Polyurethane composition

Abstract

The present invention relates to a process for preparing a polyurethane composition comprising the step (i) of reacting a bio-sourced alkoxylated polyol (A) with a polyisocyanate to form a polyurethane composition having -NCO end groups, wherein the polyol (A) comprises carboxylic acid groups and has a total alkoxylate number of at least 5. The present invention further relates to a polyurethane composition, an adhesive and / or mastic composition, a process for assembling substrates and an article.

Description

Technical Field

[0001] This invention relates to methods for preparing polyurethane compositions, polyurethane compositions, adhesive and / or putty compositions, methods for assembling substrates, and articles thereof. Background Technology

[0002] Polyurethanes are commonly used as adhesives, putties, and coatings, for example, in the aerospace, motor vehicle, or construction industries. Polyurethanes can be silylated; in this case, they typically contain alkoxysilane-type end groups directly or indirectly attached to the main chain of the polyurethane type. Industrially, they can be obtained by reacting prepolymers with isocyanate end groups with silyl compounds containing alkoxysilane functional groups.

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

[0004] Alkoxysilane-terminated polyurethane-based compositions (also known as silyl polyurethanes) have the advantage of not containing any free isocyanates (once silyl polyurethanes are formed). Therefore, these compositions constitute an alternative to NCO-terminated polyurethane-based compositions, which is preferred from a toxicological point of view.

[0005] However, commercially available polyurethanes are typically derived from raw materials derived from petroleum resources. In the long run, this dependence on fossil resources risks limiting or even preventing monomer production and thus polymer manufacturing. Furthermore, some petroleum-derived raw materials are subject to ecological and economic criticism, increasing regulatory restrictions on them.

[0006] Therefore, there is a need for novel polyurethanes that are at least partially bio-based.

[0007] In addition, there is a need for polyurethanes used as adhesives and / or putties that are at least partially bio-based and have suitable mechanical properties, particularly in terms of viscosity, tensile strength and elongation at break. Summary of the Invention

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

[0009] Another objective of the present invention is to provide polyurethane compositions that can be obtained by the method according to the present invention.

[0010] The present invention also relates to adhesive and / or putty compositions that can be obtained by the method according to the invention.

[0011] Furthermore, the subject of this invention is a method for assembling a substrate, comprising:

[0012] - Apply the adhesive and / or putty composition according to the invention to at least one surface of the substrate to be assembled, then

[0013] - To bring the substrate into contact.

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

[0015] Surprisingly, it has been found that polyurethane compositions obtained from alkoxylated bio-based polyols (A) enable compositions with reduced viscosity and improved elongation at break, while maintaining acceptable tensile strength. Detailed Implementation

[0016] Method for preparing polyurethane compositions

[0017] polyols ( A )

[0018] The polyol (A) is bio-based and alkoxylated, and contains a carboxylic acid group.

[0019] The term "bio-based" refers to resources derived from biological sources, particularly plant-based ones, and which may undergo chemical modification. In particular, since the polyol (A) is alkoxylated, it has undergone at least alkoxylation as a form of chemical modification.

[0020] Alkoxylation can be defined as the introduction of an ether functional group, for example, by the reaction of one or more hydroxyl groups carried by a polyol (especially polyphenols, carbohydrates, and / or fatty acid glycerides) with an epoxide (especially propylene oxide and / or ethylene oxide). Preferably, the polyol (A) is ethoxylated and / or propoxylated, more preferably ethoxylated.

[0021] When the polyol (A) is ethoxylated, one or more of its hydroxyl groups react with ethylene oxide to form at least one –O–(CH2CH2O). n – group, where n is not 0.

[0022] When the polyol (A) is propoxylated, one or more of its hydroxyl groups react with propylene oxide to form at least one group –O–(CH(CH3)CH2O).m –and / or –O–(CH2CH(CH3)O) m – where m is not 0, and if the polyol contains –O–(CH(CH3)CH2O) m – and –O–(CH2CH(CH3)O) m – then m can be the same or different in each group.

[0023] The total alkoxylation number (particularly EO and / or PO) of the alkoxylated bio-based polyol (A) can be between 5 and 100, preferably between 25 and 60, and more preferably between 30 and 50. Preferably, the polyol (A) is ethoxylated and its total EO number is between 5 and 100, preferably between 25 and 60, and more preferably between 30 and 50. The total alkoxylation number (particularly the total alkoxylation number of EO when the polyol (A) is ethoxylated) can be determined as the molar ratio of epoxide / the compound to be alkoxylated (preferably the polyol (A1) as defined below).

[0024] Hydroxyl value I of polyol (A) OH The concentration can be between 10 mg KOH / g and 100 mg KOH / g, preferably between 30 mg KOH / g and 80 mg KOH / g. The hydroxyl value is expressed as mg KOH / g polyol (A). Hydroxyl value I OH It can be measured according to standard ASTM E1899-16, for example as shown in Example 1.

[0025] Acid value I of polyol (A) COOH The acid value can be between 5 mg KOH / g and 50 mg KOH / g, preferably between 10 mg KOH / g and 40 mg KOH / g, and more preferably between 21 mg KOH / g and 40 mg KOH / g. The acid value is expressed in mg KOH / g of polyol (A). The acid value can be measured according to methods well known to those skilled in the art, such as potentiometry.

[0026] Advantageously, the polyol (A) has a functionality f(OH) greater than 1.0, preferably between 1.2 and 2.5, where f(OH) represents the average number of hydroxyl groups per polyol molecule.

[0027] The functionality f(OH) of a polyol can be measured, for example, according to the standard ASTM E1899-16. OH To determine this, the functionality f(OH) can then be calculated as follows: f(OH) = (I OH *M 多元醇 ) / 56100, where I OH The hydroxyl value is calculated as mg KOH / g polyol and M 多元醇It is the number-average molecular weight of polyols in g / mol.

[0028] Advantageously, the polyol (A) has a functionality f(COOH) greater than or equal to 0.5, preferably between 0.5 and 1.3, where f(COOH) represents the average number of carboxylic acid groups per polyol molecule.

[0029] The functionality f(COOH) of a polyol can be determined by measuring its I... COOH This can be determined, for example, by potentiometric measurement. The functionality f(COOH) can then be calculated as follows: f(COOH) = (I COOH *M 多元醇 ) / 56100, where I COOH The acid value is calculated as mg KOH / g polyol and M 多元醇 It is the number-average molecular weight of polyols in g / mol.

[0030] The number-average molecular weight of the alkoxylated bio-based polyol (A) can be between 1500 g / mol and 50000 g / mol, preferably between 1800 g / mol and 30000 g / mol, and more preferably between 2000 g / mol and 10000 g / mol.

[0031] In this paper, number-average molecular weight can be determined by gel permeation chromatography (GPC), particularly using polystyrene-based standards, such as those described in Example 1 below.

[0032] Preferably, the alkoxylated bio-based polyol (A) is obtained from a bio-based polyol (A1), wherein the polyol (A1) is a polyphenol (especially lignin), a carbohydrate (especially sucrose, glucose, fructose, starch, hemicellulose or cellulose), and / or a fatty acid glyceride. It should be understood that these compounds may undergo chemical modifications other than alkoxylation (e.g., hydroxylation).

[0033] 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 described above, wherein M 多元醇 The molar mass of the polyol is expressed in g / mol. When the polyol is a polymer, its molar mass is its number-average molar mass Mn.

[0034] Lignin is commonly found in wood, but also in other plant resources. It is a polyphenol macromolecule containing several hydroxyl groups.

[0035] Sucrose is mainly extracted from sugarcane and sugar beets. It is a disaccharide of glucose and fructose.

[0036] Glucose can be obtained from various plants. It is a monosaccharide containing six carbon atoms.

[0037] Fructose is mainly found in fruits and honey. It is also a monosaccharide containing six carbon atoms.

[0038] Starch is found in many plants. It is a mixture of amylose and amylopectin, and its empirical formula is (C6H2O)2 + 2H2O. 10 O5) n , where n is an integer usually between 500 and 1000.

[0039] Cellulose is commonly found in the walls of plant cells. It is a linear polysaccharide composed of glucose units.

[0040] Hemicellulose is mainly found in plant cell walls and wood. It is a linear or branched polysaccharide that contains the same or different sugar units, but is not composed of only glucose units.

[0041] The term "fatty acid" refers to a molecule containing an aliphatic chain, which may contain one or more double bonds and a carboxylic acid group (-C(=O)OH). In particular, fatty acids contain between 4 and 28 carbon atoms, preferably between 10 and 22 carbon atoms, more preferably between 16 and 20 carbon atoms, for example, 18 carbon atoms.

[0042] In the context of this invention, the range of values ​​should be understood to include limit values. For example, the range "between 4 and 28" specifically includes the values ​​4 and 28.

[0043] The term "glyceride" refers to an ester obtained from glycerol and fatty acids, which may be the same or different. In particular, fatty acid glycerides may be mixtures of fatty acid monoglycerides, fatty acid diglycerides, and / or fatty acid triglycerides. Preferably, fatty acid glycerides comprise at least one fatty acid triglyceride.

[0044] Fatty acid glycerides can be in the form of plant resources directly (e.g., castor oil). Plant resources can also be modified prior to alkoxylation; for example, hydroxyl groups can be introduced onto the fatty acid chain (e.g., via double bond epoxidation).

[0045] Preferably, the bio-based polyol (A1) is a fatty acid glyceride. In this case, the polyol (A1) can be castor oil and / or hydroxylated vegetable oils, such as soybean oil, rapeseed oil, corn oil, cottonseed oil, flaxseed oil, olive oil, sesame oil, walnut oil, sunflower oil, acorn oil (e.g., acorn oil from cork oak), tall oil, safflower oil, grape oil, etc. Vegetable oils are referred to as "hydroxylated" when they have been modified to introduce hydroxyl groups onto the fatty acid chains of the glycerides. The hydroxyl groups can be directly or indirectly, preferably directly bonded to the carbon atoms of the fatty acid chains. For example, when the hydroxyl groups are indirectly bonded, they may have been introduced through hydroformylation / double bond hydrogenation.

[0046] More preferably, the bio-based polyol (A1) is a glycerol ester of ricinoleic acid, particularly a triglyceride. In this case, the bio-based polyol (A1) is advantageously castor oil.

[0047] Bio-based polyols (A1) are different from alkoxylated bio-based polyols (A). In particular, they are not alkoxylated.

[0048] Alkoxylated bio-based polyols (A) contain carboxylic acid groups. In this document, unless otherwise stated (e.g., “exactly one”), “one” or “a” means one or more.

[0049] Advantageously, at least one carboxylic acid group of the alkoxylated bio-based polyol (A) is derived from the esterification of the alkoxylated bio-based polyol (A2) with a cyclic anhydride (preferably substituted), the polyol (A2) corresponding to the bio-based polyol (A1) following alkoxylation (and optionally other chemical modifications, in addition to esterification with the cyclic anhydride). Specifically, during esterification, a portion of the hydroxyl group of the polyol (A2) reacts with the anhydride functional group of the anhydride, resulting in the formation of a carboxylic acid group (–C(=O)OH). The anhydride may also contain a carboxylic acid group, which will result in a higher acid value I. COOH .

[0050] Alkoxylated bio-based polyols (A2) preferably have the same total number of alkoxylations (especially EO and / or PO) as alkoxylated bio-based polyols (A).

[0051] The functionality f(OH) of the alkoxylated bio-based polyol (A) can vary depending on the anhydride / polyol (A2) molar ratio. In fact, some hydroxyl groups of the polyol (A2) react with the anhydride to form ester bonds, and a high anhydride / polyol (A2) molar ratio results in an alkoxylated bio-based polyol (A) with a low functionality f(OH). Therefore, it is advantageous to select the anhydride / polyol (A2) molar ratio to obtain an alkoxylated bio-based polyol (A) with the functionality f(OH) described above.

[0052] Polyols (A2) (i.e., alkoxylated bio-based polyols (A1)) are commercially available, for example under the name “Surfaline® R”, which corresponds to ethoxylated castor oil (CAS: 61791-12-6).

[0053] The term "cyclic anhydride" refers to a molecule containing anhydride functional groups (–C(=O)–O–C(=O)–) that participate in the ring. Specifically, cyclic anhydrides have formula (I):

[0054]

[0055] (I)

[0056] Where R 7 It is a saturated or unsaturated, optionally branched divalent hydrocarbon group, which may contain one or more optionally aromatic rings and optionally contain one or more heteroatoms selected from oxygen and sulfur, preferably one or more optionally selected from oxygen.

[0057] Preferably, the cyclic anhydride is substituted. This can be achieved in formula (I) via R 7 The reflection is that the R 7 It contains at least one carbon atom with a valence of 3 or 4 (that is, directly bonded to 3 or 4 atoms other than hydrogen).

[0058] When the cyclic anhydride is substituted, the substituent may be straight-chain or branched, and may optionally contain an aromatic ring, or may form an optionally aromatic ring with the anhydride ring (e.g., phthalic anhydride). Preferably, the substituent contains 1 to 22 carbon atoms, more preferably 3 to 22 carbon atoms.

[0059] Cyclic anhydrides may have a molar mass between 86 g / mol and 1000 g / mol, preferably between 98 g / mol and 500 g / mol.

[0060] Cyclic anhydrides can be selected from itaconic anhydride, citraconic anhydride, maleic anhydride, dimethylmaleic anhydride, succinic anhydride, 2,3-dimethylsuccinic anhydride, octenylsuccinic anhydride, decenylsuccinic anhydride, dodecenylsuccinic anhydride (e.g., CAS: 26544-38-7 (isomers with branched olefin chains) and / or CAS: 19780-11-1 (n-dodecenylsuccinic anhydride), tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, eicosenesuccinic anhydride, glutaric anhydride, 2,4- Dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride, 3-dimethylglutaric anhydride, adipic anhydride, glycolic anhydride, cis-aconitine anhydride, 2-(2'-carboxyethyl)maleic anhydride, 1-methyl-2-(2'-carboxyethyl)maleic anhydride, phenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, high-phthalic anhydride, trimellitic anhydride, nadic anhydride, methylnadic anhydride and mixtures thereof.

[0061] Advantageously, the cyclic anhydride is a substituted cyclic anhydride selected from substituted maleic anhydride, substituted succinic anhydride, substituted glutaric anhydride, and mixtures thereof, wherein the substituent preferably comprises 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 branched olefin chains) and / or CAS: 19780-11-1 (n-dodecenylsuccinic anhydride), tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, eicosenesuccinic anhydride, etc. Anhydrides, 2,4-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride, 3-dimethylglutaric anhydride, cis-aconitine anhydride, 2-(2'-carboxyethyl)maleic anhydride, 1-methyl-2-(2'-carboxyethyl)maleic anhydride, phenylsuccinic anhydride, S-acetylmercaptosuccinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, high-phthalic anhydride, trimellitic anhydride, nadic anhydride, methylnadic anhydride, and mixtures thereof.

[0062] Preferably, the substituted cyclic anhydride is selected from octenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, eicoseneyl succinic anhydride, phenyl succinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, high-phthalic anhydride, nadic anhydride, methyl nadic anhydride, and mixtures thereof.

[0063] More preferably, the substituted cyclic anhydride is selected from decenyl succinic anhydride, dodecenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, phenyl succinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, high phthalic anhydride and mixtures thereof, especially dodecenyl succinic anhydride, phthalic anhydride and mixtures thereof.

[0064] According to one embodiment, the polyol (A) is ethoxylated and / or propoxylated and has an average total alkoxylation number between 25 and 60. The polyol (A) is obtained from fatty acid glycerides, preferably esterified with substituted cyclic anhydrides.

[0065] Preferably, the polyol (A) is ethoxylated and / or propoxylated, having an average total alkoxylation number between 30 and 50. The polyol (A) is obtained from castor oil esterified with a substituted cyclic anhydride, wherein the substituted cyclic anhydride is preferably selected from decenyl succinic anhydride, dodecenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, phenyl succinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, high phthalic anhydride and mixtures thereof, particularly dodecenyl succinic anhydride, phthalic anhydride and mixtures thereof.

[0066] The characteristics of the polyol (A) disclosed above are applicable to this embodiment (including preferred embodiments and characteristics).

[0067] Alkoxylated bio-based polyols (A) can be obtained via a method comprising the following steps (particularly the following steps):

[0068] - Alkoxylation of bio-based polyols (A1), where bio-based polyols (A1) are polyphenols, carbohydrates, and / or fatty acid glycerides, particularly lignin, sucrose, glucose, fructose, starch, hemicellulose, cellulose, and / or fatty acid glycerides, to obtain alkoxylated bio-based polyols (A2), then

[0069] - Esterification of polyols (A2) with substituted cyclic anhydrides.

[0070] Preferably, the alkoxylated bio-based polyol (A) is obtained via a method comprising the following steps (particularly the following steps):

[0071] - Alkoxylation of bio-based polyols (A1), where bio-based polyols (A1) are fatty acid glycerides, particularly ricinoleic acid glycerides, to obtain alkoxylated bio-based polyols (A2), then

[0072] - Esterification of a polyol (A2) with a substituted cyclic anhydride selected from octenyl succinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, eicosene succinic anhydride, phenyl succinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, high-phthalic anhydride, nadic anhydride, methyl nadic anhydride, and mixtures thereof.

[0073] More preferably, the alkoxylated bio-based polyol (A) is obtained via a method comprising the following steps (particularly consisting of the following steps):

[0074] - Alkoxylation of the bio-based polyol (A1) of castor oil to obtain the alkoxylated bio-based polyol (A2), then

[0075] - Esterification of a polyol (A2) with a substituted cyclic anhydride selected from decenyl succinic anhydride, dodecenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, phenyl succinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, high phthalic anhydride and mixtures thereof, especially dodecenyl succinic anhydride, phthalic anhydride and mixtures thereof.

[0076] The characteristics of the polyols (A), (A1), and (A2) disclosed above are applicable to the method for obtaining polyol (A). In particular, alkoxylation is advantageously carried out at a selected epoxide / polyol (A1) molar ratio to obtain a polyol (A) having the total alkoxylation number as described above, and the cyclic anhydride / polyol (A2) molar ratio is advantageously selected to obtain a polyol (A) having the functionality f(OH) as described above.

[0077] Alkoxylation is a reaction well known to those skilled in the art. For example, it can be carried out by reacting a bio-based polyol (A1) with an epoxide in the presence of a catalyst (e.g., a Brønsted base, such as KOH or NaOH, or a Lewis acid, preferably a Brønsted base), particularly at a temperature between 120°C and 190°C.

[0078] As mentioned above, the alkoxylated bio-based polyol (A2) is commercially available (therefore the alkoxylation step is performed by the supplier of the polyol (A2)).

[0079] Esterification can be carried out advantageously under anhydrous conditions.

[0080] Esterification is advantageously carried out at temperatures between 60°C and 120°C, preferably between 80°C and 100°C.

[0081] Esterification can be carried out at atmospheric pressure.

[0082] Polyisocyanates

[0083] The term "polyisocyanate" refers to a compound containing at least two isocyanate groups (-NCO), preferably exactly two isocyanate groups (i.e., diisocyanate). When a polyisocyanate is a diisocyanate, it can therefore be represented by formula (II): OCN-R 1 -NCO, where R 1 It is a divalent hydrocarbon group containing 4 to 45 carbon atoms, and optionally contains one or more heteroatoms selected from oxygen, sulfur and nitrogen.

[0084] Polyisocyanates can be:

[0085] -a) Polyisocyanates derived from vegetable oils containing unsaturated fatty acids (such polyisocyanates can be obtained by following the methods described in G. Çaylı et al., Biobased polyisocyanates from plant oil triglycerides: synthesis, polymerization and characterization, J. Appl. Polym. Sci., 2008, 109, 2948–2955), particularly polyisocyanates derived from soybean oil, and / or

[0086] -b) Diisocyanate of formula (II): OCN-R 1 -NCO, R 1 The diisocyanate is selected from:

[0087] - Furan-based diisocyanates, such as 2,5-diisocyanate-furan, 2,5-bis(isocyanate-methyl)furan, 2,2'-(1-methylethylidene)bis[5-isocyanate-furan] (CAS 1008130-81-1), 2-isocyanate-5-[(5-isocyanate-furan-2-yl)methyl]furan (CAS 88768-51-8), 2-isocyanate-5-[1-(5-isocyanate-furan-2-yl)ethyl]furan (CAS 88768-52-9), [oxybis(methylene-5,2-furandimethyl)]diisocyanate (CAS 96732-82-0), 2-(isocyanate-methyl)-5-[2-[5-(isocyanate-methyl)furan-2-yl]propyl-2-yl]furan (CAS 1008130-81-1), 2-isocyanate-5-[(5-isocyanate-methyl)furan-2-yl]prop ... 88768-56-3),

[0088] - Diisocyanates based on dihydrohexitol having the following formula:

[0089]

[0090] -The following formula is based on methoxyphenyl diisocyanates:

[0091] Where R 8 This represents a hydrogen atom or a methoxy group, and m is an integer between 1 and 3.

[0092] Hexamethylene diisocyanate (HDI) urea carbamate of formula (IIa):

[0093] Formula (IIa)

[0094] in:

[0095] -i is an integer in the range of 2 to 5;

[0096] -j is an integer ranging from 1 to 2;

[0097] -R 11 It refers to a saturated or unsaturated, cyclic, straight-chain or branched hydrocarbon group containing 6 to 14 carbon atoms;

[0098] -R 12 Indicates a divalent propylene group;

[0099] -i, j, R 11 and R 12 This results in the hexamethylene diisocyanate urea ester corresponding to formula (IIa) comprising an isocyanate group NCO content ranging from 12% to 14% by weight relative to the weight of the urea ester.

[0100] -Pentamethylene diisocyanate (PDI),

[0101] - Hexamethylene diisocyanate (HDI),

[0102] -1,7-diisocyanate-heptane,

[0103] -1,8-Diisocyanate octane,

[0104] -1,9-Diisocyanate-based nonane,

[0105] -1,16-diisocyanate-8-hexadecene,

[0106] -1-Isocyanate-10-[(isocyanate-methyl)thio]decane,

[0107] -dimeryl diisocyanate (CAS 68239-06-5),

[0108] methyl L-lysine diisocyanate (CAS 34050-00-5),

[0109] -L-lysine diisocyanate ethyl ester (CAS 45172-15-4),

[0110] -2,4-Diisocyano-1-pentadecanylbenzene

[0111] -Isophorone diisocyanate (IPDI),

[0112] -4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate (HMDI),

[0113] -2,4- and / or 2,6-toluene diisocyanate (TDI),

[0114] -4,4'- and / or 2,4'-diphenylmethane diisocyanate (MDI),

[0115] -m-xylene diisocyanate (m-XDI)

[0116] - Hydrogenated m-xylene diisocyanate (m-H6XDI), and

[0117] - Its mixture.

[0118] Advantageously, the polyisocyanate is selected from pentamethylene diisocyanate, hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, dimerized 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-xylene diisocyanate, hydrogenated m-xylene diisocyanate, and mixtures thereof.

[0119] Preferably, the polyisocyanate is selected from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 4,4'- and / or 2,4'-diphenylmethane diisocyanate, m-xylene diisocyanate, hydrogenated m-xylene diisocyanate, and mixtures thereof.

[0120] More preferably, the polyisocyanate is selected from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and / or 2,4'-dicyclohexylmethane diisocyanate, m-xylene diisocyanate, hydrogenated m-xylene diisocyanate and mixtures thereof, especially isophorone diisocyanate.

[0121] Advantageously, step (i) is carried out with an excess of the molar equivalent of the -NCO groups of the polyisocyanate relative to the molar equivalent of the -OH groups of the polyol (A). Preferably, step (i) is carried out with a -NCO / -OH molar equivalent ratio between 1.1 and 4, more preferably between 1.2 and 3, for example between 1.3 and 2.

[0122] The -NCO / -OH molar equivalent ratio is defined as equal to the molar equivalent number of the -NCO groups of the polyisocyanate divided by the sum of the molar equivalent numbers of the -OH groups used in step (i) (especially the polyols (A) and optional alcohols (B) described below).

[0123] The molar equivalent number of the –NCO group in a polyisocyanate is equal to: f(–NCO)*(m 多异氰酸酯 / M 多异氰酸酯 ), where f(–NCO) is the number of –NCO groups in the polyisocyanate, m is the mass of the introduced polyisocyanate in g, and M 多异氰酸酯 It is the molar mass of the polyisocyanate in g / mol. Preferably, the polyisocyanate is a diisocyanate, and therefore f(–NCO) equals 2.

[0124] The molar equivalent number of the -OH group in an alcohol (especially a polyol (A) or alcohol (B)) is equal to: (I OH *m OH ) / 56100, where I OH The hydroxyl value is calculated as mg KOH / g alcohol, and m is the value of the alcohol. OH It is the mass of alcohol introduced, expressed in grams.

[0125] alcohol ( B )

[0126] 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 contain any carboxylic acid groups (-C(=O)OH).

[0127] The alcohol (B) has a number-average molar mass Mn greater than or equal to 500 g / mol.

[0128] The alcohol (B) may have a functionality f(OH) between 1 and 6, preferably between 2 and 4, more preferably between 2 and 3, and particularly equal to 2. The functionality f(OH) represents the average number of hydroxyl functional groups (-OH) per molecule of polyol.

[0129] The functionality f(OH) can be determined as shown above for polyol (A).

[0130] For example, the alcohol (B) may be a bio-based polyol (A1) as described above, which may optionally be modified, particularly alkoxylated (especially polyphenols, carbohydrates and / or fatty acid glycerides), poly(farnesene) glycol, isosorbide, polyether polyol, polyester polyol, polycarbonate polyol, polyacrylate polyol, polysiloxane polyol and / or polyolefin polyol, preferably a polyether polyol such as polypropylene glycol or polyethylene glycol.

[0131] Poly(farnesene) glycols can be obtained from plant resources. In fact, some plant resources, such as apples, contain farnesene. As an example of commercial poly(farnesene) glycols, Krasol® F 3000, sold by Total, is worth mentioning.

[0132] Isosorbide can also be obtained from plant resources because it can be obtained from glucose, which is a very common sugar in plants.

[0133] In particular, alcohols (B) can have the formula HO-R 9 -OH, where the group R 9 Selected from the following divalent groups, which show two free valences as shown in the following formula:

[0134] - Poly(farnesene) diol derivatives:

[0135]

[0136] -Isosorbide derivatives:

[0137] - Polypropylene glycol derivatives:

[0138] - Polypropylene glycol derivatives:

[0139] - Polyester diol derivatives:

[0140] -Polybutadiene diol derivatives:

[0141] - Polyacrylate diol derivatives:

[0142]

[0143] - Polysiloxane diol derivatives:

[0144] in:

[0145] -x and y are integers; preferably, x and y such that the number-average molar mass Mn of the poly(farnese) glycol is between 500 g / mol and 8000 g / mol, more preferably between 1000 g / mol and 5000 g / mol.

[0146] -q represents an integer, such that the group R 9 The number-average molar mass ranges from 500 g / mol to 20,000 g / mol, preferably from 3,000 g / mol to 14,000 g / mol.

[0147] -r and s represent zero or non-zero integers, such that the group R 9 The number-average molar mass ranges from 500 g / mol to 20,000 g / mol, preferably from 3,000 g / mol to 14,000 g / mol. It should be understood that the sum r+s is not zero.

[0148] -Q 1 This indicates a preferred linear or branched, saturated or unsaturated aromatic or aliphatic divalent alkylene group containing 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms.

[0149] -Q 2 This indicates a preferred divalent alkylene group containing 2 to 36 carbon atoms, more preferably 1 to 8 carbon atoms, either straight-chain or branched.

[0150] -Q 3 Q 4 Q 5 Q 6 Q 7 and Q 8 Each group represents a hydrogen atom independently or preferably contains 1 to 12 carbon atoms, more preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms of an alkyl, alkenyl, or aromatic group.

[0151] Preferably, the group R 9 This indicates a group derived from polyether, particularly a group derived from polyethylene glycol or polypropylene glycol as described above.

[0152] The amount of alcohol (B) introduced during step (i) relative to the weight of polyol (A) can range up to 80% by weight, preferably up to 50% by weight and more preferably up to 20% by weight.

[0153] Additives in step (i)

[0154] Step (i) is typically carried out in the presence of a catalyst, which can be any catalyst known to those skilled in the art for catalyzing the formation of polyurethane through the reaction of a polyisocyanate and at least one polyol. Such a catalyst is, for example, selected from carboxylates of bismuth and / or zinc, particularly neodecanoates. As a commercially available example, Borchi® KAT 315 from OMB Borchers, which is bismuth neodecanoate, or Borchi® KAT15 from the same company, which is zinc neodecanoate, may be mentioned.

[0155] The amount of catalyst introduced during step (i) relative to the weight of polyol (A) can be between 0.01 wt% and 0.5 wt%, preferably between 0.02 wt% and 0.4 wt%, and more preferably between 0.04 wt% and 0.2 wt%.

[0156] Step (i) may be carried out in the presence of a UV stabilizer (or antioxidant). Typically, a UV stabilizer is introduced to prevent degradation resulting from a reaction with oxygen, which may occur via heat or light. The UV stabilizer may include an antioxidant capable of scavenging free radicals.

[0157] Advantageously, the UV stabilizer (or antioxidant) is selected from benzotriazole, benzophenone, hindered phenols, such as ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], 2,2'-methylene bis(6-(tert-butyl)-4-methylphenol), 2,2'-methylene bis(6-(tert-butyl)-4-ethylphenol), 2,2'-methylene bis(4-methyl-6-cyclohexylphenol) or 2,2'-methylene bis(4,6-bis(tert-butyl)phenol), 4,4'-methylene bis(2,6-bis(tert-butyl)phenol) and 2,6-bis(tert-butyl)-4- Methylphenol, hindered amines, such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (CAS No.: 41556-26-7), methyl 1,2,2,6,6-pentamethyl-4-piperidinyl sebacate (CAS No.: 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-bis(α,α-dimethylbenzyl) diphenylamine and mixtures thereof. Products such as Irganox® 245, Irganox® 1076, Tinuvin® 292, Tinuvin® 765 or Tinuvin® 770 DF sold by BASF and Riasorb UV-123 sold by Rianlon may be mentioned.

[0158] Preferably, the UV stabilizer (or antioxidant) is selected from hindered phenols, more preferably from ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], 2,2'-methylene bis(6-(tert-butyl)-4-methylphenol), 2,2'-methylene bis(6-(tert-butyl)-4-ethylphenol), 2,2'-methylene bis(4-methyl-6-cyclohexylphenol), 2,2'-methylene bis(4,6-bis(tert-butyl)phenol), 4,4'-methylene bis(2,6-bis(tert-butyl)phenol), 2,6-bis(tert-butyl)-4-methylphenol, and mixtures thereof.

[0159] The amount of UV stabilizer (or antioxidant) introduced during step (i) may range from 0.1% to 5% by weight relative to the weight of polyol (A), preferably from 0.2% to 3% by weight.

[0160] Other features of step (i)

[0161] The %NCO weight of the polyurethane composition with -NCO end groups obtained at the end of step (i) can range from 0.3% to 5% relative to the total weight of the composition, preferably from 0.5% to 3%.

[0162] The %NCO weight of the polyurethane composition can be determined by any method known to those skilled in the art, especially using an automated titrator, such as that described in Example 1.

[0163] The %NCO weight of the polyurethane composition may vary depending on the molar ratio of polyol (A) to polyisocyanate.

[0164] According to one implementation scheme, in addition to the polyol (A), step (i) is performed using at least the following:

[0165] - Polyisocyanates selected from pentamethylene diisocyanate, hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, 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-xylene diisocyanate, hydrogenated m-xylene diisocyanate, and mixtures thereof.

[0166] -A catalyst for the formation of polyurethane through the reaction of a polyisocyanate and at least one polyol, and

[0167] -Optional, UV stabilizer (or antioxidant).

[0168] Preferably, in addition to the polyol (A), step (i) is performed using at least the following:

[0169] - Polyisocyanates selected from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, m-xylene diisocyanate, hydrogenated m-xylene diisocyanate, and mixtures thereof, particularly isophorone diisocyanate.

[0170] -A catalyst, selected from bismuth and / or zinc carboxylates, especially neodecanoates, and

[0171] -Optionally, a UV stabilizer (or antioxidant) selected from hindered phenols.

[0172] The features of step (i) disclosed above are applicable to this embodiment. In particular, the quantities used in this embodiment are advantageously as described above.

[0173] Step (i) is advantageously carried out under anhydrous conditions.

[0174] Step (i) is advantageously carried out at a temperature between 50°C and 120°C, preferably between 60°C and 100°C.

[0175] Step (i) can be performed at atmospheric pressure.

[0176] Step (ii): Silicylation

[0177] Advantageously, the method according to the invention further includes step (ii): silanizing the polyurethane composition with -NCO end groups obtained in step (i) (preferably obtained directly from step (i)) with a silyl compound to form a silyl polyurethane composition, said silyl compound having formula (III):

[0178]

[0179] (III)

[0180] in:

[0181] -R 3 This refers to a straight-chain or branched dialkylene group containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.

[0182] -R 4 This indicates a straight-chain or branched alkyl group containing 1 to 4 carbon atoms, and when p equals 2, the group R... 4 Same or different,

[0183] -R 5This indicates a straight-chain or branched alkyl group containing 1 to 4 carbon atoms, an alkyl carbonyl group containing 2 to 8 carbon atoms, or a dialkyl imino group containing 3 to 8 carbon atoms, and when p equals 0 or 1, the group R... 5 Same or different, two groups OR 5 They may participate in the same ring; preferably, R 5 This refers to a straight-chain or branched alkyl group containing 1 to 4 carbon atoms.

[0184] -X indicates selection from -N(R) 6 Divalent groups of -, -NH- and -S-,

[0185] -R 6 The saturated or unsaturated hydrocarbon group contains 1 to 20 carbon atoms, is a straight or branched open chain, or contains one or more optionally aromatic rings, and may also contain one or more heteroatoms; preferably, R 6 This refers to a straight-chain or branched alkyl group containing 1 to 20 carbon atoms, and

[0186] -p is an integer equal to 0, 1, or 2, preferably equal to 0 or 1.

[0187] Unless otherwise stated, the various groups, radicals and letters included in the formulas described herein shall remain in the same definition throughout this document.

[0188] Advantageously, the silyl compound has formula (III), wherein:

[0189] -R 3 This refers to a straight-chain or branched dialkylene group containing 1 to 3 carbon atoms, preferably n-propylene.

[0190] -R 5 This indicates a methyl or ethyl group, preferably methyl;

[0191] -X represents a divalent group –N(R) 6 )–,

[0192] -R 6 This refers to a straight-chain or branched alkyl group containing 1 to 4 carbon atoms, preferably n-butyl, and

[0193] -p equals 0.

[0194] The silyl compounds of formula (III) are widely available commercially. For example, N-(3-(trimethoxysilyl)propyl)butylamine, available from Evonik under the name Dynasylan® 1189, may be mentioned.

[0195] The statement “a polyurethane composition with –NCO end groups obtained from step (i)” means a polyurethane composition or a derived composition with –NCO end groups obtained directly at the end of step (i) (especially an ionic polyurethane composition with –NCO end groups obtained during step (iii) below).

[0196] Step (ii) corresponds to the following reaction: the silyl compound reacts with the NCO group of the polyurethane composition obtained from step (i), particularly the NCO group of the polyurethane composition with -NCO end groups formed at the end of step (i) (to form a nonionic silyl polyurethane composition) or the NCO group of the ionic polyurethane composition with -NCO end groups obtained from step (iii) (to form an ionic silyl polyurethane composition).

[0197] In the method according to the invention, step (ii) can be performed with a -XH / -NCO molar equivalent ratio equal to 1, preferably between 0.90 and 1.15.

[0198] The -XH / -NCO molar equivalent ratio is defined as the molar equivalent number of the -XH groups of the silyl compound of formula (III) divided by the molar equivalent number of the -NCO groups of the polyurethane composition with -NCO end groups formed by step (i).

[0199] The molar equivalent number of the -XH group of the silyl compound of formula (III) is equal to the number of moles of the silyl compound of formula (III) introduced in step (ii).

[0200] The molar equivalent number of the -NCO groups in the polyurethane composition with -NCO end groups obtained from step (i) corresponds to the molar equivalent number of the -NCO groups of the polyisocyanate that were excessively introduced during step (i) relative to the molar equivalent number of the -OH groups of the polyol (A).

[0201] Step (ii) is advantageously carried out under anhydrous conditions.

[0202] Step (ii) is advantageously carried out at a temperature in the range of 20°C to 90°C, preferably 30 to 80°C.

[0203] Step (ii) is advantageously carried out at atmospheric pressure.

[0204] Step (iii)

[0205] The method according to the invention may further include step (iii): reacting the polyurethane composition obtained from step (i) with a tertiary amine having a pKa greater than 8 at 25°C to form an ionic polyurethane composition.

[0206] The term “polyurethane composition obtained from step (i)” means a polyurethane composition or derived composition with -NCO end groups obtained directly at the end of step (i) (especially a silyl polyurethane composition obtained during step (ii) above).

[0207] Specifically, step (iii) corresponds to the reaction of the tertiary amine with the carboxylic acid groups of the polyurethane composition obtained in step (i), particularly the polyurethane composition with -NCO end groups formed in step (i) (to form an ionic polyurethane composition with -NCO end groups). Or the nonionic silyl polyurethane composition formed in step (ii) (to form an ionic silyl polyurethane composition). For convenience, the interaction between the tertiary amine and the carboxylic acid groups is described as ionic. However, it should be understood that this interaction is not necessarily completely ionic and may, for example, involve hydrogen bonding. This interaction prevents the yellowing of compositions obtained from the ionic polyurethane compositions according to the invention.

[0208] The tertiary amine used in step (iii) has a pKa greater than 8, preferably between 9 and 15, and more preferably between 10 and 12 at 25°C.

[0209] Throughout this application, the term "pKa of a tertiary amine" refers to the pKa of its conjugate acid (i.e., the protonated tertiary amine). The pKa of an acid is equal to –log 10 (Ka), where Ka is the acid dissociation constant in water.

[0210] Tertiary amines may have the formula (IV): N(R)(R')(R”), where R, R', and R” may be the same or different, each representing a saturated or unsaturated hydrocarbon group, optionally containing one or more heteroatoms selected from N, O, and S, and R and R' and / or R and R'' and / or R' and R” may form heterocycles with the nitrogen atom to which they are attached.

[0211] According to one embodiment, the tertiary amine is selected from triethylamine (or TEA), 1,8-diazabicyclo[5.4.0]undecane-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), 2,2'-dimorpholinodiethyl ether (or DMDEE), triazabicyclodecene (TBD), methyltriazabicyclodecene (MTBD), trihexylamine (or THA), and mixtures thereof.

[0212] When the method according to the invention further includes a silylation step (ii), the tertiary amine is advantageously selected from TEA, DBU, DABCO, DBN, DCHMA, TBD, MTBD, THA, and mixtures thereof.

[0213] Preferably, the tertiary amine is selected from DBU, DABCO, DBN, DCHMA and mixtures thereof, especially DCHMA.

[0214] In step (iii) of the method of the present invention, the molar ratio of (tertiary amine / -C(=O)OH) can range from 0.5 to 2.5, preferably from 1 to 2, and more preferably equal to 1.

[0215] The molar ratio of tertiary amine to -C(=O)OH is defined as equal to the number of moles of the tertiary amine introduced in step (iii) divided by the molar equivalent number of the -C(=O)OH groups of the polyol (A).

[0216] The molar equivalent number of the -C(=O)OH group in polyol (A) is equal to: f(-C(=O)OH)*(m 酸酐 / M 酸酐 ), where f(-C(=O)OH) is the sum of the number of functional groups of the anhydride and the number of -C(=O)OH groups of the cyclic anhydride introduced during esterification, m 酸酐 It is the mass of the acid anhydride introduced, expressed in g, and M 酸酐 It is the molar mass of the acid anhydride in g / mol.

[0217] Step (iii) is advantageously carried out under anhydrous conditions.

[0218] Step (iii) is advantageously carried out at a temperature between 20°C and 80°C, preferably between 20°C and 50°C.

[0219] Step (iii) is advantageously carried out at atmospheric pressure.

[0220] plasticizer

[0221] Plasticizers can be used in the method according to the invention. Preferably, step (i) is carried out in the presence of a plasticizer.

[0222] The presence of plasticizers reduces the viscosity of the reaction medium and the resulting polyurethane composition.

[0223] The plasticizer may be any plasticizer conventionally used in the field of adhesives and / or putty compositions.

[0224] Specifically, the plasticizer can be selected from:

[0225] - A mixture of methyl esters of fatty acids, particularly a mixture of methyl esters of fatty acids containing 18 carbon atoms, such as fatty acids derived from castor oil, especially containing ricinoleic acid (e.g., Esterol A sold by Arkema).

[0226] - A mixture of alkyl sulfonic acids and phenol esters, such as a mixture identified by CAS number 91082-17-6 (e.g., Mesamoll® sold by Lanxess),

[0227] - Diisodecyl phthalate (e.g., Palatinol® DIDP sold by BASF),

[0228] - Diisononyl phthalate (DINP) (e.g., Palatinol® N sold by BASF),

[0229] -1,2-cyclohexanediol diisononyl ester (e.g., Hexamoll Dinch® sold by BASF),

[0230] - Pentaerythritol tetravalerate (e.g., Pevalen sold by Perstorp) TM ),

[0231] - Polysiloxane resins, particularly silsesquioxanes having a number-average molar mass Mn in the range of 400 g / mol to 4000 g / mol, preferably 500 g / mol to 2500 g / mol, such as Dow Corning® 3074 sold by Dow, with Mn between 1300-1500 g / mol, and

[0232] - Its mixture.

[0233] Preferably, the plasticizer is:

[0234] - A mixture of methyl esters of fatty acids, particularly fatty acids containing 18 carbon atoms (e.g., fatty acids derived from castor oil, especially ricinoleic acid), and / or

[0235] A mixture of alkyl sulfonic acids and phenol esters, such as the mixture identified by CAS number 91082-17-6.

[0236] According to one embodiment, the plasticizer comprises at least 50% by weight of a bio-based plasticizer, particularly a mixture of fatty acid methyl esters, such as fatty acids derived from castor oil, preferably between 85% and 100% by weight relative to the total weight of the plasticizer used in the method according to the invention. An example of a bio-based plasticizer is Esterol A, sold by Arkema.

[0237] The amount of plasticizer used in the method according to the invention may be up to 30% by weight relative to the total weight of the polyurethane composition, preferably between 3% and 25% by weight, and more preferably between 10% and 20% by weight.

[0238] solvent

[0239] The method according to the invention can advantageously be carried out in the absence of a solvent.

[0240] The term "solvent" specifically refers to solvents used in the field of adhesives and / or putties.

[0241] 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.

[0242] Preferably, the method according to the invention is carried out in the absence of water as a solvent. Therefore, the method according to the invention is carried out without the addition of free water (i.e., water other than that inherently included in the components used). In particular, the water content introduced into the method according to the invention is less than 3% by weight, preferably less than 1% by weight, relative to the total weight of the components used. Furthermore, the polyol (A) is preferably dehydrated (e.g., at about 100°C and under vacuum, especially at less than 0.6 kPa) before its use in step (i) until the water content is less than 0.1% by weight relative to the weight of the polyol (A). Other components (particularly plasticizers) can also be dehydrated in the same manner.

[0243] Water content can be measured using the Karl Fischer coulometric method, for example, using the Hydranal method. TM It is used as a titrant and its equivalent point is detected by electrical measurement.

[0244] desiccant

[0245] The hygroscopic agent can be used in the method according to the invention, especially after step (i), and especially at the end of step (ii) when this step is performed (once the silylation of the polyurethane composition with -NCO end groups is completed).

[0246] Suitable hygroscopic agents (or desiccants) are particularly alkoxysilanes, such as trialkoxysilanes (especially trimethoxysilanes). Such agents advantageously extend the shelf life of polyurethane compositions during storage and transportation prior to their use.

[0247] Advantageously, the hygroscopic agent is selected from vinyltrimethoxysilane, trimethoxymethylsilane, propyltrimethoxysilane, vinyltriethoxysilane, alkoxyarylsilane (e.g., Geniosil® XL 70 sold by Wacker), and mixtures thereof.

[0248] Preferably, the hygroscopic agent is selected from vinyltrimethoxysilane, vinyltriethoxysilane and mixtures thereof, more preferably vinyltrimethoxysilane.

[0249] The content of the desiccant relative to the total weight of the polyurethane composition is between 0.2% by weight and 3% by weight, preferably between 0.5% by weight and 2% by weight.

[0250] Bio-based ingredients

[0251] According to one embodiment, at least 50% by weight, preferably at least 70% by weight, of the components used in the method according to the invention are bio-based, relative to the total weight of the components used in the method according to the invention.

[0252] Therefore, the polyurethane composition obtained by the method according to the invention advantageously contains at least 50% by weight of bio-based components relative to the total weight of the composition, preferably at least 70% by weight.

[0253] Bio-based ingredients, especially polyols (A) and optional plasticizers.

[0254] Preferred implementation scheme

[0255] According to a preferred embodiment, the method according to the present invention comprises (preferably consisting of):

[0256] (i) the step of reacting an alkoxylated bio-based polyol (A) containing a carboxylic acid group with a polyisocyanate to form a polyurethane composition with -NCO end groups, wherein:

[0257] - The polyol (A) is ethoxylated and / or propoxylated, having an average total alkoxylation number between 25 and 60. The polyol (A) is obtained from fatty acid glycerides, preferably esterified with substituted cyclic anhydrides.

[0258] - The polyisocyanate is selected from pentamethylene diisocyanate, hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,9-diisocyanatononane, 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-xylene diisocyanate, hydrogenated m-xylene diisocyanate, and mixtures thereof, wherein the molar equivalent number of the -NCO group of the polyisocyanate is in excess relative to the molar equivalent number of the -OH group of the polyol (a).

[0259] -A catalyst, preferably selected from bismuth and / or zinc carboxylates, is used relative to the weight of polyol (A), between 0.01 wt% and 0.5 wt%.

[0260] - Optionally, a UV stabilizer (or antioxidant), preferably selected from hindered phenols, is used at a weight of 0.1% to 5% relative to the weight of the polyol (A).

[0261] Then

[0262] (ii) Preferably, step (ii) involves silanizing the polyurethane composition containing -NCO end groups obtained in step (i) (preferably obtained directly at the end of step (i)) with a silyl compound to form a silyl polyurethane composition having formula (III), wherein:

[0263] -R 3 This refers to a straight-chain or branched dialkylene group containing 1 to 3 carbon atoms, preferably n-propylene.

[0264] -R 5 This indicates a methyl or ethyl group, preferably methyl;

[0265] -X represents a divalent group –N(R) 6 )–,

[0266] -R 6 This refers to a straight-chain or branched alkyl group containing 1 to 4 carbon atoms, preferably n-butyl, and

[0267] -p equals 0; and

[0268] (iii) Optionally, reacting the polyurethane composition obtained in step (i) with a tertiary amine having a pKa greater than 8 at 25°C to form an ionic polyurethane composition.

[0269] Relative to the total weight of the polyurethane composition, the method uses up to 30% by weight of plasticizer, and

[0270] Optionally, a desiccant may be used in the method.

[0271] In particular, the method according to the invention comprises (especially the following):

[0272] (i) the step of reacting an alkoxylated bio-based polyol (A) containing a carboxylic acid group with a polyisocyanate to form a polyurethane composition with -NCO end groups, wherein:

[0273] - The polyol (A) is ethoxylated and / or propoxylated, having an average total alkoxylation value between 30 and 50. The polyol (A) is obtained from castor oil esterified with a substituted cyclic anhydride, preferably selected from decenyl succinic anhydride, dodecenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, phenyl succinic anhydride, hexahydrophthalic anhydride, 1,2-cyclopentanedicarboxylic anhydride, 1,2-cyclobutanedicarboxylic anhydride, phthalic anhydride, high-phthalic anhydride, and mixtures thereof, particularly dodecenyl succinic anhydride, phthalic anhydride, and mixtures thereof.

[0274] - The polyisocyanate is selected from pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'- and / or 2,4'-dicyclohexylmethane diisocyanate, m-xylene diisocyanate, hydrogenated m-xylene diisocyanate, and mixtures thereof, especially isophorone diisocyanate, with a -NCO / -OH molar equivalent ratio between 1.2 and 3.

[0275] -A catalyst, preferably selected from bismuth and / or zinc carboxylates, is used at a weight relative to the polyol (A), between 0.04 wt% and 0.2 wt%.

[0276] - Optionally, a UV stabilizer (or antioxidant), preferably selected from hindered phenols, is used at a concentration between 0.2% and 3% by weight relative to the weight of the polyol (A).

[0277] Then

[0278] (ii) Preferably, step (ii) involves silanizing the polyurethane composition containing -NCO end groups obtained in step (i) (preferably obtained directly at the end of step (i)) with a silyl compound to form a silyl polyurethane composition having formula (III), wherein:

[0279] -R 3 It represents a straight-chain or branched dialkylene group containing 1 to 3 carbon atoms; preferably n-propylene;

[0280] -R 5 This indicates a methyl or ethyl group, preferably methyl;

[0281] -X represents a divalent group –N(R) 6 )–,

[0282] -R 6 This refers to a straight-chain or branched alkyl group containing 1 to 4 carbon atoms, preferably n-butyl, and

[0283] -p equals 0; and

[0284] (iii) Optionally, reacting the polyurethane composition obtained in step (i) with a tertiary amine having a pKa greater than 8 at 25°C to form an ionic polyurethane composition.

[0285] Relative to the total weight of the polyurethane composition, in the method, preferably during step (i), a plasticizer of between 10% and 20% by weight is used, and

[0286] Optionally, a desiccant may be used in the method.

[0287] The features of steps (i) to (iii) disclosed above are applicable to this embodiment (including preferred embodiments and features). In particular, the amounts used in this embodiment are advantageously as described above.

[0288] Polyurethane compositions obtainable by the method according to the invention

[0289] Another objective of the present invention is to obtain polyurethane compositions that can be obtained by the method according to the invention as described above (including preferred embodiments and features).

[0290] The polyurethane content in the composition can range from 60% to 100% by weight relative to the total weight of the composition, and preferably from 70% to 95% by weight.

[0291] The viscosity of the polyurethane composition at 23°C can be in the range of 1 to 350 Pa·s, and advantageously between 1 and 250 Pa·s, preferably between 5 and 100 Pa·s.

[0292] This viscosity can be measured, for example, at 23°C according to the Brookfield-type method (especially as shown in Example 1).

[0293] The polyurethane composition obtained by the method according to the invention may contain a plasticizer. The plasticizer is as described above. The total content of the plasticizer in the composition relative to the total weight of the composition may range up to 30% by weight, preferably between 3% and 25% by weight, more preferably between 10% and 20% by weight.

[0294] The polyurethane composition obtained by the method according to the invention may contain a hygroscopic agent. The hygroscopic agent is as described above. The content of the hygroscopic agent relative to the total weight of the composition is between 0.2% by weight and 3% by weight, preferably between 0.5% by weight and 2% by weight.

[0295] The polyurethane composition obtained by the method according to the invention may contain a UV stabilizer (or antioxidant). The UV stabilizer (or antioxidant) is as described above. The content of the UV stabilizer (or antioxidant) relative to the total weight of the composition may range from 0.1% by weight to 3% by weight, preferably from 0.2% by weight to 2% by weight.

[0296] Advantageously, the polyurethane composition obtained by the method according to the invention does not contain any solvent as defined above. In particular, the composition contains less than 3% by weight of water, preferably less than 1% by weight, relative to the total weight of the composition.

[0297] Furthermore, the characteristics described above relating to polyurethane compositions obtained by the method according to the invention are applicable to polyurethane compositions obtainable by the method according to the invention.

[0298] In particular, the polyurethane composition that can be obtained by the method according to the invention advantageously contains at least 50% by weight of bio-based components relative to the total weight of the composition, preferably at least 70% by weight.

[0299] According to a first embodiment, the polyurethane composition is a polyurethane composition with -NCO end groups that can be obtained by the method according to the invention, including step (i) as defined above. When the polyurethane is ionic, the composition can be obtained by the method according to the invention, including step (iii) as defined above.

[0300] The NCO weight % of the polyurethane composition with -NCO end groups relative to the total weight of the composition can range between 0.3% and 5%, preferably between 0.5% and 3%.

[0301] The %NCO weight of the polyurethane composition can be determined by any method known to those skilled in the art, especially using an automatic titrator, such as that described in Example 1.

[0302] According to a second embodiment, the polyurethane composition is a silane polyurethane composition obtained by the method according to the invention, including steps (i) and (ii) as defined above. When the polyurethane is ionic, the composition can be obtained by the method according to the invention, further including step (iii) as defined above.

[0303] Polyurethane compositions can be stored, preferably protected from moisture, before being formulated for their final application (particularly in the form of adhesives and / or putties).

[0304] Adhesive and / or putty compositions

[0305] The present invention also relates to an adhesive and / or putty composition, preferably an adhesive composition comprising a polyurethane composition (preferably a silylated composition, more preferably a nonionic silylated composition) obtainable by the method according to the present invention.

[0306] The polyurethane content (especially that present in polyurethane compositions obtainable by the method according to the invention) may be between 8% by weight and 50% by weight relative to the total weight of the adhesive and / or putty composition, preferably 12% by weight to 40% by weight, more preferably 15% by weight and 30% by weight of ester.

[0307] Advantageously, the adhesive and / or putty compositions according to the invention also contain fillers.

[0308] The filler content is advantageously between 20% and 70% by weight relative to the total weight of the composition, preferably between 30% and 65% by weight, more preferably between 40% and 60% by weight.

[0309] The fillers that can be used in the adhesives and / or putty compositions according to the invention may be selected from mineral fillers, organic fillers and mixtures thereof, preferably mineral fillers.

[0310] As examples of mineral fillers, any mineral filler conventionally used in the field of adhesives and / or adhesive compositions may be mentioned. These fillers are in the form of particles of various geometries. For example, they may be spherical, fibrous, or irregularly shaped.

[0311] Advantageously, the mineral filler is formed by a group consisting of clay, quartz, hollow mineral microspheres and carbonate fillers.

[0312] Among hollow mineral microspheres, hollow glass microspheres can be mentioned, and more particularly those made of sodium calcium borosilicate or aluminosilicate.

[0313] Preferably, the mineral filler is formed by a group of carbonate fillers.

[0314] Advantageously, the carbonate filler is selected from alkali metal or alkaline earth metal carbonates and mixtures thereof. Preferably, the carbonate filler comprises calcium carbonate; more preferably, the carbonate filler is chalk or hydrophobically treated calcium carbonate (e.g., coated with fatty acids), and even more preferably, hydrophobically treated calcium carbonate.

[0315] When calcium carbonate is hydrophobically treated, this prevents the calcium carbonate from absorbing components of the composition and rendering them ineffective. The hydrophobic coating of calcium carbonate can account for 0.1% to 3.5% by weight relative to the total weight of calcium carbonate.

[0316] Preferably, when the hydrophobic treatment is a fatty acid coating, the fatty acid comprises or consists of more than 50% by weight of stearic acid relative to the total weight of the fatty acid.

[0317] Examples of organic fillers include any organic fillers, especially polymer fillers, that are routinely used in the field of adhesives and / or putty compositions.

[0318] For example, the organic filler may be composed of the group consisting of polyvinyl chloride (PVC), polyolefins, rubber, ethylene / vinyl acetate (EVA), expandable or non-expandable hollow thermoplastic polymer microspheres (e.g., hollow vinylidene chloride / acrylonitrile microspheres) and aromatic polyamide fibers (e.g., Kevlar®), preferably formed of PVC.

[0319] The average particle size of the filler can be between 10 nm and 400 μm, preferably between 20 nm and 100 μm, and more preferably between 30 nm and 1 μm.

[0320] The average particle size advantageously corresponds to the d50 particle size, which is the maximum size of the smallest particle by volume of 50%, and can be measured by a particle size analyzer, especially by laser diffraction on a Malvern-type machine (e.g., according to standard NF ISO13320).

[0321] Unless otherwise stated, the standards mentioned throughout the application are those that were in effect as of the date of filing.

[0322] Advantageously, the adhesive and / or putty compositions according to the invention comprise a plasticizer. The plasticizer may already be included in a polyurethane composition obtainable by the method according to the invention, and / or may be added to the adhesive and / or putty composition. The plasticizer is preferably selected from the plasticizers described above, and particularly from:

[0323] - A mixture of methyl esters of fatty acids, particularly fatty acids containing 18 carbon atoms (such as fatty acids derived from castor oil, especially ricinoleic acid),

[0324] Mixtures of alkyl sulfonic acids and phenol esters, such as mixtures identified by CAS number 91082-17-6, and

[0325] - Its mixture.

[0326] The total content of plasticizer in the adhesive and / or putty composition may range from 3% to 30% by weight relative to the total weight of the composition, preferably from 5% to 25% by weight, and more preferably from 7% to 20% by weight.

[0327] The adhesive and / or putty compositions according to the invention may further comprise a crosslinking catalyst. The term "crosslinking catalyst" refers to catalysts known to those skilled in the art for the condensation of silanols or for the crosslinking of NCO-terminated polyurethanes. Preferably, when the adhesive and / or putty composition comprises a silane-based polyurethane, it also comprises a catalyst for the condensation of silanols, preferably a tin-based catalyst.

[0328] As an example of a crosslinking catalyst for silanol condensation, the following can be mentioned:

[0329] -Organic titanium derivatives, such as titanium acetylacetonate, tetrapropoxy titanium, or tetrabutoxy titanium.

[0330] - Organozyrax derivatives, such as zirconium acetylacetonate, zirconium tetrapropoxy, or zirconium tetrabutoxy.

[0331] -amines, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 2,2'-dimorpholinodiethyl ether (DMDEE), 1,4-diazabicyclo[2.2.2]octane (DABCO), and 1,5,7-trizabicyclo[4.4.0]dec-5-ene (TBD).

[0332] - Catalysts based on zinc carboxylate (such as K-KAT® 670 sold by King Industries),

[0333] - Tin-based catalysts, such as compounds derived from dioctyltin or dibutyltin, such as dioctyltin oxide, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dicarboxylate, dibutyltin diacetylacetone (CAS: 22673-19-4), dibutyltin dilaurate (DBTDL), dibutyltin diacetate and / or dibutyltin oxide,

[0334] -Guinean derivatives, such as 1-(o-tolyl)biguanide (CAS No.: 93-69-6), such as Rhenocure 1000 C (sold by RheinChemie Additives).

[0335] As an example of a crosslinking catalyst used for crosslinking NCO-terminated polyurethanes, the following can be mentioned:

[0336] -Bismuth carboxylate (e.g., bismuth acetate, bismuth neodecanoate, etc

[0337] - Zinc carboxylate (e.g., zinc acetate, zinc neodecanoate, etc.),

[0338] -amines, such as DABCO or DMDEE,

[0339] -Organic titanium derivatives, such as titanium acetylacetonate, tetrapropoxy titanium, or tetrabutoxy titanium.

[0340] - Organozyrax derivatives, such as zirconium acetylacetonate, zirconium tetrapropoxy, or zirconium tetrabutoxy.

[0341] - Tin-based catalysts, such as compounds derived from dioctyltin or dibutyltin, such as dioctyltin oxide, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dicarboxylate, dibutyltin diacetylacetone, DBTDL, dibutyltin diacetate and / or dibutyltin oxide.

[0342] The content of the crosslinking catalyst may be between 0.01% by weight and 5% by weight, preferably 0.05% by weight to 2% by weight, relative to the total weight of the adhesive and / or putty composition according to the invention.

[0343] The adhesive and / or putty compositions according to the present invention may also contain one or more additives selected from hygroscopic agents, adhesion promoters, rheology modifiers, UV stabilizers, pigments, and mixtures thereof.

[0344] Advantageously, the adhesive and / or putty compositions according to the invention comprise a mixture of additives selected from hygroscopic agents, rheology modifiers and adhesion promoters.

[0345] The total content of additives relative to the total weight of the adhesive and / or putty composition according to the invention can range up to 15% by weight, preferably from 1% to 10% by weight.

[0346] The desiccant is advantageously selected as described above. Preferably, the desiccant is selected from vinyltrimethoxysilane, vinyltriethoxysilane, and mixtures thereof, more preferably vinyltrimethoxysilane.

[0347] The total content of the hygroscopic agent relative to the total weight of the adhesive and / or putty composition according to the invention may be between 0.5% by weight and 5% by weight, preferably between 2% by weight and 4% by weight.

[0348] The adhesion promoter may be selected from amino-, mercapto-, and epoxy-alkoxysilanes and mixtures thereof. Preferably, the adhesion promoter is selected from aminoalkoxysilanes and mixtures thereof, more preferably from aminotrialkoxysilanes and mixtures thereof, and even more preferably from aminotrimethoxysilanes and mixtures thereof, such as (3-aminopropyl)trimethoxysilane.

[0349] As an example of an epoxyalkoxysilane, (3-glycidyloxypropyl)trimethoxysilane (also known as GLYMO) may be mentioned.

[0350] Aminotrimethoxysilanes can be formed from the group consisting of: 4-amino-3,3-dimethylbutyltrimethoxysilane (e.g., Silquest A-Link 600 sold by Momentive), (3-aminopropyl)trimethoxysilane (e.g., Dynasylan® AMMO sold by Evonik), N-(3-(trimethoxysilyl)propyl)ethylenediamine (e.g., Geniosil® GF9 sold by Wacker), and mixtures thereof, particularly (3-aminopropyl)trimethoxysilane.

[0351] The content of the adhesion promoter may be between 0.1% by weight and 5% by weight, preferably between 0.5% by weight and 3% by weight, relative to the total weight of the adhesive and / or putty composition according to the invention.

[0352] The rheology modifier may be any rheology modifier conventionally used in the field of adhesives and / or putty compositions.

[0353] Preferably, the rheology modifier is selected from:

[0354] -PVC plastisols, corresponding to a suspension of PVC in a plasticizer miscible with PVC, are obtained in situ by heating to a temperature ranging from 60°C to 80°C. These plastisols may be those specifically described in the publication Polyurethane Sealants, Robert M. Evans, ISBN 087762-998-6.

[0355] - Fumed silica (optionally hydrophobic), such as HDK® N20 or HDK® H15 sold by Wacker,

[0356] - Urea derivatives obtained by reacting aromatic diisocyanate monomers (e.g., 4,4'-MDI) with aliphatic amines (e.g., butylamine). The preparation of such urea derivatives is particularly described in patent application FR 1 591 172.

[0357] - Waxes derived from castor oil, such as Thixcin® R, available from Elementis.

[0358] -Amide waxes, preferably micronized amide waxes, such as Crayvallac sold by Arkema ® SLX, Crayvallac ® SLW or Crayvallac ® Super, or Thixatrol available from Elementis ® AS8053 or Thixatrol ®MAX (EC No.: 432-430-3), or Rheobyk 7503 sold by BYK, and

[0359] - Its mixture.

[0360] In particular, the rheology modifier is fumed silica, especially hydrophobic fumed silica.

[0361] The term "wax derived from castor oil" refers to waxes obtained from castor oil, particularly hydrogenated castor oil. Waxes derived from castor oil are solid at 23°C.

[0362] The term "amide wax" refers to a wax containing one or more compounds having at least one amide group. In particular, amide waxes can be obtained from fatty acids (e.g., ricinoleic acid) and (di)amines.

[0363] The term “micronization” refers to an average particle size of less than 1 mm, advantageously less than 500 μm, preferably less than 100 μm, and more preferably less than 10 μm.

[0364] The average particle size advantageously corresponds to the d50 particle size, which is the maximum size of the smallest particle by volume of 50%, and can be measured by a particle size analyzer, especially by laser diffraction on a Malvern-type machine (e.g., according to standard NF ISO13320).

[0365] The rheology modifier content may range from 1% to 30% by weight, preferably from 2% to 20% by weight, and more preferably from 3% to 10% by weight, relative to the total weight of the adhesive and / or putty composition according to the invention.

[0366] The adhesive and / or putty composition according to the invention may contain one or more UV stabilizers (or antioxidants) up to 1% by weight relative to the total weight of the composition. The UV stabilizers (or antioxidants) are advantageously as described above.

[0367] Pigments can be selected from organic pigments, inorganic pigments and mixtures thereof, such as titanium dioxide, carbon black, manganese ferrite and mixtures thereof.

[0368] The pigment content may range up to 5% by weight, preferably up to 3% by weight, relative to the total weight of the adhesive and / or putty composition.

[0369] Advantageously, the adhesive and / or putty compositions according to the invention do not contain any solvents as defined above. In particular, the compositions contain less than 3% by weight of water, preferably less than 1% by weight, relative to the total weight of the composition.

[0370] According to one embodiment, the adhesive and / or putty composition according to the invention comprises:

[0371] - Polyurethane, preferably silane-based polyurethane, between 8% and 50% by weight.

[0372] - Fillers between 20% and 70% by weight

[0373] - Plasticizers between 3% and 30% by weight

[0374] - Crosslinking catalysts between 0.01 wt% and 5 wt%, and

[0375] -Optionally, up to 15% by weight of one or more additives selected from hygroscopic agents, adhesion promoters, rheology modifiers, UV stabilizers, pigments, and mixtures thereof.

[0376] Weight percentage is expressed relative to the total weight of the adhesive and / or putty composition.

[0377] Preferably, the adhesive and / or putty composition according to the invention is substantially composed of the above-described components. The term "substantially composed of" means that, relative to the total weight of the composition, the adhesive and / or putty composition contains less than 5% by weight of components other than those described above, preferably less than 2% by weight, and even more preferably less than 1% by weight.

[0378] The components and their specific contents of this embodiment are as described above, including preferred features and embodiments.

[0379] The adhesive and / or putty 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, and more preferably between 5 and 100 Pa·s.

[0380] This viscosity can be measured, for example, at 23°C according to the Brookfield-type method (especially as shown in Example 1).

[0381] The adhesive and / or putty composition according to the invention can be prepared by simply mixing its components.

[0382] Preferably, the adhesive and / or putty composition according to the invention is prepared at atmospheric pressure and at a temperature between 10°C and 80°C, more preferably between 18°C ​​and 70°C.

[0383] When the preparation of the adhesive and / or putty composition according to the invention involves heating to a temperature above 55°C, if the final adhesive and / or putty composition contains ionic polyurethane, the polyurethane is advantageously introduced in a nonionic form and step (iii) is performed once the temperature of the adhesive and / or putty composition has dropped back to about 20°C-35°C.

[0384] Examples of preparing adhesive and / or putty compositions according to the present invention are described in Example 5.

[0385] Use of adhesive and / or putty compositions

[0386] The present invention also relates to the use of the adhesive and / or putty compositions according to the invention as adhesives and / or putties, preferably as adhesives.

[0387] In particular, the present invention relates to the use of adhesive and / or putty compositions according to the invention as adhesives and / or putty in the field of building construction, in the field of manufacturing of transportation vehicles (e.g., motor vehicles, railways, aerospace or shipbuilding industries), and especially in the field of building construction (e.g., for bonding parquet flooring to flooring (particularly concrete flooring)).

[0388] The adhesive and / or putty compositions according to the present invention are as described above, including preferred embodiments and features.

[0389] Method for assembling substrates

[0390] Furthermore, the subject of this invention is a method for assembling a substrate, comprising:

[0391] - Apply the adhesive and / or putty composition according to the invention to at least one surface of the substrate to be assembled, then

[0392] - To bring the substrate into contact.

[0393] The adhesive and / or putty compositions according to the present invention are as described above, including preferred embodiments and features.

[0394] It should be understood that during the coating and contact steps, the adhesive and / or putty composition according to the invention is in an uncured state.

[0395] The substrates can be the same or different.

[0396] Preferably, the assembly method according to the invention is carried out at an ambient temperature (particularly between 18°C ​​and 25°C, for example at about 23°C).

[0397] The term "approximately X" is intended to indicate that the value of X is added to or subtracted by 10%.

[0398] Suitable substrates include, for example, inorganic substrates such as glass, ceramics, concrete, metals and / or alloys (e.g., aluminum, steel, non-ferrous metals, galvanized metals), and / or organic substrates such as wood and / or plastics (e.g., PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyester, epoxy resin).

[0399] Products

[0400] The present invention also relates to articles comprising adhesive and / or putty compositions (cured or uncured) according to the present invention.

[0401] The adhesive and / or putty compositions according to the present invention are as described above, including preferred embodiments and features.

[0402] According to a first embodiment, the composition bonds at least two substrates of the article.

[0403] The article can be obtained by means of the method for assembling a substrate according to the present invention (including preferred embodiments and features).

[0404] The substrate is preferably as described above for the method of assembling the substrate according to the present invention.

[0405] According to the second embodiment, the article is contained in an airtight, sealed package containing an adhesive and / or putty composition according to the invention.

[0406] The airtight packaging is preferably a polyethylene bag or a polyethylene cartridge with a lid.

[0407] All of the above embodiments can be combined with each other. In particular, various of the above-described components of the adhesive and / or putty compositions according to the invention, and especially the preferred embodiments, can be combined with each other.

[0408] The following examples are given only to illustrate the invention and should not be construed as limiting its scope.

[0409] Example

[0410] Example 1: Composition and Measurement Method

[0411] Ingredients used

[0412] Use the following ingredients:

[0413] - Castor oil (from Arkema): (CAS: 8001-79-4, a mixture containing approximately 89% by weight of a compound having a molar mass of approximately 933 g / mol of ricinoleic acid triglyceride relative to the total weight of the mixture, the castor oil having a hydroxyl value between 157 and 167 mg KOH / g) OHThat is, the functionality is approximately 2.7 (meaning each molecule of ricinoleic acid triglyceride has an average of 2.7 -OH groups).

[0414] -K-12 (from Vertellus): Dodecenylsuccinic anhydride (CAS: 26544-38-7, a mixture of isomers),

[0415] -Surfaline® R40 (from Arkema): Ethoxylated castor oil with a total ethylene oxide number of 40.

[0416] -Borchi®Kat 315 (from OMG Borchers): Bismuth neodecanoate with a molar mass of 722.75 g / mol, a catalyst.

[0417] -Irganox® 245 (from BASF): Ethylene bis(oxoethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] (CAS: 36443-68-2), antioxidant.

[0418] -IPDI (from Covestro): Isophorone diisocyanate with a molar mass of 222.3 g / mol (CAS No.: 4098-71-9).

[0419] -Dynasylan® 1189 (from Evonik): has a molar mass of N-(3-(trimethoxysilyl)propyl)butylamine equal to 235.4 g / mol.

[0420] -Esterol A (from Arkema): Methyl esters of C16-C18 fatty acids and unsaturated C18 fatty acids (CAS: 67762-38-3), plasticizer.

[0421] -VTMO (from Sigma-Aldrich): Vinyltrimethoxysilane, a hygroscopic agent.

[0422] -HDK® H15 (from Wacker): Hydrophobic fumed silica, rheology modifier.

[0423] -Omya BSH® (from Omya), hydrophobically treated calcium carbonate, filler.

[0424] -Dynasylan® AMMO (from Evonik): (3-aminopropyl)trimethoxysilane, adhesion promoter.

[0425] -TIB Kat® 223 (from TIB Chemicals): Dioctyltin diacetylacetone (CAS: 54068-28-9), catalyst.

[0426] Measurement methods

[0427] The hydroxyl value of a polyol (denoted as I) OH The number of hydroxyl functional groups per gram of polyol is expressed in milligrams of potassium hydroxide (KOH) used in the determination of hydroxyl functional groups, as determined according to standard ASTM E1899-16.

[0428] The acid value of polyols (expressed as I) COOH The number of carboxylic acid functional groups per gram of polyol is expressed as milligrams of potassium hydroxide (KOH) used to determine the carboxylic acid functional groups, determined by potentiometric titration as follows: Titrate 0.5 mL of a mixture of 0.1% phenolphthalein commercial alcohol solution and 100 mL of 70% isopropanol aqueous solution with 0.1 N KOH ethanol solution. Then add 100 g of polyol to the same container and titrate with 0.1 N KOH solution; the required volume of KOH solution is determined as V1, in ml. The acid value I of the polyol is... COOH It equals (V1*56.1*0.1) / 100, expressed in mg KOH / g.

[0429] The number-average molecular weight (Mn) of the polyol P2 prepared in Example 3 below was determined by gel permeation chromatography (GPC) using polystyrene standards. Specifically, the following conditions were applied:

[0430] System: Waters Alliance GPC

[0431] - Columns: 5 μm pre-column (50*7.8 mm), 103 Å column (300*7.8 mm) (refer to Phenomenex 00H-0444-KO), two 104 Å columns (300*7.8 mm) (refer to Phenomenex 00H-0445-KO), Shodex F6028050 column (GPC-KF-805),

[0432] - Eluent: Tetrahydrofuran,

[0433] - Flow rate: 1 mL / min

[0434] Temperature: 35°C

[0435] - Injection volume and sample concentration: 50 μL, 10 mg / mL

[0436] - Detector: UV, 254 nm, refractive index.

[0437] The viscosities of the silyl polymers and adhesives prepared in the following examples were measured at 23°C according to the Brookfield method (Brookfield RVT (Conventional Viscosity Torque) viscometer, S7 rotor, 10 rpm).

[0438] %NCO was determined automatically using a T5 Excellence titrator (sold by Mettler Toledo). A sample of the reaction medium was removed and introduced into the titrator, followed by the automatic addition of a 5% (v / v) solution of dicyclohexylamine in DMF (N,N-dimethylformamide). Titration of excess amine was also performed automatically with 0.1N hydrochloric acid. %NCO was determined relative to the total weight of the compounds introduced into the reaction medium.

[0439] Tensile strength and elongation at break are measured at a constant speed of 100 mm / min according to standard ISO 37 (2012).

[0440] Specifically, the following conditions apply:

[0441] The standard type 2 (H2) dumbbell-shaped test specimen is used as shown in international standard ISO 37 (2012). The narrow section of the dumbbell used has a length of 20 mm, a width of 4 mm, and a thickness of 3 mm.

[0442] To prepare dumbbells, the test composition (pre-packaged in a tube) was extruded into a Teflon mold and crosslinked for 14 days under standard conditions (23°C and 50% relative humidity).

[0443] The principle of the measurement involves tensile testing a standard test specimen in a tensile testing machine (e.g., a Zwick Roell 2.5KN), where the movable jaws of the tensile testing machine move at a constant speed of 100 mm / min, and the results are recorded.

[0444] - Elongation at break (expressed as a percentage), which corresponds to the elongation of the test specimen under tension observed at fracture, and

[0445] - Tensile strength (TS, in MPa) is the tensile stress at which the test specimen breaks.

[0446] Repeat the measurements on five test specimens and calculate the average value of the results.

[0447] Example 2: Preparation of non-ethoxylated castor oil P1 modified with dodecenyl succinic anhydride (comparative)

[0448] 78.43 g of castor oil was introduced into the reactor, and then the reactor was placed under vacuum (0.1 kPa to 0.5 kPa) at 110°C for 1 hour to dehydrate the castor oil.

[0449] The reactor was then cooled to 90°C to allow the introduction of 21.57 g of K⁻¹⁰ under nitrogen and atmospheric pressure. The mixture was kept stirred until the characteristic band of the acid anhydride (1849 cm⁻¹) was no longer detectable by infrared spectroscopy. -1 and 1779 cm -1 ).

[0450] The obtained polyol has an I content of approximately 87 mg KOH / g. OH .

[0451] Example 3: Preparation of ethoxylated castor oil P2 modified with dodecenyl succinic anhydride (this invention)

[0452] 86.84 g of Surfaline® R40 was introduced into the reactor, and then the reactor was placed under vacuum (0.1 kPa to 0.5 kPa) at 110°C for 1 hour to dehydrate it.

[0453] The reactor was then cooled to 90°C to allow the introduction of 13.16 g of K⁻¹⁰ under nitrogen and atmospheric pressure. The mixture was kept stirred until the characteristic band of the acid anhydride (1849 cm⁻¹) was no longer detectable by infrared spectroscopy. -1 and 1779 cm -1 ).

[0454] The I of the obtained polyol OH It is approximately 61 mg KOH / g, I COOH It is approximately 27 mg KOH / g, and the number-average molar mass is approximately 2157 g / mol.

[0455] Example 4: Preparation of silane-based polyurethane

[0456] Using the amounts of compounds shown in Table 1 below, silyl polyurethanes were prepared using polyols P1 and P2 according to the method described below.

[0457] Polyols P1 or P2, along with Borchi® Kat 315, Irganox® 245, and Esterol A, were introduced into a reactor, which was then placed under vacuum (0.1 kPa to 0.5 kPa). The reactor was maintained at 110°C for 1 hour to dehydrate these compounds.

[0458] The reactor was then cooled to a temperature between 70°C and 75°C to allow the introduction of IPDI under nitrogen and atmospheric pressure. The mixture was kept stirred until the following NCO weight % was achieved, which corresponds to an excess of -NCO groups of IPDI introduced relative to the -OH groups of the polyol.

[0459] Then Dynasylan® 1189 is introduced in an amount corresponding to a –NH / –NCO molar equivalent ratio of approximately 1. The mixture is stirred until the band feature of the –NCO functional group is no longer detectable by infrared spectroscopy (approximately 2260 cm⁻¹). -1 ).

[0460] Finally, add VTMO while stirring.

[0461] Table 1

[0462]

[0463] * Percentage by weight relative to the total weight of the polyols, Borchi® Kat 315, Irganox® 245, Esterol A, and IDPI introduced into the reactor.

[0464] The viscosities of the silyl polyurethanes S2 and S3 according to the present invention are lower than the viscosities of the comparative silyl polyurethane S1.

[0465] Example 5: Adhesive preparation and properties

[0466] Adhesives (A1 to A3, respectively) were prepared using previously prepared silyl polyurethanes S1, S2, and S3, and their compositions are as follows:

[0467] -25 g of silyl polyurethane S1, S2 or S3

[0468] -11 g of Esterol A,

[0469] -4 g of HDK® H15,

[0470] -57 g of Omya BSH®

[0471] -2 g VTMO,

[0472] -1.8 g of Dynasylan® AMMO, and

[0473] -0.3 g of TIB Kat® 223.

[0474] In the first step, silyl polyurethane, Esterol A, HDK® H15 and Omya BSH® are mixed at a temperature between 50 and 60°C under vacuum (approximately 0.1-0.5 kPa) for approximately 30 to 60 minutes.

[0475] Then add VTMO and Dynasylan® AMMO and mix the mixture for about 10 minutes.

[0476] Finally, add TIB Kat® 223 and mix everything for a few seconds.

[0477] The stirring speed is approximately 500-2000 rpm (revolutions per minute).

[0478] The properties of adhesives A1 to A3 (measured according to Example 1) are summarized in Table 2 below.

[0479] Table 2

[0480]

[0481] The adhesives A2 and A3 using the silyl polyurethanes S2 and S3 according to the invention have lower viscosity than the comparative adhesive A1, which makes them easier to apply and improves their shelf life.

[0482] In addition, compared to adhesive A1, which has a very low elongation at break, it tends to break easily.

[0483] On the other hand, the use of silyl polyurethanes S2 and S3 according to the invention makes it possible to significantly improve the elongation at break of the adhesive while maintaining acceptable tensile strength.

Claims

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

2. The method according to claim 1, wherein the polyol (A) is ethoxylated and / or propoxylated, more preferably ethoxylated.

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

4. The method according to any one of claims 1 to 3, wherein the acid value of the polyol (A) is I. COOH The concentration is between 5 mg KOH / g and 50 mg KOH / g, preferably between 10 mg KOH / g and 40 mg KOH / g, and more preferably between 21 mg KOH / g and 40 mg KOH / g.

5. The method according to any one of claims 1 to 4, wherein the polyol (A) is obtained from a bio-based polyol (A1), the polyol (A1) being a polyphenol, a carbohydrate, and / or a fatty acid glyceride, preferably a fatty acid glyceride.

6. The method according to any one of claims 1 to 5, wherein at least one carboxylic acid group of the alkoxylated bio-based polyol (A) is obtained by esterification of the alkoxylated bio-based polyol (A2) with a cyclic anhydride, said cyclic anhydride preferably being substituted, and the polyol (A2) corresponding to the alkoxylated bio-based polyol (A1).

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

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

9. The method according to any one of claims 1 to 8, further comprising step (ii): silylating the polyurethane composition with -NCO end groups obtained in step (i) with a silyl compound to form a silyl polyurethane composition, the silyl compound having formula (III): in: -R 3 This refers to a straight-chain or branched dialkylene group containing 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. -R 4 This indicates a straight-chain or branched alkyl group containing 1 to 4 carbon atoms, and when p equals 2, the group R... 4 Same or different, -R 5 This indicates a straight-chain or branched alkyl group containing 1 to 4 carbon atoms, an alkyl carbonyl group containing 2 to 8 carbon atoms, or a dialkyl imino group containing 3 to 8 carbon atoms, and when p equals 0 or 1, the group R... 5 Same or different, two groups OR 5 They may participate in the same ring; preferably, R 5 This refers to a straight-chain or branched alkyl group containing 1 to 4 carbon atoms. -X indicates selection from -N(R) 6 Divalent groups of -, -NH- and -S-, -R 6 The term indicates a saturated or unsaturated hydrocarbon group comprising 1 to 20 carbon atoms, being a straight or branched open chain, or comprising one or more optionally aromatic rings, and may also contain one or more heteroatoms; preferably R 6 This refers to a straight-chain or branched alkyl group containing 1 to 20 carbon atoms, and -p is an integer equal to 0, 1, or 2, preferably equal to 0 or 1.

10. A polyurethane composition, which can be obtained by the method according to any one of claims 1 to 9.

11. An adhesive and / or putty composition comprising the polyurethane composition according to claim 10.

12. The adhesive and / or putty composition according to claim 11, further comprising filler.

13. A method for assembling a substrate, comprising: - Apply the adhesive and / or putty composition according to claim 11 or 12 to at least one surface of the substrate to be assembled, then - To bring the substrate into contact.

14. An article comprising the adhesive and / or putty composition according to claim 11 or 12.

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