EP3898871A1

EP3898871A1 - Composition made from epoxy resin and polyurethane

Info

Publication number: EP3898871A1
Application number: EP19845613.9A
Authority: EP
Inventors: Guillaume Michaud; Marjorie PEREIRA-BAYART
Original assignee: Bostik SA
Current assignee: Bostik SA
Priority date: 2018-12-20
Filing date: 2019-12-18
Publication date: 2021-10-27
Also published as: CN113227301B; FR3090672A1; CN113227301A; FR3090672B1; WO2020128326A1; US20220073799A1

Abstract

The present invention relates to a composition comprising: - a composition A comprising: - at least one polyurethane P comprising at least two acrylate terminal functions; and - at least one epoxy resin; and - a composition B comprising: - at least one polyamine B1 comprising at least two functions chosen from the primary and secondary amines; - at least one polyamine B2, different from the polyamine B1, comprising at least two functions chosen from the primary and secondary amines; the composition being characterised in that: - it does not comprise polythiol; and - the weight ratio of polyurethane(s) P/epoxy resin(s) in the composition A ranges from 1/49 to 99/1.

Description

Composition based on epoxy resin and polyurethane

FIELD OF THE INVENTION

The present invention relates to a composition based on polyurethane and epoxy resin.

The invention also relates to the use of said composition for the repair and / or the semi-structural or structural bonding of materials in the field of transport, marine or construction.

TECHNOLOGICAL BACKGROUND

The choice of adhesives is determined by their applications and their preparation processes. Adhesives in the transport sector, such as the automotive field, are classified in structural adhesives or elastic adhesives. Structural adhesives are high modulus adhesives, while elastic adhesives are low modulus adhesives.

Typically, compositions based on epoxy and / or polyurethane are used for structural bonding in the automotive field.

The epoxy-based compositions generally lead to adhesives having little elongation, and which therefore prove to be brittle and fragile.

Polyurethane-based adhesive compositions generally have the drawback of using an -NCO component comprising significant residual contents of diisocyanate monomers originating from the synthesis reaction of the polyurethane prepolymer carrying NCO groups (or with NCO endings). These residual diisocyanate monomers are indeed capable of leading to a certain number of undesirable effects.

The presence of high residual monomer contents is dangerous for the handling and the health of the users, which implies restrictions of use and the implementation of ventilation systems. The implementation of these systems is not always possible, for example in the context of bonding or repairing auto parts (garage owners), or in construction. In addition, in order to take into account the undesirable effects linked to the presence of these diisocyanate monomers, the regulations require for certain types of products special labeling of the product, as soon as the concentration of aromatic diisocyanate monomers exceeds 0.1% by weight of the weight of the product and / or when the concentration of aliphatic diisocyanate monomers exceeds 0.5% by weight of the weight of the product, or even 0.1% by weight of the weight of the product. There is in particular a need to provide new compositions for semi-structural or structural bonding, having a low level of residual monomers, and / or leading to adhesives having a good compromise in tensile strength / elongation at break.

DESCRIPTION OF THE INVENTION

In this application, in the absence of an indication to the contrary:

- the quantities expressed as a percentage correspond to weight / weight percentages;

- The hydroxyl index of an alcoholic compound represents the number of hydroxyl functions per gram of product, which is expressed in the form of the equivalent number of milligrams of potash (KOH) used in the determination of hydroxyl functions, per gram of product;

- the primary alkalinity represents the number of -Nhh functions per gram of product, which is expressed in the form of the number of milliequivalents of -Nhh per gram of product. It can be measured by NMR or by potentiometry according to methods well known to those skilled in the art;

- secondary alkalinity represents the number of -NH- functions per gram of product, which is expressed in the form of the number of milliequivalents of -NH- per gram of product. It can be measured by NMR or by potentiometry according to methods well known to those skilled in the art;

- total alkalinity represents the number of amino functions (of primary, secondary and tertiary amine type) per gram of product, which is expressed in the form of milliequivalents of HCl per gram of product. Total alkalinity can be determined by NMR or potentiometric assay;

- the viscosity measurement at 23 ° C (or 25 ° C) can be done using a Brookfield viscometer according to ISO 2555. Typically, the measurement carried out at 23 ° C (or 25 ° C) can be done using a Brookfield RVT viscometer, a needle suitable for the viscosity range and at a rotation speed of 20 revolutions per minute (rpm). The viscosity of a product is preferably measured at least 24 hours after manufacture of said product;

- the number average molecular weights (Mn) of the polyols expressed in g / mole are calculated from their hydroxyl indices and their functionalities;

- the molar masses of the polyamines (B1) expressed in g / mole are calculated from their primary and / or total alkalinities, and from their functionality;

- the molar masses (or average molar masses in the case of mixing) of the polyamines (B2) are calculated from their chemical structures ( ¹ H / ¹³ C NMR) and their primary and / or secondary and / or tertiary and / or tertiary alkalinities or total. A. Composition

The present invention relates to a composition, preferably adhesive, comprising:

- a composition A comprising:

- At least one polyurethane P comprising at least two acrylate terminal functions; and

- at least one epoxy resin;

and

- a composition B comprising:

- At least one polyamine B1 comprising at least two functions chosen from primary and secondary amines;

- At least one polyamine B2, different from polyamine B1, comprising at least two functions chosen from primary and secondary amines;

said composition being characterized in that:

- it does not contain polythiol; and

the polyurethane (P) / epoxy resin (s) mass ratio in composition A ranges from 51/49 to 99/1.

A.1. Composition A

Epoxy resin

The epoxy resin can be aliphatic, cycloaliphatic, heterocyclic or aromatic.

The epoxy resin can be monomeric or polymeric.

Preferably, the epoxy resin has a viscosity measured at 25 ° C ranging from 7 to 13,000 mPa.s, preferably from 400 to 5,000 mPa.s.

According to one embodiment, the epoxy resins are chosen from polyglycidyl ethers of polyphenolic compounds, preferably comprising from 2 to 6 glycidyl ether functions per mole of resin.

A phenolic compound is a compound having at least two aromatic hydroxyl groups.

The phenolic compounds can be chosen from the group consisting of resorcinol, catechol, hydroquinone, bisphenol A (2,2-bis- (4-hydroxyphenyl) propane), bisphenol AP (1, 1-bis- (4 -hydroxyphenyl) -1-phenylethane), bisphenol AF (2,2-bis- (4-hydroxyphenyl) -hexafluoropropane), bisphenol B ((2,2-bis- (4-hydroxyphenyl) butane), bisphenol BP (bis- (4-hydroxyphenyl) -diphenylmethane), bisphenol C (2,2-bis- (3-methyl-4-hydroxyphenyl) propane), bisphenol Cil (bis (4-hydroxyphenyl) -2,2- dichloroethylene), bisphenol E (1, 1-bis- (4-hydroxyphenyl) ethane), bisphenol F (bis (4-hydroxyphenyl) -2,2-dichloroethylene), bisphenol FL (4.4 '- (9H-fluoren- 9-ylidene) bisphenol, bisphenol G (2,2-bis- (4-hydroxy-3-isopropylphenyl) propane), bisphenol M (1, 3-bis- (2- (4-hydroxyphenyl) -2-propyl) benzene ), bisphenol P (1, 4-bis (2-4-hydroxyphenyl) -2- propyl) benzene), bisphenol PH (5.5 '- (1-methylethylidene) -bis [1, 1' - (bisphenyl) - 2ol] propane), bisphenol S (bis (4-hydroxyphenyl) sulfone), bisphenol TMC (1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane); bisphenol Z (1, 1-bis (4-hydroxyphenyl) cyclohexane), bisphenol K, tetraethylbiphenol, and mixtures thereof.

The epoxy resin can have an epoxy functional content ranging from 0.3 to 10.8 meq per gram of resin.

The epoxy functionality of the epoxy resin can range from 2 to 6.

The epoxy functionality of the epoxy resin is the average number of epoxy functions per mole of epoxy resin.

The resins can be chosen from the following resins:

- the resins having the following formula (I):

in which :

- I represents a number ranging from 0 to 8, preferably from 0 to 4,

each R ′ represents, independently of each other, an alkyl radical comprising from 1 to 20 carbon atoms, preferably a methyl;

- each of R ', R ^j , R ^k , and R', independently of each other, represents one of the following radicals: H; a linear or branched, cyclic or aliphatic alkyl radical, comprising from 1 to 10 carbon atoms; an aryl radical comprising from 6 to 12 carbon atoms; or a radical -CF ₃ ;

- Each x represents an integer ranging from 0 to 4, preferably x being 0 or 1;

- N, N-diglycidyl-4-glycidyloxyaniline (TGAP):

- the resins of formula (II) below:

in which :

- n is an integer ranging from 1 to 25, preferably from 1 to 5;

- each of R ^a and R ^b is, independently of one another, one of the following radicals: H; a linear or branched, cyclic or aliphatic alkyl radical, comprising from 1 to 10 carbon atoms; an aryl radical comprising from 6 to 12 carbon atoms; or a radical -CF ₃ .

- and their mixtures.

By "mixture" means a mixture of several resins mentioned above. It may for example be a mixture of resins of formula (I) different, or else a mixture of a resin of formula (I) with a resin of formula (II), or else any other possible mixture.

Preferably, among the resins of formula (I), mention may, for example, be made of the following resins:

The resins of the above-mentioned formula (II) are preferably those where R ^a and R ^b represent, independently of one another, H or methyl.

According to a preferred embodiment, composition A comprises at least one epoxy resin of the above-mentioned formula (I), and in particular of the above-mentioned formula (1-1).

Many epoxy resins are typically available commercially. Mention may for example be made of the DER ™ 331 and DER ™ 383 resins sold by the company DOW CHEMICALS, the EPON 862 resin sold by HEXION SPECIALITY CHEMICALS, the EPOSIR® resins based on bisphenol A sold by SIR INDUSTRIAL (for example EPOSIR® 7120, EPOSIR® resins based on bisphenol A / bisphenol F (for example EPOSIR® F556).

Polyurethane P

The polyurethane P according to the invention comprises at least two terminal acrylate functions.

The terminal acrylate functions of polyurethane P have the following formula (III): CHi _: = CH-C (= 0} ~

(III)

The polyurethane P according to the invention can have an acrylate function content ranging from 0.2 to 3 meq per gram of polyurethane P, preferably from 0.5 to 2 meq per gram of polyurethane P, preferably from 0.90 to 1 , 3 meq per gram of polyurethane P, and advantageously from 0.90 to 1.2 meq per gram of polyurethane P.

The acrylate functionality of polyurethane P can range from 1 to 4, preferably from 2 to 3.

The acrylate functionality is the average number of acrylate functions per mole of polyurethane P.

The aforementioned polyurethane P can have a number average molecular mass (Mn) ranging from 1000 to 50,000, preferably from 2000 to 20,000, preferably from 3000 to 15000 g / mol.

The viscosity of polyurethane P measured at 23 ° C can range from 1 to 200,000 mPa.s, preferably from 1 to 185,000 mPa.s.

The aforementioned polyurethane P can be obtained by reaction:

- i) a polyurethane comprising at least two terminal functions -OH, and at least one compound chosen from the chloride of acrylic acid or an ester of acrylic acid; or

ii) a polyurethane comprising at least two terminal functions -OH, and at least one compound chosen from an isocyanatoalkylacrylate;

or

- iii) a polyurethane comprising at least two terminal functions -NCO, and at least compound chosen from a hydroxylated ester of acrylic acid.

Case /)

According to a first embodiment, the aforementioned polyurethane P is prepared by reaction of a polyurethane comprising at least two terminal functions -OH; and at least one acrylic acid chloride or at least one ester of acrylic acid.

In particular, the aforementioned polyurethane P is prepared according to a process comprising the following stages:

- E1) the preparation of a polyurethane with OH endings by a polyaddition reaction: i) of at least one polyisocyanate, preferably chosen from diisocyanates, triisocyanates, and mixtures thereof;

ii) with at least one polyol, preferably chosen from polyester polyols, polyether polyols, poly (ether-ester) polyols, polyene polyols, polycarbonate polyols, poly (ether carbonate) polyols, polycaprolactone polyols and their mixtures;

in amounts such that the NCO / OH molar ratio (r1) is strictly less than 1, preferably ranges from 0.2 to 0.8, and preferably ranges from 0.3 to 0.5;

and

- E2) the reaction of the product formed at the end of step E1) with the chloride of acrylic acid or with an ester of acrylic acid, in amounts such as the OH / -C molar ratio (= 0) X '(with X' representing Cl or O) (r2) is less than or equal to 1, preferably ranges from 0.90 to 1.00, and preferably ranges from 0.95 to 1.00.

In the context of the invention, and unless otherwise stated, (r1) 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 by all of the polyisocyanate (s) and polyol (s) present in the reaction medium of step E1).

In the context of the invention, and unless otherwise stated, (r2) is the OH / - C molar ratio (= 0) X '(with X' representing Cl or O) corresponding to the molar ratio of the number of hydroxyl groups (OH ) on the number of groups -C (= 0) -Cl (acid chloride) or -C (= 0) - O (esters) carried respectively by all of the alcohol compounds (polyurethane with -OH endings obtained at 1 from step E1) and optionally the unreacted polyol (s) at the end of step E1)), and acrylic derivatives (chloride of acrylic acid or ester acrylic acid present in the reaction medium of step E2).

The polyisocyanates and polyols are as described below.

Case //)

According to a second embodiment, the polyurethane P according to the invention is prepared by reaction of a polyurethane comprising at least two terminal functions -OH, and at least one compound chosen from isocyanatoalkylacrylates.

By isocyanatoalkylacrylate means a compound having the following formula:

CH _? = CH-C (= 0} ~ 0-R ^s -NC0

in which R ^s represents a linear or branched alkylene radical comprising from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms.

- EΊ) the preparation of a polyurethane with OH endings by a polyaddition reaction: i) of at least one polyisocyanate, preferably chosen from diisocyanates, triisocyanates, and mixtures thereof; ii) with at least one polyol, preferably chosen from polyester polyols, polyether polyols, poly (ether-ester) polyols, polyene polyols, polycarbonate polyols, poly (ether-carbonate) polyols, polycaprolactone polyols and their mixtures;

in amounts such that the NCO / OH molar ratio (r3) is strictly less than 1, preferably ranges from 0.2 to 0.8, and preferably ranges from 0.3 to 0.5;

and

- E'2) the reaction of the product formed at the end of step EΊ) with at least one isocyanatoalkylacrylate, in amounts such that the OH / NCO molar ratio (r4) is less than or equal to 1, preferably will from 0.90 to 1.00, and preferably ranges from 0.95 to 1.00.

In the context of the invention, and unless otherwise stated, (r3) 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 by all of the polyisocyanate (s) and polyol (s) present in the reaction medium of step EΊ).

In the context of the invention, and unless otherwise stated, (r4) is the OH / NCO molar ratio corresponding to the molar ratio of the number of hydroxyl groups (OH) to the number of isocyanate groups (NCO) carried by all of the polyol (s) (polyurethane with OH endings obtained at the end of step EΊ and optionally residual polyol (s)) and polyisocyanate (s) (isocyanatoalkylacrylate (s) and optionally residual polyisocyanate (s)) of step EΊ) present in the reaction medium of step E'2).

The polyisocyanates and polyols are as described below.

Case iii)

According to a third embodiment, the aforementioned polyurethane P is prepared by reaction of a polyurethane comprising at least two terminal functions -NCO; and at least one hydroxylated ester of acrylic acid.

In the context of the invention, and unless otherwise stated, the term "hydroxylated ester of acrylic acid" means an ester of acrylic acid in which the ester radical is substituted by at least one hydroxyl group. One can for example represent a hydroxylated ester of acrylic acid by the following formula:

CH _ï = CH-C (= 0) -0-R in which R represents an organic radical substituted by at least one hydroxyl group.

According to one embodiment, the hydroxylated ester of acrylic acid has the following formula (IV): C Hs = C H- C (= 0} OR ^ü -OH

(IV)

in which R ° represents a linear or branched divalent hydrocarbon radical, aliphatic or cyclic, saturated or unsaturated, preferably comprising from 2 to 240 carbon atoms, and being optionally interrupted by one or more heteroatoms (such as for example O, S, and in particular O), and / or optionally interrupted by one or more aromatic groups, and / or optionally interrupted by one or more divalent groups -N (R _C ) - with R _c representing a linear or branched alkyl radical comprising from 1 to 22 carbon atoms (tertiary amine), -C (= 0) 0- (ester), -C (= 0) NH- (amide), -NHC (= 0) 0- (carbamate), - NHC (= 0 ) -NH- (urea), or -C (= O) - (carbonyl), and / or being optionally substituted.

Preferably, the hydroxylated ester of acrylic acid has one of the following formulas:

- Formula (IV-1):

CH ₂ = CH-C (= 0) -0-R ¹ -0H in which R ¹ represents a divalent linear or branched, aliphatic or cyclic, saturated or unsaturated alkylene radical, comprising from 2 to 22 carbon atoms, preferably of 2 to 18, preferably from 2 to 14, even more preferably from 2 to 10, and advantageously from 2 to 6 carbon atoms;

- Formula (IV-2):

CH ₂ = CH-C (= 0) -0-R ² -0- [C {= 0) - {CH2} r0] _s -H in which:

- r is an integer ranging from 1 to 10, preferably from 1 to 5, and preferably r is equal to 5;

- s is an integer ranging from 1 to 10, s being preferably equal to 2;

R ² represents a linear or branched divalent alkylene radical, aliphatic or cyclic, saturated or unsaturated, comprising from 2 to 22 carbon atoms, preferably from 2 to 18, preferably from 2 to 14, even more preferably from 2 to 10, and advantageously from 2 to 6 carbon atoms;

- Formula (IV-3):

in which R ³ represents a linear or branched, aliphatic or cyclic, saturated or unsaturated, divalent alkylene radical comprising from 2 to 4 carbon atoms, t is an integer ranging from 2 to 120, preferably from 1 to 10, t being preferably equal to 2 or 3. Among the hydroxylated esters of acrylic acid of formula (11-1), there may be mentioned for example 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate (4-HBA) , 2-hydroxybutyl acrylate (HBA) (for example available from SARTOMER, COGNIS or BASF).

Among the compounds of formula (II-2) above, there may be mentioned for example the polycaprolactone acrylate SR 495B (CAPA) available from SARTOMER or the hydroxyethylcaprolactone acrylate (HECLA) available from BASF.

Among the ethoxylated and / or propoxylated derivatives of acrylic acid of formula (II-3) mentioned above, mention may for example be made of BLEMMER® AP-150, BLEMMER® AP-200, BLEMMER® AP-400, BLEMMER ® AP-550, BLEMMER ® AP-800, BLEMMER ® AP-1000, BLEMMER ® AE-90, BLEMMER ® AE-150, BLEMMER ® AE-200, BLEMMER ® AE-350, BLEMMER ® AE-400, sold by NIPPON OIL & FATS CORPORATION, or the SR 604 from SARTOMER.

Preferably, the hydroxylated ester of acrylic acid has the above-mentioned formula (IV-1), and in particular one of the following formulas (IV-1-1) or (IV-1-2):

- formula (IV-1-1): 2-hydroxyethylacrylate (HEA):

CH = CH-C (= 0) -0-CH: -CH:> - 0H

- formula (IV-1-2): 2-hydroxypropylacrylate (HPA)

CH:., = CH-C (= 0) -0-CH ₂ -CH (Me) -0H

Preferably, the aforementioned polyurethane P is prepared by a process comprising the following stages:

- E ”1) the preparation of a polyurethane with NCO endings by a polyaddition reaction:

i) at least one polyisocyanate, preferably chosen from diisocyanates, triisocyanates, and mixtures thereof;

ii) with at least one polyol, preferably chosen from polyester polyols, polyether polyols, poly (ether-ester) polyols, polyene polyols, polycarbonate polyols, poly (ether-carbonate) polyols, polycaprolactone polyols and their mixtures;

in amounts such that the NCO / OH molar ratio (r5) is strictly greater than 1, preferably ranges from 1.3 to 2.0, and preferably ranges from 1.5 to 1.7;

and

- E ”2) the reaction of the product formed at the end of step E1) with at least one hydroxylated ester of acrylic acid as defined above, in amounts such as the OH / NCO molar ratio ( r6) is less than or equal to 1, preferably ranges from 0.90 to 1.00, and preferably ranges from 0.95 to 1.00. Preferably, step E ”2) is carried out with at least one hydroxylated ester of acrylic acid as defined above, preferably of formulas (IV-1-1) or (IV-1-2) mentioned above.

In the context of the invention, and unless otherwise stated, (r5) 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 by all of the polyisocyanate (s) and polyol (s) present in the reaction medium of step E ”1).

When the polyurethane with NCO endings is obtained in step E ”1) from a mixture of polyisocyanates or several polyisocyanates added successively, the calculation of the molar ratio (r5) takes into account on the one hand the NCO groups carried by all of the polyisocyanate (s) present in the reaction medium of step E ”1), and on the other hand of the OH groups carried by the polyol (s) present (s) ) in the reaction medium of step E ”1).

In the context of the invention, and unless otherwise stated, (r6) is the OH / NCO molar ratio corresponding to the molar ratio of the number of hydroxyl groups (OH) to the number of isocyanate groups (NCO) carried respectively by the assembly alcohol (s), and isocyanate (s) (especially polyurethane with NCO endings and optionally the polyisocyanate (s) unreacted at the end of step E ” 1)) present in the reaction medium of step E ”2).

The polyurethane comprising at least two terminal functions -NCO obtained in step E ”1) may have from 1 to 1.8 milliequivalents per gram of NCO functions per gram of said polyurethane, more preferably from 1 to 1.5 milliequivalents per gram of NCO functions per gram of said polyurethane.

The polyurethane comprising at least two terminal functions -NCO obtained in step E1 ”) may have an NCO group content ranging from 4% to 7% by weight, preferably from 4.4% to 6.3% by weight per relative to the total weight of said polyurethane.

Preferably, the NCO functionality of the polyurethane comprising at least two terminal functions -NCO ranges from 2 to 3.

The NCO functionality of the polyurethane comprising at least two NCO terminal functions is the average number of NCO functions per mole of polyurethane.

Steps E1). EΊ) and E ”1)

Polvol (s)

The polyols below can also be used in step E1), EΊ) or E ”1) as defined above. The polyol (s) used according to the invention can be chosen from those whose number-average molecular mass (Mn) ranges from 200 to 20,000 g / mol, preferably from 300 to 12,000 g / mol, and preferably from 400 to 4,000 g / mol.

Preferably, their hydroxyl functionality ranges from 2 to 6, preferably from 2 to 3. The hydroxyl functionality is the average number of hydroxyl functions per mole of polyol.

Preferably, the polyol (s) which can be used according to the invention has (s) a hydroxyl index (IOH) (average) ranging from 5 to 840 milligrams of KOH per gram of polyol (mg KOH / g) , preferably 9 to 560 mg KOH / g, preferably 28 to 420 mg KOH / g, more preferably 100 to 400 mg KOH / g.

According to a particular embodiment, the hydroxyl number of polyol (s) having a hydroxyl functionality of 2 ranges from 5 to 560 mg KOH / g, preferably from 9 to 374 mg KOH / g, preferably from 28 to 280 mg KOH / g, more preferably 100 to 280 mg KOH / g.

According to one embodiment, the hydroxyl number of polyol (s) having a hydroxyl functionality of 3 ranges from 8 to 840 mg KOH / g, preferably 14 to 560 mg KOH / g, preferably from 42 to 420 mg KOH / g, more preferably 200 to 400 mg KOH / g.

The polyol (s) that can be used can be chosen from polyester polyols, polyether polyols, poly (ether-ester) polyols, polyene polyols, polycarbonate polyols, poly (ether-carbonate) polyols, polycaprolactone polyols, poly (meth) acrylate polyols and their mixtures.

The polyol (s) which can be used can be chosen from aromatic polyols, aliphatic polyols, arylaliphatic polyols and mixtures of these compounds.

According to the invention, the polyester polyol (s) can (have) a number-average molecular mass ranging from 1,000 g / mol to 10,000 g / mol, preferably from 1,000 g / mol to 6,000 g / mol.

The polyester polyols can be chosen from polyester diols and polyester triols, and preferably from polyester diols.

Among the polyester polyols, there may be mentioned, for example:

- polyesters polyols of natural origin such as castor oil;

- the polyester polyols resulting from the polycondensation:

- 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 trimeric fatty alcohol and mixtures thereof, with

one or more polycarboxylic acid or its ester or anhydride derivative such as 1, 6-hexanedioic acid (adipic acid), dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, 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 l maleic or phthalic anhydride, or a lactone such as for example caprolactone.

- the polyol estolides resulting from the polycondensation of one or more hydroxy acids, such as ricinoleic acid, on a diol (mention may for example be made of “POLYCIN® D-1000” and “POLYCIN® D-2000” available from VERTELLUS ).

The polyester polyols raised can be prepared in a conventional manner, and are for the most part commercially available.

Among the polyesters polyols, one can for example quote the following products of hydroxyl functionality equal to 2:

- "TONE® 0240" (marketed by UNION CARBIDE) which is a polycaprolactone of average molecular mass in number of around 2000 g / mol, and a melting point of approximately 50 ° C.,

- "DYNACOLL® 7381" (marketed by EVONIK) with an average molecular weight of around 3,500 g / mol, and having 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 around 3500 g / mol, and a melting point of 55 ° C approximately,

- "DYNACOLL® 7330" (marketed by EVONIK) with an average molecular weight of around 3,500 g / mol, and having a melting point of approximately 85 ° C.,

- “DYNACOLL®7363” (marketed by EVONIK) which also results from the condensation of adipic acid with hexanediol, and has a number average molecular mass of approximately 5500 g / mol, and a melting point of 57 ° C approximately,

- "DYNACOLL® 7250" (marketed by EVONIK): polyester polyol having a viscosity of 180 Pa.s at 23 ° C, a number average molecular mass Mn equal to 5,500 g / mol, and a T _g equal to - 50 ° C,

- "KURARAY® P-6010" (marketed by KURARAY): polyester polyol having a viscosity of 68 Pa.s at 23 ° C, an average molecular mass in number Mn equal to 6000 g / mol, and a T _g equal at -64 ° C,

- "KURARAY® P-10010" (marketed by KURARAY): polyester polyol having a viscosity of 687 Pa.s at 23 ° C, and a number average molecular mass Mn equal to 10,000 g / mol, - "REALKYD® XTR 10410" (marketed by the company CRAY VALLEY): polyester polyol having an average molecular mass in number Mn close to 1000 g / mol and whose hydroxyl index ranges from 108 to 1116 mg KOH / g. It is a product resulting from the condensation of adipic acid, diethylene glycol and monoethylene glycol,

- "DEKATOL® 3008" (marketed by the company BOSTIK) with an average molar mass in number Mn of around 1060 g / mol and whose hydroxyl index ranges from 102 to 112 mg KOH / g. It is a product of the condensation of adipic acid, diethylene glycol and monoethylene glycol.

According to the invention, the polyether polyol (s) can (wind) have a number-average molecular mass ranging from 200 to 20,000 g / mol, preferably from 300 to 12,000 g / mol, and preferably from 400 at 4,000 g / mol.

The polyether polyol (s) which can be used 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.

More preferably, the polyether polyol (s) which can be used 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 with 4 carbon atoms, more preferably from 2 to 3 carbon atoms.

By way of example of polyoxyalkylene diols or triols which can be used according to the invention, there may be mentioned:

- polyoxypropylene diols or triols (also known as polypropylene glycol (PPG) diols or triols) having a number average molecular weight (Mn) ranging from 300 to 20,000 g / mol;

- polyoxyethylene diols or triols (also known as polyethylene glycol (PEG) diols or triols) having a number average molecular weight (Mn) ranging from 300 to 20,000 g / mol;

- and their mixtures.

The polyether polyols raised can be prepared in a conventional manner, and are widely available commercially. They can be obtained by polymerization of the corresponding alkylene oxide in the presence of a basic catalyst (for example potash) or a catalyst based on a double metal-cyanide complex.

By way of example of a polyether diol, mention may be made of the polyoxypropylene diol sold under the name "VORANOL® P 400" by the company DOW with a number average molecular mass (Mn) close to 400 g / mol and whose hydroxyl number ranges from 250 to 270 mg KOH / g.

By way of example of polyether triol, mention may be made of polyoxypropylene triol sold under the name "VORANOL® CP 450" by the company DOW, mass number average molecular (Mn) close to 450 g / mol and whose hydroxyl index ranges from 370 to 396 mg KOH / g, or the polyoxypropylene triol marketed under the name "VORANOL® CP3355" by the company DOW, of molecular mass number average close to 3,554 g / mol.

The polyene polyol (s) which can be used according to the invention can be chosen preferably from polyenes comprising terminal hydroxyl groups, and their corresponding hydrogenated or epoxidized derivatives, having in particular a number average molecular mass (Mn) ranging from 1,000 to 10,000 g / mol, preferably from 1,000 to 5,000 g / mol.

Preferably, the polyene polyol (s) which can be used according to the invention is (are) chosen from polybutadienes or polyisoprenes comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized. Preferably, the polyene polyol (s) which can be used according to the invention is (are) chosen from homopolymers and copolymers of butadiene and / or isoprene comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized .

In the context of the invention, and unless otherwise stated, the term "terminal hydroxyl groups" of a polyene polyol means the hydroxyl groups located at the ends of the main chain of the polyene polyol.

The hydrogenated derivatives mentioned above can be obtained by total or partial hydrogenation of the double bonds of a polydiene comprising terminal hydroxyl groups, and are therefore saturated (s) or unsaturated (s).

The epoxidized 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 comprise at least one epoxy group in its main chain.

As examples of polyene polyols, there may be mentioned:

- butadiene diol homopolymers, saturated or unsaturated, comprising terminal hydroxyl groups such as those sold under the name "POLY BD® R45HT" (Mn = 2800 g / mol) or KRASOL® "(Mn = 2400 to 3100 g / mol ) by the company CRAY VALLEY or else “POLY BD® R15HT” (Mn = 1200 g / mol) sold by the company IDEMITSU KOSAN;

- the homopolymer diols of isoprene, saturated or unsaturated, comprising terminal hydroxyl groups, such as for example those marketed under the name "POLY IP ™" (unsaturated, Mn = 2000 g / mol) or "EPOL ™" ( saturated, Mn = 2,600 g / mol) by the company IDEMITSU KOSAN. The polycarbonate polyols can be chosen from polycarbonate diols or triols, in particular having a number average molecular weight (M _n ) ranging from 300 to 12,000 g / mol.

As an example of a polycarbonate diol, there may be mentioned:

- "CONVERGE® POLYOL 212-10" and "CONVERGE® POLYOL 212-20" marketed by the company NOVOMER respectively of molecular mass in number (M _n ) equal to 1000 and 2000 g / mol whose hydroxyl indices are respectively 1 12 and 56 mg KOH / g,

- “DESMOPHEN® C XP 2716” marketed by COVESTRO with a molecular mass in number (M _n ) equal to 326 g / mol and whose hydroxyl index is 344 mg KOH / g,

- "POLYOL C-590, C1090, C-2090 and C-3090" marketed by KURARAY having a number molecular mass (M _n ) ranging from 500 to 3000 g / mol and a hydroxyl number ranging from 224 to 37 mg KOH / g.

The polycaprolactone polyol (s), which can be used according to the invention, can (wind) have a number-average molecular mass (Mn) ranging from 240 to 10,000 g / mol, and preferably from 1,000 to 6,000 g / mol.

By way of example of polycaprolactone polyol (s), mention may be made of the CAPA ™ polyols sold by PERSTORP, such as for example:

- CAPA ™ diols: CAPA ™ 2201 (Mn = 2,000 g / mol), CAPA ™ 2303 (Mn = 3,000 g / mol);

- CAPA ™ triols: CAPA ™ 3201 (Mn = 2,000 g / mol), CAPA ™ 3301 (Mn = 3,000 g / mol);

- CAPA ™ tetrols: CAPA ™ 4101 (Mn = 1000 g / mol).

Among the poly (ether-ester) polyols, mention may, for example, be made of those described in WO2013 / 1 10512, WO2012 / 02048 or US 7,893,189.

The poly (meth) acrylate polyol (s) which can be used according to the invention can (wind) have a number-average molecular mass (Mn) ranging from 1000 to 22,000 g / mol, preferably from 1000 to 10 000 g / mol, and even more preferably from 1000 to 6000 g / mol.

The poly (meth) acrylate polyol (s) which can be used according to the invention is (are) preferably chosen from homopolymers, copolymers and terpolymers of acrylate monomer (s) and / or methacrylate (s).

More preferably, the poly (meth) acrylate polyol (s) which can be used according to the invention is (are) preferably chosen from poly (meth) acrylates and poly (meth) acrylates triols ( telechelics).

By way of example of poly (meth) acrylate polyol (s), mention may be made of TEGO® DIOL MD-1000, BD-1000, BD-2000 and OD-2000 sold by the company EVONIK TEGO CHEMIE. According to a preferred embodiment, step E ”1) is carried out in the presence of at least one polyether polyol, preferably at least one polyether diol.

Polvisocvanate (s)

The polyisocyanate (s) which can be used according to the invention in steps E1), EΊ) and E ”1) can be added sequentially or reacted in the form of a mixture.

According to one embodiment, the polyisocyanate (s) which can be used are diisocyanate (s), preferably chosen from the group consisting of isophorone diisocyanate (I 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, cyclohexane diisocyanate, cyclohexane diisocyanate, -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), du (2,6) - bis (isocyanatom ethyl) 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 HDI allophanate having for example the following formula (Y):

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

and their mixtures.

Preferably, the allophanate of above-mentioned formula (Y) is such that p, q, R _c and R _d are chosen such that the above HDI allophanate derivative comprises an NCO isocyanate group content ranging from 12 to 14 % by weight relative to the weight of said derivative.

According to one embodiment, the polyisocyanate (s) which can be used are triisocyanate (s), preferably chosen from isocyanurates, biurets, and adducts of diisocyanates and triols.

In particular, the isocyanurate (s) can 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).

Preferably, the diisocyanate isocyanurate (s) which can be used according to the invention corresponds (s) to the following general formula (W):

in which :

R ⁴ represents an alkylene group, linear or branched, cyclic, aliphatic, arylaliphatic or aromatic, comprising from 4 to 9 carbon atoms,

with the proviso that the NCO groups are not linked by a covalent bond to a carbon atom forming part of an aromatic hydrocarbon ring such as a phenyl group.

By way of example of diisocyanate trimers which can be used according to the invention, there may be mentioned:

- the trimer isocyanurate of hexamethylene diisocyanate (HDI):

- the isophorone diisocyanate isocyanurate trimer (I PDI):

- the trimer isocyanurate of pentamethylene diisocyanate (PDI):

- the isocyanurate trimer of meta-xylylene diisocyanate (m-XDI):

- the isocyanurate trimer of m-XDI, in hydrogenated form:

By way of example of adducts of diisocyanates and triols which can be used according to the invention, mention may be made of the adduct of meta-xylylene diisocyanate and trimethylolpropane, as shown below. This adduct is marketed for example by the company MITSUI CHEMICALS, Inc. under the name "TAKENATE® D-1 10N".

The polyisocyanate (s) which can be used for preparing the polyurethane used according to the invention are widely available commercially. By way of example, mention may be made of “SCURANATE® TX” sold by the company VENCOREX, corresponding to a 2,4-TDI of purity of the order of 95%, “SCURANATE® T100” sold by the company VENCOREX , corresponding to a 2,4-TDI of purity greater than 99% by weight, “DESMODUR® I” marketed by the company COVESTRO, corresponding to an IPDI or even “DESMODUR® N3300” marketed by the company COVESTRO, corresponding to an HDI isocyanurate, the "TAKENATE ™ 500" marketed by MITSUI CHEMICALS corresponding to an m-XDI, the "TAKENATE ™ 600" marketed by MITSUI CHEMICALS corresponding to an m-H6XDI, the "VESTANAT® H12MDI" marketed by EVONIK an H12MDI.

Preferably, the polyisocyanate (s) is (are) chosen from toluene diisocyanate (in particular the 2,4 TDI isomer, the 2,6-TDI isomer or their mixtures), the meta- xylylene, HDI isocyanurate, and mixtures thereof. In particular, the polyisocyanate is toluene diisocyanate.

Reaction conditions

The polyaddition reaction of step E1), EΊ) or E ”1) can be carried out at a temperature below 95 ° C and / or under anhydrous conditions.

The polyaddition reaction of step E1), EΊ) or E ”1) can be carried out in the presence or not of at least one reaction catalyst. The reaction catalyst (s) which can be used during the polyaddition reaction of step E1), EΊ) or E ”1) can be any catalyst known to those skilled in the art for catalyzing the formation of polyurethane by reacting at least one polyisocyanate with at least one polyol.

An amount of up to 0.3% by weight of catalyst (s) relative to the weight of the reaction medium of step E1), EΊ) or E ”1) can be used. In particular, it is preferred to use from 0.02% to 0.2% by weight of catalyst (s) relative to the weight of the reaction medium of step E1), E’1) or E ”1).

Step E2), E’2) and E ”2)

In the presence of an ester of acrylic acid, the transesterification reaction of step E2) can be carried out at a temperature above 110 ° C, preferably above 120 ° C.

Among the acrylic acid esters, mention may, for example, be made of methyl acrylate, butyl acrylate, propyl acrylate and pentyl acrylate.

In the presence of acrylic acid chloride, the reaction of step E2) can be carried out at a temperature preferably below 95 ° C., under preferably anhydrous conditions.

In the presence of isocyanatoalkylacrylate, the reaction of step E’2) can be carried out at a temperature preferably below 95 ° C., under preferably anhydrous conditions.

In the presence of ester (s) hydroxylated (s) of acrylic acid, or amide (s) hydroxylated (s) of acrylic acid, the reaction of step E ”2) can be carried out at a temperature preferably below 95 ° C., under preferably anhydrous conditions.

The hydroxylated esters of acrylic acid can be used either pure or in the form of a mixture of different hydroxylated esters of acrylic acid having an average hydroxyl number of said mixture ranging from 8 to 483 mg KOH / g of said mixed.

Additional ingredients

According to a preferred embodiment, composition A does not comprise a multifunctional polyol (meth) acrylate ester. According to the invention, the multifunctional polyol (meth) acrylate ester is a polyol comprising at least two OH functions in the form of an ester of acrylic acid or of methacrylic acid.

The multifunctional polyol (meth) acrylate ester can comprise non-esterified OH functions.

It can, for example, be the esters defined in US 4,051, 195. Multifunctional polyol (meth) acrylate esters can be obtained from diols or triols, optionally ethoxylated and / or propoxylated.

Mention may for example be made of 1,3-propanediol diacrylate, esterdiol diacrylate (EDDA - CAS number: 30145-51-8), 1,6-hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), 3-methyl-1,5-pentadiol diacrylate (MPDA), trimethylolpropane triacrylate (TMPTA), pentaerythritol tetraacrylate (PETTA), di-trimethylolpropane tetraacrylate (DiTMPtylate diacetylacrylate) CAS: 84170-74-1), and mixtures thereof.

Composition A can optionally comprise at least one aliphatic urethane-acrylate oligomer.

It may for example be CN925® (aliphatic tetrafunctional urethane-acrylate having an Mn of approximately 2,500 g / mol) or CN 9245S® (aliphatic trifunctional urethane-acrylate having a Mn of approximately 5,000 g / mol ) marketed by Sartomer.

Composition A can have a viscosity measured at room temperature (23 ° C) ranging from 100 to 250,000 mPa.s, preferably ranging from 10,000 to 80,000 mPa.s.

Preferably, the weight ratio polyurethane (s) P / epoxy resin (s) in composition A ranges from 55/45 to 95/5, preferably from 60/40 to 90/10, advantageously from 65/35 to 85/25 , and for example the ratio is 70/30.

A.2. Composition B

Composition B according to the invention comprises:

- At least one polyamine B2, different from polyamine B1, comprising at least two functions chosen from primary and secondary amines.

Polyamine B1

Preferably, polyamine B1 comprises at least two primary amine functions

-NH ₂ .

Polyamine B1 can have a primary alkalinity greater than or equal to 7 meq / g, preferably greater than or equal to 10 meq / g, preferably greater than or equal to 13 meq / g.

According to one embodiment, the polyamine B1 has the following formula (V):

NH _ï -CH Z-CHs- H _ï (V)

in which Z represents a divalent hydrocarbon radical, linear or branched, cyclic, aliphatic or aromatic, saturated or unsaturated, preferably comprising from 1 to 22 carbon atoms, said hydrocarbon radical being optionally interrupted by one or more heteroatoms chosen from -S- , -O- and / or one or more divalent tertiary amine groups - NR ^'” - with R representing a linear or branched, saturated or unsaturated alkyl group, comprising 1 to 22 carbon atoms, preferably 1 to 18, preferably from 1 to 14, preferably from 1 to 10 and advantageously from 1 to 6 carbon atoms. Preferably, the polyamine B1 corresponds to one of the formulas (V-1), (V-2) or (V3) below:

(V-3) in which:

- R ⁴ is a linear or branched divalent alkylene radical, or a divalent arylene radical, comprising from 1 to 18 carbon atoms, R ⁴ preferably representing a linear alkylene radical comprising 6, 10 or 12 carbon atoms;

R ⁵ represents a linear or branched divalent alkylene radical comprising from 2 to 12 carbon atoms, preferably ethylene or propylene,

R ⁶ represents a linear or branched divalent alkylene radical comprising from 2 to 10 carbon atoms, preferably ethylene or propylene,

- X _a = O, S, NR ⁷ in which R ⁷ represents H or a linear or branched, saturated or unsaturated alkyl group, comprising from 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, X preferably representing O ;

- n ₃ is an integer ranging from 0 to 4, and advantageously being equal to 1 or 2;

- n ₄ is an integer ranging from 0 to 2, and advantageously being equal to 1. Polyamine B1 is preferably a polyamine of formula (V-2) above, in which X _a preferably represents O, and n ₃ is preferably 1.

Preferably, polyamine B1 is chosen from diethylenetriamine (DETA): H2N- CH2-CH2-NH-CH2-CH2-NH2, 1, 10-decanediamine: H ₂ N- (CH ₂ ) IO-NH ₂ , 1, 12 dodecanediamine: H2N- (CH2) i2-NH2, 1, 6-hexametylenediamine (HMDA), polyetherdiamines of formulas H2N-CH2-CH2-O-CH2-CH2-O-CH2-CH2-NH2 and H ₂ N-CH ₂ -CH ₂ - CH2-O-CH2-CH2-O-CH2-CH2-CH2-NH2 (available for example under the trade names "JEFFAMINE® EDR 148" and "JEFFAMINE® EDR 176" respectively from HUNTSMAN company).

Polyamine B2

Preferably, the polyamine B2 comprises at least two, preferably at least three, primary amine functions -IMH2.

The polyamine B2 or the mixture of polyamines B2 may have a primary alkalinity strictly less than 10.00 meq / g, preferably between 3.0 and less than 10.00 meq / g.

According to one embodiment, the polyamine B2 is chosen from the group consisting of polyetheramines, polyamidoamines, fatty dimer or trimer amines, polyethyleneimines (PEI), polyethyleneimines dendrimers, polypropyleneimines (PPI), polypropyleneimines dendrimers, polyallylamines , poly (propylene-ethylene) imines, and mixtures thereof, said polyamine preferably having a primary alkalinity strictly less than 10.00 meq / g, preferably between 3.0 and less than 10.00 meq / g.

According to one embodiment, the polyamine B2 is chosen from polyetheramines, in particular chosen from:

- polyether diamines such as for example:

- the polyether diamines corresponding to the formula below:

CH ₃ CH _j in which x is an integer such that the primary alkalinity of the polyetherdiamine is between 0.5 and less than 10 meq / g, preferably x ranging from 2 to 68 (such polyetherdiamines are for example marketed under the name JEFFAMINES D-230, D-400, D-2000 and D-4000 by the company HUNTSMAN and have respective primary alkalinities of 8.7, 5.0, 1.0 and 0.5 meq / g);

- the polyether diamines corresponding to the formula below:

in which x, y and z are whole numbers such that the primary alkalinity is between 1 and less than 10 meq / g, preferably y ranging from 2 to 39 and x + z ranging from 1 to 6 (such polyether diamines are marketed for example under the name JEFFAMINES HK-51 1, ED-600, ED-900 and ED-2003 by the company HUNTSMAN and have respective primary alkalinities of 9.1, 3.3, 2.2 and 1, 0 meq / g);

- the polyether diamines corresponding to the following formula:

H _s -X _t . (- 0-X _t .) ",. 0- (0H ₂ -CH _s -CH _s -CHr0) _h - (X _s -0) _m -iX _fc -NH ₂ in which X _b is a linear or branched alkylene group, preferably comprising from 2 to 20 atoms of carbon, preferably from 2 to 10 carbon atoms, m is an integer ranging from 1 to 20, and n is an integer ranging from 1 to 100, m and n being preferably such that the primary alkalinity of the polyetherdiamines is strictly lower at 10 meq / g;

- polyethertriamines such as, for example, those corresponding to the formula below:

in which R is a hydrogen atom or a C1 to C2 alkyl group, x, y, z and n are whole numbers, such that the primary alkalinity of polyether triamine is between 0.5 and less than 10 meq / g, preferably n ranging from 0 to 1 and x + y + z ranging from 5 to 85 (such polyethertriamines are sold, for example, under the name JEFFAMINES T-403, T-3000, and T-5000 by the company HUNTSMAN and have respective primary alkalinities of 6.8, 1.0 and 0.6 meq / g).

According to another embodiment, the polyamine B2 is chosen from dimer and trimer fatty amines comprising two or three primary amine groups of primary alkalinity ranging from 3.28 meq / g to 5.20 meq / g. These dimeric and trimeric fatty amines can be obtained from corresponding dimerized and trimerized fatty acids. By way of example of such partially or fully hydrogenated dimer fatty amines, mention may be made of those corresponding to the following formulas:

The dimer and trimer fatty acids used to prepare the abovementioned fatty amines can be obtained by high-temperature polymerization under pressure of monocarboxylic unsaturated fatty acids (monomeric acid), comprising from 6 to 22 carbon atoms, preferably from 12 to 20 carbon atoms, and come from plant or animal sources. As an example, such unsaturated fatty acids can be cited, Cie acids having one or two double bonds (respectively oleic or linoleic acid) obtained from tall oil which is a by-product of the manufacture of paper pulp. After polymerization of these unsaturated fatty acids, a technical mixture is obtained in particular containing on average 30-35% by weight of fatty acids monocarboxylic acids often isomerized with respect to the starting monocarboxylic unsaturated fatty acids, 60-65% by weight of dicarboxylic acids (dimer acids) comprising twice the carbon number relative to the starting monocarboxylic unsaturated fatty acids and 5-10% by weight tricarboxylic acids (trimer acids) having three times the carbon number compared to the starting monocarboxylic unsaturated fatty acids. By purification of this mixture, the various commercial grades of dimeric, monomeric or trimeric acids are obtained in particular. These dimer and trimer fatty acids are then typically subjected to a reductive ammoniation reaction (NH ₃ / H2) in the presence of a catalyst, making it possible to obtain the dimerized fatty amines.

According to another embodiment, the polyamine B2 is chosen from polyethyleneimines (PEI), preferably having a number average molecular mass (Mn) ranging from 450 to 25,000 g / mol and a primary alkalinity / total alkalinity ratio ranging from 0.35 to 0.45, and in particular having at least one radical of the following formula:

Mention may for example be made of the polyethyleneimines sold under the name "LUPASOL" sold by BASF, such as the "LUPASOL FG" of Mn having a molar mass of 800 g / mol, a primary alkalinity of 10.00 meq / g and an alkalinity total of 24.00 meq / g, a sum of primary and secondary alkalinity being 19 meq / g, a ratio of primary alkalinity / total alkalinity of 0.42, and a secondary alkalinity / total alkalinity of 0 , 38 determined by ¹³ C NMR.

Preferably, the polyamine B2 is chosen from polyetheramines, polyethyleneimines (PEI) as defined above, and their mixtures.

According to one embodiment, composition B has a primary alkalinity / total alkalinity ratio ranging from 0.25 to 1.00.

The mass ratio of polyamine (s) B1 / polyamine (s) B2 in composition B can range from 90/10 to 10/90, preferably from 80/20 to 20/80, preferably from 30/70 to 70/30, even more preferably from 60/40 to 40/60, and better still is about 50/50. Composition B can be prepared by simple mixing of the constituents, preferably at a temperature ranging from 10 ° C to 50 ° C, preferably at room temperature, preferably using a mechanical mixer with or without addition of solvent .

A.3. Composition

Composition A and / or B can comprise at least one additive chosen from the group consisting of fillers, catalysts, dyes, adhesion promoters, thixotropic agents, solvents, and mixtures thereof.

Composition A and / or B may also comprise at least one solvent, preferably in an amount ranging from 10% to 50% by weight, more preferably ranging from 15% to 40% by weight, and better still ranging from 20 to 30% by weight, relative to the total weight of composition A (or B).

The solvent can be chosen from organic and alcoholic solvents such as ethyl acetate, methyl ethyl ketone, xylene, ethanol, isopropanol, tetrahydrofuran, methyl-tetrahydrofuran, or even from " ISANE® ”(based on isoparaffins, available from TOTAL) or“ EXXOL® D80 ”(based on aliphatic hydrocarbons, available from EXXON MOBIL CHEMICAL).

The catalyst (s) can be any catalyst usually used to accelerate the addition reaction of a compound comprising a primary or secondary amine on a compound comprising an acrylate group.

According to one embodiment, the catalyst is chosen from the group consisting of Lewis bases and Bronstedt bases whose conjugated acids have a pKa> 10, hydroxides (such as for example LiOH, NaOH, or KOH), hydrides (such as for example NaH, KH, or CaH2), carbonates (such as for example CaCC> 3, Na2CC> 3, or K2CO3), alkali metal alcoholates (such as for example sodium methylate, sodium methylate potassium, sodium ethylate, potassium tert-butoxide, titanium tetraisopropylate), and mixtures thereof.

The Lewis bases and Bronstedt bases whose conjugate acids have a pKa> 10 can typically be those described in Houben-Weyl, vol. XI / 1, (1957), page 277 ff. and in Patai, "The Chemistry of the Amino Group, pp 61-65, Interscience, New York (1968).

Preferably, the Lewis bases are chosen from the group consisting of cycloaliphatic amines, such as 1, 4-diazabicyclo [2.2.2] octane (DABCO) or diethyl ether-2,2'-morpholine (DMDEE); aliphatic tertiary amines such as, for example triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, N-methyldiisopropylamine or N-butyldiethanolamine; amidines such as, for example, 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU); of guanidines such as, for example, N, N, N ', N'-tetramethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) or N-methyl triazabicyclodecene (Me-TBD) ; copolymers of 2,3,4-vinylpyridine or of amino acrylates such as 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate or 3-dimethylaminopropyl acrylate; phosphazenes such as for example 2-tert-butylimino-2-diethylamino-1, 3-dimethylperhydro-1, 3,2-diazaphosphoride (BMEP); alkyl or aryl alkyl phosphanes such as for example tributylphosphane, triphenylphosphane, tris-p-tolylphosphane, methyldiphenylphosphane; hydroxy and amino phosphanes; basic ion exchange resins; and their mixtures.

Among the Lewis bases which are particularly preferred according to the invention, there may be mentioned:

- guanidines such as for example:

1, 5,7-triazabicyclo [4.4.0] dec-5-ene (TBD):

N-methyl triazabicyclodecene (Me-TBD):

- amidines such as for example:

1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU): 1,5-diazabicyclo [4.3.0] non-5-ene (DBN):

- tertiary amines such as for example:

2,2'-dimorpholinodiethylether (DMDEE): 1, 4-diazabicyclo [2.2.2] octane (DABCO):

An amount ranging from 0.05 to 5% by weight, preferably from 0.1 to 3% by weight of catalyst (s) relative to the total weight of the composition according to the invention can be added.

The composition according to the invention can also comprise at least one organic and / or mineral filler. The filler (s) may / may be present in composition A and / or in composition B.

The (or) mineral filler (s) that can be used is (are) advantageously chosen (s) so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.

As an example of mineral filler (s) that can be used, any mineral filler (s) usually used in the field of adhesive compositions can be used. These charges are typically in the form of particles of diverse geometry. They may for example be spherical, fibrous, or have an irregular shape.

Preferably, the filler (s) is (are) chosen (s) from the group consisting of clay, quartz, carbonate fillers, kaolin, gypsum, clays, and their mixtures, preferably the filler (s) is (are) chosen from carbonate fillers, such as carbonates of alkali or alkaline earth metals, and more preferably calcium carbonate or chalk.

These fillers can be untreated or treated, for example using an organic acid such as stearic acid, or a mixture of organic acids mainly consisting of stearic acid.

It is also possible to use hollow mineral microspheres such as hollow glass microspheres, and more particularly those in sodium and calcium borosilicate or in aluminosilicate.

The composition according to the invention can also comprise at least one adhesion promoter, preferably chosen from silanes, such as aminosilanes, epoxysilanes or acryloyl silanes. The adhesion promoter (s) is (are) preferably present in composition A.

Preferably, the composition according to the invention is such that the molar ratio (r5) as defined below ranges from 0.5 to 2, preferably from 0.7 to 1, 3 preferentially from 0.8 to 1, 2:

with:

- x representing the sum of the number of primary amine functions (NH2) and the number of secondary amine functions (expressed in meq per gram of the polyamine B1 and B2 mixture) present in the reagents of composition B;

- y representing the sum of the number of epoxy functions (expressed in meq per gram of epoxy resin (s)) and of acrylate functions (expressed in meq per gram of polyurethane (s) P) present in the reagents of composition A.

B. Ready-to-use kit

The present invention also relates to a ready-to-use kit, comprising composition A as defined above on the one hand and composition B as defined above on the other hand, packaged in two separate compartments.

Indeed, the composition according to the invention can be in a two-component form, for example in a ready-to-use kit, comprising composition A on the one hand in a first compartment or barrel and the composition B on the other hand in a second compartment or barrel, in proportions suitable for a direct mixing of the two compositions, for example using a metering pump.

According to one embodiment of the invention, the kit also comprises one or more means allowing the mixing of the two compositions A and B. Preferably, the mixing means are chosen from metering pumps, static mixers of diameter adapted to the quantities used.

C. Uses

The present invention also relates to the use of a composition as defined above, as an adhesive, sealant or coating, preferably as an adhesive.

The invention also relates to the use of said composition for the repair and / or the structural or semi-structural bonding of materials in the field of transport, automobile (car, bus or truck), marine, or construction. The present invention also relates to a method of assembling two substrates by bonding, comprising:

- coating on at least one of the two substrates to be assembled with an adhesive composition obtained by mixing compositions A and B as defined above; then

- bringing the two substrates into effective contact.

Suitable substrates are, for example, inorganic substrates such as concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or else organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and composites coated with paint.

The composition according to the invention advantageously leads to an adhesive seal having:

- a tensile strength greater than or equal to 3 MPa, preferably between 3 and 15 MPa, advantageously between 3 and 10 MPa, and in particular between 5 and 8 MPa; and or

- An elongation at break greater than or equal to 20%, preferably ranging from 20% to 200%, preferably from 25% to 150%, and in particular between 40% and 90%.

All of the embodiments described above can be combined with each other. In particular, the various aforementioned constituents of the composition, and in particular the preferred modes, of the composition can be combined with one another.

In the context of the invention, by "lying between x and y", or "ranging from x to y", is meant an interval in which the limits x and y are included. For example, the range "between 0% and 25%" includes in particular the values 0% and 25%.

The invention is now described in the following exemplary embodiments which are given purely by way of illustration, and should not be interpreted to limit its scope.

EXPERIMENTAL PART

The following ingredients were used:

- VORANOL ™ P2000 available from the company DOW is a Polypropylene Glycol (PPG) with functionality F = 2 having an IOH of 55 mg KOH / g, ie a number average molecular mass (Mn) of around 2040 g / mol;

- BORCHI® KAT 315 available from the company BORCHERS is a Bismuth neodecanoate used as a tin-free catalyst; - SCURANATE® TX available from the company VENCOREX is a toluene diisocyanate (TDI) having 48.1% by weight of NCO functions and comprising 95% by weight of 2,4-TDI isomer;

- 2-hydroxyethyl acrylate (HEA) available from the company BASF has a purity of 98.5% by weight and contains 250 ± 50 ppm of MEHQ;

- JEFFAMINE® EDR-148 available from the company HUNTSMAN is a diamine (of type B1) corresponding to the formula H2N-CH2-CH2-O-CH2-CH2-O-CH2-CH2-NH2 having a molar mass of 148 g / mol, a primary and total alkalinity of 13.50 meq / g and a primary alkalinity / total alkalinity ratio of 1.00 determined by potentiometry;

- LUPASOL® FG available from the company BASF is a polyamine (type B2) of polyethyleneimine type (PEI) having a molar mass of 800 g / mol, a primary alkalinity of 10.00 meq / g and a total alkalinity of 24 .00 meq / g, a sum of primary and secondary alkalinity being 19 meq / g, a primary alkalinity / total alkalinity ratio of 0.42, and a determined secondary alkalinity / total alkalinity of 0.38 by ¹³ C NMR, ie a ratio of the sum of the primary alkalinity and the secondary alkalinity / total alkalinity of 0.79;

- D.E.R. ™ 331 available from DOW CHEMICALS is a liquid DGEBA resin obtained by reaction between bisphenol A and epichlorohydrin, and having an epoxy content ranging from 5.2 to 5.5 meq / g.

EXAMPLE 1 Preparation of a Polyurethane Based on Polvether Polvol

15.6 g of SCURANATE® TX are introduced into a reactor and the mixture is heated to 40 ° C. 72.0 g of VORANOL® P2000 are then introduced, taking care that the temperature of the mixture does not exceed 80 ° C. When the mixing temperature has stabilized, the mixture is heated for about 1 hour at 80-85 ° C.

The end of the reaction is followed by controlling the mass percentage of NCO functions in the medium, the latter having in theory to be approximately ...% by weight. When the reaction is complete, the mixture is cooled to 70 ° C. and 12.4 g of 2-hydroxyethyl acrylate and 0.01 g of BORCHI KAT® 315 are introduced. The mixture is kept at 70 ° C for 6 to 8 hours until there is no longer any NCO function visible to the Infra-Red (IR) (disappearance of the characteristic band of the NCO function at approximately 2250 cm ¹ ).

The polyurethane obtained has a viscosity measured at 23 ° C of 59,600 mPa.s. Example 2: preparation of a composition A

Composition A was prepared by mixing at room temperature (23 ° C) the polyurethane obtained in Example 1 with D.E.R. 331 in a 70/30 mass ratio (polyurethane / epoxy resin).

Example 3 Preparation of Compositions B

The compositions B which have been tested were prepared by simple mixing of the polyamine (s) B1 and / or of the polyamine (s) B2 at an ambient temperature (around 23 ° C.) in a weight ratio B1 / B2 shown below in Table 1.

Example 4 Preparation of the Adhesive Compositions

The mixing of compositions A and B detailed in Examples 2 and 3 was carried out in an A / B weight ratio indicated below in Table 1.

Table 1

Example 5: Performance evaluation

Measurement of resistance and elongation at break by tensile test:

The measurement of the resistance (breaking stress) and of the elongation at break (or “elongation at break” in English) by tensile test was carried out according to the protocol described below.

The principle of the measurement consists in drawing in a tensile machine, the movable jaw of which moves at a constant speed equal to 100 mm / minute, a standard test tube made up of the crosslinked composition and to record, at the moment when the rupture occurs. of the test piece, the applied tensile stress (in MPa) as well as the elongation of the test piece (in%). The standard test piece is dumbbell-shaped, as illustrated in international standard ISO 37 of 2011. The narrow part of the dumbbell used is 20 mm long, 4 mm wide and 500 mpΊ thick. Bonding tests

The collages are made on beech or painted sheet metal sterigms from the Rocholl company. On a sterigma, an area of 25 ^* 12.5 mm was delimited with teflon shims 1 mm thick an area of 25 ^* 12.5 mm. This zone was filled with the composition to be tested, then a second sterigme of the same material was laminated. The assembly was maintained by forceps and placed in an air-conditioned room at 23 ° C and 50% RH (relative humidity) for one week before traction on a dynamometer. The purpose of pulling on a dynamometer is to assess the maximum force (in Mpa) to be exerted on the assembly to separate it. The use of a traction machine makes it possible to subject a simple overlap joint placed between two rigid supports to a shear stress until rupture by exerting a traction on the supports parallel to the surface of the assembly and to the main axis. of the test tube. The result to be recorded is the force or the stress at break. The shear stress is applied via the movable jaw of the traction machine with a displacement at the speed of 100 mm / min. This traction method is carried out as defined by standard EN 1465 of 2009.

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

Claims

1. Composition, preferably adhesive, comprising:

- a composition A comprising:

- at least one epoxy resin;

and

- a composition B comprising:

said composition being characterized in that:

- it does not contain polythiol; and

the polyurethane (P) / epoxy resin (s) mass ratio in composition A ranges from

51/49 to 99/1.

2. Composition according to claim 1, characterized in that the epoxy resin has a viscosity measured at 23 ° C ranging from 7 to 13,000 mPa.s, preferably from 400 to 5,000 mPa.s.

3. Composition according to any one of claims 1 or 2, characterized in that the epoxy resins are chosen from the following resins:

- the resins having the following formula (I):

in which :

- 1 represents a number ranging from 0 to 8, preferably from 0 to 4, each R ′ represents, independently of each other, an alkyl radical comprising from 1 to 20 carbon atoms, preferably a methyl;

- Each x represents an integer ranging from 0 to 4, preferably x being 0 or 1;

- N, N-diglycidyl-4-glycidyloxyaniline (TGAP):

- 4,4'-methylenebis (N, N-diglycidylaniline) (TGDDM)

- the resins of formula (II) below:

in which :

- n is an integer ranging from 1 to 25, preferably from 1 to 5;

- each of R ^a and R ^b is, independently of one another, one of the following radicals: H; a linear or branched, cyclic or aliphatic alkyl radical, comprising from 1 to 10 carbon atoms; an aryl radical comprising from 6 to 12 carbon atoms; or a radical -CF ₃ ;

- and their mixtures.

4. Composition according to any one of claims 1 to 3, characterized in that the polyurethane P has an acrylate function content ranging from 0.2 to 3 meq per gram of polyurethane P, preferably from 0.5 to 2 meq per gram of polyurethane P, preferably from 0.90 to 1.3 meq per gram of polyurethane P, and advantageously from 0.90 to 1.2 meq per gram of polyurethane P.

5. Composition according to any one of claims 1 to 4, characterized in that the acrylate functionality of the polyurethane P ranges from 1 to 4, preferably from 2 to 3.

6. Composition according to any one of claims 1 to 5, characterized in that the polyurethane P is obtained by reaction:

or

7. Composition according to claim 6, characterized in that the hydroxylated ester of acrylic acid has one of the following formulas (IV-1-1) or (IV-1-2):

- (IV-1-1): 2-hydroxyethylacrylate (HEA):

CHs = CH-C {= 0 0-CH? -CHs-0H

- (IV-1-2): 2-hydroxypropylacrylate (HPA):

8. Composition according to any one of claims 1 to 7, characterized in that the polyurethane P is prepared by a process comprising the following stages:

in amounts such that the NCO / OH molar ratio (r5) is strictly greater than 1, preferably ranges from 1.3 to 2.0, and preferably ranges from 1.5 to 1.7; and

- E ”2) the reaction of the product formed at the end of step E1) with at least one hydroxylated ester of acrylic acid as defined above, in amounts such as the OH / NCO molar ratio ( r6) is less than or equal to 1, preferably ranges from 0.90 to 1.00, and preferably ranges from 0.95 to 1.00.

9. Composition according to any one of claims 1 to 8, characterized in that the mass ratio of polyurethane (s) P / epoxy resin (s) in composition A ranges from 55/45 to 95/5, preferably from 60/40 to 90/10, advantageously from 65/35 to 85/25, and for example the ratio is 70/30.

10. Composition according to any one of claims 1 to 9, characterized in that composition A and / or composition B comprises at least one additive chosen from the group consisting of fillers, catalysts, dyes, promoters of adhesion, thixotropic agents, solvents, and mixtures thereof.

1 1. Composition according to any one of claims 1 to 10, characterized in that the molar ratio (r5) ranges from 0.5 to 2, preferably from 0.7 to 1, 3, preferably from 0.8 to 1 , 2:

with:

- x representing the sum of the number of primary amine functions (NH2) and the number of secondary amine functions (in meq per gram of the polyamine B1 and B2 mixture) present in the reagents of composition B;

- y representing the sum of the number of epoxy functions (expressed in meq per gram of epoxy resins) and the number of acrylate functions (expressed in meq per gram of polyurethane (P)) present in the reagents of composition A .

12. Composition according to any one of claims 1 to 11, characterized in that the polyamine B1 has a primary alkalinity greater than or equal to 7 meq / g, of preferably greater than or equal to 10 meq / g, preferably greater than or equal to 13 meq / g.

13. Composition according to any one of claims 1 to 12, characterized in that the polyamine B1 has the following formula (V):

N Ha-CHs-Z- C Ha- H £

(V) in which Z represents a divalent hydrocarbon radical, linear or branched, cyclic, aliphatic or aromatic, saturated or unsaturated, preferably comprising from 1 to 22 carbon atoms, said hydrocarbon radical being optionally interrupted by one or more heteroatoms chosen from -S-, -O- and / or one or more divalent tertiary amine groups -NR ^'” - with R representing a linear or branched, saturated or unsaturated alkyl group, comprising 1 to 22 carbon atoms, preferably from 1 to 18 , preferably from 1 to 14, preferably from 1 to 10 and advantageously from 1 to 6 carbon atoms.

14. Composition according to any one of claims 1 to 13, characterized in that the polyamine B1 is chosen from diethylenetriamine, 1, 10-decanediamine, 1, 12 dodecanediamine, 1, 6-hexametylenediamine, polyetherdiamines of formulas H2N-CH2-CH2-O-CH2-CH2-O-CH2-CH2-NH2 and H2N-CH2-CH2-CH2-O-CH2- CH2-O-CH2-CH2-CH2-NH2.

15. Composition according to any one of claims 1 to 14, characterized in that the polyamine B2 or the mixture of polyamines B2 has a primary alkalinity strictly less than 10.00 meq / g, preferably between 3.0 and less of 10.00 meq / g.

16. Composition according to any one of claims 1 to 15, characterized in that the polyamine B2 is chosen from the group consisting of polyetheramines, polyamidoamines, fatty dimer or trimer amines, polyethyleneimines (PEI), polyethyleneimine dendrimers, polypropyleneimines (PPI), polypropyleneimines dendrimers, polyallylamines, poly (propylene-ethylene) imines, and mixtures thereof.

17. Composition according to any one of claims 1 to 16, characterized in that it leads to an adhesive seal having: - a tensile strength greater than or equal to 3 MPa, preferably between 3 and 15 MPa, advantageously between 3 and 10 MPa, and in particular between 5 and 8 MPa; and or

18. Method of assembling two substrates by gluing, comprising:

- coating on at least one of the two substrates to be assembled with a composition obtained by mixing compositions A and B as defined according to any one of claims 1 to 16; then

- bringing the two substrates into effective contact.