Crosslinkable composition based on a mixture of aldimines

Abstract

The present invention relates to a crosslinkable composition comprising: - a polyaldimine P1 obtained from a polyetherdiamine A and an aldehyde having a boiling point greater than or equal to 200°C, and - a polyaldimine P2 (different from P1) obtained from a polyetherdiamine B and an aldehyde having a boiling point greater than or equal to 200°C; and - a polyurethane comprising at least two isocyanate groups; as well as the uses thereof.

Description

[0001] Crosslinkable composition based on a mixture of aldimines

[0002] FIELD OF INVENTION

[0003] The present invention relates to a crosslinkable composition comprising a mixture of aldimines.

[0004] The present invention also relates to the use of this composition as an adhesive, sealant or coating.

[0005] TECHNICAL BACKGROUND

[0006] Various polymer-based compositions are available on the market, which can be used in numerous fields, particularly as sealants. Sealants allow for the assembly (or joining or bonding) of two substrates, which can be chosen from a wide variety of materials, and can also be used as gaskets. Sealants provide the resulting assembly with advantageous mechanical properties such as strength, elasticity and / or flexibility, as well as fluid tightness.

[0007] For example, polymer-based compositions can be used as sealants in building construction, shipbuilding, or the transport sector (e.g., road, sea, rail, or aerospace).

[0008] Desirable properties of a construction sealant include its ability to adhere to a variety of substrates, its resistance to weathering (UV, ozone, water), and its elasticity. A sealant's flexural capacity is closely linked to its modulus of elasticity. The modulus of elasticity can predict a sealant's tensile and compressive properties. The modulus is typically the ratio between the force (strain) required to stretch a sealant and the cross-sectional area of ​​the material at a given point, typically 100%. Elongation is the length the sealant can stretch, expressed as a percentage of its initial size. The modulus directly affects elongation, as the lower the tensile strength, the more easily the sealant can stretch.

[0009] It is important to look for sealants with a high capacity for deformation and resilience (elastic recovery), to adapt to significant movements without generating too much tension on the sealant or the substrate.

[0010] For polyurethane sealants, it is also advantageous to look for systems that prevent bubble formation during curing. The use of aldimines as moisture-activated latent hardeners offers a significant advantage in preventing bubble formation, since cross-linking with aldimines does not lead to the release of CO2 (unlike the direct cross-linking of isocyanate groups in the presence of moisture).

[0011] Polyurethane-based sealants containing aldimines made from diamine and benzaldehyde are described. However, these compositions often lead to the release of aldehydes when the aldimine opens with atmospheric moisture. This results in the release of volatile organic compounds into the atmosphere, which is harmful to the environment.

[0012] Furthermore, the aldimines currently in use can be classified as concerning for the environment and for users.

[0013] Therefore, there is a need for new sealant compositions that do not have at least one of the aforementioned disadvantages.

[0014] Preferably, there is a need for new compositions adapted for the preparation of polyurethane sealants exhibiting a good compromise between good mechanical properties, good elastic properties (elastic recovery), no bubbling and good adhesion properties, while reducing the risk to the environment and users.

[0015] DESCRIPTION OF THE INVENTION

[0016] The present invention relates to a crosslinkable composition comprising:

[0017] - a polyaldimine P1 obtained from a polyetherdiamine A and an aldehyde having a boiling point greater than or equal to 200°C, and

[0018] - a polyaldimine P2 (different from P1) obtained from a polyetherdiamine B and an aldehyde having a boiling point greater than or equal to 200°C; and - a polyurethane comprising at least two isocyanate groups.

[0019]

[0020] Preferably, polyurethane comprises at least two isocyanate groups in terminal position.

[0021] Polyurethane is preferably obtained by a process comprising a polyaddition reaction step E1:

[0022] (i) of a composition comprising at least one polyol; and

[0023] ii) of a composition comprising at least one polyisocyanate;

[0024] in quantities such that the NCO / OH molar ratio (r1 ) is greater than 1.

[0025] Within the framework of the invention, and unless otherwise stated, n is the NCO / OH molar ratio corresponding to the molar ratio of the number of isocyanate groups (NCO) to the number of hydroxyl groups (OH) carried respectively by all the polyisocyanate(s) and polyol(s) present in the reaction medium of step E1.

[0026] Preferably, the NCO / OH molar ratio (r1) is from 1.0 to 2.0, preferably from 1.2 to 2.0.

[0027] Polyol

[0028] By "polyol" we mean a compound comprising at least two hydroxyl groups (-OH).

[0029] The polyol(s) used according to the invention may be chosen from those whose number-average molecular mass (Mn) ranges from 50 to 50000 g / mol, preferably from 100 to 20000 g / mol, preferably from 400 to 20000 g / mol, and advantageously from 400 to 12000 g / mol.

[0030] Their hydroxyl functionality can range from 2 to 6, preferably from 2 to 3. Hydroxyl functionality is the average number of hydroxyl functions per mole of polyol.

[0031] The usable polyol(s) may be chosen from polyester polyols, polyether polyols, polyene polyols, polycarbonate polyols, poly(ether-carbonate) polyols, and their mixtures.

[0032] The usable polyol(s) may be chosen from aromatic polyols, aliphatic polyols, arylaliphatic polyols and mixtures of these compounds.

[0033] Polyester polyols can be chosen from polyester diols and polyester triols, and preferably from polyester diols.

[0034] Examples of polyester polyols include:

[0035] - naturally derived polyol polyesters such as castor oil;

[0036] - polyester polyols resulting from polycondensation:

[0037] - of one or more aliphatic (linear, branched or cyclic) or aromatic polyols 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, sucrose, glucose, sorbitol, pentaerythritol, mannitol, N-methyldiethanolamine, triethanolamine, a dimeric fatty alcohol, a trimerous fatty alcohol and mixtures thereof, with

[0038] - 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 trimeric 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.

[0039] - 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).

[0040] The aforementioned polyester polyols can be prepared conventionally, and are mostly commercially available.

[0041] Among the polyol polyesters, examples include the following products with a hydroxyl functionality of 2: "TONE® 0240" (marketed by UNION CARBIDE), a polycaprolactone with a number-average molecular weight of approximately 2,000 g / mol and a melting point of approximately 50°C; "DYNACOLL® 7381" (marketed by EVONIK), with a number-average molecular weight of approximately 3,500 g / mol and a melting point of approximately 65°C; "DYNACOLL® 7360" (marketed by EVONIK), which results from the condensation of adipic acid with hexanediol and has a number-average molecular weight of approximately 3,500 g / mol and a melting point of approximately 55°C; and "DEKATOL® 3008" (marketed by BOSTIK). The number-average molar mass of Mn is close to 1060 g / mol and the hydroxyl number ranges from 102 to 112 mg KOH / g. It is a product resulting from the condensation of adipic acid, diethylene glycol and monoethylene glycol.

[0042] The polyether polyol(s) usable according to the invention is / are preferably chosen from polyoxyalkylene polyols, the alkylene part of which, linear or branched, comprises from 1 to 4 carbon atoms, more preferably from 2 to 3 carbon atoms.

[0043] More preferably, the polyether polyol(s) usable according to the invention is (are) preferably chosen from polyoxyalkylene diols or polyoxyalkylene triols, the alkylene part of which, linear or branched, comprises from 1 to 4 carbon atoms, more preferably from 2 to 3 carbon atoms, and mixtures thereof.

[0044] Examples of polyoxyalkylene diols or triols usable according to the invention include: polyoxypropylene diols or triols (also referred to as polypropylene glycol (PPG) diols or triols) having a number-average molecular weight (Mn) ranging from 400 g / mol to 12000 g / mol; polyoxyethylene diols or triols (also referred to as polyethylene glycol (PEG) diols or triols) having a number-average molecular weight (Mn) ranging from 400 g / mol to 12000 g / mol; and mixtures thereof.

[0045] The aforementioned polyether polyols can be prepared conventionally and are widely available commercially. They can be obtained by polymerization of the corresponding alkylene oxide in the presence of a basic catalyst (e.g., potassium hydroxide) or a catalyst based on a metal-cyanide double complex. Examples of polyether diols include polyoxypropylene diol, marketed under the name "VORANOL® P 1010" by Dow, with a number-average molecular weight (Mn) of approximately 1020 g / mol and a hydroxyl value of approximately 110 mg KOH / g, and "VORANOL® P2000," also marketed by Dow, with a number-average molecular weight of approximately 2040 g / mol and a hydroxyl value of approximately 55 mg KOH / g.

[0046] The polyene polyol(s) usable according to the invention may preferably be chosen from among polyenes having terminal hydroxyl groups, and their corresponding hydrogenated or epoxidized derivatives.

[0047] Preferably, the polyene polyol(s) usable according to the invention is / are chosen from polybutadienes having terminal hydroxyl groups, optionally hydrogenated or epoxidized. Preferably, the polyene polyol(s) usable according to the invention is / are chosen from butadiene homopolymers and copolymers having terminal hydroxyl groups, optionally hydrogenated or epoxidized.

[0048] In the context of the invention, and unless otherwise stated, "terminal hydroxyl groups" of a polyene polyol are understood to mean the hydroxyl groups located at the ends of the main chain of the polyene polyol.

[0049] The hydrogenated derivatives mentioned above can be obtained by total or partial hydrogenation of the double bonds of a polydiene containing terminal hydroxyl groups, and are therefore saturated or unsaturated.

[0050] The epoxide derivatives mentioned above can be obtained by chemoselective epoxidation of the double bonds of the main chain of a polyene having terminal hydroxyl groups, and therefore have at least one epoxy group in its main chain.

[0051] Examples of polyene polyols include homopolymers of butadiene, saturated or unsaturated, comprising terminal hydroxyl groups, possibly epoxidized, such as those marketed under the name "POLY BD® or KRASOL®" by the company CRAY VALLEY.

[0052] Polycarbonate polyols can be chosen from among polycarbonate diols or triols. As an example of a polycarbonate diol, one can cite "CONVERGE® POLYOL 212-20" marketed by the company NOVOMER, with a molecular weight in number (M). n ) equal to 2,000 g / mol with a hydroxyl value of 56 mg KOH / g, the "POLYOL C1090, C-2090 and C-3090" marketed by KURARAY having a molecular mass in number (M n ) ranging from 1000 to 3000 g / mol and a hydroxyl value ranging from 35 to 118 mg KOH / g.

[0053] Preferably, polyurethane is obtained from a composition i) comprising one or more polyether polyols. Preferably, polyurethane is obtained from a composition i) comprising a mixture of polyether diol and polyether triol.

[0054] Polyisocyanate

[0055] By "polyisocyanate" we mean a compound comprising at least two isocyanate groups (-NCO).

[0056] Polyisocyanate can be chosen from diisocyanates, triisocyanates, and mixtures thereof.

[0057] Examples of diisocyanates include isophorone diisocyanate (IPDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate) (4,4'-HMDI), norbornane diisocyanate, norbornene diisocyanate, 1,4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, and cyclohexane dimethylene diisocyanate. 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 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), tetramethylxylylene diisocyanate (TMXDI) (in particular tetramethyl (meta)xylylene diisocyanate), of an allophanate of PDI (n = 5) or of HDI (n = 6) having for example the following formula (Y):.

[0058] of

[0059]

[0060] in which p is an integer from 1 to 2, q is an integer from 0 to 9, and preferably 2 to 5, R crepresents 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;

[0061] and their mixtures.

[0062] Examples of triisocyanates include isocyanurates, biurets, and diisocyanate and triol adducts.

[0063] Isocyanurates may be used in the form of a technical mixture of (poly)isocyanurate(s) of purity greater than or equal to 70% by weight isocyanurate(s).

[0064] Examples of diisocyanate trimers include:

[0065] - the hexamethylene diisocyanurate (HDI) isocyanurate trimer:

[0066]

[0067] - isophorone diisocyanate trimer isocyanurate (I PDI):

[0068]

[0069] As an example of diisocyanate and triol adducts usable according to the invention, one can cite the meta-xylylene diisocyanate (m-XDI) adduct with a triol. Such adducts can typically be obtained by an addition reaction involving said compounds. The details of such an addition reaction are described, for example, in EP3101044.

[0070] The triol used is preferably a trimethylolalkane comprising an alkane with 1 to 20 carbon atoms and 3 methylol groups such as, for example, trimethylolmethane, trimethylolethane, trimethylolpropane, tri-methyloln-butane, trimethylolisobutane, trimethylols-butane, trimethylolt-butane, trimethylolpentane, trimethylolhexane, trimethylolheptane, trimethyloloctane, trimethylolnonane, trimethyloldecane, trimethylolundecane, and trimethyloldo-decane.

[0071] Preferably, among the triols that can be used to obtain the m-XDI and triol adduct, we can mention Glycerol with the formula HOH2C-CHOH-CH2OH, Trimethylolmethane (TMM) with the formula HC(CH2-OH)3, Trimethylolethane (TME) with the formula H3C-C(CH2-OH)3 and Trimethylolpropane (TMP) with the formula CH3-CH2-C(CH2-OH)3. MDI can be in the form of an isomer or a mixture of isomers, such as 4,4'-MDI or 2,4'-MDI.

[0072] TDI can exist as a single isomer or a mixture of isomers, such as 2,4-TDI₃ or 2,6-TDL₂.

[0073] Usable diisocyanates are widely available commercially. Examples include SCURANATE® TX, marketed by VENCOREX, which corresponds to a 2,4-TDI with a purity of approximately 95%; SCURANATE® T100, also marketed by VENCOREX, which corresponds to a 2,4-TDI with a purity exceeding 99% by weight; DESMODUR® I, marketed by COVESTRO, which corresponds to an IPDI; and ISONATE® M125, marketed by DOW, which corresponds to an MDI containing at least 97% 4,4'-MDL

[0074] Preferably, the polyisocyanate is chosen from among the diisocyanates.

[0075] Preferably, the polyisocyanate is chosen from 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 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI) (in particular m-xylylene diisocyanate (m-XDI)).

[0076] Even more preferentially, polyisocyanate is toluene diisocyanate.

[0077] Preferably, polyurethane is obtained by a process comprising a polyaddition reaction step E1:

[0078] i) of a composition comprising a polyether diol and a polyether triol;

[0079] ii) of a composition comprising a diisocyanate selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, preferably toluene diisocyanate.

[0080] Step E1

[0081] During step E1, the polyaddition reaction can be carried out at a temperature ranging from 50°C to 100°C, preferably from 60° to 80°C.

[0082] The polyaddition reaction of step E1 can be carried out in the presence or absence of at least one reaction catalyst.

[0083] The catalyst can be any catalyst known to a person skilled in the art to catalyze the formation of polyurethane by reaction of at least one polyisocyanate with at least one polyol.

[0084] Up to 0.3% by weight of catalyst(s) relative to the weight of the reaction medium in step E1 may be used.

[0085] The reaction in step E1 can also be carried out in the presence of a solvent. The solvent can be chosen from the group consisting of esters, ketones, aromatic compounds, and mixtures thereof. The solvent can be added during step E1 or can be derived from the starting reagents already dissolved in the solvent. For example, the solvent can be chosen from the group consisting of esters, ketones, aromatic compounds, and mixtures thereof. Examples include ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, and mixtures thereof.

[0086] The reaction in step E1 can also be carried out in the presence of a plasticizer. This can be any plasticizer typically used in the field of PU sealants.

[0087] Polyurethane preferably has an NCO group content of 0.5 to 10%, more preferably 1% to 5%.

[0088] The composition according to the invention preferably comprises 5% to 60% by weight of polyurethane, even more preferably 10% to 50% by weight relative to the total weight of said composition.

[0089] Polyaldimines

[0090] The composition according to the invention comprises:

[0091] - a polyaldimine P1 obtained from a polyetherdiamine A and an aldehyde having a boiling point greater than or equal to 200°C, and

[0092] - a polyaldimine P2 (different from P1) obtained from a polyetherdiamine B and an aldehyde having a boiling point greater than or equal to 200°C.

[0093] Polyaldimines P1 and P2 are different. Therefore, the composition includes at least two different polyaldimines.

[0094] Polyetherdiamine A preferably has a weight average molecular mass (Mw) of 100 to 5000 g / mol, preferably 150 to 350 g / mol.

[0095] The weight average molecular mass (Mw) of polyetherdiamine A can be measured by SEC (Size Exclusion Chromatography).

[0096] Polyetherdiamine A can be chosen from:

[0097] Polyetherdiamines, for example, correspond to formula (I) below:

[0098]

[0099] (I)

[0100] in which x is an integer preferably ranging from 1 to 50 (for example, the Jeffamines D230, D400 and D2000 marketed by Huntsman can be cited);

[0101] polyethderdiamines corresponding to formula (II) below:? py | £

[0102] CH S CHj (| |)

[0103]

[0104] in which x, y and z are integers, with x + z preferably ranging from 1 to 6 (for example, the Jeffamines HK-511, ED-600 marketed by Huntsman);

[0105] polyetherdiamines of the following formula (III):

[0106] HïN-XbC-O-XbJnM-O-tCHrCHs-CHrCHs-Oln-fXb-OJ^rXb-NHï (|| |)

[0107]

[0108] in which X b is a linear or branched alkylene group, preferably comprising from 2 to 20 carbon atoms, m is an integer from 1 to 20, and n is an integer from 1 to 100.

[0109] Preferably, polyetherdiamine A is chosen from those of formula (I), preferably those of formula (I) in which x goes from 1 to 4.

[0110] Polyetherdiamine B preferably has a weight average molecular mass (Mw) ranging from 100 to 5000 g / mol, preferably from 360 to 3000 g / mol.

[0111] The weight-average molecular mass (Mw) of polyetherdiamine can be measured by SEC (Size Exclusion Chromatography).

[0112] Polyetherdiamine B can be chosen from:

[0113] Polyetherdiamines, for example, correspond to formula (I) below:

[0114]

[0115] (I)

[0116] in which x is an integer preferably ranging from 1 to 50 (for example, the Jeffamines D230, D400 and D2000 marketed by Huntsman can be cited);

[0117] polyethderdiamines corresponding to formula (II) below:

[0118]

[0119] in which x, y and z are integers, with x + z preferably ranging from 1 to 6 (for example, the Jeffamines HK-511, ED-600 marketed by Huntsman);

[0120] polyetherdiamines of the following formula (III):

[0121] H2N-Xb(-OX b ) m .rO-(CH2-CH2-CHrCHrO) n -(X b -O) m .iX b -NH2

[0122]

[0123] (III) in which Xbest is a linear or branched alkylene group, preferably comprising from 2 to 20 carbon atoms, m is an integer from 1 to 20, and n is an integer from 1 to 100.

[0124] Preferably, polyetherdiamine B is chosen from those of formula (I), preferably those of formula (I) in which x goes from 1 to 6.

[0125] The aldehyde having a boiling point greater than or equal to 200°C is preferably chosen from aromatic aldehydes.

[0126] The adehyde having a boiling point greater than or equal to 200°C may be the same or different for polyaldimine P1 and polyaldimine P2. Preferably, it is the same.

[0127] The aldehyde having a boiling point greater than or equal to 200°C is preferably chosen from the group consisting of o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, 4-ethylbenzaldehyde, 4-propylbenzaldehyde, 4-butylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, p-anisaldehyde, veratraldehyde and mixtures thereof.

[0128] Even more preferentially, the aldehyde is p-anisaldehyde.

[0129] Polyaldimine P1 can be obtained by any process known to those skilled in the art. In particular, polyaldimine P1 can be obtained by a process comprising a reaction step between polyetherdiamine A and an aldehyde having a boiling point greater than or equal to 200°C, optionally in the presence of a solvent and / or an acid catalyst.

[0130] The solvent can be toluene or xylene. The solvent can be distilled at the end of the reaction.

[0131] The catalyst can be chosen from the group consisting of acids such as acetic acid, formic acid...

[0132] The process typically includes a step of distilling the water produced during the reaction.

[0133] The aldehyde:polyetherdiamine molar ratio can range from 3:1 to 1:1.

[0134] Polyaldimine P2 can be obtained by a similar process.

[0135] Polyaldimine P1 (or polyaldimine P2) can be obtained by a process comprising a reaction step of a mixture of polyetherdiamines A and B, and an aldehyde having a boiling point greater than or equal to 200°C, optionally in the presence of a solvent and / or a catalyst. In this case, the molar ratio of aldehyde to polyetherdiamines A + B can range from 2 to 3. Preferably, the mass ratio of polyetherdiamine A to polyetherdiamine B ranges from 60:40 to 50:50, preferably from 58:42 to 52:48.

[0136] The composition according to the invention preferably comprises from 0.05% to 15% by weight of the polyaldimine P1 and polyaldimine P2 mixture, even more preferably from 0.1% to 10% by weight, relative to the total weight of the composition.

[0137] Preferably, the composition comprises 0.5% to 5% by weight of the polyaldimine P1 and polyaldimine P2 mixture relative to the total weight of said composition.

[0138] Rheology agent

[0139] The composition according to the invention preferably comprises at least one rheology agent.

[0140] The rheological agent is preferably a thixotropic agent. A thixotropic agent generally influences the thixotropy of a composition. Thixotropy is the property of certain compositions to become less viscous when a constant force (e.g., constant stress shear) is applied and, after the stress is removed, the viscosity returns to its initial state after an appropriate time. The greater the force, the greater the decrease in viscosity.

[0141] In particular, the thixotropic agent can be chosen from:

[0142] - PVC plastisols, corresponding to a suspension of PVC in a plasticizing agent miscible with PVC, obtained in particular in situ by heating to 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;

[0143] - pyrogenated silica;

[0144] - suspensions in a plasticizer of bis-urea resulting from the reaction of a diisocyanate with a primary aliphatic amine;

[0145] - waxes derived from castor oil, such as for example THIXCIN® R available from ELEMENTIS;

[0146] - amide waxes, preferably micronized, such as, for example, CRAYVALLAC® SLX, CRAYVALLAC® SLW or CRAYVALLAC® SUPER marketed by Arkema, or THIXATROL® AS8053 or THIXATROL® MAX which are available from ELEMENTIS, or RHEOBYK 7503 marketed by BYK; and

[0147] - their mixtures.

[0148] Preferably, the thixotropic agent is chosen from amide waxes, suspensions in a plasticizer of bis-urea obtained from the reaction of a diisocyanate with a primary aliphatic amine, and mixtures thereof.

[0149] The bis-urea suspension in a plasticizer preferably comprises:

[0150] - from 1% to 40% by weight of a bis-urea obtained by reaction of a primary aliphatic amine with a diisocyanate of molar mass less than 500 g / mol, relative to the total weight of said suspension, and

[0151] - from 60% to 99% by weight of a plasticizer chosen from among alkyl phthalates, pentaerythritol tetravalerate, alkylsulfonic acid and phenol esters, diisononyl-1,2-cyclohexane dicarboxylate, 3,3-[methylenebis(oxymethylene)]bis[heptane], dioctyl carbonate and mixtures thereof, relative to the total weight of said suspension,

[0152] said suspension being a suspension of solid bis-urea particles in a continuous phase of plasticizer.

[0153] Advantageously, bis-urea is obtained by reacting an n-alkylamine comprising 1 to 22 carbon atoms, preferably n-butylamine, with a diisocyanate of formula NCO-R 6 -NCO, in which R 6 is chosen from one of the following divalent radicals, whose formulas below show the 2 free valences:

[0154] - i) the divalent radical derived from isophorone:

[0155]

[0156] CH3

[0157] - ii) the divalent radical 4,4'-methylene-bis(cyclohexyl):

[0158]

[0159] - iii) the divalent radical derived from toluene 2,4-diisocyanate (or 2,4-TDI) or toluene 2,6-diisocyanate (or 2,6-TDI) with respective formulas:

[0160]

[0161] - iv) the divalent radical derived from diphenylmethylene 4,2'-diisocyanate (or 4,2-MDI) or diphenylmethylene 4,4-diisocyanate (or 4,4'-MDI), with respective formulas:

[0162]

[0163] - v) the hexamethylene radical: -(CH2)e-,

[0164] - vi) the m-xylylene radical:

[0165]

[0166] - vii) the hexahydro-m-xylylene radical:

[0167]

[0168] Preferably, R 6 is the divalent radical derived from 4,2'-MDI or 4,4'-MDI, more preferably from 4,4'-MDL

[0169] Preferably, bis-urea is obtained by reacting n-butylamine with a diisocyanate of formula NCO-R 6 -NCO, in which R 6 is the divalent radical derived from 4,2'-MDI or 4,4'-MDI, preferably from 4,4'-MDL

[0170] As indicated above for this embodiment, the plasticizer used in the bis-urea suspension is chosen from alkyl phthalates, pentaerythritol tetravalerate, alkylsulfonic acid and phenol esters, diisononyl-1,2-cyclohexane dicarboxylate, 3,3-[methylenebis(oxymethylene)]bis[heptane], dioctyl carbonate and mixtures thereof.

[0171] Alkyl phthalates are preferably formed by the group consisting of diisodecyl phthalate (DIDP), di(2-propylheptyl) phthalate and mixtures thereof.

[0172] Advantageously, the plasticizer is chosen from among the alkyl phthalates, preferably from diisodecyl phthalate, di(2-propylheptyl) phthalate and their mixtures, more preferably diisodecyl phthalate.

[0173] According to a preferred embodiment, the bis-urea suspension in a plasticizer consists of:

[0174] from 1% to 40% by weight of a bis-urea obtained by reaction of a primary aliphatic amine with a diisocyanate of molar mass less than 500 g / mol, relative to the total weight of said suspension, and from 60% to 99% by weight of a plasticizer selected from alkyl phthalates, pentaerythritol tetravalerate, alkylsulfonic acid and phenol esters, diisononyl-1,2-cyclohexane dicarboxylate, 3,3-[methylenebis(oxymethylene)]bis[heptane], dioctyl carbonate and mixtures thereof, relative to the total weight of said suspension,

[0175] said suspension being in the form of a suspension of solid particles of bis-urea in a continuous phase of plasticizer, and the bis-urea and the plasticizer being as described above, including embodiments.

[0176] Advantageously, the suspension comprises, and preferably consists of, 5 to 30% by weight of bis-urea and 70 to 95% by weight of plasticizer, the percentages being relative to the total weight of the suspension. The bis-urea and the plasticizer are as described above, including the embodiments.

[0177] The suspension of bis-urea in a plasticizer can be prepared according to the process described below.

[0178] The reaction of primary aliphatic amine with diisocyanate is highly exothermic. To prevent the large amount of heat generated by the reaction from causing the decomposition of the bis-urea formed, both primary aliphatic amine and diisocyanate are dissolved in a plasticizer before being reacted. The plasticizer thus serves to dissipate the heat generated by the reaction. Advantageously, the two solutions of primary aliphatic amine and diisocyanate in plasticizer are each introduced into a reactor via injectors under a pressure of 40 to 200 bar, preferably 80 to 120 bar, bringing the two solutions into contact in a sprayed liquid state. The quantities of reactants preferably correspond to a ratio of (number of moles of primary aliphatic amine) / (number of moles of diisocyanate) of approximately 2.Bis-urea is produced by the reaction in the form of solid particles dispersed in a continuous phase of plasticizer, the Brookfield viscosity of the corresponding suspension, measured at a temperature of 23 °C, being generally between 1 and 50 Pa.s, preferably between 10 and 25 Pa.s.

[0179] By "waxes derived from castor oil" we mean waxes obtained from castor oil, in particular hydrogenated castor oil.

[0180] The term "amide waxes" refers to waxes comprising one or more compounds with at least one amide group. In particular, amide waxes can be obtained from organic acid(s) (e.g., fatty acid(s)) and (di)amine(s).

[0181] The amide waxes are preferably micronized, that is, they have an average particle size of less than 1 mm. Advantageously, the amide waxes have an average particle size of less than 500 pm, preferably less than 100 pm, and more preferably less than 10 pm. In this description, the average particle size advantageously corresponds to the d50 particle size distribution, that is, the maximum size of 50% of the smallest particles by volume, and can be measured with a particle size analyzer, in particular by laser diffraction on a MALVERN-type instrument (for example, according to ISO 13320).

[0182] Unless otherwise stated, the standards mentioned throughout the application are those in effect on the date the application was filed.

[0183] Preferably, the content of rheology agent in the composition is between 1% and 45% by weight relative to the total weight of said composition, more preferably between 2% and 40% by weight, and more preferably between 5% and 35% by weight.

[0184] Charge

[0185] The composition according to the invention preferably comprises at least one filler.

[0186] The filler can be chosen from mineral fillers, organic fillers, and mixtures thereof, preferably from mineral fillers.

[0187] As an example of a mineral filler, any mineral filler commonly used in adhesive compositions can be used. These fillers typically take the form of particles with various geometries. They can be, for example, spherical, fibrous, or irregularly shaped.

[0188] Mineral fillers can be chosen from clays, quartz, carbonate fillers, kaolins, gypsum, hollow mineral microspheres, zeolites, and mixtures thereof.

[0189] Among the hollow mineral microspheres, we can mention hollow glass microspheres, and more particularly those made of sodium and calcium borosilicate or aluminosilicate.

[0190] Preferably, mineral fillers are chosen from carbonate fillers, zeolites, and their mixtures.

[0191] Advantageously, the carbonate filler is selected from alkali or alkaline earth metal carbonates and mixtures thereof. Preferably, the carbonate filler comprises calcium carbonate; more preferably, the carbonate filler is ground calcium carbonate and / or calcium carbonate coated with fatty acids (the latter preferably being precipitated).

[0192] When calcium carbonate is coated with fatty acids, it imparts total or partial hydrophobicity to the calcium carbonate particles. Furthermore, the fatty acid coating acts as a hydrophobic layer that can prevent the calcium carbonate from absorbing the constituents of the composition and rendering them ineffective. The hydrophobic coating of the calcium carbonate can represent from 0.1% to 3.5% by weight, relative to the total weight of calcium carbonate.

[0193] Preferably, the fatty acids coating the calcium carbonate comprise or consist of more than 50% by weight of stearic acid relative to the total weight of fatty acids.

[0194] Among the alkali or alkaline-earth metal carbonates, we can cite for example the BL 200 TB chalk marketed by OMYA (DV50 = 9 microns), the SOCAL 312 marketed by SOLVAY (hydrophobic calcium carbonate with a DV50 of 1 micron), or the OMYA BSH marketed by OMYA (hydrophobic calcium carbonate).

[0195] Advantageously, the zeolites are chosen from synthetic zeolites of type A, X and / or Y, preferably type A, and have a pore diameter between 3 Å and 5 Å, preferably 3 Å.

[0196] The average particle size of the mineral charge can range from 10 nm to 400 pm, preferably from 20 nm to 100 pm, more preferably from 30 nm to 50 pm.

[0197] As an example of an organic filler, one can cite any organic filler, especially polymeric, commonly used in the field of adhesive compositions.

[0198] Examples include polyvinyl chloride (PVC), polyolefins, rubber, ethylene vinyl acetate (EVA), expandable or non-expandable thermoplastic polymer hollow microspheres (such as vinylidene chloride / acrylonitrile hollow microspheres) and / or aramid fibers (such as Kevlar®).

[0199] PVC can be a homopolymer and / or a copolymer of PVC, preferably a homopolymer of PVC.

[0200] Examples of PVC copolymers include copolymers obtained by polymerizing vinyl chloride with one or more monomers chosen from acrylonitrile, ethylene, propylene, vinylidene chloride and / or vinyl acetate, in particular vinyl acetate.

[0201] The particle size of the PVC filler can vary between 0.05 µm and 0.8 µm, preferably between 0.1 µm and 0.5 µm. Particle size can be measured by electron microscopy, particularly scanning electron microscopy.

[0202] The PVC filler can be obtained by emulsion.

[0203] Various types of PVC fillers are commercially available. Hollow microspheres made of expandable or non-expandable thermoplastic polymers can also be used. Hollow microspheres made of vinylidene chloride / acrylonitrile are a notable example.

[0204] Preferably, the composition according to the invention comprises at least one carbonate filler (preferably calcium carbonate), and one PVC filler.

[0205] Preferably, the composition according to the invention comprises from 5% to 50% by weight of total fillers, preferably from 10% to 50% by weight relative to the total weight of said composition.

[0206] Additives

[0207] The composition according to the invention may further comprise at least one additive selected from plasticizers, solvents, UV stabilizers, debubbling agents, adhesion promoters, and mixtures thereof.

[0208] Preferably, the composition includes an additive chosen from among the plasticizers.

[0209] The additive chosen from among the plasticizers can be any plasticizer commonly used in the field of adhesive compositions.

[0210] This additive chosen from among the plasticizers can for example be chosen from diisodecyl phthalate, diisononyl phthalate (DINP), an ester of alkylsulfonic acid and phenol (for example MESAMOLL® marketed by LANXESS), diisononyl hexahydrophthalate, pentaerythritol tetravalerate, and mixtures thereof.

[0211] The content of the chosen additive among the plasticizers can be up to 10% by weight relative to the total weight of the composition.

[0212] The solvent may be chosen from aliphatic hydrocarbons (such as pentane, hexane, heptane, octane, nonane, decane, dodecane, isohexane, isooctane, isododecane, tetradecane, dodecylbenzene, cyclohexane, kerosene and naphthene), aromatic hydrocarbons (such as benzene, toluene, xylene, alkylbenzene, solvent naphtha, phenylxylyl ethane and diisopropylnaphthalene), halogenated hydrocarbons (such as carbon tetrachloride, chloroform, dichloromethane, ethyl bromide, trichloroethylene, tetrachloroethylene, trifluoroethylene, tetrafluoroethylene, trichlorotrifluoroethylene and tetrachlorodifluoroethylene), and mixtures thereof, preferably from aromatic hydrocarbons, in particular diisopropylnaphthalene.

[0213] The solvent content can be up to 10% by weight relative to the total weight of the composition, preferably from 0% to 5% by weight.

[0214] The composition according to the invention may comprise up to 1% by weight of one or more UV stabilizers (or antioxidants) relative to the total weight of said composition. UV stabilizers are typically introduced to protect the composition from degradation resulting from a reaction with oxygen that may be formed by the action of heat or light. These compounds may include antioxidants capable of scavenging free radicals.

[0215] The UV stabilizer (or antioxidant) can be chosen from among benzotriazoles, benzophenones, and so-called hindered amines such as bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (CAS No. 41556-26-7), methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate (CAS No. 82919-37-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, and their derivatives. mixtures.

[0216] Defoaming agents are usually used by those skilled in the art to enable the rapid elimination of bubbles formed during the preparation and application of compositions having a component including a polyisocyanate.

[0217] The debubbling agent can be any debubbling agent commonly used in the field of adhesive compositions.

[0218] For example, the debubbling agent may be a polysiloxane, an aldimine and / or an oxazolidine, in particular a polysiloxane.

[0219] The debubbling agent content can be up to 2% by weight relative to the total weight of the two-component composition, preferably from 0% to 1% by weight.

[0220] The adhesion promoter can be selected from among amino alkoxysilanes (such as (3-aminopropyl)trimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane), mercapto alkoxysilanes, epoxy alkoxysilanes (such as (3-glycidyloxypropyl)trimethoxysilane), and mixtures thereof.

[0221] A particularly popular combination is one that includes:

[0222] - a polyaldimine P1 obtained from a polyetherdiamine A and an aldehyde having a boiling point greater than or equal to 200°C, and

[0223] - a polyaldimine P2 (different from P1) obtained from a polyetherdiamine B and an aldehyde having a boiling point greater than or equal to 200°C; and - 10% to 50% by weight of polyurethane comprising at least two isocyanate groups;

[0224] - 5% and 35% by weight of rheology agent;

[0225] - from 10% to 50% in load weight;

[0226] - at least one additive selected from plasticizers, solvents, UV stabilizers, debubbling agents, adhesion promoters, and mixtures thereof; said composition comprising from 0.5% to 5% by weight of the mixture of polyaldimine P1 and polyaldimine P2,

[0227] the percentages by weight being in relation to the total weight of said composition.

[0228] Preferably, the composition is a composition of adhesive, sealant or coating.

[0229] The composition according to the invention can be prepared by simply mixing its ingredients.

[0230] Use of the composition

[0231] The present invention also relates to the use of the composition as defined above as an adhesive, in particular as a semi-structural adhesive, as a sealant or as a coating.

[0232] In particular, the present invention aims at the use of the composition as defined above as an adhesive, sealant or coating, in the field of building construction, in the field of manufacturing means of transport, such as the automotive, railway, aerospace or naval industries.

[0233] The composition according to the invention is as described above, including preferred embodiments and features.

[0234] The composition according to the invention advantageously offers at least one of the following advantages:

[0235] It advantageously leads to an adhesive exhibiting rapid crosslinking with preferably a skin formation time of 70 minutes and a depth of crosslinking of 3.6 mm in 24 hours;

[0236] It advantageously leads to an adhesive joint exhibiting, after curing, good mechanical performance, preferably with a modulus at 100% greater than or equal to 0.65MPa and an elastic recovery greater than or equal to 84%;

[0237] It allows for easy application by the end user, for example via a spray gun; it advantageously presents a total concentration of volatile organic compounds significantly lower than the threshold value of 750 pg / m³ 3 (110) at J+3, and less than 60 pg / m 3at J+28 (16). According to the Emicode® classification, the composition is therefore advantageously classified EC1 +: it is therefore considered a very low emission composition. A person skilled in the art knows how to determine the elastic recovery and the modulus at 100% elongation.

[0238] Elastic recovery can be measured in accordance with ISO 11600 of 2002 which refers to ISO7389 of 2002 and at a constant speed of 5.5 mm / min.

[0239] The modulus at 100% elongation can be measured according to ISO8339:2005. In particular, the elastic recovery and the modulus at 100% can be measured as described in the experimental section below.

[0240] Substrate assembly process

[0241] The present invention also relates to a method for assembling substrates comprising:

[0242] - the coating, on at least one surface of the substrates to be assembled, of the composition as defined above, then

[0243] - bringing the substrates into contact.

[0244] The composition according to the invention is as described above, including preferred embodiments and features.

[0245] It is understood that, during the coating stage and the contacting stage, the composition according to the invention is in the unhardened state.

[0246] The substrates can be identical or different.

[0247] The substrates concerned are very varied and are, for example, inorganic substrates such as concrete, metals and / or alloys (such as aluminium alloys, steel, non-ferrous metals and galvanised metals), and / or organic substrates such as wood and / or plastics (such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins).

[0248] Article

[0249] The present invention also relates to an article comprising the composition according to the invention (hardened or not), said composition binding at least two substrates of said article.

[0250] The composition according to the invention is as described above, including preferred embodiments and features.

[0251] The article can be obtained through the substrate assembly process according to the invention (including preferred embodiments and features).

[0252] The substrates are preferably as described above for the substrate assembly method according to the invention. In the context of the invention, "between x and y" or "ranging from x to y" means a range 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%.

[0253] The invention is now described in the following embodiment examples which are given for illustrative purposes only, and should not be interpreted to limit its scope.

[0254] EXAMPLES

[0255] The following ingredients were used:

[0256] - PVC powder (homopolymer) obtained by emulsion;

[0257] - IPDI (Evonik): isophorone diisocyanate

[0258] - Omya BL (OMYA): calcium carbonate

[0259] - TiO2 (Kronos): rutile titanium dioxide

[0260] - Silane A187 (Evonik): ([3-(2,3-epoxypropoxy)propyl]trimethoxysilane)

[0261] - Desmodur L75 (Covestro): aromatic polyisocyanate (ca. 75% in ethyl acetate) - 10% salicylic acid solution in a plasticizer;

[0262] - Catex E70 (Tib Chemicals): dibutyltin dilaurate

[0263] - VORANOL™ P2000 marketed by DOW is a Polypropylene Glycol (PPG) with a functionality F = 2 having an IOH of 55 mg KOH / g, i.e., a number-average molecular mass (Mn) close to 2040 g / mol;

[0264] - Polyol P: polyether polyol having a functionality of 3, and an IOH ranging from 45 to 50 mg KOH / g;

[0265] - Polyisocyanate T: 80 / 20 mixture of 2,4- and 2,6-TDI;

[0266] - IRGANOX® 1076: antioxidant marketed by BASF;

[0267] - TINUVIN® 765: hindered liquid amine marketed by BASF;

[0268] - DINP: Diisononyl phthalate marketed by Sigma Aldrich

[0269] - Jeffamine® D230, D400: polyetherdiamines marketed by Huntsman

[0270] preparation of a finished polyurethane NCO

[0271] The ingredients are mixed in a reactor maintained under constant stirring and nitrogen, at 70°C.

[0272] The mixture is kept at this temperature until the hydroxyl groups of the polyols are completely consumed.

[0273] The progress of the reaction is controlled by measuring the NCO group content by back titration of dibutylamine, using hydrochloric acid according to standard NF T52-132. The reaction is stopped when the measured NCO group content is approximately equal to the desired NCO group content (1.8%).

[0274] The proportions of ingredients for the preparation of said polyurethane are indicated in the following table 1 (% by weight):

[0275] VORANOL™ 2000L 47.56%

[0276] Polyol P 22.87%

[0277] PLASTICIZER 19.34%

[0278] Polyisocyanate T 9.53%

[0279] IRGANOXO1076 0.42%

[0280] TINUVIN® 765 0.27%

[0281] CATEX E70 0.01%

[0282]

[0283] The percentages are percentages by weight relative to the total weight of the composition.

[0284] Example 2: Preparation of bis-urea (rheological agent)

[0285] Two solutions are being prepared:

[0286] - a solution A of n-butylamine in diisodecyl phthalate (DIDP), consisting of 17.17% by weight of n-butylamine and 82.83% by weight of DIDP, the percentages being based on the total weight of solution A, then

[0287] - a solution B of 4,4'-MDI in DIDP, consisting of 29.46% by weight of 4,4'-MDI in 70.54% by weight of DIDP, the percentages being on the total weight of solution B.

[0288] The two solutions A and B are heated to 100°C, then introduced, each under a pressure of 100 bars, into a reactor, in which they are continuously sprayed onto each other in a ratio A / B = 50.1 / 49.9 by weight, corresponding to a molar ratio n-butylamine / MDI equal to 2. The reaction is immediate and the temperature of the reactor reaches 140°C at the end of the manufacturing process.

[0289] At the reactor outlet, a stable dispersion of 23.3% by weight (relative to the total weight of the dispersion) of a bis-urea with the following formula is obtained in the DIDP:

[0290] ^Hç-HN-C— NB— NH-C-NH— HC4H9

[0291]

[0292] The Brookfield viscosity of the suspension measured at 23°C is 15 Pa.s.

[0293] Example 3: Preparation of the Aldimine Mixture. In a reactor equipped with a stirrer and a Dean-Stark apparatus, 125 parts of Jeffamine D400 (0.3 moles), 152.8 parts of Jeffamine D230 (0.7 moles), and 1.1 parts of formic acid are dissolved in 500 mL of toluene under an inert atmosphere (nitrogen). After 10 minutes of mixing, 325 parts of p-anisaldehyde (2.4 moles) are added dropwise over 30 minutes. The mixture is then heated to 100°C with regular vacuum cycles to remove the water formed. After 5 hours of mixing, the mixture is heated to 150°C under maximum vacuum to remove all remaining unreacted products, including the toluene. The aldimine mixture is obtained with a quantitative yield.

[0294] Example 4: Preparation of aldimine X

[0295] In a reactor equipped with a stirrer and a Dean Stark immersion device, 230 parts of Jeffamine D230 (1 mole) and 1.1 parts of formic acid are dissolved in 500 mL of toluene under an inert atmosphere (nitrogen). After 10 minutes of mixing, 325 parts of p-anisaldehyde (2.4 moles) are added dropwise over 30 minutes. The mixture is then heated to 100°C with regular vacuum cycles to remove the water formed. After 5 hours of mixing, the mixture is heated to 150°C under maximum vacuum to remove all remaining unreacted products, including the toluene. Aldimine X is obtained with a quantitative yield.

[0296] Example 5: Preparation of a moisture-curable composition C1 (invention) and a comparative composition C2

[0297] Compositions C1 (invention) and C2 (comparative) described in Table 2 were prepared according to the following procedure:

[0298] In a reactor, DINP and polyurethane from Example 1 are added and mixed for 30 minutes at 23°C. Omya BL, PVC powder, and titanium dioxide are then added to the reaction mixture and mixed for 10 minutes. Next, IPDI is added and the mixture is mixed under vacuum (-0.8 bar) for 10 minutes. Finally, bis-urea from Example 2 is added under vacuum (-0.8 bar) for 5 minutes and mixed for another 10 minutes under vacuum before the addition of the aldimines and other ingredients.

[0299] The mixture is then stirred under vacuum (-0.8 bars) for 10 to 20 minutes.

[0300] For composition C1, the aldimine mixture from example 3 was added, while for comparative composition C2, Aldimine X from example 4 was added. Ingredients Composition Composition C1

[0301] Comparative C2 DINP 5.72 5.82 Polyurethane of example 1 31.1 31.1

[0302] Omya BL 25.00 25.48

[0303] PVC powder 9.4 9.4

[0304] TiO24.5 4.5

[0305] IPDI 0.29 0.29

[0306] Bis-urea from example 2 21.00 21.00 Aldimine mixture from example 3 1.95 - Aldimine X from example 4 - 1.38

[0307] Silane A187 0.09 0.09 Desmodur L75 0.46 0.46

[0308] DBTL 0.03 0.03

[0309] Soil 10% salicylic acid 0.46 0.45

[0310]

[0311] Total by weight (%) 100 100

[0312] The ingredients in the table are indicated as a percentage by weight relative to the total weight of the composition.

[0313] Composition C2 is comparative in that it comprises only aldimine X (example 4) and not a mixture of polyaldimines of example 3. Compositions C1 and C2 comprise the same molar number of aldimine functions.

[0314] Example 6: Properties of composition C1 and comparative composition C2

[0315] Skinning time was measured according to ISO 291 at 23°C and 50% relative humidity.

[0316] The tensile strength and elongation at break were measured according to the protocol described below. The Young's modulus was also measured.

[0317] The measurement principle consists of stretching a standard specimen made of the cross-linked composition in a tensile testing machine, whose moving jaw travels at a constant speed of 500 mm / minute. At the moment of fracture, the applied tensile stress (in MPa) and the elongation of the specimen (in %) are recorded. The standard specimen is dumbbell-shaped, as illustrated in the international standard ISO 37. To prepare the dumbbell, the composition to be tested (previously packaged in a cartridge) is extruded into a Teflon mold and allowed to cure for 14 days under standard conditions (23°C and 50% relative humidity). The narrow end of the dumbbell used is 20 mm long (+ / - 0.5), 4 mm wide, and 2 mm thick.

[0318] The elastic recovery was determined according to the test in ISO11600 of 2002, which refers to ISO7389 of 2002 (conditioning method B).

[0319] The modulus at 100% elongation was measured according to the test in the ISO11600 standard of 2002, which refers to the ISO8339 standard of 2005: tensile stress corresponding to an elongation of 100% of the specimen.

[0320] EM I CODE certification test:

[0321] Certification is a quality label that allows adhesives to be classified in terms of emissions. There are four emission classes, with the Emicode EC1 Plus class being the strictest and including adhesives with very low emissions.

[0322] During the emissions test, the adhesive is applied to a glass plate. This is then placed in a stainless steel test chamber and ventilated with very clean air.

[0323] The room parameters are adjusted to be representative of average room conditions in a European country (23°C, 50% relative humidity, air exchange rate: 1 per hour, 0.4 m³). 2 sample per m 3 (of room air).

[0324] After 3 days and 28 days, VOC emissions are measured at the chamber outlet, expressed in terms of concentrations in a European reference room (CEN TC).

[0325] 351), and these emissions are evaluated according to the classes of the EMICODE.

[0326] The results are shown in the following table: Composition C1 Comparative composition C2 Skin formation time (in min) 70 95 Extrusion speed (in g / min - flow rate 3 bars,

[0327] 115 53 nozzle diameter = 4 mm)

[0328] Deep crosslinking (24h - mm) 3.6 3.4 Elongation at break (%) 510 ± 59 490 ± 58 Modulus at 100% elongation (MPa) 0.79 ± 0.08 0.57 ± 0.04 0.70 ± 0.07 0.79 ± 0.11 Young's modulus

[0329] Elastic recovery (in %) (ISO 7389 - 86.5 ± 2.1 81.2 ± 2.7 packaging B)

[0330] Total concentration of organic compounds

[0331] 110 >750 volatiles at J+3

[0332] ([C] (pg / m 3 )

[0333] Total concentration of organic compounds

[0334] 16 >60 volatiles at J+28

[0335]

[0336] ([C] (pg / m 3 )

[0337] The C1 composition advantageously results in an adhesive with rapid curing, a skin formation time of 70 minutes, and a depth of curing of 3.6 mm in 24 hours. Thus, the product becomes less sticky on the surface more quickly, allowing for rapid application and avoiding surface dust problems.

[0338] Composition C1 advantageously leads to an adhesive joint exhibiting, after curing, good mechanical performance with an elongation of 510%, a modulus at 100% of 0.79MPa and an elastic recovery of 86.2%.

[0339] Composition C1 has an extrusion speed of 115 g / min which allows for easy application by the end user, for example via a gun.

[0340] Composition C1 advantageously exhibits a total concentration of volatile organic compounds significantly lower than the threshold value of 750 pg / m³ 3 (110) at J+3, and less than 60 pg / m 3at J+28 (16). According to the Emicode® classification, the composition is therefore classified EC1 +: it is therefore considered a very low emission composition.

Claims

28 DEMANDS 1. Crosslinkable composition comprising: a polyaldimine P1 obtained from a polyetherdiamine A and an aldehyde having a boiling point greater than or equal to 200°C, and a polyaldimine P2 (different from P1) obtained from a polyetherdiamine B and an aldehyde having a boiling point greater than or equal to 200°C; and a polyurethane comprising at least two isocyanate groups.

2. Composition according to claim 1, characterized in that the polyurethane is obtained by a process comprising a polyaddition reaction step E1: (i) of a composition comprising at least one polyol; and ii) of a composition comprising at least one polyisocyanate; in quantities such that the NCO / OH molar ratio (r1) is greater than 1.

3. Composition according to any one of claims 1 to 2, characterized in that the polyurethane is obtained by a process comprising a polyaddition reaction step E1: i) of a composition comprising a polyether diol and a polyether triol; ii) of a composition comprising a diisocyanate selected from toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, preferably toluene diisocyanate.

4. Composition according to any one of claims 1 to 3, characterized in that it comprises from 5% to 60% by weight of polyurethane, preferably from 10% to 50% by weight relative to the total weight of said composition.

5. Composition according to any one of claims 1 to 4, characterized in that: Polyetherdiamine A has a weight-average molecular mass ranging from 100 to 5000 g / mol; and / or Polyetherdiamine B has a weight-average molecular mass ranging from 100 to 5000 g / mol.

6. Composition according to any one of claims 1 to 5, characterized in that: polyetherdiamine A has a weight-average molecular mass ranging from 150 to 350 g / mol; and Polyetherdiamine B has a weight average molecular mass ranging from 360 to 3000 g / mol.

7. Composition according to any one of claims 1 to 6, characterized in that polyetherdiamine A is selected from: Polyetherdiamines, for example, correspond to formula (I) below: (I) in which x is an integer preferably ranging from 1 to 50; polyethderdiamines corresponding to formula (II) below: in which x, y and z are integers, with x + z preferably ranging from 1 to 6; polyetherdiamines of the following formula (III): H2N-X b (-OX b ) m -iO-(CH2-CH2-CH2-CH2-O)n-(X b -O)miX b -NH2 in which Xbest is a linear or branched alkylene group, preferably comprising from 2 to 20 carbon atoms, m is an integer from 1 to 20, and n is an integer from 1 to 100.

8. Composition according to claim 7, characterized in that the polyetherdiamine A is selected from those of formula (I), preferably of formula (I) in which x goes from 1 to 4.

9. Composition according to any one of claims 1 to 8, characterized in that polyetherdiamine B is selected from: Polyetherdiamines, for example, correspond to the formula (I) below: H2N^' ,x NH 2 Cbh CH3 (I) in which x is an integer preferably ranging from 1 to 50; polyethderdiamines corresponding to formula (II) below: in which x, y and z are integers, with x + z preferably ranging from 1 to 6; polyetherdiamines of the following formula (III): H2N-Xb(-OX b ) m-1 -O-(CH2-CH2-CH2-CH2-O)n-(X b -O) m -iX b -NH2 in which Xbest is a linear or branched alkylene group, preferably comprising from 2 to 20 carbon atoms, m is an integer from 1 to 20, and n is an integer from 1 to 100.

10. Composition according to any one of claims 7 to 9, characterized in that the polyetherdiamine B is selected from those of formula (I), preferably of formula (I) in which x goes from 1 to 6.

11. Composition according to any one of claims 1 to 10, characterized in that the aldehyde having a boiling point greater than or equal to 200°C is selected from the group consisting of o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, 4-ethylbenzaldehyde, 4-propylbenzaldehyde, 4-butylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, p-anisaldehyde, veratraldehyde and mixtures thereof.

12. Composition according to any one of claims 1 to 11, characterized in that the aldehyde is p-anisaldehyde.

13. Composition according to any one of claims 1 to 12, characterized in that polyaldimine P1 is obtained by a process comprising a reaction step of a mixture of polyetherdiamines A and B, and an aldehyde having a boiling point greater than or equal to 200°C, optionally in the presence of a solvent and / or a catalyst.

14. Composition according to claim 13, characterized in that the mass ratio polyetherdiamine A : polyetherdiamine B ranges from 60:40 to 50:50, preferably 58:42 to 52:

48.

15. Composition according to any one of claims 1 to 14, characterized in that it comprises from 0.05% to 15% by weight of the polyaldimine P1 and polyaldimine P2 mixture, more preferably from 0.1% to 10% by weight, relative to the total weight of the composition.

16. Composition according to any one of claims 1 to 15, characterized in that it comprises at least one rheology agent, preferably in a content of between 1% and 45% by weight relative to the total weight of said composition, more preferably between 2% and 40% by weight, and more preferably between 5% and 35% by weight.

17. Composition according to any one of claims 1 to 16, characterized in that it comprises at least one filler, preferably it comprises at least one carbonate filler, and one PVC filler.

18. Composition according to any one of claims 1 to 17 characterized in that it comprises from 5% to 50% by weight of total fillers, preferably from 10% to 50% by weight relative to the total weight of said composition.

19. Use of the composition as defined according to any one of claims 1 to 18, as an adhesive, in particular as a semi-structural adhesive, as a sealant or as a coating.

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