COMPOSITION A BASE DE POLYURETHANE

Abstract

POLYURETHANE-BASED COMPOSITION The present invention relates to a composition comprising: a component –NCO comprising: A) at least one polyurethane having at least two NCO terminal groups; B) optionally a polyisocyanate compound comprising at least one polyisocyanate P having at least three NCO isocyanate functions; a component –OH comprising: a polybutadiene polyol P1 having at least two hydroxyl functions, said polyol P1 having a number-average molecular mass from 1,000 g / mol to 15,000 g / mol; a polyol P2 selected from diols, triols or mixtures thereof, said polyol P2 having a number-average molar or molecular mass from 60 to 500 g / mol;a P3 polyol comprising a hydroxyl functionality greater than or equal to 2, said P3 polyol being selected from the group consisting of polyether polyols, naturally occurring polyols, polyester polyols, and mixtures thereof, said P3 polyol having a number-average molecular weight ranging from 800 to 5,000 g / mol; at least one filler, the total filler content being greater than or equal to 30% by weight relative to the total weight of said component –OH. Figure: None;

Description

Title of the invention: POLYURETHANE-BASED COMPOSITION FIELD OF INVENTION

[0001] The present invention relates to a polyurethane-based composition.

[0002] The invention also relates to the use of said composition for bonding materials in the field of structural assembly such as automotive, aeronautical and / or construction. TECHNOLOGICAL BACKGROUND

[0003] Epoxy resins are now widely used in industry and in high-tech sectors such as automotive and electronics. They are often used in the form of two main components: an epoxy resin and a hardener. It is the polymerization (or cross-linking) reaction between the two components once mixed that gives epoxy resins their strength and adhesion. These resins have very effective structural properties and are usable in many fields.

[0004] However, existing epoxy resins have the disadvantage of being rigid and brittle at low temperatures. Yet, in structural assembly in general, there is a need for sealant-type adhesives with structural properties that are also flexible enough to withstand movement and deformation over a wide temperature range. For example, in the automotive industry, it is important to have adhesives that can be used and have suitable properties across a range, for example, from -60°C to 50°C. Indeed, bonding near engines can be subjected to low temperatures in countries where the outside temperature is below freezing, and conversely, to high temperatures in hot countries. A similar situation exists in aeronautics, where the temperature variation between takeoff and the temperature at 1000 feet varies considerably.

[0005] There is therefore a need for new compositions which make it possible to overcome at least some of these drawbacks.

[0006] More particularly, there is a need for new compositions which have structural and flexible properties over a wide temperature range, even at low temperatures such as for example -60°C.

[0007] There is also a need for new compositions which possess structural properties over a wide temperature range, while maintaining good adhesive and rheological properties such as, for example, the absence of fining. DESCRIPTION OF THE INVENTION A. Composition

[0008] The present invention relates to a composition comprising: - an NCO component comprising: • A) at least one polyurethane comprising at least two NCO terminal groups; • B) optionally a polyisocyanate compound comprising at least one polyisocyanate P comprising at least three isocyanate functions NCO; - an -OH component comprising: • a polybutadiene polyol PI comprising at least two hydroxyl functions, said polyol PI having a number-average molecular mass ranging from 1,000 g / mol to 15,000 g / mol g / mol; • a polyol P2 selected from diols, triols or mixtures thereof, said polyol P2 having a number-average molar or molecular mass ranging from 60 to 500 g / mol; • a P3 polyol comprising having a hydroxyl functionality greater than or equal to 2, said P3 polyol being selected from the group consisting of polyether polyols, naturally occurring polyols, polyester polyols, and mixtures thereof, said P3 polyol having a number-average molecular mass ranging from 800 to 5,000 g / mol; • at least one filler, the total content of filler(s) being greater than or equal to 30% by weight relative to the total weight of said component -OH. COMPONENT -NCO

[0009] The composition according to the invention comprises an -NCO component comprising: - A) at least one polyurethane comprising at least two NCO terminal groups; - B) optionally a polyisocyanate compound comprising at least one polyisocyanate P comprising at least three isocyanate functions NCO; A) Polyurethane with NCO terminations

[0010] Polyurethane A) comprising at least two NCO terminal groups can be obtained by polyaddition reaction: - of a composition comprising at least one polyisocyanate; - of a composition comprising at least one polyol. Polyisocyanate

[0011] The polyisocyanate can be chosen from monomeric polyisocyanates, polymeric polyisocyanates and mixtures thereof.

[0012] In the context of the invention, and unless otherwise stated, the term "polymeric polyisocyanate" covers oligomeric polyisocyanates.

[0013] Monomeric polyisocyanates can be selected from diisocyanates, triisocyanates and mixtures thereof. Diisocyanates can be selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate) (4,4'-HMDI), norbomene diisocyanate, norbomene diisocyanate, 1,4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate, ethyl γ-clohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethyl γ-clohexane diisocyanate, cyclohexane dimethylene diisocyanate, and 1,5-diisocyanato-2-methylpentane. (MPDI), 1,6-diisocyanato-2,4,4-trimethylhexane, 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), (2,5)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (2,5-NBDI), (2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (2,6-NBDI), 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6-XDI), 1,4-bis(isocyanatomethyl)-cyclohexane (1,4-H6-XDI), xylylene diisocyanate (XDI) (in particular m-xylylene diisocyanate (m-XDI)), toluene diisocyanate (in particular 2,4-toluene diisocyanate (2,4-TDI) and / or 2,6-toluene diisocyanate (2,6-TDI)), diphenylmethane diisocyanate (in particular 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and / or the 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), tetramethylxylylene diisocyanate (TMXDI) (in particular tetramethyl (meta)xylylene diisocyanate), of an allophanate of HDI having for example the following formula (Y): .

[0014] [Chem.l] ...J

[0015] (Y)

[0016] in which p is an integer from 1 to 2, q is an integer from 0 to 9, and preferably from 2 to 5, Rc represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms, preferably from 6 to 14 carbon atoms, Rd represents a divalent alkylene group, linear or branched, having from 2 to 4 carbon atoms, and preferably a divalent propylene group;

[0017] and mixtures thereof.

[0018] Triisocyanates can be selected from isocyanurates, biurets, and diisocyanate and triol adducts.

[0019] Polymeric polyisocyanates can be chosen from among polymeric MDIs (PMDI, or polymethylenepolyphenylene polyisocyanate).

[0020] Polymeric MDIs typically contain a mixture of monomeric MDI with MDI oligomers. For example, polymeric MDIs may have the following general formula:

[0021] [Chem.2] ,JJ U IA. D(..N - ' MCO

[0022] in which n can vary from 1 to 8, and in particular from 1 to 5.

[0023] Polymeric MDIs may have an average NCO functionality greater than 2, preferably ranging from 2.3 to 3.5, and even more preferably from 2.7 to 3.0.

[0024] By "average NCO functionality of a mixture" is meant the average number of NCO functions per mole of mixture.

[0025] Polymeric MDIs are marketed in particular by DOW CHEMICAL COMPANY, such as Voranate PAPI®20, PAPI®27, M229 and by BORSODCHEM, such as Ongronat®2510.

[0026] According to a preferred embodiment, polyurethane A) is obtained from a composition comprising at least one polyisocyanate, said composition having an average NCO functionality ranging from 2.3 to 3.5, preferably still from 2.7 to 3.0.

[0027] According to a preferred embodiment, polyurethane A) is obtained from polymeric MDI. Polyol

[0028] The polyol usable for preparing the aforementioned polyurethane A) can be chosen from polyether polyols, polyester polyols, and their mixtures.

[0029] The polyol may have a number-average molecular mass ranging from 200 g / mol to 20,000 g / mol, preferably from 400 g / mol to 18,000 g / mol, or even more preferably from 400 g / mol to 12,000 g / mol, advantageously from 400 g / mol to 8,000 g / mol, even more advantageously from 400 to 4,000 g / mol.

[0030] The polyol can in particular be chosen from those whose number-average molecular mass Mn is less than or equal to 4,000 g / mol, advantageously strictly less than 2,000 g / mol, and more preferably those whose number-average molecular mass Mn ranges from 400 to 1,500 g / mol.

[0031] The number-average molecular mass of the polyols can be calculated from the hydroxyl number (HN) expressed in mg KOH / g and the functionality of the polyol or determined by methods well known to those skilled in the art, for example by size exclusion chromatography (or SEC) with PEG (polyethylene glycol) as a standard.

[0032] The polyol usable for preparing polyurethane A) may have a hydroxyl functionality greater than or equal to 2, preferably greater than or equal to 3.

[0033] Polyether polyols can be chosen from polyoxyalkylene-polyols in which the alkylene (saturated) part, linear or branched, comprises 2 to 4 carbon atoms, and preferably 2 to 3 carbon atoms.

[0034] Polyether polyols are preferably chosen from polyoxyalkylene diols or polyoxyalkylene triols, and even better from polyoxyalkylene triols, the alkylene part of which, linear or branched, comprises from 1 to 4 carbon atoms, preferably from 2 to 3 carbon atoms.

[0035] By way of example of polyoxyalkylene diols or triols usable according to the invention, we may cite for example polyoxypropylene diol or triol (also referred to as polypropylene glycols (PPG) diol or triol), polyoxyethylene diol or triol (also referred to as polyethylene glycols (PEG) diol or triol), polyoxybutylene glycols (also referred to as polybutylene glycols (PBG) diol or triol), copolymers or terpolymers of PPG / PEG / PBG diol or triol, polytetrahydrofuran (PolyTHF), polytetramethylene glycols (PTMG), and their mixtures.

[0036] Preferably, the polyether polyols are chosen from polyoxypropylene triols. The polyether polyols mentioned above can be prepared conventionally and are widely available commercially. They can, for example, be obtained by polymerization of the corresponding alkylene oxide in the presence of a catalyst.

[0037] Examples of polyether triols include polyoxypropylene triol marketed under the name "VORANOL CP3355" by DOW, with a number-average molecular mass of approximately 3,554 g / mol, or DOW's "VORANOL CP1050" with a number-average molecular mass of approximately 1078 g / mol.

[0038] The polyester polyols that can be used to prepare the aforementioned polyurethane A) may be chosen from:

[0039] - polyester polyols resulting from the polycondensation of at least one diacid carboxylic acid or at least one of its corresponding anhydrides or diesters, with at least one diol,

[0040] - polyester polyols of the estolide polyol type resulting from the condensation of at least a hydroxycarboxylic acid (e.g., ricinoleic acid) or at least one of its esters, with at least one diol,

[0041] - polyester polyols resulting from ring-opening polymerization minus one cyclic lactone with at least one diol, such as polycaprolactone polyols.

[0042] The dicarboxylic acids usable for the synthesis of the aforementioned polyester polyols may be linear or branched, cyclic or acyclic, saturated or unsaturated, aromatic or aliphatic, and preferably comprise from 3 to 40 carbon atoms, and more preferably from 5 to 10 carbon atoms. Examples include succinic acid, adipic acid, sebacic acid, azelaic acid, or mixtures thereof.

[0043] The diols usable for the synthesis of the aforementioned polyester polyols may be chosen from polyalkylene diols, polyoxyalkylene diols, and mixtures of these compounds, the alkylene (saturated) portion of these compounds being preferably linear or branched, and preferably comprising from 2 to 40 carbon atoms, and more preferably from 2 to 8 carbon atoms. Examples include monoethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, or mixtures thereof.

[0044] The cyclic lactones usable for the synthesis of the aforementioned polyester polyols preferably comprise 3 to 7 carbon atoms.

[0045] The polyester polyols that can be used to prepare the aforementioned polyurethane A) can be prepared conventionally, and / or are typically commercially available.

[0046] The polyester polyols that can be used to prepare the aforementioned polyurethane A) may, in particular, be amorphous polyester polyols having a number-average molecular weight ranging from 800 to 5,000 g / mol, preferably from 800 to 3,000 g / mol. They may have a Brookfield viscosity less than or equal to 10,000 mPa·s at 25 °C, preferably ranging from 1,000 mPa·s to 5,000 mPa·s.

[0047] In the context of the invention, and unless otherwise stated, "amorphous polyester polyol" means a polyester polyol which, in analysis by Differential Scanning Calorimetry (DSC), shows that it does not have a melting point.

[0048] According to a preferred embodiment, the polyol is chosen from among the polyether polyols.

[0049] According to one embodiment, the aforementioned polyurethane A) is obtained from: - of a composition comprising at least one polyoxyalkylene-polyol (preferably polyoxyalkylene-triol), the alkylene portion (saturated), linear or branched, comprising 2 to 4 carbon atoms, and preferably 2 to 3 carbon atoms, - of a composition comprising at least polymeric MDI.

[0050] The polyaddition step can be carried out in quantities of polyisocyanate(s) and polyol(s) such that the NCO / OH molar ratio is strictly greater than 1, for example between 1.1 and 10, preferably between 5 and 8.

[0051] In the context of the invention, and unless otherwise stated, the NCO / OH molar ratio corresponds to the molar ratio of the number of isocyanate groups (NCO) to the number of hydroxyl groups (OH) carried respectively by the polyisocyanates and polyols used.

[0052] Polyurethane A) as defined above can be prepared in the presence or not of at least one reaction catalyst, preferably at a reaction temperature Tl below 95°C and preferably from 65°C to 80°C, and preferably also under anhydrous conditions. B) Polyisocyanate compound

[0053] The -NCO component may comprise a polyisocyanate compound B) comprising at least one polyisocyanate P comprising at least three NCO functions.

[0054] The polyisocyanate compound B) may consist of polyisocyanate P alone, or may be a mixture of polyisocyanate, said mixture necessarily comprising at least one polyisocyanate P as defined in the present invention.

[0055] The polyisocyanate P can be chosen from biurets, isocyanurates, diisocyanate adducts and triols.

[0056] The polyisocyanate P can be chosen from aromatic polyisocyanates, and in particular from those having the following formula:

[0057] [Chem.3] y / X' 'X DCN NCO NCO

[0058] in which n can vary from 1 to 8, preferably from 1 to 5.

[0059] According to a preferred embodiment, the polyisocyanate compound B) is a mixture of polyisocyanates comprising at least one polyisocyanate P having at least three NCO groups. It may be a mixture comprising: - at least one diisocyanate monomer; and - at least one polyisocyanate P having at least three NCO functions.

[0060] When the polyisocyanate compound B) is a mixture, the average NCO functionality of the mixture may be greater than 2, preferably from 2.3 to 3.5, and even more preferably from 2.7 to 3.0.

[0061] By "average NCO functionality of a mixture", we mean the average number of NCO functions per mole of mixture.

[0062] The diisocyanate monomers can be aliphatic, cycloaliphatic or aromatic monomers, preferably aromatic.

[0063] Preferably, the polyisocyanate compound B) is a mixture comprising: - at least one MDI monomer; - at least one polyisocyanate P having the following formula:

[0064] [Chem.4]

[0065] in which n can vary from 1 to 8, preferably from 1 to 5.

[0066] This type of mixture is typically available from DOW CHEMICAL COMPANY, under the trade name Voranate PAPI®20, PAPI®27, M229 and from BORSORDCHEM under the trade name Ongronat®2510 which are polymeric MDIs (PMDI).

[0067] The -NCO component may comprise a mass content of NCO groups ranging from 10% to 30%, preferably from 12% to 24% by mass relative to the total mass of said -NCO component.

[0068] The -NCO component can be prepared by simply mixing its ingredients at room temperature (23°C), preferably under anhydrous conditions.

[0069] The -NCO component according to the invention may comprise more than 50% by weight, preferably more than 60% by weight, even more preferably more than 65% by weight of polyurethane (A) as defined above, relative to the total weight of said -NCO component.

[0070] The -NCO component according to the invention may comprise more than 50% by weight, preferably more than 60% by weight, even more preferably more than 70% by weight of polyurethane (A) as defined above, relative to the total weight of said -NCO component.

[0071] According to a first embodiment, the -NCO component according to the invention comprises:

[0072] - from 1% to 40% by weight, preferably from 5% to 30% by weight of polyurethane(s) A) as defined above; and

[0073] - from 50% to 90% by weight, preferably from 55% to 80% by weight of compound(s) polyisocyanate(s) B) as defined above.

[0074] According to a second embodiment, the -NCO component according to the invention comprises:

[0075] - more than 50% by weight, preferably from 55% to 90% by weight of polyurethane(s) A) as defined above; and

[0076] - from 1% to 20% by weight, preferably from 5% to 15% by weight of compound(s) polyisocyanate(s) B) as defined above.

[0077] Preferably, the -NCO component comprises the polyisocyanate compound B). Charge

[0078] The -NCO component may include at least one load.

[0079] The charge can be chosen from mineral charges, molecular sieves, zeolites, organic charges, and mixtures thereof.

[0080] As an example of a mineral filler, any mineral filler commonly used in the field of adhesive compositions may be used. These fillers typically take the form of particles of various geometries. They may, for example, be spherical, fibrous, or have an irregular shape.

[0081] Mineral fillers can be chosen from the group consisting of clays, quartz, carbonate fillers, kaolin, gypsum, hollow glass microspheres, and mixtures thereof.

[0082] Some of these fillers may be untreated or treated, for example with an organic acid such as stearic acid, or a mixture of organic acids consisting mainly of stearic acid.

[0083] Hollow glass microspheres can be made of sodium and calcium borosilicate or aluminosilicate. For example, they could be the glass bead microspheres marketed by 3M.

[0084] Hollow glass microspheres can have an average particle size (D50v) ranging from 1 to 70 µm, preferably from 20 to 60 µm.

[0085] Hollow glass microspheres can have a density ranging from 0.100 to 0.600 g / cm3, preferably from 0.150 to 0.300 g / cm3.

[0086] By "average particle size", including fillers or hollow microspheres, is meant the size measurement for a volumetric particle size distribution corresponding to 50% by volume of the analyzed particle sample. When the particles are spherical, the average particle size corresponds to the diameter median (D50 or Dv50) which corresponds to the diameter such that 50% of the particles by volume have a size expressed in micrometers and determined according to the standard NF ISO 13320-1 (1999) by laser diffraction on a MALVERN type device.

[0087] By "sphere" or "spherical," including hollow charges or microspheres, is meant a particle having a shape ratio close to 1, ranging from 0.5 to 1.5, for example, such as particles of oblong, ovoid, or ellipsoidal shape, and preferably equal to 1, i.e., having a spherical shape. Such a shape ratio is defined as the ratio of the maximum distance between two points on the surface of the particle, along a principal direction, to the minimum distance between two points on the surface of the particle, along a direction substantially perpendicular to the principal direction.

[0088] Carbonate fillers can be chosen from alkali or alkaline-earth metal carbonates, and more particularly calcium carbonate or chalk.

[0089] As an example of organic fillers, any organic fillers, and in particular polymeric fillers, commonly used in the field of adhesive compositions can be used.

[0090] For example, polyvinyl chloride (PVC), polyolefins, rubber, ethylene vinyl acetate (EVA), aramid fibers such as Kevlar® can be used.

[0091] Hollow microspheres made of expandable or non-expandable thermoplastic polymers can also be used. Hollow microspheres made of vinylidene chloride / acrylonitrile are a particular example.

[0092] The average particle size of the organic load is preferably less than or equal to 50 qm, preferably between 5 and 20 qm.

[0093] Preferably, the -NCO component comprises from 0% to 10% by weight, preferably from 2% to 8% by weight, and even more preferably from 3% to 8% by weight of hollow glass microspheres relative to the total weight of said -NCO component. Additives

[0094] The -NCO component may include at least one additive selected from the group consisting of plasticizers, catalysts, solvents, pigments, adhesion promoters, moisture absorbers, UV stabilizers (or antioxidants), dyes, rheological agents, and mixtures thereof.

[0095] The total content of the aforementioned additive(s) in the -NCO component can range from 0% to 40% by weight, preferably from 1% to 35% by weight, advantageously from 5% to 30% by weight relative to the total weight of said -NCO component.

[0096] Preferably, the -NCO component does not comprise a solvent, said solvent being an organic solvent such as ethyl acetate, methyl ethyl ketone, tetrahydrofuran, methyl tetrahydrofuran, or even ISANE® (based isoparaffins, available from TOTAL) or EXXOL® D80 (based on aliphatic hydrocarbons, available from EXXON MOBIL Chemical) or chlorobenzene, naphtha, acetone, n-heptane, xylene.

[0097] As an example of a rheology agent (thixotropic), one can cite any rheology agent commonly used in the field of adhesive compositions, sealants.

[0098] Preferably, the rheological / thixotropic agents are chosen from:

[0099] - PVC plastisols, corresponding to a suspension of PVC in an agent Plasticizer miscible with PVC, obtained in situ by heating at temperatures ranging from 60°C to 80°C. These plastisols may be those described in particular in the book "Polyurethane Sealants", Robert M. Evans, ISBN 087762-998-6,

[0100] - fumed silica, possibly modified, such as for example sold under the Designation HDK® N20 by the company WACKER;

[0101] - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such that 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in application FR 1 591 172;

[0102] - micronized amide waxes, such as, for example, CRAYVALLAC SLX marketed by ARKEMA.

[0103] Preferably, the -NCO component comprises at least one rheological / thixotropic agent, even more preferably in a content ranging from 5% to 20% by weight relative to the total weight of said -NCO component.

[0104] The -NCO component may comprise a mass content of NCO groups ranging from 13% to 23%, preferably from 15% to 20% by mass relative to the total mass of said -NCO component.

[0105] The -NCO component can be prepared by simply mixing its ingredients at room temperature (23°C), preferably under anhydrous conditions. COMPONENT -OH Polyol PI

[0106] The -OH component comprises at least one polybutadiene polyol PI comprising at least two hydroxyl functions, said polyol PI having a number-average molecular mass ranging from 1,000 g / mol to 15,000 g / mol.

[0107] Polybutadiene polyol can be a homopolymer or a copolymer.

[0108] If it is a copolymer, the co-monomer content is less than 50% by weight of the polybutadiene polyol. The co-monomer may be selected from ethylene, propylene, isoprene, farnesene, dicyclopentadiene and mixtures thereof.

[0109] Preferably, polybutadiene polyol is a homopolymer.

[0110] The polybutadiene polyol PI according to the invention also covers its partially hydrogenated derivatives.

[0111] The polybutadiene polyol PI preferably comprises terminal hydroxyl functions.

[0112] In the context of the invention, and unless otherwise stated, the term "terminal hydroxyl functions" of a polybutadiene means the hydroxyl functions located at the ends of the main chain of the polybutadiene.

[0113] Polybutadiene polyol PI may have an average number of hydroxyl functions per molecule greater than or equal to 2.

[0114] In particular, the ratio of cis-1,4, trans-1,4 and 1,2-vinyl unsaturations present in polybutadiene is not critical.

[0115] The number and position of the hydroxyl groups in polybutadiene PI may depend on the preparation process. Such processes are described, for example, in US 5,303,843 or US 5,418,296.

[0116] Polybutadiene polyol PI may have a number-average molecular weight (Mn) ranging from 1,500 to 10,000 g / mol, and preferably from 2,000 to 5,000 g / mol.

[0117] Commercially available polybutadiene polyols are also available, such as, for example, POLY BD® from CRAY VALLEY or IDEMITSU, or POLYVEST® HT from EVONIK.

[0118] The total content of PI polyol(s) may range from 1% to 30% by weight, preferably from 2% to 20% by weight, and even more preferably from 3% to 8% by weight, relative to the total weight of said -OH component. Polyol P2

[0119] The -OH component comprises a polyol P2 selected from diols, triols or mixtures thereof, said polyol P2 having a number-average molar or molecular mass of 60 to 500 g / mol, preferably 60 to 250 g / mol.

[0120] The P2 polyol can be selected from the group consisting of estolide polyols resulting from the polycondensation of one or more hydroxy acids, such as ricinoleic acid, on a diol (for example, "POLYCIN® D-265", "POLYCIN® D-290" and "POLYCIN® T-400" available from VERTELLUS).

[0121] The polyol P2 may be selected from the group consisting of linear, branched, or cycloaliphatic diols, such as ethylene glycol (CAS: 107-21-1), diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,6-hexanediol, 3-ethyl-2-methyl-1,5-pentanediol, 2-ethyl-3-propyl-1,5-pentanediol, 2,4-dimethyl-3-ethyl-1,5-pentanediol, 2-ethyl-4-methyl-3-propyl-1,5-pentadiol, 2,3-diethyl-4-methyl-1,5-pentanediol, 3-ethyl-2,2,4-trimethyl-1,5-pentadiol, the 2,2-Dimethyl-4-ethyl-3-propyl-1,5-pentanediol, 2-methyl-2-propyl-1,5-pentanediol, 2,4-Dimethyl-3-ethyl-2-propyl-1,5-pentanediol, 2,3-Dipropyl-4-ethyl-2-methyl-1,5-pentanediol, 2-Butyl-2-ethyl-1,5-pentanediol, 2-Butyl-2,3-Diethyl-4-methyl-1,5-pentanediol, 2-Butyl-2,4-Diethyl-3-propyl-1,5-pentanediol, 3-Butyl-2-propyl-1,5-pentanediol, 2-Methyl-1,5-pentanediol (CAS: 42856-62-2), 3-Methyl-1,5-pentanediol (MPD, CAS: 4457-71-0), 2,2-Dimethyl-1,3-pentanediol (CAS: 2157-31-5), 2,2-Dimethyl-1,5-pentanediol (CAS: 3121-82-2), 3,3-Dimethyl-1,5-pentanediol (CAS: 53120-74-4), 2,3-Dimethyl-1,5-pentanediol (CAS: 81554-20-3), 2,2-Dimethyl-1,3-propanediol (Neopentyl glycol - NPG, CAS: 126-30-7), 2,2-Diethyl-1,3-propanediol (CAS: 115-76-4), 2-Methyl-2-propyl-1,3-propanediol (CAS: 78-26-2), 2-Butyl-2-ethyl-1,3-propanediol (CAS: 115-84-4), 2-Methyl-1,3-propanediol (CAS: 2163-42-0), 2-benzyloxy-l,3-propanediol (CAS: 14690-00-7), 2,2-dibenzyl-l,3-propanediol (CAS: 31952-16-6), 2,2-dibutyl-l,3-Propanediol (CAS: 24765-57-9), 2,2-Diisobutyl-1,3-propanediol, 2,4-Diethyl-1,5-pentanediol, 2-Ethyl-1,6-hexanediol (CAS: 15208-19-2), 2,5-Dimethyl-1,6-hexanediol (CAS: 49623-11-2), 5-Methyl-2-(1-methylethyl)-1,3-hexanediol (CAS: 80220-07-1), 1,4-Dimethyl-1,4-butanediol, 1,5-Hexanediol (CAS: 928-40-5), 3-Methyl-1,6-hexanediol (CAS: 4089-71-8), the 3-tert-butyl-l,6-hexanediol (CAS: 82111-97-5), 1,3-heptanediol (CAS: 23433-04-7), 1,2-octanediol (CAS: 1117-86-8), 1,3-octanediol (CAS: 23433-05-8), 2,2,7,7-tetramethyl-l,8-octanediol (CAS: 27143-31-3), 2-methyl-l,8-octanediol (CAS: 109359-36-6), 2,6-dimethyl-l,8-octanediol (CAS: 75656-41-6), 1,7-octanediol (CAS: 3207-95-2), the cyclohexanedimethanol (CAS Number: 105-08-8), 4,4,5,5-tetramethyl-3,6-dioxa-l,8-octanediol (CAS: 76779-60-7), 2,2,8,8-tetramethyl-l,9-nonanediol (CAS: 85018-58-2), 1,2-nonanediol (CAS: 42789-13-9), 2,8-dimethyl-l,9-nonanediol (CAS: 40326-00-9),1,5-Nonanediol (CAS: 13686-96-9), 2,9-Dimethyl-2,9-Dipropyl-1,10-Decanediol (CAS: 85018-64-0), 2,9-Dibutyl-2,9-Dimethyl-1,10-Decanediol (CAS: 85018-65-1), 2,9-Dimethyl-2,9-Dipropyl-1,10-Decanediol (CAS: 85018-64-0), 2,9-Diethyl-2,9-Dimethyl-1,10-Decanediol (CAS: 85018-63-9), 2,2,9,9-Tetramethyl-1,10-Decanediol (CAS: 35449-36-6), 2-nonyl-1,10-decanediol (CAS: 48074-20-0), 1,9-decanediol (CAS: 128705-94-2), 2,2,6,6,10,10-hexamethyl-4,8-dioxal-1,11-undecanediol (CAS: 112548-49-9), 1-phenyl-1,11-undecanediol (CAS: 109217-58-5), 2-octyl-1,11-undecanediol (CAS: 48074-21-1), 2,10-diethyl-2,10-dimethyl-1,11-undecanediol (CAS: 85018-66-2), 2,2,10,10-tetramethyl-1,11-undecanediol (CAS: 35449-37-7), l-phenyl-1,11-undecanediol (CAS: 109217-58-5), 1,2-undecanediol (CAS: 13006-29-6), 1,2-dodecanediol (CAS: 1119-87-5), 2,11-dodecanediol (CAS: 33666-71-6), 2,11-diethyl-2,11-dimethyl-1,12-dodecanediol (CAS: 85018-68-4), 2,11-dimethyl-2,11-dipropyl-1,12-dodecanediol (CAS: 85018-69-5), 2,1-dibutyl-2,1-dimethyl-1,12- dodecanediol (CAS: 85018-70-8), 2,2,11,1-tetramethyl-1,12-dodecanediol (CAS: 5658-47-9), 1,11-dodecanediol (CAS: 80158-99-2), 11-methyl-1,7-dodecanediol (CAS: 62870-49-9), 1,4-dodecanediol (CAS: 38146-95-1), 1,3-dodecanediol (CAS: 39516-24-0), 1,10-dodecanediol (CAS: 39516-27-3), 2,1-dimethyl-2,1-dodecanediol (CAS: 22092-59-7), 1,5-dodecanediol (CAS: 20999-41-1), 6,7-dodecanediol (CAS: 91635-53-9), 1,12-dodecanediol (CAS: 5675-51-4), and alkoxylated derivatives of these diols.

[0122] The polyol P2 may be selected from the group consisting of linear or branched aliphatic triols, or cycloaliphatic triols, such as glycerol (CAS: 56-81-5), 1,2,6-hexanetriol (CAS: 106-69-4), 1,2,4-butanetriol (CAS 3068-00-6), 1,2,5-pentanetriol (CAS 14697-46-2), 1,2,6-hexanetriol (CAS 106-69-4), 1,2,5-hexanetriol (CAS 10299-30-6), octahydro-4,7-methano-1H-indene-1,2,5-triol (CAS 13318-18-8), trimethylolalkanes comprising from 1 to 20 atoms of carbon and 3 methylol groups, among which we can cite for example trimethylolmethane (CAS: 4704-94-3), trimethylolethane (CAS: 77-85-0), trimethylolpropane (CAS: 77-99-6), trimethylolbutane (CAS: 7426-71-3), trimethylolisobutane (CAS: 20762-78-1), trimethylolpentane (CAS: 4704-89-6), trimethylolhexane (CAS: 20762-79-2), trimethylolheptane, trimethyloloctane, trimethylolnonane, trimethyloldecane, trimethylolundecane, trimethyloldodecane, octahydro-4,7-methano-1H-indene-1,2,5-triol (CAS: 13318-18-8), 1,3,5-cyclohexanetriol or Phloroglucitol (CAS: 2041-15-8), and the alkoxylated derivatives of these triols. ,

[0123] The polyol P2 can be selected from polyoxyalkylene diols or triols. Preferably, the polyoxyalkylene diols or triols are selected from polyoxypropylene triols.

[0124] As an example of polyoxyalkylene triol, one can cite for example VORANOL CP450 from DOW.

[0125] Preferably, the P2 diol is chosen from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, propane-1,3-diol, butane-1,4-diol, neopentyl glycol, 2-methyl-1,3-propanediol, hexane-1,6-diol, ethyl-2-hexane-1,3-diol, and mixtures thereof.

[0126] Even more preferably, the polyol P2 is chosen from ethyl-2-hexane-1,3-diol, dipropylene glycol and mixtures thereof.

[0127] The total content of polyol(s) P2 can range from 1% to 50%, preferably from 5% to 40%, even more preferably from 10% to 30% by weight relative to the total weight of the -OH component. Polyol P3

[0128] The -OH component comprises at least one polyol P3 having a hydroxyl functionality greater than or equal to 2, said polyol P3 being selected from the group consisting of polyether polyols, naturally occurring polyols, polyester polyols, and mixtures thereof, said polyol P3 having a number-average molecular mass ranging from 800 to 5,000 g / mol.

[0129] The number-average molecular mass of the P3 polyol preferably ranges from 800 g / mol to 2,500 g / mol, preferably from 800 g / mol to 2,000 g / mol, and even more preferably from 800 g / mol to 1,500 g / mol.

[0130] Polyester polyols can be chosen from polyester diols and polyester triols, and preferably from polyester triols.

[0131] Polyester polyols can result from polycondensation:

[0132] - of one or more aliphatic polyols (linear, branched or cyclic) or aromatics such as, for example, monoethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, butenediol, 1,6-hexanediol, cyclohexane dimethanol, tricyclodecane dimethanol, neopentyl glycol, cyclohexane dimethanol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, N-methyldiethanolamine, triethanolamine, a dimeric fatty alcohol, a trimerous fatty alcohol and mixtures thereof, with

[0133] - one or more polycarboxylic acids or their ester or anhydride derivatives such as 1,6-Hexanedioic acid (adipic acid), dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, 1,18-octadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, a dimeric fatty acid, a trimerous fatty acid and mixtures of these acids, an unsaturated anhydride such as, for example, maleic or phthalic anhydride, or a lactone such as, for example, caprolactone.

[0134] - polyol estolides resulting from the polycondensation of one or more hydroxy acids, such as ricinoleic acid, on a diol (for example, "POLYCIN® D-1000" and "POLYCIN® D-2000" available from VERTELLUS).

[0135] The aforementioned polyester polyols can be prepared conventionally, and are mostly commercially available.

[0136] Among the polyol polyesters, we can cite for example the following products with hydroxyl functionality greater than or equal to 2: caprolactone CAPA3050 from INGEVITY.

[0137] Naturally derived polyols include, in particular, their derivatives, such as hydrophobic derivatives. Naturally derived polyols may be selected from the group consisting of castor oil, or hydroxylated derivatives of unsaturated natural oils such as soybean, rapeseed, sunflower oils, and mixtures thereof.

[0138] Hydrophobic derivatives of naturally occurring polyols can be found commercially, such as castor oil oligoesters available from VANDEPUTTE OLEOCHEMICALS, Setathane® DI 150 (branched hydrophobic liquid polyol derived from castor oil, having a number average molecular mass close to 980 g / mol) marketed by ALLNEX, Sovermol® 805 marketed by BASF.

[0139] Naturally derived polyester polyols (including their derivatives) may have a number-average molecular weight ranging from 800 to 5,000 g / mol, preferably from 800 to 3,000 g / mol, and they may have a Brookfield viscosity less than or equal to 10,000 mPa.s at 25 °C, preferably ranging from 1,000 mPa.s to 5,000 mPa.s.

[0140] The P3 polyol may have a hydroxyl functionality greater than or equal to 2, preferably greater than or equal to 2.5, and even more preferably greater than or equal to 3.

[0141] Polyether polyols can be selected from polyoxyalkylene-polyols in which the alkylene (saturated) portion, linear or branched, comprises 2 to 4 carbon atoms, and preferably 2 to 3 carbon atoms.

[0142] Polyether polyols are preferably selected from polyoxyalkylene diols or polyoxyalkylene triols, and even better from polyoxyalkylene triols, the alkylene portion of which, linear or branched, comprises from 1 to 4 carbon atoms, preferably from 2 to 3 carbon atoms.

[0143] By way of example of polyoxyalkylene diols or triols usable according to the invention, we may cite for example polyoxypropylene diol or triol (also referred to as polypropylene glycols (PPG) diol or triol), polyoxyethylene diol or triol (also referred to as polyethylene glycols (PEG) diol or triol), polyoxybutylene glycols (also referred to as polybutylene glycols (PBG) diol or triol), copolymers or terpolymers of PPG / PEG / PBG diol or triol, polytetrahydrofuran (PolyTHF) diol or triol, polytetramethylene glycols (PTMG), and mixtures thereof.

[0144] Preferably, the polyether polyols are chosen from polyoxypropylene triols. The polyether polyols mentioned above can be prepared conventionally and are widely available commercially. They can, for example, be obtained by polymerization of the corresponding alkylene oxide in the presence of a catalyst based on a metal-cyanide double complex.

[0145] Examples of polyether triols include polyoxypropylene triol marketed under the name "VORANOL CP3355" by DOW, with a number-average molecular mass of approximately 3,554 g / mol, or DOW's "VORANOL CP1050" with a number-average molecular mass of approximately 1078 g / mol.

[0146] According to a preferred embodiment, the P3 polyol is selected from triol polyethers and naturally occurring polyol derivatives.

[0147] The total content of polyol(s) P3 can range from 5% to 40%, preferably from 5% to 30%, even more preferably from 8% to 20% by weight relative to the total weight of the -OH component. Charge

[0148] The -OH component comprises at least one filler, the total content of filler(s) being greater than or equal to 30% by weight relative to the total weight of said -OH component.

[0149] The charge can be chosen from mineral charges, molecular sieves, zeolites, organic charges, and mixtures thereof.

[0150] As an example of a mineral filler, any mineral filler commonly used in the field of adhesive compositions may be used. These fillers typically take the form of particles of various geometries. They may, for example, be spherical, fibrous, or have an irregular shape.

[0151] Mineral fillers can be selected from the group consisting of clays, quartz, carbonate fillers, kaolin, gypsum, hollow glass microspheres, and mixtures thereof.

[0152] Some of these fillers may be untreated or treated, for example with an organic acid such as stearic acid, or a mixture of organic acids consisting mainly of stearic acid.

[0153] Hollow glass microspheres can be made of sodium and calcium borosilicate or aluminosilicate. For example, they could be the glass bead microspheres marketed by 3M.

[0154] Hollow glass microspheres can have an average particle size (D50v) ranging from 1 to 70 µm, preferably from 20 to 60 µm.

[0155] Hollow glass microspheres can have a density ranging from 0.100 to 0.600 g / cm3, preferably from 0.150 to 0.300 g / cm3.

[0156] Carbonate fillers can be chosen from alkali or alkaline-earth metal carbonates, and more particularly calcium carbonate or chalk.

[0157] As an example of organic fillers, any organic fillers, and in particular polymeric fillers, commonly used in the field of adhesive compositions may be used.

[0158] For example, polyvinyl chloride (PVC), polyolefins, rubber, ethylene vinyl acetate (EVA), aramid fibers such as Kevlar® can be used.

[0159] Hollow microspheres made of expandable or non-expandable thermoplastic polymers can also be used. Hollow microspheres made of vinylidene chloride / acrylonitrile are a particular example.

[0160] The average particle size of the organic load is preferably less than or equal to 50 qm, preferably between 5 and 20 qm.

[0161] The -OH component may comprise a total amount of charge(s) greater than or equal to 40% by weight, preferably greater than or equal to 45% by weight, and advantageously greater than or equal to 50% by weight relative to the total weight of the -OH component.

[0162] Preferably, the -OH component comprises: - at least one carbonate filler, preferably with a content greater than or equal to 35% by weight, preferably greater than or equal to 40% by weight relative to the total weight of said component -OH; - from 0% to 10% by weight, preferably from 2% to 8% by weight, and even more preferably from 3% to 8% by weight of hollow glass microspheres relative to the total weight of said component -OH. Additives

[0163] The -OH component may include at least one additive selected from the group consisting of plasticizers, catalysts, solvents, pigments, adhesion promoters, moisture absorbers, UV stabilizers (or antioxidants), dyes, rheological agents, and mixtures thereof.

[0164] The total content of the aforementioned additive(s) in the -OH component may range from 0% to 30% by weight, preferably from 1% to 25% by weight, advantageously from 1% to 20% by weight relative to the total weight of said -OH component.

[0165] As an example of a rheology (thixotropic) agent, any one can be cited rheology agent usually used in the field of adhesive compositions, sealants.

[0166] Preferably, the rheological / thixotropic agents are chosen from:

[0167] - PVC plastisols, corresponding to a suspension of PVC in an agent Plasticizer miscible with PVC, obtained in situ by heating at temperatures ranging from 60°C to 80°C. These plastisols may be those described in particular in the book "Polyurethane Sealants", Robert M. Evans, ISBN 087762-998-6,

[0168] - fumed silica, possibly modified, such as for example sold under the Designation HDK® N20 by the company WACKER;

[0169] - urea derivatives resulting from the reaction of an aromatic diisocyanate monomer such that 4,4'-MDI with an aliphatic amine such as butylamine. The preparation of such urea derivatives is described in particular in application FR 1 591 172;

[0170] - micronized amide waxes, such as the commercially available CRAYVALLAC SLX by ARKEMA.

[0171] Preferably, the -OH component comprises at least one rheological agent / thixotropic, even more preferably in a content ranging from 1% to 8% by weight relative to the total weight of said component -OH. Composition

[0172] The composition according to the invention may be an adhesive composition or a sealant composition.

[0173] The volume ratio of component -OH / component -NCO, within the composition, may range from 1 / 3 to 3 / 1, preferably 1 / 2 to 2 / 1, said volume ratio being advantageously equal to 1 / 1.

[0174] The composition according to the invention advantageously exhibits at least one of the following properties: - good rheological properties: reduction or even absence of fineness (or dripping) of the uncrosslinked mixture, especially when applied in a vertical position, easily extrudable, especially when applied in beads; - a fairly long pot life (for example more than 5 min, preferably more than 10 min, or even more than 30 minutes); - leads, after cross-linking, to an adhesive joint with good structural and flexible properties over a wide temperature range, for example between -60°C and 50°C.

[0175] After curing, the adhesive joint advantageously exhibits two glass transition temperatures, namely: - a glass transition temperature Tgl advantageously between -80°C and -65°C; - a glass transition temperature Tg2 advantageously between 40°C and 85°C.

[0176] The glass transition temperature is determined by dynamic mechanical analysis, in particular as described in the experimental part. B. Ready-to-use kit

[0177] The present invention also relates to a ready-to-use kit, comprising the OH component as defined above on the one hand and the NCO component as defined above on the other hand, packaged in two separate compartments.

[0178] Indeed, the composition according to the invention can be in a two-component form, for example within a ready-to-use kit, comprising the OH component on the one hand in a first compartment or drum and the NCO component on the other in a second compartment or drum, in proportions adapted for a direct mixing of the two components, for example using a dosing pump.

[0179] According to one embodiment of the invention, the kit further comprises one or more means for mixing the two components OH and NCO. Preferably, the mixing means are selected from metering pumps and static mixers of a diameter adapted to the quantities used. C. Uses

[0180] The present invention also relates to the use of a composition as defined above, as an adhesive, sealant, or coating. Among sealants, this may, for example, be a bonding, shim, and / or caulking sealant. Preferably, it is a bonding sealant.

[0181] The composition can in particular be used for bonding in the field of structural assembly such as, for example, automotive, aeronautical, and / or construction.

[0182] In the automotive field, this could involve, for example, the bonding of metal parts close to the engine.

[0183] The present invention also relates to a method for assembling two substrates by bonding, comprising: - coating at least one of the two substrates to be assembled with an adhesive composition obtained by mixing the components -OH and -NCO as defined above; then - the effective contacting of the two substrates.

[0184] Suitable substrates are, for example, inorganic substrates such as concrete, metals or alloys (such as aluminium alloys, steel, non-ferrous metals and galvanised metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and paint-coated composites (as in the automotive field for example).

[0185] All the embodiments described above can be combined with each other. In particular, the various aforementioned components of the composition, and especially the preferred modes, of the composition can be combined with each other.

[0186] In the context of the invention, "between x and y" or "ranging from x to y" means an interval in which the bounds x and y are included. For example, the range "between 0% and 25%" includes, in particular, the values ​​0% and 25%.

[0187] The invention is now described in the following embodiment examples which are given purely for illustrative purposes, and should not be interpreted to limit its scope.

[0188]

[0189] Examples: The following ingredients were used: - VORANATE™ M229 available from DOW is a low viscosity polymeric MDI (PMDI) with an NCO percentage of 31.4% and an average functionality of 2.7. ONGRONAT® 2510 available from BORSODCHEM is a low viscosity polymeric MDI (PMDI) with an NCO percentage of 31.0% and an average functionality of 2.9. - VORANOL™ CP1050 available from DOW is a polypropylene glycol of functionality 3 with an IOH = 156 mg KOH / g, i.e. a number average molecular mass (Mn) of 1078 g / mol. - SILIPORITE® SA 1720 marketed by the company ARKEMA is a 3A molecular sieve. - AEROSIL® R202 available from EVONIK is a hydrophobic pyrogenated silica post-treated with a polydimethylsiloxane with a specific surface area (BET) of 100 ± 20 m2 / g. - GEL PASTE, available from BOSTIK, is a rheological agent consisting of a dispersion of a diurea-type adduct (MDEButylamine) in a plasticizer (DIDP). ETHYL-2-HEXANEDIOL-1,3 (CAS No.: 94-96-2) available from MONUMENT CHEMICAL is a branched aliphatic diol with a molar mass of 146.23 g / mol. DIPROPYLENE GLYCOL (CAS No. 25265-71-8) available from DOW is a diol with a molar mass of 134.17 g / mol. - POLYVEST® HT available from EVONIK is a liquid polybutadiene diol with an IOH = 45-51 mg KOH / g, i.e. a number average molecular mass (Mn) ranging from 2,200 to 2,500 g / mol, and a viscosity ranging from 4,000 to 5,500 mPa.s at 30°C. - SETATHANE® DI 150 available from ALLNEX is a branched hydrophobic liquid polyol derived from castor oil with an OH content of 4.7%, i.e. an IOH of 155 mg KOH / g and an average molar mass of approximately 980 g / mol and a viscosity of 3,000 to 4,000 mPa.s at 23°C. - MIKHART® 10 available from LA PROVENÇALE is a calcium carbonate with an average diameter of 10 qm. CALOFORT® SV14, available from MINERAL TECHNOLOGIES, and Hakuenka CCR S10, available from SHIRAISHI OMYA, are carbonates. precipitated calcium (PCC) and treated with calcium stearate having an average diameter of 70 nm. THIXATROL® AS 8053 available from ELEMENTIS is a diamide-type powder rheological agent with an average diameter of less than 5 mm and a melting point of 120 to 130°C. - DOWSIL™ 163 additive available from DOW is a silicone-type antifoam. Example 1: Preparation of the -NCO component:

[0190] LA, Preparation of polyurethanes (PU1 and PU2) with NCO terminations:

[0191] The NCO-terminated PU polyurethanes used in the following examples were prepared using the various ingredients listed in Table 1. The quantities of polyisocyanate(s) and polyol(s) used (expressed as % by weight of commercial product relative to the weight of -NCO component) correspond to an NCO / OH (rl) molar ratio of approximately 7 as indicated in Table 1.

[0192] The polyisocyanate(s) and polyol(s) are mixed in a reactor maintained under constant stirring and under nitrogen, at a temperature Tl ranging from 65°C to 80°C. The temperature is controlled so as not to exceed 82°C.

[0193] The mixture is kept at this temperature until the complete consumption of the hydroxyl functions of the polyols.

[0194] The progress of the reaction is controlled by measuring the NCO group content by back titration of dicyclohexylamine using hydrochloric acid according to the internal method for the determination of free NCOs. The reaction is stopped when the measured NCO group content is approximately equal to the desired NCO group content. Preparation of PU1 and PU2 polyurethanes

[0195] [Table 1]: PU with NCO-terminates PU1 PU2 VORANATE® M229 72 - ONGRONAT® 2510 - 72 VORANOL® CP1050 28 28 wt% 100 100 NCO / OH molar ratio (r 1) 7 7% NCO 19 19 LB. Preparation of the -NCO component by mixing its ingredients:

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202] In the same reactor maintained under constant agitation and nitrogen, the NCO-terminated polyurethane obtained is then mixed with the other ingredients constituting the -NCO component, in the proportions indicated in Table 2 (expressed as % by weight of commercial product relative to the total weight of -NCO component). After homogenization of the mixture (30 to 120 minutes), the NCO group content is measured in the -NCO component respectively. The NCO group content in the -NCO component, expressed as a percentage by weight relative to the weight of the -NCO component (%NCO), is measured according to standard NF T52-132. Table 2 NCO component n°1 NCO component n°2 Polyurethane PU1 79.6 - Polyurethane PU2 - 14 VORANATE® M 229 - 68 Siliporite® SA 1720 5.05 4.4 Gel paste 15.35 13.60 Total ingredients of component -NCO 100 100% NCO by weight of component NCO 15.5 23.8 Example 2: Preparation of the -OH component In a reactor maintained under constant stirring and under nitrogen, the different ingredients constituting the -OH component are mixed in the proportions indicated in Table 3 at a temperature ranging from 20°C to 80°C. After homogenization of the mixture (approximately 3 hours), the OH group content in the -OH component is measured, expressed in milligrams of KOH per gram of -OH component (mg KOH / g).

[0203] Table 3 OH Component No. 1 OH Component No. 2 Ethyl-2-hexane-1,3-diol 14.96 10.79 Dipropylene glycol - 9.88 POLYVEST® HT 5.26 5.72 VORANOL® CP1050 16.34 SETATHANE® D1150 - 10.48 TAMIS SA 1720 3.16 4.95 MIKHART® 10 47.95 50.46 CALOFORT® SV14 8.65 THIXATROL® AS 8053 3.16 2.91 Black dye 0.21 0.27 DOWSIL 163 0.32 0.24 Total ingredients of component -OH 100 100 Example 3: Preparation of adhesive compositions A and B The -NCO component prepared in example 1 and the -OH component prepared in

[0204]

[0205]

[0206]

[0207] Example 2 were mixed in the quantities indicated in Table 4. The mixing is carried out using a 50ml dual-cartridge system. temperature of approximately 23°C. Adhesive Composition A Adhesive Composition B NCO Component NCO Component #1 NCO Component #2 Mixture of -OH and -NCO Component OH Component OH Component #1 OH Component #2 NCO / OH Molar Ratio 1.04 1.32 Volume Mixing Ratio 1 / 1 1 / 1 Tgl measured by DMA -70°C -76°C Tg2 measured by DMA 66°C 82°C Example 4: Performance Evaluation

[0208] Creep test: The composition was extruded from a two-component cartridge (comprising the -OH component on one side, and the -NCO component on the other) at through a static mixer in order to vertically deposit a cord with a cross-section of 1 cm and a length of 10 to 20 cm.

[0209] It was visually checked whether the cord was fine or not (dimensional stability of the cord).

[0210] Pot life: This is estimated using a medical-grade wooden spatula or tongue depressor (150 mm x 19 mm x 1.5 mm, rounded ends) in a small dish according to the following protocol:

[0211] The components -OH and -NCO were previously stabilized at 23°C. 50 ml of the mixture of said components -NCO and -OH is weighed, in a volume ratio 1 / 1.

[0212] Pot life is the time after which no further glue transfer is observed on the wooden spatula (no more strings). It is assessed by periodically dipping a new spatula into at least 1 mm of the mixture, starting from 50% of the theoretical pot life.

[0213] Determination of the glass transition by dynamic mechanical analysis (DMA)

[0214] Preparation of specimen for analysis in DMA: The mastic is poured into a Teflon mold to prepare dumbbell-type specimens with the following dimensions: length 20 mm, width 4 mm and thickness 3 mm.

[0215] A sample is subjected to a torsional stress from -100°C to 100°C. The magnitude of the glass transition corresponds to the peak of tan 3 (ratio of loss and conservation moduli).

[0216] Intrinsic mechanical performance tests were carried out according to the standard ISO 527-2017).

[0217] The measurement of the elongation at break (or elongation at break) by tensile test was carried out according to the protocol described below.

[0218] The measurement principle consists of stretching a standard specimen made of the cross-linked composition in a tensile testing machine, the movable jaw of which moves at a constant speed of 10 mm / minute, and recording, at the moment of fracture of the specimen, the applied tensile stress (in MPa) as well as the elongation of the specimen (in %). The standard specimen is dumbbell-shaped, as illustrated in the international standard ISO 527. The narrow part of the dumbbell used has a length of 80 mm, a width of 10 mm, and a thickness of 4 mm.

[0219] The properties obtained from the prepared compositions are summarized in the following table:

[0220] Adhesive Composition A Adhesive Composition B Creep Test - 1 cm Bead No creep No creep Pot life (minutes) 20 50 Intrinsic Mechanical Performance Tests (23°C- 50%RH) Modulus at break (MPa) 16.8 27.0 Elongation at break (%) 9.9 1.4 Young's modulus (MPa) 984 2460 Intrinsic Mechanical Performance Tests (40°C- 50%RH) Modulus at break (MPa) 8.01 22.1 Elongation at break (%) 50.9 2.2 Young's modulus (MPa) 338 1480 Compositions A and B advantageously lead, after mixing of the OH and NCO components, to an absence of fineness after application, particularly in vertical position.

[0221]

[0222]

[0223] Furthermore, compositions A and B advantageously exhibit a high Young's modulus after crosslinking while exhibiting an elongation at break greater than 1% at 23°C (1.4% for composition B and 9.9% for composition A at 23°C) and even greater than 2% at 40°C (2.2% for composition B and 50.9% for composition A). Compositions A and B advantageously offer a good compromise between structural properties and flexibility over a wide temperature range (23°C, 40°C).

Claims

Demands

1. Composition comprising: - an NCO component comprising: • A) at least one polyurethane comprising at least two NCO terminal groups; • B) optionally a polyisocyanate compound comprising at least one polyisocyanate P comprising at least three isocyanate functions NCO; - an -OH component comprising: • a polybutadiene polyol PI comprising at least two hydroxyl functions, said polyol PI having a number-average molecular mass ranging from 1,000 g / mol to 15,000 g / mol g / mol; • a polyol P2 selected from diols, triols or mixtures thereof, said polyol P2 having a number-average molar or molecular mass ranging from 60 to 500 g / mol; • a P3 polyol comprising having a hydroxyl functionality greater than or equal to 2, said P3 polyol being selected from the group consisting of polyether polyols, naturally occurring polyols, polyester polyols, and mixtures thereof, said P3 polyol having a number-average molecular mass ranging from 800 to 5,000 g / mol; • at least one filler, the total content of filler(s) being greater than or equal to 30% by weight relative to the total weight of said component -OH, characterized in that the total content of PI polyol(s) ranges from 1% to 30% by weight relative to the total weight of said component -OH.

2. Composition according to claim 1, characterized in that polyurethane A) is obtained from:

3.

4. - of a composition comprising at least one polyoxyalkylene-polyol, the saturated alkylene portion of which, linear or branched, comprises 2 to 4 carbon atoms, and preferably 2 to 3 carbon atoms, - of a composition comprising at least polymeric MDI. Composition according to any one of claims 1 or 2 characterized in that the component -NCO comprises a polyisocyanate compound B), said polyisocyanate compound B) being a polyisocyanate mixture comprising at least one polyisocyanate P comprising at least three NCO functions. Composition according to any one of claims 1 to 3, characterized in that the component -NCO comprises a polyisocyanate compound B), said polyisocyanate compound B) being a mixture comprising: - at least one MDI monomer; - at least one polyisocyanate P having the following formula: [Chem. 5]

5.

6. in which n can vary from 1 to 8. Composition according to any one of claims 1 to 4, characterized in that the -NCO component comprises more than 50% by weight, preferably more than 60% by weight, even more preferably more than 70% by weight of polyurethane A) relative to the total weight of said -NCO component. Composition according to any one of claims 1 to 4, characterized in that the component -NCO comprises: -from 1% to 40% by weight, preferably from 5% to 30% by weight of polyurethane(s) A); and - 50% to 90% by weight, preferably 55% to 80% by weight of polyisocyanate compound(s) B).

7. Composition according to any one of claims 1 to 5, characterized in that the component -NCO comprises at least one additive selected from the group consisting of plasticizers, catalysts, solvents, pigments, adhesion promoters, moisture absorbers, UV stabilizers (or antioxidants), colorants, rheological agents, and mixtures thereof.

8. Composition according to any one of claims 1 to 7, characterized in that the -NCO component comprises from 0% to 10% by weight, preferably from 2% to 8% by weight, and even more preferably from 3% to 8% by weight of hollow glass microspheres relative to the total weight of said -NCO component.

9. Composition according to any one of claims 1 to 8, characterized in that the total content of PI polyol(s) ranges from 2% to 20% by weight, and even more preferably from 3% to 8% by weight, relative to the total weight of the -OH component.

10. Composition according to any one of claims 1 to 9, characterized in that the diol P2 is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, propane-1,3-diol, butane-1,4-diol, neopentyl glycol, 2-methyl-1,3-propanediol, hexane-1,6-diol, ethyl-2-hexane-1,3-diol, and mixtures thereof.

11. Composition according to any one of claims 1 to 10, characterized in that the number-average molecular weight of the P3 polyol ranges from 800 g / mol to 2,500 g / mol, preferably from 800 g / mol to 2,000 g / mol, and even more preferably from 800 g / mol to 1,500 g / mol.

12. Composition according to any one of claims 1 to 11, characterized in that the P3 polyol is selected from triol polyethers and derivatives of naturally occurring polyols.

13. Composition according to any one of claims 1 to 12, characterized in that the total content of polyol(s) P3 ranges from 5% to 40%, preferably from 5% to 30%, even more preferably from 8% to 20% by weight relative to the total weight of the -OH component.

14. Composition according to any one of claims 1 to 13, characterized in that the -OH component comprises a total amount of filler(s) greater than or equal to 40% by weight, preferably greater than or equal to 45% by weight, and advantageously greater than or equal to 50% by weight relative to the total weight of the -OH component.

15. Composition according to any one of claims 1 to 14, characterized in that the -OH component comprises: - at least one carbonate filler, preferably in a content greater than or equal to 35% by weight, preferably greater than or equal to 40% by weight relative to the total weight of said -OH component; - from 0% to 10% by weight, preferably from 2% to 8% by weight, and even more preferably from 3% to 8% by weight of hollow glass microspheres relative to the total weight of said -OH component.

16. Composition according to any one of claims 1 to 15, characterized in that the volume ratio of component -OH / component -NCO, within the composition, ranges from 1 / 3 to 3 / 1, preferably 1 / 2 to 2 / 1, said volume ratio advantageously being equal to 1 / 1.

17. Use of a composition as defined according to any one of claims 1 to 16, as an adhesive, sealant or coating, preferably as a bonding sealant.