Polyurethane composition

Abstract

The present invention relates to a process for preparing a polyurethane composition comprising a step (i) of reacting an alkoxylated bio-sourced polyol (A) with a polyisocyanate to form a polyurethane composition with –NCO end groups, in which said polyol (A) comprises a carboxylic acid group and has a total alkoxylation number at least equal to 5. The present invention also relates to a polyurethane composition, an adhesive and / or sealant composition, a process for assembling substrates and an article. Figure for abstract: none

Description

Title of the invention: Polyurethane composition Field of invention

[0001] The present invention relates to a method of preparing a polyurethane composition, a polyurethane composition, an adhesive and / or sealant composition, a method of joining substrates and an article. Technical background

[0002] Polyurethanes are generally used as adhesives, sealants, coatings, for example in the aeronautical, automotive or construction industries. Polyurethanes can be silylated; in this case, they generally comprise 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 terminations and a silylated compound comprising alkoxysilane functions.

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

[0004] Compositions based on polyurethane with alkoxysilane end groups (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 -NCO end groups.

[0005] However, polyurethanes on the market are generally obtained from raw materials derived from petroleum resources. This dependence on fossil resources risks limiting, or even preventing, the manufacture of monomers and therefore polymers in the long term. In addition, certain raw materials of petroleum origin are criticized from an ecological and economic point of view, which increases the regulatory limitations concerning them.

[0006] There is therefore a need for new polyurethanes which are at least partially bio-sourced.

[0007] Furthermore, there is a need for polyurethanes which are at least partially bio-sourced and have suitable mechanical properties, in particular viscosity, tensile strength and elongation at break, for use as adhesive and / or sealant. Summary of the invention

[0008] The present invention relates to a process for preparing a polyurethane composition comprising a step (i) of reacting an alkoxylated bio-sourced polyol (A) with a polyisocyanate to form a polyurethane composition with -NCO end groups, in which said polyol (A) comprises a carboxylic acid group and has a total alkoxylation number at least equal to 5.

[0009] The invention also relates to a polyurethane composition capable of being obtained by the process according to the invention.

[0010] The invention also relates to an adhesive and / or mastic composition capable of being obtained by the process according to the invention.

[0011] Furthermore, the invention relates to a method for assembling substrates comprising:

[0012] - coating, on at least one surface of the substrates to be assembled, the composition adhesive and / or sealant according to the invention, then

[0013] - bringing the substrates into contact.

[0014] The present invention also relates to an article comprising the adhesive and / or sealant composition according to the invention.

[0015] Surprisingly, it was found that the polyurethane composition obtained from the alkoxylated bio-sourced polyol (A) made it possible to obtain compositions of reduced viscosity and having improved elongation at break, while maintaining acceptable tensile strength. Description of the invention

[0016] Process for preparing a polyurethane composition Polyol (A)

[0017] The polyol (A) is biosourced and alkoxylated, and comprises a carboxylic acid group.

[0018] By "bio-sourced" is meant obtained from resources of biological origin, in particular plant-based, and which may have undergone chemical modifications. In particular, since the polyol (A) is alkoxylated, it has at least undergone alkoxylation as a chemical modification.

[0019] An alkoxylation can be defined as the introduction of ether functions, for example by reaction of one or more hydroxyl groups carried by a polyol (in particular a polyphenol, a carbohydrate and / or a glyceride of fatty acid(s)) with an epoxide, in particular propylene oxide and / or ethylene oxide. Preferably, the polyol (A) is ethoxylated and / or propoxylated, more preferably ethoxylated.

[0020] When the polyol (A) is ethoxylated, one or more of its hydroxyl groups have reacted with ethylene oxide, leading to the formation of at least one -O-(CH2CH2O)n- group, in which n is other than 0.

[0021] When the polyol (A) is propoxylated, one or more of its hydroxyl groups have reacted with propylene oxide, leading to the formation of at least one -O-(CH(CH3)CH2O)m- and / or -O-(CH2CH(CH3)O)m- group, in which m is different from 0 and may be the same or different in each group if the polyol comprises both -O-(CH(CH3)CH2O)m- and -O-(CH2CH(CH3)O)m-.

[0022] The total number of alkoxylations (in particular EO and / or PO) of the alkoxylated biosourced polyol (A) may be between 5 and 100, preferably between 25 and 60, more preferably between 30 and 50. Preferably, the polyol (A) is ethoxylated and its total number of EOs is between 5 and 100, preferably between 25 and 60, more preferably between 30 and 50. The total number of alkoxylations (in particular EOs when the polyol (A) is ethoxylated) may be determined as being the molar ratio of alkylene oxide / compound to be alkoxylated (preferably the polyol (A1) as defined below).

[0023] The hydroxyl number I0H of the polyol (A) may be between 10 mg KOH / g and 100 mg KOH / g, preferably between 30 mg KOH / g and 80 mg KOH / g. The hydroxyl number is expressed in mg of KOH per g of polyol (A). The hydroxyl number IOH may be measured according to ASTM E1899-16, for example as indicated in Example 1.

[0024] The acid number Icooh of the polyol (A) may be between 5 mg KOH / g and 50 mg KOH / g, preferably between 10 mg KOH / g and 40 mg KOH / g. The acid number is expressed in mg of KOH per g of polyol (A). The acid number may be measured according to methods well known to those skilled in the art, for example by potentiometry.

[0025] Advantageously, the polyol (A) has a functionality f(OH) greater than 1.0, preferably between 1.2 and 2.5, f(OH) representing the average number of hydroxyl groups per molecule of polyol.

[0026] The functionality f(OH) of a polyol can be determined by measuring its IOH, for example according to ASTM E1899-16. Said functionality f(OH) can then be calculated as follows: f(OH)= (IOH*Mpoiyoi) / 56100, where IOH is the hydroxyl number in mg KOH / g of the polyol and Mpoiyoi is the number average molecular weight of the polyol in g / mol.

[0027] The number-average molecular mass of the alkoxylated biosourced polyol (A) may be between 1500 g / mol and 50000 g / mol, preferably between 1800 g / mol and 30000 g / mol, more preferably between 2000 g / mol and 10000 g / mol.

[0028] In the present text, the number-average molecular mass can be determined by gel permeation chromatography (GPC), in particular using polystyrene-type standards, for example according to Example 1 below.

[0029] Preferably, the alkoxylated biosourced polyol (A) is obtained from a polyol (Al) bio-sourced, the polyol (Al) being a polyphenol (in particular lignin), a carbohydrate (in particular sucrose, glucose, fructose, starch, hemicellulose, cellulose) and / or a glyceride of fatty acid(s). It is understood that these compounds may have undergone chemical modifications other than alkoxylation (for example hydroxylation).

[0030] Advantageously, the polyol (Al) has a functionality f(OH) greater than or equal to 2, preferably greater than or equal to 2.0, more preferably greater than 2.0, for example between 2.5 and 3.0. The functionality f(OH) of the polyol (Al) can be determined as indicated above, with Mpoiyoi being the molar mass of the polyol in g / mol. When the polyol is a polymer, its molar mass is its number-average molar mass Mn.

[0031] Lignin is generally found in wood, but also in other plant resources. It is a polyphenolic macromolecule comprising several hydroxyl groups.

[0032] Sucrose is mainly extracted from sugar cane and sugar beet. It is a disaccharide of glucose and fructose.

[0033] Glucose can be obtained from various plants. It is a monosaccharide comprising six carbon atoms.

[0034] Fructose is found mainly in fruits and honey. It is also a monosaccharide comprising six carbon atoms.

[0035] Starch is found in many plants. It is a mixture of amylose and amylopectin, and its molecular formula is (C6Hi0O5)n where n is an integer generally between 500 and 1000.

[0036] Cellulose is generally found in the wall of plant cells. It is a linear polysaccharide made up of glucose units.

[0037] Hemicellulose is found mainly in the wall of plant cells and in wood. It is a linear or branched polysaccharide comprising sugar units which may be the same or different, but which does not consist solely of glucose units.

[0038] 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.

[0039] In the context of the invention, the ranges of values ​​are understood to include the limits. For example, the range “between 4 and 28” includes in particular the values ​​4 and 28.

[0040] By "glyceride" is meant an ester obtained from glycerol and fatty acid(s), which may be the same or different. In particular, the glyceride of fatty acid(s) may be a mixture of fatty acid monoglyceride(s), fatty acid diglyceride(s) and / or fatty acid triglyceride(s). Preferably, the fatty acid glyceride(s) comprises at least one fatty acid triglyceride.

[0041] The fatty acid glyceride may be directly in the form of a plant resource (for example, the fatty acid glyceride may be castor oil). The plant resource may also have been modified prior to an alkoxylation reaction; for example, hydroxyl groups may have been introduced onto the fatty acid chains (such as by double bond epoxidation).

[0042] Preferably, the bio-sourced polyol (Al) is a glyceride of fatty acid(s). In this case, the polyol (Al) may be castor oil and / or a hydroxylated vegetable oil, said vegetable oil being able, for example, to be soybean oil, rapeseed oil, corn oil, cottonseed oil, linseed oil, olive oil, sesame oil, walnut oil, sunflower oil, acorn oil (for example cork oak), tall oil, safflower oil, grape oil, etc. A vegetable oil is said to be “hydroxylated” when it has been modified so as to introduce hydroxyl groups onto the fatty acid chains of the glycerides. The hydroxyl group may be directly or indirectly, preferably directly, bonded to a carbon atom of the fatty acid chain. For example, when the hydroxyl group is indirectly bonded, it may have been introduced by hydroformylation / hydrogenation of a double bond.

[0043] More preferably, the bio-sourced polyol (Al) is a glyceride, in particular a triglyceride, of ricinoleic acid. In this case, the bio-sourced polyol (Al) is advantageously castor oil.

[0044] The bio-sourced polyol (Al) is different from the alkoxylated bio-sourced polyol (A). In particular, it is not alkoxylated.

[0045] The alkoxylated bio-sourced polyol (A) comprises a carboxylic acid group. In the present text, and unless otherwise stated (such as “exactly one”), “one” means one or more.

[0046] Advantageously, at least one carboxylic acid group of the alkoxylated biosourced polyol (A) is derived from an esterification with a cyclic anhydride, preferably substituted, of an alkoxylated biosourced polyol (A2), the polyol (A2) corresponding to the biosourced polyol (Al) after alkoxylation (and possibly other chemical modifications, except an esterification with a cyclic anhydride). Indeed, during the esterification, a portion of the hydroxyl groups of the polyol (A2) reacts with the anhydride function of said anhydride to lead to the formation of a carboxylic acid group (-C(=O)OH). Said anhydride may also carry a carboxylic acid group, which will lead to a higher acid number Icooh.

[0047] The alkoxylated bio-sourced polyol (A2) preferably has the same total alkoxylation number (in particular EO and / or PO) as the alkoxylated bio-sourced polyol (A).

[0048] The f(OH) functionality of the alkoxylated bio-sourced polyol (A) can vary depending on the anhydride / polyol (A2) molar ratio. Indeed, a portion of the hydroxyl groups of the polyol (A2) react with the anhydride to form an ester bond, and a high anhydride / polyol (A2) molar ratio leads to an alkoxylated bio-sourced polyol (A) having a low f(OH) functionality. Thus, the anhydride / polyol (A2) molar ratio is advantageously chosen so as to obtain an alkoxylated bio-sourced polyol (A) having an f(OH) functionality as described above.

[0049] Polyols (A2) (i.e. biosourced polyols (Al) which have been alkoxylated) are commercially available, for example under the name “Surfaline® R” by ARKEMA which correspond to ethoxylated castor oil (CAS: 61791-12-6).

[0050] By "cyclic anhydride" is meant a molecule comprising an anhydride function (-C(=O)-OC(=O)-) engaged in a cycle. In particular, the cyclic anhydride is of formula (I): HAS R7

[0051] (I)

[0052] in which R7 is a saturated or unsaturated, optionally branched, divalent hydrocarbon radical, which may comprise one or more optionally aromatic cycles, and optionally comprising one or more heteroatoms chosen from oxygen and sulfur, preferably optionally one or more heteroatoms chosen from oxygen.

[0053] Preferably, the cyclic anhydride is substituted. This can be translated in formula (I) by R7 comprising at least one carbon atom of valence equal to 3 or 4 (i.e. directly linked to 3 or 4 atoms other than hydrogen).

[0054] When the cyclic anhydride is substituted, the substituent may be a straight or branched chain which may include an optionally aromatic ring, or may form an optionally aromatic ring with the ring of the anhydride (e.g., phthalic anhydride). Preferably, the substituent comprises 1 to 22 carbon atoms, more preferably 3 to 22 carbon atoms.

[0055] 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.

[0056] The cyclic anhydride may be chosen from itaconic anhydride, citraconic anhydride, maleic anhydride, dimethylmaleic anhydride, succinic anhydride, 2,3-dimethylsuccinic anhydride, octenylsuccinic anhydride, decenylsuccinic anhydride, dodecenylsuccinic anhydride (for example CAS: 26544-38-7 (isomers having a branched olefin chain) and / or CAS: 19780-11-1 (n-dodecenylsuccinic anhydride)), tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, ei-cosenylsuccinic anhydride, glutaric anhydride, 2,4-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride, 3-dimethylglutaric anhydride, adipic anhydride, glycolic anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, l-methyl-2-(2'-carboxyethyl)maleic anhydride, phenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, trimellitic anhydride, nadic anhydride, methylnadic anhydride, and mixtures thereof.

[0057] Advantageously, the cyclic anhydride is a substituted cyclic anhydride chosen from substituted maleic anhydrides, substituted succinic anhydrides, substituted glutaric anhydrides, and mixtures thereof, the substituent preferably comprising 1 to 22 carbon atoms, more preferably 3 to 22 carbon atoms.For example, the substituted cyclic anhydride may be selected from itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, 2,3-dimethylsuccinic anhydride, allylsuccinic anhydride, octenylsuccinic anhydride, decenylsuccinic anhydride, dodecenylsuccinic anhydride (e.g., CAS: 26544-38-7 (isomers having a branched olefin chain) and / or CAS: 19780-11-1 (n-dodecenylsuccinic anhydride)), tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, ei-cosenylsuccinic anhydride, 2,4-Dimethylglutaric anhydride, 3,3-Dimethylglutaric anhydride, 3-Dimethylglutaric anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, l-methyl-2-(2'-carboxyethyl)maleic anhydride, phenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, hexahydrophthalic anhydride, anhydride. 1,2-cyclopentanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, phthalic anhydride, homophthalic anhydride, trimellitic anhydride, nadic anhydride, methylnadic anhydride, and mixtures thereof.

[0058] Preferably, the substituted cyclic anhydride is selected from octenylsuccinic anhydride, decenylsuccinic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, eicosenylsuccinic anhydride, phenylsuccinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, phthalic anhydride, homophthalic anhydride, nadic anhydride, anhydride methylnadic, and mixtures thereof.

[0059] More preferably, the substituted cyclic anhydride is chosen from decenylsuccinic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, phenylsuccinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, and mixtures thereof, in particular dodecenylsuccinic anhydride, phthalic anhydride, and mixtures thereof.

[0060] According to one embodiment, the polyol (A) is ethoxylated and / or propoxylated, and has a total average alkoxylation number of between 25 and 60, the polyol (A) being obtained from a glyceride of fatty acid(s), preferably esterified with a substituted cyclic anhydride.

[0061] Preferably, the polyol (A) is ethoxylated and / or propoxylated, has a total average alkoxylation number of between 30 and 50, the polyol (A) being obtained from castor oil esterified with a substituted cyclic anhydride, preferably chosen from decenylsuccinic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, phenylsuccinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, and mixtures thereof, in particular dodecenylsuccinic anhydride, phthalic, and their mixture.

[0062] The characteristics of the polyol (A) disclosed above apply to this embodiment (including the preferred embodiments and characteristics).

[0063] The alkoxylated bio-sourced polyol (A) can be obtained by a process comprising (in particular consisting of):

[0064] - the alkoxylation of a biosourced polyol (Al) being a polyphenol, a carbohydrate and / or a glyceride of fatty acid(s), in particular lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose and / or a glyceride of fatty acid(s), to obtain an alkoxylated bio-sourced polyol (A2), then

[0065] - esterification of the polyol (A2) with a substituted cyclic anhydride.

[0066] Preferably, the alkoxylated bio-sourced polyol (A) is obtained by a process comprising (in particular consisting of):

[0067] - the alkoxylation of a biosourced polyol (Al) being a glyceride of fatty acid(s), in par particular ricinoleic acid, to obtain a bio-sourced alkoxylated polyol (A2), then

[0068] - esterification of the polyol (A2) with a substituted cyclic anhydride chosen from octenylsuccinic anhydride, decenylsuccinic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, eicosenylsuccinic anhydride, phe- anhydride nylsuccinic anhydride, hexahydrophthalic anhydride, anhydride 1,2-cyclopentanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, phthalic anhydride, homophthalic anhydride, nadic anhydride, methylnadic anhydride, and mixtures thereof.

[0069] More preferably, the alkoxylated biosourced polyol (A) is obtained by a process comprising (in particular consisting of):

[0070] - the alkoxylation of a biosourced polyol (Al) being castor oil, to obtain a alkoxylated bio-sourced polyol (A2), then

[0071] - esterification of the polyol (A2) with a substituted cyclic anhydride chosen from decenylsuccinic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, phenylsuccinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, and mixtures thereof, in particular dodecenylsuccinic anhydride, phthalic anhydride, and mixtures thereof.

[0072] The characteristics of the polyols (A), (A1) and (A2) disclosed above apply to this process for obtaining the polyol (A). In particular, the alkoxylation is advantageously carried out with an alkylene oxide / polyol (A1) molar ratio chosen so as to obtain a polyol (A) having a total alkoxylation number as described above, and the cyclic anhydride / polyol (A2) molar ratio is advantageously chosen so as to obtain a polyol (A) having an f(OH) functionality as described above.

[0073] Alkoxylation is a reaction well known to those skilled in the art. For example, it can be carried out by reacting the bio-sourced polyol (Al) with an alkylene oxide in the presence of a catalyst (for example, a Brônsted base such as KOH or NaOH, or a Lewis acid, preferably a Brônsted base), in particular at a temperature between 120°C and 190°C.

[0074] As indicated above, alkoxylated biosourced polyols (A2) are commercially available (the alkoxylation step is therefore carried out by the supplier of the polyol (A2)).

[0075] The esterification is advantageously carried out under anhydrous conditions.

[0076] The esterification is advantageously carried out at a temperature between between 60°C and 120°C, preferably between 80°C and 100°C.

[0077] Esterification can be carried out at atmospheric pressure. Polyisocyanate

[0078] By "polyisocyanate" is meant a compound comprising at least two isocyanate groups (-NCO), preferably exactly two isocyanate groups (i.e. a diisocyanate). When the polyisocyanate is a diisocyanate, it can therefore be represented by the formula (II): OCN-R'-NCO in which R1 is a divalent hydrocarbon radical comprising from 4 to 45 carbon atoms, and optionally comprising one or more heteroatoms chosen from oxygen, sulfur and nitrogen.

[0079] The polyisocyanate can be:

[0080] - a) a polyisocyanate derived from vegetable oil comprising unsaturated fatty acids (such a polyisocyanate can be obtained by following the method described in G. Çayh et al., Biobased polyisocyanates from plant oil triglycerides Synthesis, polymerization, and characterization, J. Appl. Polym. Sci., 2008, 109, 2948-2955), in particular a polyisocyanate derived from soybean oil, and / or

[0081] - b) a diisocyanate of formula (II): OCN-R'-NCO, R1 being such that the diisocyanate is chosen from:

[0082] - a diisocyanate derived from furan such as 2,5-diisocyanatofuran, 2,5-bis(isocyanatomethyl)furan, 2,2'-(l-methylethylidene)bis[5-isocyanatofuran] (CAS 1008130-81-1), 2-isocyanato-5-[(5-isocyanatofuran-2-yl)methyl]furan (CAS 88768-51-8), 2-isocyanato-5-[l-(5-isocyanatofuran-2-yl)ethyl]furan (CAS 88768-52-9), [oxybis(methylene-5,2-furandiylmethylene)]diisocyanate (CAS 96732-82-0), 2-(isocyanatomethyl)-5-[2-[5-(isocyanatomethyl)furan-2-yl]propan-2-yl]furan (CAS 88768-56-3),

[0083] - a diisocyanate derived from dianhydrohexitol of formula: - a diisocyanate derived from methoxyphenyl of formula: ,NCO

[0084] vr' OCH. GCH

[0085] in which R8 represents a hydrogen atom or a methoxy group and m is an integer between 1 and 3,

[0086] - a hexamethylene diisocyanate (HDI) allophanate of formula (IIa):

[0087] "OLXr MX) in which:

[0088] - i is an integer ranging from 2 to 5;

[0089] - j is an integer ranging from 1 to 2;

[0090] - R11 represents a hydrocarbon radical, saturated or unsaturated, cyclic, linear or branched, comprising 6 to 14 carbon atoms;

[0091] - R12 represents a divalent propylene group;

[0092] - i, j, R11 and R12 being such that the hexamethylene diisocyanate allophanate cor corresponding to formula (IIa) comprises an isocyanate group NCO content ranging from 12 to 14% by weight relative to the weight of said allophanate,

[0093] - pentamethylene diisocyanate (PDI),

[0094] - hexamethylene diisocyanate (HDI),

[0095] - 1,7-diisocyanatoheptane,

[0096] - 1,8-diisocyanatooctane,

[0097] - 1,9-diisocyanatononane,

[0098] -1,16-diisocyanato-8-hexadecene,

[0099] - l-isocyanato-10-[(isocyanatomethyl)thio]decane,

[0100] - dimeryl diisocyanate (CAS 68239-06-5),

[0101] - L-lysine diisocyanate methyl ester (CAS 34050-00-5),

[0102] - L-lysine diisocyanate ethyl ester (CAS 45172-15-4),

[0103] - 2,4-diisocyanato-l-pentadecylbenzene,

[0104] - isophorone diisocyanate (IPDI),

[0105] - 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate (HMDI),

[0106] - 2,4- and / or 2,6-toluene diisocyanate (TDI),

[0107] - 4,4'- and / or 2,4'-diphenylmethane diisocyanate (MDI),

[0108] - m-xylylene diisocyanate (m-XDI),

[0109] - hydrogenated m-xylylene diisocyanate (m-H6XDI), and

[0110] - their mixtures.

[0111] Advantageously, the polyisocyanate is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, dimeryl diisocyanate, L-lysine diisocyanate methyl ester, L-lysine diisocyanate ethyl ester, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 4,4'- and / or 2,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate and mixtures thereof.

[0112] 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.

[0113] More preferably, the polyisocyanate is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylethane diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate and mixtures thereof, in particular isophorone diisocyanate.

[0114] Advantageously, step (i) 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 (A). Preferably, step (i) is carried out with an -NCO / -OH molar equivalent ratio of between 1.1 and 4, more preferably between 1.2 and 3, for example between 1.3 and 2.

[0115] The molar equivalent ratio -NCO / -OH is defined as being equal to the molar equivalent number of -NCO groups of the polyisocyanate divided by the sum of the molar equivalent number of -OH groups used during step (i) (in particular of the polyol (A) and of the optional alcohol (B) described below).

[0116] The molar equivalent number of -NCO groups of the polyisocyanate is equal to: f(-NCO)*(mpoiyisocyanate / Mpoiyisocyanate), where f(-NCO) is the number of -NCO groups of the polyisocyanate, mpoiyisocyanate is the mass introduced in g of the polyisocyanate and Mpoiyisocyanate is the molar mass in g / mol of the polyisocyanate. Preferably, the polyisocyanate is a diisocyanate and f(-NCO) is therefore equal to 2.

[0117] The molar equivalent number of -OH groups of an alcohol (in particular of the polyol (A) or of the alcohol (B)) is equal to: (Ioh*hiOh) / 56100, where I0H is the hydroxyl number in mg KOH / g of the alcohol and where m0H is the mass introduced in g of the alcohol. Alcohol (B)

[0118] An alcohol (B), preferably a polyol, may be added to carry out step (i). The alcohol (B) is different from the polyol (A). Preferably, the alcohol (B) does not comprise a carboxylic acid group (-C(=O)OH).

[0119] The alcohol (B) has a number-average molar mass Mn greater than or equal to 500 g / mol.

[0120] The alcohol (B) 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.

[0121] Said functionality f(OH) can be determined as indicated above for the polyol (A).

[0122] For example, the alcohol (B) may be the biosourced polyol (Al) as described above, optionally modified, in particular alkoxylated (in particular a polyphenol, a carbohydrate and / or a glyceride of fatty acid(s), a poly(farnesene) diol, isosorbide, a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyacrylate polyol, a polysiloxane polyol and / or a polyolefin polyol, preferably a polyether polyol

[0123]

[0124]

[0125]

[0126] such as polypropylene glycol or polyethylene glycol. Poly(farnesene) diol can be obtained from a plant resource. Indeed, some plant resources such as apples contain farnesene. An example of a commercial poly(farnesene) diol is Krasol® F 3000 marketed by Total. Isosorbide can also be obtained from a plant resource, as it can be obtained from glucose, a sugar that is very common in plants. In particular, the alcohol (B) may be of formula HO-R9-OH in which the radical R 9 is chosen from the following divalent radicals whose formulas below show the two free valencies: - derivative of a poly(farnesene) diol:

[0127]

[0128]

[0129]

[0130]

[0131]

[0132] - isosorbide derivative: H / H - derived from a polyethylene glycol: - derived from a polypropylene glycol: - derived from a polyester diol: - derivative of a polybutadiene diol: - derivative of a polyacrylate diol: -0- ty Q CH: Q' ©' 0 CH- GO

[0133] - derivative of a polysiloxane diol: Q3 Q5 Q' <1 r । “ii 2 —Q—Si-O-LsiO^Si— Q— QQQ

[0134] in which:

[0135] - x and y are integers; preferably x and y are such that the average molar mass in number Mn of the poly(famesene) diol is between 500 g / mol and 8000 g / mol, more preferably between 1000 g / mol and 5000 g / mol,

[0136] - q represents an integer such that the number-average molar mass Mn of the radical R9 ranges from 500 g / mol to 20000 g / mol, preferably from 3000 g / mol to 14000 g / mol,

[0137] - r and s represent zero or a non-zero integer such that the average molar mass in number of the radical R9 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,

[0138] - Q1 represents a linear aromatic or aliphatic divalent alkylene radical or branched, saturated or unsaturated, preferably having from 1 to 18 carbon atoms, more preferably from 1 to 8 carbon atoms,

[0139] - Q2 represents a linear or branched divalent alkylene radical having preferably from 2 to 36 carbon atoms, more preferably from 1 to 8 carbon atoms,

[0140] - Q3, Q4, Q5, Q6, Q7 and Q8, represent, independently of each other, an atom of hydrogen or an alkyl, alkenyl or aromatic radical, preferably having from 1 to 12 carbon atoms, preferably from 2 to 12 carbon atoms, more preferably from 2 to 8 carbon atoms.

[0141] Preferably, the radical R9 represents a radical derived from a polyether, in particular from a polyethylene glycol or from a polypropylene glycol as described above.

[0142] The quantity of alcohol (B) introduced during step (i) can be up to 80% by weight relative to the weight of the polyol (A), preferably up to 50% by weight, more preferably up to 20% by weight. Additives from step (i)

[0143] Step (i) is generally carried out in the presence of a catalyst which may be any catalyst known to those skilled in the art for catalyzing the formation of polyurethane by reaction of a polyisocyanate and at least one polyol. Such a catalyst is for example chosen from carboxylates, in particular neodecanoate, of bismuth and / or zinc. As commercially available examples, we can cite Borchi®Kat 315 from the company OMG Borchers which is a bismuth neodecanoate, or Borchi®Kat 15 from the same company which is a zinc neodecanoate.

[0144] The quantity of catalyst introduced during step (i) can vary between 0.01% and 0.5% by weight relative to the weight of the polyol (A), preferably between 0.02% and 0.4%, more preferably between 0.04% and 0.2%.

[0145] Step (i) may be carried out in the presence of a UV stabilizer (or antioxidant). A UV stabilizer is typically introduced to prevent degradation resulting from a reaction with oxygen which is likely to be formed by the action of heat or light. UV stabilizers may include antioxidants capable of scavenging free radicals.

[0146] Advantageously, the UV stabilizer (or antioxidant) is chosen from benzotriazoles, benzophenones, so-called hindered phenols such as ethylenebis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], 2,2'-methylenebis(6-(tert-butyl)-4-methylphenol), 2,2'-methylenebis(6-(tert-butyl)-4-ethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4,6-di(tert-butyl)phenol), 4,4'-methylenebis(2,6-di(tert-butyl)phenol) and 2,6-di(tert-butyl)-4-methylphenol, so-called hindered amines such as bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate (CAS No. 41556-26-7), methyl l,2,2,6,6-pentamethyl-4-piperidyl sebacate (CAS No. 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 4,4'-bis(a,a-dimethylbenzyl)diphenylamine, and mixtures thereof.Examples include the products Irganox® 245, Irganox® 1076, TINUVIN® 292, TINUVIN® 765 or TINUVIN® 770 DF marketed by BASF and RIASORB UV-123 marketed by RIANLON.

[0147] 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

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154] their mixtures. The amount of UV stabilizer (or antioxidant) introduced during step (i) may vary between 0.1% and 5% by weight relative to the weight of the polyol (A), preferably between 0.2% and 3%. Other features of step (i) The %NCO by weight of the polyurethane composition with -NCO end groups obtained at the end of step (i) can vary between 0.3% and 5% relative to the total weight of said composition, preferably between 0.5% and 3%. The %NCO by weight of said polyurethane 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 composition may vary depending on the polyol (A) / polyisocyanate molar ratio. According to one embodiment, step (i) is carried out with, in addition to the polyol (A), at least: - a polyisocyanate selected from pentamethylene diisocyanate, hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, dimeryl diisocyanate, L-lysine diisocyanate methyl ester, L-lysine diisocyanate ethyl ester, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 4,4'- and / or 2,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate and mixtures thereof, - 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 (i) is carried out with, in addition to the polyol (A), at least: - one polyisocyanate chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate and mixtures thereof, in particular isophorone diisocyanate, - a catalyst chosen from carboxylates, in particular neodecanoate, of bismuth and / or zinc, and - optionally a UV stabilizer (or antioxidant) chosen from so-called hindered phenols. The characteristics of step (i) disclosed above apply to this embodiment. In particular, the quantities used in this embodiment are advantageously as described above.

[0155] Step (i) is advantageously carried out under anhydrous conditions.

[0156] Step (i) is advantageously carried out at a temperature between 50°C and 120°C, preferably between 60°C and 100°C.

[0157] Step (i) can be carried out at atmospheric pressure. Step (ii): silylation

[0158] Advantageously, the process according to the invention further comprises a step (ii) of silylation of the polyurethane composition with -NCO end groups resulting from step (i) (preferably directly resulting from step (i)) with a silylated compound to form a silylated polyurethane composition, the silylated compound being of formula (III):

[0159] (III)

[0160] in which:

[0161] - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms,

[0162] - R4 represents a linear or branched alkyl radical comprising from 1 to 4 atoms of carbon, and when p is equal to 2, the radicals R4 are identical or different,

[0163] - R5 represents a linear or branched alkyl radical comprising from 1 to 4 atoms of carbon, 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 R5 are identical or different, two OR5 groups being able to be engaged in the same cycle, preferably R5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms,

[0164] - X represents a divalent radical chosen from -N(R6)-, -NH- and -S-,

[0165] - R6 represents a hydrocarbon radical comprising from 1 to 20 carbon atoms, saturated or unsaturated, open chain, linear or branched, or comprising one or more optionally aromatic cycles, and which may also comprise one or more heteroatoms, preferably R6 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms, and

[0166] - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.

[0167] The various groups, radicals and letters which are included in the formulas described in this text retain, throughout this text, and in the absence of any indication to the contrary, the same definition.

[0168] Advantageously, the silylated compound is of formula (III) in which:

[0169] - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene,

[0170] - R5 represents a methyl or ethyl radical, preferably methyl,

[0171] - X represents a divalent radical -N(R6)-,

[0172] - R6 represents a linear or branched alkyl radical comprising from 1 to 4 atoms of carbon, preferably n-butyl, and

[0173] - p is equal to 0.

[0174] Silylated compounds of formula (III) are widely available commercially. Examples include N-(3(trimethoxysilyl)propyl)butylamine available under the name Dynasylan® 1189 from Evonik.

[0175] By "polyurethane composition with -NCO end groups resulting from step (i)" is meant the polyurethane composition with -NCO end groups obtained directly at the end of step (i) or a derived composition (in particular an ionic polyurethane composition with -NCO end groups obtained during step (iii) described below).

[0176] Step (ii) corresponds to the reaction of a silylated compound with the NCO groups of the polyurethane composition resulting from step (i), in particular of the polyurethane composition with -NCO end groups formed at the end of step (i) (to form a non-ionic silylated polyurethane composition) or of the ionic polyurethane composition with -NCO end groups obtained by step (iii) (to form a silylated ionic polyurethane composition).

[0177] In the process according to the invention, step (ii) can be carried out with an equivalent molar ratio -XH / -NCO equal to 1, preferably between 0.90 and 1.15.

[0178] 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 (III) divided by the molar equivalent number of -NCO groups of the polyurethane composition with -NCO end groups formed from step (i).

[0179] The molar equivalent number of -XH groups of the silylated compound of formula (III) is equal to the number of moles of the silylated compound of formula (III) introduced in step (ii).

[0180] The molar equivalent number of -NCO groups in the polyurethane composition with -NCO end groups from step (i) corresponds to the molar equivalent number of -NCO groups of polyisocyanate introduced in excess relative to the molar equivalent number of -OH groups of the polyol (A) during step (i).

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

[0182] Step (ii) is advantageously carried out at a temperature of between range from 20°C to 90°C, preferably from 30°C to 80°C.

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

[0184] The method according to the invention may further comprise a step (iii) of reaction of the polyurethane composition from step (i) with a tertiary amine having a pKa at 25°C greater than 8, to form an ionic polyurethane composition.

[0185] By "polyurethane composition resulting from step (i)" is meant the polyurethane composition with -NCO end groups obtained directly at the end of step (i) or a derived composition (in particular a silylated polyurethane composition obtained during step (ii) described above).

[0186] In particular, step (iii) corresponds to the reaction of a tertiary amine with the carboxylic acid group(s) of the polyurethane composition resulting from step (i), in particular the polyurethane composition with -NCO end groups formed in step (i) (to form an ionic polyurethane composition with -NCO end groups) or the non-ionic silylated polyurethane composition formed in step (ii) (to form a silylated ionic polyurethane composition). For convenience, the interaction between tertiary amine and carboxylic acid group is described as being ionic. However, it is understood that this interaction is not necessarily totally ionic, and may be for example a hydrogen bond. This interaction could prevent yellowing of the compositions obtained from the ionic polyurethane composition according to the invention.

[0187] 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.

[0188] Throughout the application, the term "pKa of the tertiary amine" means the pKa of its conjugate acid (i.e., the protonated tertiary amine). The pKa of an acid is equal to —logio (Ka), where Ka is the acidity constant of the acid in water.

[0189] The tertiary amine may be of formula (IV): N(R)(R')(R") in which R, R' and R", identical or different, each represent a saturated or unsaturated hydrocarbon radical, optionally comprising one or more heteroatoms chosen from N, O and S, and R and R' and / or R and R” and / or R' and R" being able to form a heterocycle with the nitrogen atom to which they are attached.

[0190] 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 ether-2,2'-morpholine (or DMDEE), triazabicyclodecene (TBD), methyltriazabicyclodecene (MTBD), trihexylamine (or THA) and mixtures thereof.

[0191] When the process according to the invention further comprises a silylation step (ii), the tertiary amine is advantageously chosen from TEA, DBU, DABCO, DBN, DCHMA, TBD, MTBD, THA and mixtures thereof.

[0192] Preferably, the tertiary amine is chosen from DBU, DABCO, DBN, DCHMA and mixtures thereof, in particular DCHMA.

[0193] In step (iii) of the process according to the invention, the molar ratio (tertiary amine / -C(=O)OH) can vary from 0.5 to 2.5, preferably from 1 to 2, more preferably is equal to 1.

[0194] The tertiary amine / -C(=O)OH molar ratio is defined as being equal to the number of moles of tertiary amine introduced in step (iii) divided by the molar equivalent number of -C(=O)OH groups of the polyol (A).

[0195] The molar equivalent number of -C(=O)OH groups of the polyol (A) is equal to: f(-C(=O)OH)*(manhydride / Manhydride), where f(-C(=O)OH) is the sum of the number of anhydride functions and the number of -C(=O)OH groups of the introduced cyclic anhydride used during the esterification, manhydride is the mass introduced in g of said anhydride and Manhydride is the molar mass in g / mol of said anhydride.

[0196] Step (iii) is advantageously carried out under anhydrous conditions.

[0197] Step (iii) is advantageously carried out at a temperature between 20°C and 80°C, preferably between 20°C and 50°C.

[0198] Step (iii) is advantageously carried out at atmospheric pressure. Plasticizer

[0199] A plasticizer may be used in the process according to the invention. Preferably, step (i) is carried out in the presence of a plasticizer.

[0200] The presence of the plasticizer makes it possible to reduce the viscosity of the reaction medium and of the resulting polyurethane composition.

[0201] The plasticizer may be any plasticizer commonly used in the field of adhesive and / or sealant compositions.

[0202] For example, the plasticizer can be chosen from:

[0203] - 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 (for example Esterol A marketed by ARKEMA),

[0204] - a mixture of esters of alkylsulfonic acids and phenol, such as the mixture identified by CAS number 91082-17-6 (for example MESAMOLL® marketed by LANXESS),

[0205] - diisodecyl phthalate (for example PALATINOL® DIDP marketed by BASF),

[0206] - diisononyl phthalate (DINP) (for example PALATINOL® N marketed by BASF),

[0207] - 1,2-cyclohexanedicarboxylic acid diisononyl ester (e.g. HEXAMOLL DINCH® marketed by BASF),

[0208] - pentaerythritol tetravalerate (for example PEVALEN™ marketed by PERSTORP),

[0209] - a polysiloxane resin, in particular a silsesquioxane of average molar mass in number 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 / mol, and

[0210] - their mixtures.

[0211] Preferably, the plasticizer is:

[0212] - a mixture of methyl esters of fatty acids, in particular fatty acids comprising 18 carbon atoms such as fatty acids derived from castor oil including in particular ricinoleic acid, and / or

[0213] - a mixture of esters of alkylsulfonic acids and phenol, such as the mixture identified by CAS No. 91082-17-6.

[0214] According to one embodiment, the plasticizer consists of at least 50% by weight of bio-sourced plasticizer, in particular a mixture of methyl esters of fatty acids such as fatty acids derived from castor oil, relative to the total weight of plasticizer used in the process according to the invention, preferably between 85% and 100% by weight. An example of a bio-sourced plasticizer is Esterol A marketed by ARKEMA.

[0215] The amount of plasticizer used in the process according to the invention can be up to 30% by weight relative to the total weight of the polyurethane composition, preferably between 3% and 25% by weight, more preferably between 10% and 20% by weight. Solvent

[0216] The method according to the invention is advantageously carried out in the absence of solvent.

[0217] By “solvent”, we mean in particular a solvent used in the field of adhesives and / or sealants.

[0218] 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.

[0219] 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 carried out without adding free water, i.e. other than that inherently included in the ingredients used. In particular, the water content introduced into the process according to the invention is less than 3% by weight relative to the total weight of the ingredients used, preferably less than 1% by weight. In addition, the polyol (A) is preferably dehydrated (for example at approximately 100°C and under vacuum, in particular at less than 0.6 kPa) before its use in step (i) until it has a water content of less than 0.1% by weight relative to the weight of the polyol (A). The other ingredients (in particular the plasticizers) can also be dehydrated in the same way.

[0220] Water content can be measured by a Karl Fischer coulometric method, for example using HYDRANAL™ as the titrant and detecting the equivalence point electrometrically. Moisture absorber

[0221] A moisture absorber may be used in the process according to the invention, in particular after step (i), in particular at the end of step (ii) when this step is carried out (once the silylation of the polyurethane composition with -NCO end groups is complete).

[0222] A suitable moisture absorber (or desiccant) is, in particular, an alkoxysilane such as a trialkoxysilane (particularly a trimethoxysilane). Such an agent advantageously prolongs the shelf life of the polyurethane composition during storage and transport, prior to its use.

[0223] Advantageously, the moisture absorber is chosen from vinyltrimethoxysilane, trimethoxymethylsilane, propyltrimethoxysilane, vinyltriethoxysilane, alkoxyarylsilanes (for example GENIOSIL® XL 70 marketed by WACKER) and mixtures thereof.

[0224] Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, vinyltriethoxysilane and their mixture, more preferably vinyltrimethoxysilane.

[0225] The moisture absorber content may be between 0.2% and 3% by weight relative to the total weight of the polyurethane composition, preferably between 0.5% and 2% by weight. Bio-sourced ingredients

[0226] 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 70% by weight.

[0227] Thus, the polyurethane composition obtained by the process according to the invention advantageously comprises at least 50% by weight of biosourced ingredients relative to the total weight of said composition, preferably at least 70% by weight.

[0228] The bio-sourced ingredients are in particular the polyol (A) and the optional plasticizer. Preferred embodiment

[0229] According to a preferred embodiment, the method according to the invention comprises (in particular consists of):

[0230] (i) a step of reacting an alkoxylated biosourced polyol (A) comprising a carboxylic acid group with a polyisocyanate to form a polyurethane composition with -NCO end groups, wherein: - the polyol (A) is ethoxylated and / or propoxylated, has a total average alkoxylation number of between 25 and 60, the polyol (A) being obtained from a glyceride of fatty acid(s), preferably esterified with a substituted cyclic anhydride, - the polyisocyanate is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, dimeryl diisocyanate, L-lysine diisocyanate methyl ester, L-lysine diisocyanate ethyl ester, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 4,4'- and / or 2,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate and mixtures thereof, the molar equivalent number of -NCO groups of the polyisocyanate being in excess of the molar equivalent number of -OH groups of the polyol (A), - between 0.01% and 0.5% by weight relative to the weight of the polyol (A) of a catalyst is used, the catalyst preferably being chosen from carboxylates, in particular neodecanoate, of bismuth and / or zinc, and - optionally between 0.1% and 5% by weight relative to the weight of the polyol (A) of a UV stabilizer (or antioxidant) is used, preferably chosen from so-called hindered phenols,

[0231] then

[0232] (ii) preferably a step (ii) of silylation of the polyurethane composition with -NCO end groups resulting from step (i) (preferably obtained directly at the end of step (i)) with a silylated compound to form a silylated polyurethane composition, the silylated compound being of formula (III) in which:

[0233] - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene,

[0234] - R5 represents a methyl or ethyl radical, preferably methyl,

[0235] - X represents a divalent radical -N(R6)-,

[0236] - R6 represents a linear or branched alkyl radical comprising from 1 to 4 atoms of carbon, preferably n-butyl, and

[0237] - p is equal to 0, and

[0238] (iii) optionally a step of reacting the polyurethane composition from step (i) with a tertiary amine having a pKa at 25°C greater than 8, to form an ionic polyurethane composition,

[0239] up to 30% by weight of a plasticizer being used in the process relative to the total weight of the polyurethane composition, and

[0240] optionally a moisture absorber being implemented in the process.

[0241] In particular, the method according to the invention comprises (in particular consists of of) :

[0242] (i) a step of reacting an alkoxylated biosourced polyol (A) comprising a carboxylic acid group with a polyisocyanate to form a polyurethane composition with -NCO end groups, wherein: - the polyol (A) is ethoxylated and / or propoxylated, has a total average alkoxylation number of between 30 and 50, the polyol (A) being obtained from castor oil esterified with a substituted cyclic anhydride, preferably chosen from decenylsuccinic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, phenylsuccinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, homophthalic anhydride, and mixtures thereof, in particular dodecenylsuccinic anhydride, phthalic anhydride, and mixtures thereof, - the polyisocyanate is chosen from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, m-xylylene diisocyanate, hydrogenated m-xylylene diisocyanate and mixtures thereof, in particular isophorone diisocyanate, the molar equivalent ratio -NCO / -OH being between 1.2 and 3, - between 0.04% and 0.2% by weight relative to the weight of the polyol (A) of a catalyst is used, the catalyst preferably being chosen from carboxylates, in particular neodecanoate, of bismuth and / or zinc, and - optionally between 0.2% and 3% by weight relative to the weight of the polyol (A) of a UV stabilizer (or antioxidant) is used, preferably chosen from so-called hindered phenols,

[0243] then

[0244] (ii) preferably a step (ii) of silylation of the polyurethane composition with -NCO end groups resulting from step (i) (preferably obtained directly at the end of step (i)) with a silylated compound to form a silylated polyurethane composition, the silylated compound being of formula (III) in which:

[0245] - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 3 carbon atoms, preferably n-propylene;

[0246] - R5 represents a methyl or ethyl radical, preferably methyl;

[0247] - X represents a divalent radical -N(R6)-,

[0248] - R6 represents a linear or branched alkyl radical comprising from 1 to 4 atoms of carbon, preferably n-butyl, and

[0249] - p is equal to 0, and

[0250] (iii) optionally a step of reacting the polyurethane composition from step (i) with a tertiary amine having a pKa at 25°C greater than 8, to form an ionic polyurethane composition,

[0251] between 10% and 20% by weight of a plasticizer being used in the process relative to the total weight of the polyurethane composition, preferably during step (i), and

[0252] optionally a moisture absorber being implemented in the process.

[0253] The characteristics of steps (i) to (iii) disclosed above apply to this mode embodiment (including preferred embodiments and features). In particular, the quantities used in this embodiment are advantageously as described above.

[0254] Polyurethane composition capable of being obtained by the process according to the invention

[0255] The invention also relates to a polyurethane composition capable of being obtained by the process according to the invention as described above (including the preferred embodiments and characteristics).

[0256] The polyurethane content in said composition may vary from 60% to 100% by weight relative to the total weight of said composition, preferably from 70% to 95% by weight.

[0257] The viscosity at 23°C of the polyurethane composition can vary from 1 to 350 Pa.s, and is advantageously between 1 and 250 Pa.s, preferably between 5 and 100 Pa.s.

[0258] This viscosity can for example be measured according to a Brookfield type method at 23°C (in particular as indicated in Example 1).

[0259] The polyurethane composition obtainable by the process according to the invention may comprise a plasticizer. The plasticizer is as described above. The plasticizer content in said composition may be up to 30% by weight relative to the total weight of said composition, preferably between 3% and 25% by weight, more preferably between 10% and 20% by weight.

[0260] The polyurethane composition obtainable by the process according to the invention may comprise a moisture absorber. The moisture absorber is as described above. The moisture absorber content may be between 0.2% and 3% by weight relative to the total weight of said composition, preferably between 0.5% and 2% by weight.

[0261] The polyurethane composition obtainable by the process according to the invention may comprise a UV stabilizer (or antioxidant). The UV stabilizer (or antioxidant) is as described above. The content of UV stabilizer (or antioxidant) may vary between 0.1% and 3% by weight relative to the total weight of said composition, preferably between 0.2% and 2%.

[0262] Advantageously, the polyurethane composition capable of being obtained by the process 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.

[0263] Furthermore, the characteristics mentioned above concerning the polyurethane composition obtained by the process according to the invention apply to the polyurethane composition capable of being obtained by the process according to the invention.

[0264] In particular, the polyurethane composition capable of being obtained by the process according to the invention advantageously comprises at least 50% by weight of biosourced ingredients relative to the total weight of said composition, preferably at least 70% by weight.

[0265] According to a first embodiment, the polyurethane composition is a polyurethane composition with -NCO end groups capable of being obtained by the process according to the invention comprising step (i) as defined above. When said polyurethane is ionic, the composition is capable of being obtained by the process according to the invention further comprising step (iii) as defined above.

[0266] The %NCO by weight of the polyurethane composition with -NCO end groups can vary between 0.3% and 5% relative to the total weight of said composition, preferably between 0.5% and 3%.

[0267] The %NCO by weight of said polyurethane 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.

[0268] According to a second embodiment, the polyurethane composition is a silylated polyurethane composition obtainable by the process according to the invention comprising steps (i) and (ii) as defined above. When said polyurethane is ionic, the composition is obtainable by the process according to the invention further comprising step (iii) as defined above.

[0269] The polyurethane composition may be stored, preferably protected from moisture, before being formulated for its final application (in particular in the form of an adhesive and / or sealant). Adhesive and / or sealant composition

[0270] The invention also relates to an adhesive and / or mastic composition, preferably an adhesive, comprising the polyurethane composition (preferably silylated, more preferably non-ionic silylated) capable of being obtained by the process according to the invention.

[0271] The polyurethane content (in particular present in the polyurethane composition capable of being obtained by the process according to the invention) may be between 8% and 50% by weight relative to the total weight of the adhesive and / or sealant composition, preferably from 12% to 40% by weight, more preferably from 15% to 30% by weight.

[0272] Advantageously, the adhesive and / or sealant composition according to the invention further comprises a filler.

[0273] The filler content is advantageously between 20% and 70% by weight relative to the total weight of the composition, preferably from 30% to 65% by weight, more preferably from 40% to 60% by weight.

[0274] The filler that can be used in the adhesive and / or mastic composition according to the invention can be chosen from mineral fillers, organic fillers, and mixtures thereof, preferably from mineral fillers.

[0275] 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 fillers are in the form of particles of various geometry. They may, for example, be spherical, fibrous, or have an irregular shape.

[0276] Advantageously, the mineral fillers are formed by the group consisting of clay, quartz, hollow mineral microspheres and carbonate fillers.

[0277] Among the hollow mineral microspheres, mention may be made of hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate.

[0278] Preferably, the mineral fillers are formed by the group consisting of carbonate fillers.

[0279] Advantageously, the carbonated filler is chosen from alkali or alkaline earth metal carbonates and mixtures thereof. Preferably, the carbonated filler comprises calcium carbonate, more preferably the carbonated filler is chalk or hydrophobically treated calcium carbonate (for example coated with fatty acids), even more preferably hydrophobically treated calcium carbonate.

[0280] When the calcium carbonate is hydrophobically treated, this can prevent the calcium carbonate from absorbing the constituents of the composition and rendering them ineffective. The hydrophobic coating of the calcium carbonate can represent from 0.1% to 3.5% by weight, based on the total weight of calcium carbonate.

[0281] Preferably, when the hydrophobic treatment is a coating of fatty acids, the fatty acids comprise or consist of more than 50% by weight of stearic acid relative to the total weight of the fatty acids.

[0282] As an example of an organic filler, mention may be made of any organic filler, in particular polymeric, usually used in the field of adhesive and / or mastic compositions.

[0283] For example, organic fillers may be formed by the group consisting of polyvinyl chloride (PVC), polyolefins, rubber, ethylene vinyl acetate (EVA), expandable or non-expandable thermoplastic polymer hollow microspheres (such as vinylidene chloride / acrylonitrile hollow microspheres) and aramid fibers (such as Kevlar®), preferably PVC.

[0284] The average particle size of the filler may be between 10 nm and 400 pm, preferably between 20 nm and 100 pm, more preferably between 30 nm and 1 pm.

[0285] The average particle size advantageously corresponds to the d50 particle size, i.e. the maximum size of 50% of the smallest particles by volume, and can be measured with a granulometer, in particular by laser diffraction on a MALVERN type device (for example according to standard NF ISO 13320).

[0286] Unless otherwise indicated, the standards referred to throughout the application are those in effect on the date of filing of the application.

[0287] Advantageously, the adhesive and / or sealant composition according to the invention comprises a plasticizer. The plasticizer may already be included in the polyurethane composition capable of being obtained by the process according to the invention, and / or may be added to the adhesive and / or sealant composition. The plasticizer is preferably chosen from the plasticizers mentioned above, in particular from:

[0288] - 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,

[0289] - a mixture of esters of alkylsulfonic acids and phenol, such as the mixture identified by CAS No. 91082-17-6, and

[0290] - their mixture.

[0291] The total plasticizer content in the adhesive and / or sealant composition may vary from 3% to 30% by weight relative to the total weight of said composition, preferably from 5% to 25% by weight, more preferably 7% to 20% by weight.

[0292] The adhesive and / or sealant composition according to the invention may further comprise a crosslinking catalyst. 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 with NCO terminations. Preferably, when the adhesive and / or sealant composition comprises a silylated polyurethane, it further comprises a catalyst for the condensation of silanol, preferably a tin-based catalyst.

[0293] Examples of crosslinking catalysts for silanol condensation include:

[0294] - organic titanium derivatives such as titanium acetyl acetonate, tetra- titanium propoxide, titanium tetrabutylate,

[0295] - organic zirconium derivatives such as zirconium acetyl acetonate, te- zirconium tetrapropylate, zirconium tetrabutylate,

[0296] - amines such as l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), l,5-diazabicyclo[4.3.0]non-5-ene (DBN), diethyl ether-2,2'-morpholine (DMDEE), l,4-diazabicylo[2.2.2]octane (DABCO), l,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD),

[0297] - zinc carboxylate catalysts (e.g. K-KAT® 670 com sold by KING INDUSTRIES),

[0298] - tin-based catalysts such as compounds derived from dioctyltin or di- butyltin, for example dioctyltin oxide, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dicarboxylate, dibutyltin diacetylacetonate (CAS: 22673-19-4), dibutyltin dilaurate (DBTDL), dibutyltin diacetate and / or dibutyltin oxide,

[0299] - guanidine derivatives such as l-(o-tolyl)biguanide (CAS No.: 93-69-6), for example RHENOCURE 1000 C (marketed by RheinChemie Additives).

[0300] Examples of crosslinking catalysts for crosslinking NCO-terminated polyurethane include: - bismuth carboxylates (e.g. acetate, neodecanoate, etc.), - zinc carboxylates (e.g. acetate, neodecanoate, etc.), - amines such as DABCO or DMDEE, - organic titanium derivatives such as titanium acetyl acetonate, titanium tetrapropylate, titanium tetrabutylate, - organic zirconium derivatives such as zirconium acetyl acetonate, zirconium tetrapropylate, zirconium tetrabutylate, - tin-based catalysts such as compounds derived from dioctyltin or dibutyltin, for example dioctyltin oxide, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dicarboxylate, dibutyltin diacetylacetonate, DBTDL, dibutyltin diacetate and / or dibutyltin oxide.

[0301] The content of crosslinking catalyst may be between 0.01% and 5% by weight relative to the total weight of the adhesive and / or sealant composition according to the invention, preferably from 0.05% to 2% by weight.

[0302] The adhesive and / or sealant composition according to the invention may further comprise one or more additives chosen from moisture absorbers, adhesion promoters, rheology agents, UV stabilizers, pigments, and mixtures thereof.

[0303] Advantageously, the adhesive and / or sealant composition according to the invention comprises a mixture of additives chosen from moisture absorbers, rheology agents and adhesion promoters.

[0304] The total content of additives can be up to 15% by weight relative to the total weight of the adhesive and / or sealant composition according to the invention, preferably from 1% to 10% by weight.

[0305] The moisture absorber is advantageously as described above. Preferably, the moisture absorber is chosen from vinyltrimethoxysilane, vinyltrimethoxysilane and their mixture, more preferably vinyltrimethoxysilane.

[0306] The total moisture absorber content may be between 0.5% and 5% by weight relative to the total weight of the adhesive and / or sealant composition according to the invention, preferably between 2% and 4% by weight.

[0307] The adhesion promoter may be chosen from amino-, mercapto- and epoxy-alkoxysilanes, and mixtures thereof. Preferably, the adhesion promoter is chosen from aminoalkoxysilanes and mixtures thereof, more preferably from aminotrialkoxysilanes and mixtures thereof, even more preferably from aminotrimethoxysilanes and mixtures thereof, for example (3-aminopropyl)trimethoxysilane.

[0308] As an example of epoxy-alkoxysilane, mention may be made of (3-glycidyloxypropyl)trimethoxysilane (also called GLYMO).

[0309] Aminotrimethoxysilanes can be 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, in particular (3-aminopropyl)trimethoxysilane.

[0310] The content of adhesion promoter may be between 0.1% and 5% by weight relative to the total weight of the adhesive and / or sealant composition according to the invention, preferably between 0.5% and 3% by weight.

[0311] The rheology agent may be any rheology agent usually used in the field of adhesive and / or sealant compositions.

[0312] Advantageously, the rheology agent is chosen from:

[0313] - PVC plastisols, corresponding to a suspension of PVC in an agent plasticizer miscible with PVC, obtained in situ by heating at temperatures ranging from 60°C to 80°C. These plastisols can be those described in particular in the work “Polyurethane Sealants”, Robert M. Evans, ISBN 087762-998-6,

[0314] - pyrogenic silica (possibly hydrophobic), such as HD K® N20 or HD K® H15 marketed by WACKER,

[0315] - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such as than 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,

[0316] - waxes derived from castor oil, such as THIXCIN® R available from ELEMENTIS,

[0317] - amide waxes, preferably micronized, such as CRAYVALLAC® SLX, CRAYVALLAC® SLW or CRAYVALLAC® SUPER marketed by Arkema, or THIXATROL® AS8053 or THIXATROL® MAX (EC No.: 432-430-3) which are available from ELEMENTIS, or RHEOBYK 7503 marketed by BYK, and

[0318] - their mixture s.

[0319] In particular, the rheology agent is pyrogenic silica, in particular hydrophobic.

[0320] By "castor oil-derived waxes" is meant waxes obtained from castor oil, in particular hydrogenated castor oil. Castor oil-derived waxes are solid at 23°C.

[0321] By "amide waxes" is meant waxes comprising one or more compounds having at least one amide group. In particular, the amide waxes can be obtained from fatty acid(s) (for example ricinoleic acid) and (di)amine(s).

[0322] 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.

[0323] The average particle size advantageously corresponds to the d50 particle size, i.e. the maximum size of 50% of the smallest particles by volume, and can be measured with a granulometer, in particular by laser diffraction on a MALVERN type device (for example according to standard NF ISO 13320).

[0324] The content of rheology agent may vary from 1% to 30% by weight relative to the total weight of the adhesive and / or sealant composition according to the invention, preferably from 2% to 20% by weight, more preferably from 3% to 10% by weight.

[0325] 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.

[0326] The pigment may be chosen from organic pigments, inorganic pigments and mixtures thereof, for example from titanium dioxide, carbon black, manganese ferrite, and mixtures thereof.

[0327] The pigment content may be up to 5% by weight relative to the total weight of the adhesive and / or sealant composition, preferably up to 3% by weight.

[0328] Advantageously, the adhesive and / or sealant composition according to the invention does not comprise a solvent, the solvent being as defined above. In particular, said composition comprises less than 3% by weight of water relative to the total weight of said composition, preferably less than 1% by weight.

[0329] According to one embodiment, the adhesive and / or sealant composition according to the invention comprises:

[0330] - between 8% and 50% by weight of polyurethane, preferably silylated,

[0331] - between 20% and 70% by weight of filler,

[0332] - between 3% and 30% by weight of plasticizer,

[0333] - between 0.01% and 5% by weight of crosslinking catalyst, and

[0334] - optionally up to 15% by weight of one or more additives chosen from moisture absorbers, adhesion promoters, rheology agents, UV stabilizers, pigments, and mixtures thereof,

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

[0336] Preferably, the adhesive and / or sealant composition according to the invention consists essentially of the ingredients mentioned above. By "consisting essentially", it is meant that the adhesive and / or sealant composition comprises less than 5% by weight of ingredients other than the aforementioned ingredients, relative to the total weight of said composition, preferably less than 2% by weight, even more preferably less than 1% by weight.

[0337] The ingredients of this embodiment and their particular contents are as described above, including the preferred characteristics and embodiments.

[0338] The adhesive and / or sealant composition according to the invention may have a viscosity at 23°C between 1 and 350 Pa.s, preferably between 1 and 250 Pa.s, more preferably between 5 and 100 Pa.s.

[0339] This viscosity can for example be measured according to a Brookfield type method at 23°C (in particular as indicated in Example 1).

[0340] The adhesive and / or sealant composition according to the invention can be prepared by simply mixing its ingredients.

[0341] Preferably, the adhesive and / or sealant composition according to the invention is prepared at atmospheric pressure and at a temperature between 10°C and 80°C, more preferably between 18°C ​​and 70°C.

[0342] When the preparation of the adhesive and / or sealant composition according to the invention involves heating to a temperature above 55°C, if the final adhesive and / or sealant composition comprises an ionic polyurethane, this is advantageously introduced in non-ionic form and step (iii) is carried out once the temperature of the adhesive and / or sealant composition has dropped back to approximately 20°C-35°C.

[0343] An example of preparation of the adhesive and / or sealant composition according to the invention is described in Example 5.

[0344] Use of the adhesive and / or sealant composition

[0345] The invention also relates to the use of the adhesive and / or sealant composition according to the invention, as an adhesive and / or sealant, preferably an adhesive.

[0346] In particular, the present invention relates to the use of the adhesive and / or mastic composition according to the invention as an adhesive and / or mastic in the field of building construction, in the field of manufacturing means of transport, such as the automobile, railway, aerospace or naval industry, in particular in the field of building construction, for example for bonding parquet to the floor (in particular concrete).

[0347] The adhesive and / or sealant composition according to the invention is as described above, including the preferred embodiments and characteristics. Substrate assembly process

[0348] Furthermore, the invention relates to a method for assembling substrates comprising:

[0349] - coating, on at least one surface of the substrates to be assembled, the composition adhesive and / or sealant according to the invention, then

[0350] - bringing the substrates into contact.

[0351] The adhesive and / or sealant composition according to the invention is as described above, including the preferred embodiments and characteristics.

[0352] It is understood that, during the coating step and the contacting step, the adhesive and / or mastic composition according to the invention is in the uncured state.

[0353] The substrates may be the same or different.

[0354] Preferably, the assembly method according to the invention is carried out at room temperature (in particular between 18°C ​​and 25°C, for example at approximately 23°C).

[0355] By “approximately X”, we mean more or less 10% of the value of X.

[0356] Suitable substrates are, for example, inorganic substrates such as glass, ceramics, concrete, metals and / or alloys (such as aluminum, steel, non-ferrous metals, galvanized metals), and / or organic substrates such as wood and / or plastics (such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins). Article

[0357] The present invention also relates to an article comprising the adhesive and / or sealant composition according to the invention (cured or not).

[0358] The adhesive and / or sealant composition according to the invention is as described above, including the preferred embodiments and characteristics.

[0359] According to a first embodiment, said composition binds at least two substrates of said article.

[0360] The article can be obtained by the method of assembling substrates according to the invention (including preferred embodiments and characteristics).

[0361] The substrates are preferably as described above for the substrate assembly method according to the invention.

[0362] According to a second embodiment, the article comprises the adhesive and / or sealant composition according to the invention, in airtight packaging, protected from air.

[0363] Preferably, the hermetic packaging is a polyethylene bag or a polyethylene cartridge provided with a lid.

[0364] All the embodiments described above can be combined with each other. In particular, the various aforementioned ingredients of the adhesive and / or sealant composition according to the invention, and in particular the preferred embodiments, can be combined with each other.

[0365] The following examples are given purely for illustrative purposes of the invention and should not be interpreted as limiting its scope. Examples Example 1: Ingredients and measurement methods Ingredients used

[0366] The following ingredients were used:

[0367] - castor oil (by ARKEMA): CAS: 8001-79-4, mixture of compounds comprising about 89% by weight, based on the total weight of the mixture, of ricinoleic acid triglyceride having a molar mass of about 933 g / mol, the castor oil having a hydroxyl number I0H of between 157 and 167 mg KOH / g, i.e. a functionality equal to about 2.7 (i.e. an average of 2.7 -OH groups per molecule of ricinoleic acid triglyceride),

[0368] - K-12 (by Vertellus): dodecenyl succinic anhydride (CAS: 26544-38-7, mixture of isomers),

[0369] - Surfaline® R40 (by ARKEMA): ethoxylated castor oil having a total number 40 ethylene oxide,

[0370] - Borchi®Kat 315 (by OMG Borchers): bismuth neodecanoate with a molar mass equal to 722.75 g / mol, catalyst,

[0371] - Irganox® 245 (by BASF): bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] ethylenebis(oxyethylene) (CAS: 36443-68-2), antioxidant,

[0372] - IPDI (by Covestro): isophorone diisocyanate with a molar mass equal to 222.3 g / mol (CAS No.: 4098-71-9),

[0373] - Dynasylan® 1189 (by Evonik): N-(3-(trimethoxysilyl)propyl)butylamine molar mass equal to 235.4 g / mol,

[0374] - Esterai A (by ARKEMA): methyl esters of C16-C18 fatty acids and of C18 unsaturated fatty acids (CAS: 67762-38-3), plasticizer,

[0375] - VTMO (by Sigma Aldrich): vinyltrimethoxysilane, moisture absorber,

[0376] - HD K® H15 (by WACKER): hydrophobic fumed silica, rheology agent,

[0377] - OMYA BSH® (by OMYA), hydrophobically treated calcium carbonate, filler,

[0378] - DYNASYLAN® AMMO (by EVONIK): (3-aminopropyl)trimethoxysilane, membership promoter,

[0379] - TIB KAT® 223 (by TIB Chemicals): dioctyltin diacetylacetonate (CAS: 54068-28-9), catalyst. Measurement methods

[0380] The hydroxyl index (noted I0H) of a polyol represents the number of hydroxyl functions per gram of polyol and is expressed in the form of milligrams of potash (KOH) used in the determination of hydroxyl functions, determined according to the ASTME1899-16 standard.

[0381] The number-average molecular weight (Mn) of the polyol P2 prepared in Example 3 below was determined by gel permeation chromatography (GPC) with polystyrene standards. In particular, the following conditions were implemented: - System: Waters Alliance GPC, - Columns: one 5 pm precolumn (50*7.8 mm), one 103 Â column (300*7.8 mm) (Phenomenex reference 00H-0444-KO), two 104 Â columns (300*7.8 mm) (Phenomenex reference 00H-0445-KO), one Shodex F6028050 column (GPC-KF-805), - Eluent: tetrahydrofuran, - Flow rate: 1 mL / min, - Temperature: 35°C, - Injection volume and sample concentration: 50 pL, 10 mg / mL, - Detector: UV at 254 nm, refractive index.

[0382] The viscosity of the silylated polymers and adhesives prepared in the examples below was measured according to a Brookfield type method at 23°C (Brookfield RVT (“Regular Viscosity Torque”) viscometer, S7 needle, 10 rotations per minute).

[0383] The %NCO was determined automatically using a T5 Excellence titrator (marketed by Mettler Toledo). A sample of the reaction medium was taken and introduced into the titrator, then a 5% by volume solution of dicyclohexylamine in DMF (N,N-dimethylformamide) was added automatically. The titration of the excess amine is also done automatically with 0.1 N hydrochloric acid. The %NCO is determined relative to the total weight of the compounds introduced into the reaction medium.

[0384] Tensile strength and elongation at break were measured in accordance with ISO 37 (2012), at a constant speed of 100 mm / min.

[0385] In particular, the following conditions were applied:

[0386] A standard dumbbell-shaped test piece (H2), type 2, as illustrated in international standard ISO 37 (2012) is used. The narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 3 mm.

[0387] 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 and 50% relative humidity).

[0388] The principle of the measurement consists of stretching in a tensile machine (for example Zwick Roell 2.5KN), whose movable jaw moves at a constant speed equal to 100 mm / min, a standard test piece and recording:

[0389] - the elongation at break (expressed in %) which is the elongation of the test piece cor corresponding to the stretching observed at the time of rupture, and

[0390] - the tensile strength (in MPa) which is the tensile stress at which produces the rupture of the specimen (also called TS for Tensile Strength in English).

[0391] The measurement is repeated for 5 test pieces, and the corresponding average of the results obtained is calculated.

[0392] Example 2: Preparation of non-ethoxylated castor oil modified with dodecenylsuccinic anhydride PI (comparative)

[0393] In a reactor, 78.43 g of castor oil was introduced, then the reactor was left under vacuum (from 0.1 kPa to 0.5 kPa) for 1 hour at 110°C to dehydrate the castor oil.

[0394] The reactor was then cooled to 90°C in order to introduce 21.57 g of K-12 under nitrogen and at atmospheric pressure. The mixture was kept stirring until the characteristic bands of the anhydride were no longer detectable by infrared spectroscopy (1849 cm1 and 1779 cm1).

[0395] The polyol obtained has an IOH of approximately 87 mg KOH / g.

[0396] Example 3: Preparation of ethoxylated castor oil modified with dodecenylsuccinic anhydride P2 (invention)

[0397] In a reactor, 86.84 g of Surfaline® R40 were introduced, then the reactor was left under vacuum (from 0.1 kPa to 0.5 kPa) for 1 hour at 110°C to dehydrate it.

[0398] The reactor was then cooled to 90°C in order to introduce 13.16 g of K-12 under nitrogen and at atmospheric pressure. The mixture was kept stirring until the characteristic bands of the anhydride were no longer detectable by infrared spectroscopy (1849 cm1 and 1779 cm1).

[0399] The polyol obtained has an IOH of approximately 61 mg KOH / g and a number average molar mass of approximately 2157 g / mol. Example 4: Preparation of silylated polyurethanes

[0400] Polyols PI and P2 were used to prepare silylated polyurethanes according to the process described below, using the compounds in the amounts indicated in Table 1 below.

[0401] A polyol PI or P2 was introduced into a reactor with Borchi®Kat 315, Irganox® 245 and Esterol A, then the reactor was left under vacuum (from 0.1 kPa to 0.5 kPa) for 1 hour at 110°C to dehydrate these compounds.

[0402] The reactor was then cooled to a temperature between 70°C and 75°C in order to introduce IPDL under nitrogen and at atmospheric pressure. The mixture was kept stirring until reaching a %NCO by weight corresponding to the excess of -NCO groups of 1TPDI introduced compared to the -OH groups of the polyol.

[0403] Dynasylan® 1189 was then introduced, its quantity corresponding to an equivalent molar ratio -NH / -NCO equal to approximately 1. The whole was mixed until the characteristic band of the -NCO functions was no longer detectable by infrared spectroscopy (around 2260 cm1).

[0404] Finally, the VTMO was added with stirring.

[0405] [Tables 1] Silylated polyurethane SI (comparative) S2 (invention) S3 (invention) Polyol PI (g) 60.32 - - Polyol P2 (g) - 66.23 68.9 Borchi®Kat 315 (g) 0.05 0.05 0.05 Irganox® 245 (g) 0.5 0.5 0.5 Esterai A (g) 15 15.01 15.02 IPDI (g) 14.52 10.99 10.3 Dynasilan® 1189 (g) 8.61 6.24 4.25 VTMO (g) 1 1 1 TOTAL (g) 100.00 100.02 100.02 %NCO* 1.7 1.2 0.8 Viscosity at 23°C (Pa.s) 97 29 52

[0406] *Percentage by weight relative to the total weight of polyol, Borchi®Kat 315, Irganox® 245, Esterol A and 1TDPI introduced into the reactor

[0407] The viscosity of the silylated polyurethanes S2 and S3 according to the invention is lower than that

[0408]

[0409]

[0410]

[0411]

[0412]

[0413]

[0414]

[0415]

[0416]

[0417] comparative silylated polyurethane SI. Example 5: Preparation of adhesives and properties The previously prepared silylated polyurethanes SI, S2 and S3 were used to prepare adhesives (respectively A1 to A3), the composition of which is as follows: - 25 g of a silylated polyurethane SI, S2 or S3, - 11 g of Esterol A, 4 g of HDK® H15, 57 g of OMYA BSH®, 2 g of VTMO, 1.8 g of DYNASYLAN® AMMO, and 0.3 g of TIB KAT® 223. First, silylated polyurethane, Esterol A, HDK® H15, and OMYA BSH® were mixed at a temperature between 50 and 60°C and under vacuum (approximately 0.1-0.5 kPa) for approximately 30 to 60 minutes. VTMO and DYNASYLAN® AMMO were then added and the mixture was mixed for approximately 10 min. Finally, the TIB KAT® 223 was added and everything was mixed for a few seconds. The stirring speed is approximately 500-2000 rpm (rotations per minute). The properties of adhesives Al to A3 (measured according to Example 1) are summarized in Table 2 below. [Tables 2] Adhesive Al (comparative) A2 (invention) A3 (invention) Silylated polyurethane SI S2 S3 Viscosity at 23°C (Pa.s) 230 43.9 103 Tensile strength (MPa) 2.4 1 0.7 Elongation at break (%) 11 53 50 The A2 and A3 adhesives using the silylated polyurethanes S2 and S3 according to the invention have a lower viscosity than the comparative Al adhesive, which makes them easier to apply and improves their storage life. Furthermore, the comparative Al adhesive has a very low elongation at break; it will therefore tend to break easily. On the other hand, the implementation of silylated polyurethanes S2 and S3 according to the invention allows to significantly improve the elongation at break of the adhesive, while maintaining an acceptable tensile strength.

Claims

Claims

1. A process for preparing a polyurethane composition comprising a step (i) of reacting an alkoxylated bio-sourced polyol (A) with a polyisocyanate to form a polyurethane composition with -NCO end groups, wherein said polyol (A) comprises a carboxylic acid group and has a total alkoxylation number of at least 5.

2. Process according to claim 1, in which the polyol (A) is ethoxylated and / or propoxylated, more preferably ethoxylated.

3. A method according to claim 1 or 2, wherein the polyol (A) has a total alkoxylation number of between 5 and 100, preferably between 25 and 60, more preferably between 30 and 50.

4. Method according to any one of claims 1 to 3, in which the polyol (A) is obtained from a bio-sourced polyol (Al), the polyol (Al) being a polyphenol, a carbohydrate and / or a glyceride of fatty acid(s), preferably a glyceride of fatty acid(s).

5. Method according to any one of claims 1 to 4, in which at least one carboxylic acid group of the alkoxylated bio-sourced polyol (A) is derived from an esterification with a cyclic anhydride, preferably substituted, of an alkoxylated bio-sourced polyol (A2), the polyol (A2) corresponding to the bio-sourced polyol (Al) after alkoxylation.

6. The method of claim 5, wherein the cyclic anhydride is substituted and selected from substituted maleic anhydrides, substituted succinic anhydrides, substituted glutaric anhydrides, and mixtures thereof.

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

8. A method according to any one of claims 1 to 7, further comprising a step (ii) of silylating the polyurethane composition with -NCO end groups from step (i) with a silylated compound to form a silylated polyurethane composition, the silylated compound being of formula (III): HX - R3- S uR "}p(OR5);M, in which: - R3 represents a linear or branched divalent alkylene radical comprising from 1 to 6 carbon atoms, preferably from 1 to 3 carbon atoms, - R4 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, and when p is equal to 2, the R4 radicals are identical or different, - R5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, an alkylcarbonyl radical comprising from 2 to 8 carbon atoms, or a dialkylimino radical comprising from 3 to 8 carbon atoms, and when p is equal to 0 or 1, the R5 radicals are identical or different, two OR5 groups being able to be engaged in the same cycle, preferably R5 represents a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, - X represents a divalent radical chosen from -N(R6)-, -NH- and -S-,- R6 represents a hydrocarbon radical comprising from 1 to 20 carbon atoms, saturated or unsaturated, with a linear or branched open chain, or comprising one or more optionally aromatic cycles, and which may also comprise one or more heteroatoms, preferably R6 represents a linear or branched alkyl radical comprising from 1 to 20 carbon atoms, and - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1.,

9. Polyurethane composition obtainable by the process according to any one of claims 1 to 8.

10. An adhesive and / or sealant composition comprising the polyurethane composition of claim 9.

11. An adhesive and / or sealant composition according to claim 10, further comprising a filler.

12. Method for assembling substrates comprising: - coating, on at least one surface of the substrates to be assembled, the adhesive and / or mastic composition according to claim 10 or 11, then - bringing the substrates into contact.

13. An article comprising the adhesive and / or sealant composition according to claim 1, wherein the adhesive and / or sealant composition is a mixture of the following: claim 10 or 11.