane according to the invention comprises a unit (M) of the type:

in which :

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

R ¹ is as described above and is directly linked 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 ,

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 as 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 glyceride of fatty acids, R ⁷ is as described above, in particular 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-dodecenyl succinic 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,

- t and u are non-nuclear 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 through which the polyurethane chain is extended or to the nitrogen of an isocyanate group (-NCO) or to the nitrogen of a silylated group of formula (VII):

are as defined above.

The radicals of this pattern are as described above, including preferred characteristics and embodiments.

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

R, R', R” are such that the tertiary amine of formula (IV): N(R)(R')(R") is chosen from TEA, DBU, DABCO, DBN, DCHMA, DMDEE, TBD, MTBD, THA and their mixtures,

R ¹ is such that the diisocyanate of formula (III): OCN-R ¹ -NCO is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and/or 2,4' -dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate and their mixtures, in particular isophorone diisocyanate, R ² is such as 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 ricinoleic acid (tri)glyceride,

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 their mixtures, in particular maleic anhydride and/or tetrapropenylsuccinic anhydride,

- t and u are non-nuclear integers, u being greater than or equal to 2, preferably t is equal to 1 and u is equal to 2.

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 their mixtures. Advantageously, the optionally silylated ionic polyurethane according to the invention is of formula (VI):

in which :

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,

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 glyceride of fatty acids,

R ⁷ is as described above, in particular R ⁷ is such that the cyclic anhydride of formula (II) is chosen from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, l 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 chosen from a poly(farnesene) diol, isosorbide, a polyethylene glycol, a polypropylene glycol, a polyester diol, a polybutadiene diol, a polyacrylate diol and a polysiloxane diol, preferably a polyethylene glycol or a polypropylene glycol, v is a non-zero integer,

- t and u are non-nuclear integers, u being greater than or equal to 2, preferably t is equal to 1 and u is equal to 2,

- it is an integer greater than or equal to 0, preferably equal to 0,

- Y represents f or a carbamate group through which the polyurethane chain is extended, the nitrogen of said carbamate group being directly linked to R ¹ ,

- f represents an isocyanate -NCO group or a monovalent radical

O of formula (VII): — NH-CX- ^R3 -SI( ^R4 ) _P (O ^R5 ) _{3.P IN} | _AQUE || _EX R ³ , R ⁴ , R ⁵ and p are as defined above, preferably f represents a monovalent radical of formula (VII).

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 random copolymer.

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.

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 totally ionic, and can be for example a hydrogen bond. Thus, it is understood that the formulas 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 totally ionic, as long as there is an interaction between them.

The radicals in formula (VI) are as described above, including preferred characteristics and embodiments.

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 their mixtures, in particular DCHMA, R ¹ is such that the diisocyanate of formula (III): OCN-R ¹ -NCO is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate , isophorone diisocyanate, 4,4'- and/or 2,4'-dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate and mixtures thereof, in particular isophorone diisocyanate, 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,

R ⁹ is such that the alcohol of formula HO-R ⁹ -OH is chosen from a poly(farnesene) diol, isosorbide, a polyethylene glycol, a polypropylene glycol, a polyester diol, a polybutadiene diol, a polyacrylate diol and a polysiloxane diol, preferably a polyethylene glycol or a polypropylene glycol, v is a non-zero integer,

- t is equal to 1 and u is equal to 2,

- it is an integer greater than or equal to 0, preferably equal to 0,

- f represents an isocyanate -NCO group or a monovalent radical

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:

- 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;

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

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

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 has formula (VIII):

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

OOH ₇ H e ©

— C— R ⁷ — C— O HN(R)(R')(R") ₍ _|

- 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 above, including the preferred characteristics and the embodiments,

R ² represents the trivalent radical derived from ricinoleic acid triglyceride, the oxygens directly connected 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. oX

can be represented as follows:

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 pattern including the radical R ⁹ ). Preferably, b is equal to 0 in the two radicals of formula (X). In this case, a can be such that the number average molar mass Mn of the ionic polyurethane of formula (VIII) is between 1500 g/mol and 80,000 g/mol, preferably between 2000 g/mol and 30,000 g/mol.

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

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

R ¹ is such that the diisocyanate of formula (III): OCN-R ¹ -NCO is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and/or 2,4' -dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate and their mixtures, in particular isophorone diisocyanate, R ⁷ is such that the cyclic anhydride of formula (II) is chosen from maleic anhydride, the anhydride itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, succinic anhydride, tetrapropenylsuccinic anhydride, n-dodecenylsuccinic anhydride, glutaric anhydride and mixtures thereof, in particular maleic anhydride and/or tetrapropenylsuccinic anhydride , And

- preferably b is equal to zero in the two radicals of formula (X).

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

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

R ⁷ is 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 and

- preferably b is equal to zero in the two radicals of formula (X).

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:

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

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

- p is equal to 0.

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

R ⁷ is 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,

- b is equal to zero in the two radicals of formula (X), and

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

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

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

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

4 carbon atoms, preferably n-butyl, and

- p is equal to 0.

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

Adhesive and/or sealant composition

The invention also relates to an adhesive and/or putty 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 putty composition; in particular, step (iii) can be implemented at the end of the preparation of the adhesive and/or putty composition.

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 putty composition, preferably from 20% to 48% by weight, more preferably from 35% to 45% by weight.

Advantageously, the adhesive and/or putty composition according to the invention further comprises a filler.

The filler content is advantageously between 20% and 60% by weight relative to the total weight of the composition, preferably from 30% to 58% by weight, more preferably from 40% to 55% by weight.

The filler usable in the adhesive and/or putty 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 mastic compositions. These charges are in the form of particles of various geometry. They can be, for example, spherical, fibrous, or have an irregular shape.

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

Among the hollow mineral microspheres, mention may be made of hollow glass microspheres, and more particularly those of sodium and calcium borosilicate or aluminosilicate.

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

Advantageously, the carbonate filler is chosen from alkali or alkaline earth metal carbonates and their mixtures. 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.

When calcium carbonate is coated with fatty acids, this gives total or partial hydrophobicity to the calcium carbonate particles. In addition, the fatty acid coating acts as a hydrophobic coating which can prevent the calcium carbonate from absorbing the constituents of the composition and rendering them ineffective. The hydrophobic coating of calcium carbonate may represent from 0.1% to 3.5% by weight, based on the total weight of calcium carbonate.

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

As an example of an organic filler, any organic filler can be cited, in particular polymeric, usually used in the field of adhesive and/or mastic compositions.

Advantageously, the organic fillers are formed by the group consisting of polyvinyl chloride (PVC), polyolefins, rubber, ethylene vinyl acetate (EVA), hollow microspheres of expandable or non-expandable thermoplastic polymer (such as microspheres hollow vinylidene chloride/acrylonitrile) and aramid fibers (such as Kevlar®), preferably PVC.

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.

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

Unless otherwise indicated, the standards referenced throughout the application are those in effect on the date the application is filed.

According to a preferred embodiment, the adhesive and/or putty composition according to the invention comprises:

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

- 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 putty composition.

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.

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

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

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.

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

As an example of an epoxy-alkoxysilane, mention may be made of (3-glycidyloxypropyl)trimethoxysilane (also called GLYMO).

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 their mixtures. Preferably, the aminotrimethoxysilanes are N-(3-(trimethoxysilyl)propyl)ethylenediamine.

The adhesion promoter content 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.

The rheology agent can be any rheology agent usually used in the field of adhesive and/or putty compositions.

Advantageously, the rheology agent is chosen from:

- 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,

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

- 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

- amide waxes, preferably micronized, such as CRAYVALLAC® SLX, CRAYVALLAC® SLW or CRAYVALLAC® SUPER marketed by Arkema, or THIXATROL® AS8053 or THIXATROL® MAX (EC number: 432-430 - 3) which are available from ELEMENTIS, or the RHEOBYK 7503 marketed by BYK.

By “amide waxes” is meant waxes comprising one or more compounds having at least one amide group. In particular, waxes amides can be obtained from fatty acid(s) (for example ricinoleic acid) and (di)amine(s).

By “micronized” is meant an average particle size of less than 1 mm, advantageously less than 500 pm, preferably less than 100 pm, more preferably less than 10 pm.

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

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.

Advantageously, the adhesive and/or putty composition further comprises a plasticizer. When the adhesive and/or sealant composition comprises the ionic polyurethane(s) composition (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:

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

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

- their mixture.

The total plasticizer content in the adhesive and/or putty 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%. at 10% by weight.

According to one embodiment, the adhesive and/or putty 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) ) (Gifted),

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

- between 1% and 15% by weight of plasticizer,

- between 0.5% and 5% by weight of humidity absorber, and

- 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 putty composition.

Preferably, the composition according to the invention consists essentially of the ingredients mentioned above. By “essentially constituted”, 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, again more preferably less than 1% by weight.

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

Advantageously, no crosslinking catalyst is added to the adhesive and/or putty composition according to the invention.

Indeed, the optionally silylated ionic polyurethane of formula (VI) or included in the composition of ionic polyurethane(s) (D) or (E) alone makes it possible to catalyze the crosslinking reaction. Thus, it is not necessary to add a crosslinking catalyst to said possibly silylated ionic polyurethane.

Therefore, the content of crosslinking catalyst is advantageously less than 0.05% by weight relative to the total weight of the adhesive and/or putty composition, preferably less than 0.02% by weight, more preferably less than 0.015% by weight.

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.

Examples of crosslinking catalysts for silanol condensation include:

- organic derivatives of titanium such as titanium acetyl acetonate, titanium tetrapropylate, titanium tetrabutylate,

- organic zirconium derivatives such as zirconium acetyl acetonate, zirconium tetrapropylate, zirconium tetrabutylate, - amines such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), diethyl-2 ether ,2'-morpholine (DMDEE), 1,4-diazabicylo[2.2.2]octane (DABCO), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD),

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

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

Examples of crosslinking catalysts for the crosslinking of polyurethane include:

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

- organic zirconium derivatives such as zirconium acetyl acetonate, zirconium tetrapropylate, zirconium tetrabutylate,

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

Advantageously, the adhesive and/or putty 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.

The adhesive and/or putty 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 light.

The adhesive and/or putty composition according to the invention can be prepared by simply mixing its ingredients.

Preferably, the adhesive and/or putty 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.

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

An example of preparation of the adhesive and/or putty composition according to the invention is described in Example 7.

Other objects of the invention

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

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

Preferably, the airtight packaging is a polyethylene bag or a polyethylene cartridge fitted with a cover.

Furthermore, the subject of the invention is a process for assembling two substrates comprising:

- coating the adhesive and/or putty composition according to the invention, on at least one of the two substrates to be assembled; Then

- the effective bringing into contact of the two substrates.

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

By “approximately X”, we are aiming for more or less 10% of the value of X.

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 even paint-coated metal and composite substrates (for example, in the field of automobiles).

All the embodiments described above can be combined with each other. In particular, the various aforementioned ingredients of the adhesive and/or putty composition according to the invention, in particular the preferred modes, can be combined with each other.

The examples below are given purely to illustrate the invention and cannot be interpreted as limiting its scope. Examples

1 Ingredients and measurement methods

Ingredients used

The following ingredients were used:

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

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

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

- BorchiOKat 315 marketed by OMG Borchers: bismuth neodecanoate with a molar mass equal to 722.75 g/mol;

Dynasylan® 1,189 marketed by Evonik: N-(3-

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

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

GENIOSIL® GF9 marketed by Wacker: N-(3-

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

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

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

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

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

- 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 equal to 586 .8 g/mol; - PTSI marketed by Sigma Aldrich: p-toluenesulfonyl isocyanate (CAS: 4083-64-1) with a molar mass equal to 197.21 g/mol.

Measurement methods

The water content of the ingredients, in particular castor oil (modified or not), Mesamoll® and Esterol A, is measured according to a Karl Fischer coulometric method using HYDRANAL™ as titrating agent, the equivalence point being detected electrometrically.

The hydroxyl number (noted 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 standard ISO 14900:2017.

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

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

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 excess amine is also titrated automatically with hydrochloric acid.

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

The tensile strength and elongation at break were measured in accordance with standard ISO 37 (2012), at a constant speed equal to 100 mm/min.

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 is 20 mm long, 4 mm wide and 3 mm thick.

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

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

- the elongation at break (expressed in %) which is the elongation of the specimen corresponding to the stretching observed at the moment of rupture, and

- the tensile strength (in MPa) which is the tensile stress at which the rupture of the specimen occurs (also called TS for Tensile Strength in English).

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

The depth of crosslinking is determined by filling a Teflon gutter of increasing depth varying from 1 mm to 10 mm with putty. The length to depth ratio of 20/1 is constant over 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: dimensions of the block: 25 x 5 x 2 cm, dimensions of the recess: 20 x 2 x 1 mm to 10 mm.

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

At the end of these 10 days, we pull on the strip from the side of the thinnest part (i.e. 1 mm) until we reach the part not cross-linked at the core, that is to say a soft non-cohesive part, which tends to stay in the gutter. The corresponding fully crosslinked thickness is noted.

Preparation of PTSI modified castor oil (comparison)

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.

The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 15.3 g of PTSI (i.e. a molar equivalent number of -NCO groups equal to 0.078 mol) and 0.03 g of BorchiOKat 315. The mixture is kept stirring until the band characteristic of the -NCO functions is no longer detectable by infrared spectroscopy (around 2260 cm ^-1 ).

The polyol obtained has an _OH value of approximately 92 mg KOH/g.

Preparation of maleic anhydride modified castor oil

(invention)

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.

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 ).

The polyol obtained has an I _O H of approximately 100 mg KOH/g.

Preparation of a silylated polyurethane PO (comparative)

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.

The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 15.06 g of IPDI (i.e. a molar equivalent number of -NCO groups equal to 0.135 mol), 0.03 g of Borchi®Kat 315 and 0.5 g of Irganox® 245. The mixture is kept stirring until it reaches 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, or 0.037*42=1.55 g of -NCO groups).

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 ).

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

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

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

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

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 _O H) 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.

The reactor is then cooled to 90°C in order to introduce under nitrogen and at atmospheric pressure 14.08 g of IPDI (i.e. a molar equivalent number of -NCO groups equal to 0.127 mol), 0.03 g of Borchi®Kat 315 and 0.5 g of Irganox® 245. The mixture is kept stirring until it reaches a % NCO by weight of 1.7% relative to the total weight of the compounds introduced, which corresponds to the excess of groups - NCOs 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).

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

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 -NCO functions is no longer detectable by infrared spectroscopy. Finally, 1 g of VTMO is added at approximately 40°C with stirring.

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

5

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

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

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

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 putty composition S5 described below.

[Table 1]

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 of P1 and P3).

Replacing Mesamoll® with Esterol A allows the viscosity to be reduced even further (comparison of P2 and P4).

Example 7: Preparation of sealants and characteristics

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

46 g of a PO, P1, P2, P3, P4 or P’5 polymer,

- 50 g of CALOFORT® SV14,

- 3 g of VTMO,

- 1 g of GENIOSIL® GF9, and

- 4.27 g of DCHMA in S5 putty only (obtained from P’5).

The quantity of DCHMA in S2 and S5 sealants is therefore identical.

Firstly, all the ingredients except GENIOSIL® GF9, and DCHMA for S5, are added at room temperature (approximately 23°C) and at atmospheric pressure in a rapid mixer then mixed for 2 min.

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

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

For the S5 putty only, the DCHMA is added once the composition has returned to room temperature and everything is mixed for approximately 10 min.

The sealants obtained are packaged in polyethylene cartridges.

The properties of sealants S0 to S5 (measured in accordance with Example 1) are summarized in Table 2 below.

[Table 2]

The comparative SO and S1 sealants, prepared respectively from the comparative silylated polyurethanes PO and P1 (and without crosslinking catalyst), have a crosslinking time of 105 min and 85 min respectively.

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).

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 putty.

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

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. In fact, the sealants S2 to S5 according to the invention have a tensile strength greater than that of the 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.

In addition, the use of ionic silylated polyurethanes P2 to P5 according to the invention makes it possible to improve the crosslinking in the thickness of the resulting sealants. Indeed, the sealants S2 to S5 according to the invention are crosslinked throughout the entire depth of the joint (10 mm), unlike the comparative sealants S0 and S1 which are only partially crosslinked in the thickness (3 and 3, 5mm).

It should be noted that the ionic silylated polyurethane P5 was indeed obtained in situ from the silylated polyurethane P'5, because no yellowing of the S5 putty was observed (confirming that an interaction between DCHMA and the carboxylic acid groups of P'5 occurred well in the putty). Furthermore, the properties of S2 and S5 are similar. The tertiary amine can therefore be used during the preparation of the polyurethane or in the final composition.

Claims

1. Process for preparing an ionic polyurethane(s) composition comprising:

2. Method according to claim 1, in which the polyol (A) is lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and/or an acid glyceride fatty, the glyceride of fatty acids comprising several hydroxyl groups.

3. Method according to claim 1 or 2, in which 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- anhydride (2'-carboxyethyl)maleic, octenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, 1,2-cis-cyclohexanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, trimellitic anhydride and mixtures thereof.

4. Method according to any one of claims 1 to 3, in which the polyisocyanate is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, dimeryl diisocyanate, methyl ester of L-lysine diisocyanate, ethyl ester of L-lysine 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.

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. Process according to any one of claims 1 to 5, in which the tertiary amine is chosen 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 their mixtures.

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 polyurethane composition (s) silylated(s), the silylated compound being of formula (V):

HX— R ³ - Si(R ⁴ ) _p (OR ⁵ ) ₃ . _p (V) in which:

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

- p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1. Composition of ionic polyurethane(s) with -NCO (D) terminal groups obtainable 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 the type:

in which :

R, R', 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, 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 as diisocyanate of formula (III): OCN-R ¹ -NCO is chosen from the diisocyanates described in claim 4,

R ² is a plurivalent 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 divalent hydrocarbon radical, optionally branched, which may comprise one or more optionally aromatic rings, 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,

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 with a 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 chosen from a poly(farnesene) diol, isosorbide, a polyethylene glycol, a polypropylene glycol, a polyester diol, a polybutadiene diol, a polyacrylate diol and a polysiloxane diol, preferably a polyethylene glycol or a polypropylene glycol, v is a non-zero integer,

- it is an integer greater than or equal to 0, preferably equal to 0,

- f represents an isocyanate -NCO group 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 1 1, being of formula (VIII):

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

O O

It ₇ A.M. ©

— C— R ⁷ — C— O HN(R)(R')(R") ₍ _|

- 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,

- 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 polyurethane composition ionic(s) (D) or (E) according to one of claims 8 or 9, preferably (E). An adhesive and/or sealant composition according to claim 13, further comprising a filler.