WO2021089953A1

WO2021089953A1 - Epoxy resin comprising an isosorbide epoxide

Info

Publication number: WO2021089953A1
Application number: PCT/FR2020/052011
Authority: WO
Inventors: René SAINT-LOUP; Audrey SAHUT
Original assignee: Roquette Freres
Priority date: 2019-11-08
Filing date: 2020-11-05
Publication date: 2021-05-14
Also published as: EP4055077A1; KR20220099962A; FR3102987A1; FR3102987B1

Abstract

The invention relates to an epoxy prepolymer composition comprising: - (A) an isosorbide epoxide of formula (I), in which n is an integer of 0 to 300, - (B) an epoxide comprising at least 2 epoxy functions, to a curable composition comprising said epoxy prepolymer composition and a hardener (D) selected from polyamines, and to an epoxy resin formed by cross-linking said curable composition. The invention also relates to the use of said epoxy resin for the manufacture of composite materials.

Description

Title: Epoxy resin comprising isosorbide epoxy

[1] The present invention relates to the field of epoxy resins, and more particularly to a composition of epoxy prepolymers based on isosorbide epoxy, a curable composition comprising said composition of prepolymers, as well as an epoxy resin obtained by crosslinking said curable composition.

Introduction [2] Bisphenol A glycidyl ether (BADGE or DGEBA), of formula (i), is a chemical compound used as an epoxy prepolymer in the manufacture of epoxy resins. This product is now on the list of group 3 carcinogens of the IARC (International Agency for Research on Cancer), that is to say that it is a substance that cannot be classified as to its carcinogenicity for the 'man. [3] [Chem. 1]

[4] It has been known for some years that this product can be replaced by isosorbide diglycidyl ether (DGEISO), the structure of which is shown below (formula (ii)). This structure closely mimics that of the DGEBA. [5] [Chem. 2]

[6] These compounds, which belong to the more general class of bis-anhydrohexitol ethers, are now widely known and described in the literature, as is their method of synthesis.

[7] Thus, epoxy resins have been prepared from isosorbide diglycidyl ether. The main challenge is to obtain bio-based epoxy resins exhibiting performance equivalent to those obtained from petroleum-based compounds such as DGEBA.

[8] Application US 2015/0353676 A1 describes in particular epoxy resins obtained from isosorbide glycidyl ether and cis-4-cyclohexene-1, 2-dicarboxylic acid as hardener.

[9] Furthermore, application US 2018/0230261 A1 describes epoxy resins obtained from isosorbide glycidyl ether and a polyamide as hardener.

[10] Finally, application WO 2015/110758 A1 describes epoxy resins obtained from isosorbide glycidyl ether and isophorone diamine as hardener. These resins exhibit glass transition temperatures in the range of 95-100 ° C.

[11] These known bio-based solutions, however, have the drawback of leading to epoxy resins exhibiting significant water uptake, which is not compatible with use in the manufacture of composite materials.

[12] Thus, there is a need to have bio-sourced epoxy resins with a high glass transition temperature and low water uptake. Such bio-sourced epoxy resins would thus make it possible to obtain composite materials having improved impact resistance.

[13] Continuing its research through a large number of works, the Applicant company has found that a composition of epoxy prepolymers based on isosorbide epoxide and on an epoxy comprising at least 2 epoxy functions made it possible to achieve this objective.

summary [14] A first object of the present invention relates to a composition of epoxy prepolymers comprising:

- (A) an isosorbide epoxide of formula (I):

[15] [Chem. 3]

where n is an integer from 0 to 300,

- (B) an epoxy comprising at least 2 epoxy functions.

[16] A second object of the invention relates to a curable composition comprising the composition of epoxy prepolymers according to the invention and a hardener (D) chosen from polyamines.

[17] A third object of the invention relates to an epoxy resin obtained by crosslinking the curable composition according to the invention.

[18] According to another aspect, the use of an epoxide comprising at least 2 epoxy functions in a composition of epoxy prepolymers comprising an isosorbide epoxide of formula (I) is proposed: [19] [Chem. 3]

where n is an integer from 0 to 300, to decrease the water uptake of an epoxy resin obtained from said composition of epoxy prepolymers.

[20] Other characteristics and advantages of the present invention will become apparent on reading the following detailed description.

detailed description

[21] In the present patent application, the expression "between ... and ..." should be understood as including the limits.

[22] A composition of epoxy prepolymers is proposed comprising: - (A) an isosorbide epoxide of formula (I):

[23] [Chem. 3]

where n is an integer from 0 to 300,

- (B) an epoxy comprising at least 2 epoxy functions, in particular at least 3 epoxy functions.

[24] According to the present invention, the epoxy prepolymer composition comprises an isosorbide epoxide (A) monomer or polymer and having the following formula (I):

[25] [Chem. 3]

where n is an integer from 0 to 300, in particular from 0 to 10, and more particularly from 0 to 5.

[26] The isosorbide epoxide (A) can be manufactured according to the process described in application WO 2015/110758 A1.

[27] It has the advantage of being bio-based and is not an endocrine disruptor, unlike bisphenol A. It also allows high glass transition temperatures to be reached thanks to its bicycle which provides rigidity.

[28] By "isosorbide epoxide (A)" is meant a single isosorbide epoxide of formula (I) or a mixture of different isosorbide epoxides which differ from each other by the substituent R and / or the index n. When it comes to several types of isosorbide epoxide, R can vary as specified in formula (I) and / or n can vary from 0 to 300, preferably from 0 to 10, and more preferably still from 0 to 5. [29] The index n can range from 0 to 300, in particular be equal to 290, 280, 270, 260, 250, 240, 230, 220, 210, 200, 190, 180, 170, 160, 150, 140 , 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.

[30] According to one embodiment, the index n can be between 0 and 290, 0 and 280, 0 and 270, 0 and 260, 0 and 250, 0 and 240, 0 and 230, 0 and 220, 0 and 210, 0 and 200, 0 and 190, 0 and 180, 0 and 170, 0 and 160, 0 and 150, 0 and 140, 0 and 130, 0 and 120, 0 and 110, 0 and 100, 0 and 90 , 0 and 80, 0 and 70, 0 and 60, 0 and 50, 0 and 40, 0 and 30, 0 and 20, 0 and 10, 0 and 9, 0 and 8, 0 and 7, 0 and 6, 0 and 5.

[31] According to one embodiment, the index n can be between 1 and 290, 1 and 280, 1 and 270, 1 and 260, 1 and 250, 1 and 240, 1 and 230, 1 and 220, 1 and 210, 1 and 200, 1 and 190, 1 and 180, 1 and 170, 1 and 160, 1 and 150, 1 and 140, 1 and 130, 1 and 120, 1 and 110, 1 and 100, 1 and 90 , 1 and 80, 1 and 70, 1 and 60, 1 and 50, 1 and 40, 1 and 30, 1 and 20, 1 and 10,

1 and 9, 1 and 8, 1 and 7, 1 and 6, 1 and 5.

[32] According to one embodiment, the index n can be between 2 and 290, 2 and 280, 2 and 270, 2 and 260, 2 and 250, 2 and 240, 2 and 230, 2 and 220, 2 and 210, 2 and 200, 2 and 190, 2 and 180, 2 and 170, 2 and 160, 2 and 150, 2 and 140, 2 and 130, 2 and 120, 2 and 110,

2 and 100, 2 and 90, 2 and 80, 2 and 70, 2 and 60, 2 and 50, 2 and 40, 2 and 30, 2 and 20, 2 and 10,

2 and 9, 2 and 8, 2 and 7, 2 and 6, 2 and 5.

[33] According to one embodiment, the index n can be between 3 and 290, 3 and 280, 3 and 270, 3 and 260, 3 and 250, 3 and 240, 3 and 230, 3 and 220, 3 and 210, 3 and 200, 3 and 190, 3 and 180, 3 and 170, 3 and 160, 3 and 150, 3 and 140, 3 and 130, 3 and 120, 3 and 110,

3 and 100, 3 and 90, 3 and 80, 3 and 70, 3 and 60, 3 and 50, 3 and 40, 3 and 30, 3 and 20, 3 and 10,

3 and 9, 3 and 8, 3 and 7, 3 and 6, 3 and 5.

[34] According to one embodiment, the index n can be between 4 and 290, 4 and 280, 4 and 270, 4 and 260, 4 and 250, 4 and 240, 4 and 230, 4 and 220, 4 and 210, 4 and 200, 4 and 190, 4 and 180, 4 and 170, 4 and 160, 4 and 150, 4 and 140, 4 and 130, 4 and 120, 4 and 110,

4 and 100, 4 and 90, 4 and 80, 4 and 70, 4 and 60, 4 and 50, 4 and 40, 4 and 30, 4 and 20, 4 and 10, 4 and 9, 4 and 8, 4 and 7, 4 and 6, 4 and 5.

[35] According to one embodiment, the index n can be between 5 and 290, 5 and 280, 5 and 270, 5 and 260, 5 and 250, 5 and 240, 5 and 230, 5 and 220, 5 and 210, 5 and 200, 5 and 190, 5 and 180, 5 and 170, 5 and 160, 5 and 150, 5 and 140, 5 and 130, 5 and 120, 5 and 110, 5 and 100, 5 and 90, 5 and 80, 5 and 70 , 5 and 60, 5 and 50, 5 and 40, 5 and 30, 5 and 20, 5 and 10, 5 and 9, 5 and 8, 5 and 7, 5 and 6.

[36] According to one embodiment, the index n can be between 10 and 290, 10 and 280, 10 and 270, 10 and 260, 10 and 250, 10 and 240, 10 and 230, 10 and 220, 10 and 210, 10 and 200, 10 and 190, 10 and 180, 10 and 170, 10 and 160, 10 and 150, 10 and 140, 10 and 130, 10 and 120, 10 and 110, 10 and 100, 10 and 90 , 10 and 80, 10 and 70, 10 and 60, 10 and 50, 10 and 40, 10 and 30, 10 and 20.

[37] The equivalent weight of epoxy functions in isosorbide epoxide (A) can be between 120 and 1500 g / eq., In particular between 150 and 300 g / eq., More particularly between 160 and 250 g / eq. More particularly still, the equivalent weight of epoxy functions in isosorbide epoxide (A) is about 180 g / eq.

[38] The proportion of epoxy (A) in the composition of epoxy prepolymers can be between 15% and 75% by weight, in particular between 20% and 65% by weight, more particularly between 25% and 55% by weight , more particularly between 30% and 50% by weight, even more particularly between 35% and 45% by weight, relative to the total weight of the composition.

[39] The isosorbide epoxide (A) typically exhibits a Brookfield viscosity measured at 25 ° C of between 500 mPa.s and 10,000 mPa.s, in particular between 1,000 mPa.s and 8,000 mPa.s, more particularly between 2000 mPa.s and 6000 mPa.s, more particularly between 3000 mPa.s and 5000 mPa.s.

[40] According to the present invention, the epoxy prepolymer composition comprises a second epoxy (B) comprising at least 2 epoxy functions, in particular at least 3 epoxy functions.

[41] The Applicant has observed that the presence of the epoxy (B) in the composition of epoxy prepolymers according to the invention makes it possible to reduce the water uptake of the epoxy resin obtained after crosslinking with a hardener.

[42] The epoxide (B) can be chosen from polyglycidyl ethers, in particular from diglycidyl ethers, triglycidyl ethers or tetraglycidyl ethers, more particularly among triglycidyl ethers or tetraglycidyl ethers, even more particularly among triglycidyl ethers.

[43] In particular, the epoxide (B) can be chosen from the triglycidyl ether of trimethylol propane, the triglycidyl ether of trimethylol ethane, the triglycidyl ether of p-aminophenol, the triglycidyl ether of m-aminophenol, the triglycidyl ether of polyoxypropylene glycol, tetraglycidyl ether of pentaerythritol, tetraglycidyl methylene dianiline or polyglycidyl ether of sorbitol. More particularly, the epoxide (B) is the triglycidyl ether of trimethylol propane.

[44] The equivalent weight of epoxy functions in the epoxy (B) can be between 120 and 500 g / eq., In particular between 130 and 350 g / eq., More particularly between 140 and 250 g / eq. More particularly still, the number of epoxy function equivalents by weight in the epoxide (B) is approximately 160 g / eq.

[45] The proportion of epoxy (B) in the composition of epoxy prepolymers can be between 25% and 85% by weight, more particularly between 30% and 80% by weight, more particularly between 35% and 75% by weight , more particularly between 40% and 70% by weight, more particularly between 50% and 70% by weight, relative to the total weight of the composition.

[46] The mass ratio of epoxide (A) to epoxy (B) can be between 0.3 and 1.0, in particular between 0.3 and 0.8, more particularly between 0.4 and 0.7, more particularly still between 0.5 and 0.6.

[47] According to a variant of the invention, the composition of epoxy prepolymers may further comprise a reactive diluent (C) chosen from monoepoxides.

[48] The addition of a reactive diluent (C) in the composition of epoxy prepolymers according to the invention further allows to obtain an improved viscosity, in particular less than 500 mPa.s at 25 ° C.

[49] The viscosity of the composition of epoxy prepolymers according to the invention can be measured on an Anton Paar MCR501 apparatus equipped with a CP25 plane cone, by performing a shear ramp of 0 to 200 s ^-1 . [50] Examples of monoepoxides suitable as reactive diluent according to the present invention are mono glycidyl ethers. In particular, the reactive diluent (C) can be chosen from alkyl glycidyl ethers, aryl glycidyl ethers or carboxylic acid glycidyl ethers, alone or as a mixture. More particularly, the reactive diluent (C) can be chosen from alkyl glycidyl ethers.

[51] Alkyl glycidyl ethers include, for example, n-butyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether. , pentadecyl glycidyl ether, or alternatively 2-ethylhexyl glycidyl ether.

[52] The aryl glycidyl ethers include, for example, phenyl glycidyl ether, o-cresyl glycidyl ether, or alternatively 4 - (t-butyl) phenyl glycidyl ether,

[53] The glycidyl ethers of carboxylic acid include, for example, the glycidyl ether of neodecanoic acid.

[54] According to a particular embodiment, the reactive diluent (C) is chosen from a mixture of dodecyl glycidyl ether and tetradecyl glycidyl ether (C12-C14), a mixture of octyl glycidyl ether and of glycidyl ether of decyl (C8-C10), a mixture of tridecyl glycidyl ether and pentadecyl glycidyl ether (C13-C15) or a mixture of octyl glycidyl ether and tetradecyl glycidyl ether (C8-C14). More particularly, the reactive diluent (C) is a mixture of dodecyl glycidyl ether and tetradecyl glycidyl ether (C12-C14).

[55] The proportion of reactive diluent (C) in the composition of epoxy prepolymers can be between 0% and 10% by weight, in particular between 1% and 9% by weight, more particularly between 2% and 8% by weight , more particularly between 3% and 7% by weight, relative to the total weight of the composition. More particularly still, the proportion of diluent (C) in the composition of epoxy prepolymers is 5% by weight relative to the total weight of the composition. [56] The composition of epoxy prepolymers according to the invention may further comprise one or more additives, chosen from coloring agents, in particular pigments or soluble dyes, or from catalysts, such as catalysts of Lewis acid type. , tertiary amine or imidazole.

[57] The composition of epoxy prepolymers according to the invention can be prepared by simply mixing the ingredients that constitute it.

[58] Once prepared, the composition of epoxy prepolymers according to the invention can be crosslinked by contacting with a hardener to form a cured epoxy resin. Depending on the mixture of epoxy prepolymers, it may be necessary to add a catalyst to initiate or accelerate crosslinking.

[59] Thus, a second object of the invention relates to a curable composition comprising the composition of epoxy prepolymers according to the invention and a hardener (D) chosen from polyamines.

[60] By "curable composition" is meant a liquid mixture which is capable of polymerizing to form a crosslinked (cured) resin.

[61] The hardener (D) has the function of reacting with the epoxides (A) and (B), and optionally the reactive diluent (C), of the composition of epoxy prepolymers according to the invention to form an epoxy resin by crosslinking .

[62] For the purposes of the present invention, the term “polyamines” means compounds such as amines, amidoamines, polyamides and polyetheramines, comprising at least two amine functions.

[63] Thus, the hardener (D) can be chosen from:

- linear aliphatic diamines, in particular 1, 2-diaminomethane, 1, 3-diaminopropane, butane-1, 4-diamine, pentane-1, 5-diamine, 1, 6-diaminohexane, or 1 , 12-diaminododecane,

- cyclic aliphatic diamines, in particular isophorone diamine (IPDA), 4,4'-diaminodicyclohexylmethane (PACM), 1, 2-diaminocyclohexane (DACH), menthanediamine, or 1, 3-bis (aminomethyl) cyclohexane (1, 3 BAC),

- aromatic diamines, in particular 4,4'-methylenebis (2,6-diethylaniline) (MDEA), 4,4'-diaminodiphenylsulphone (DDS), 9,9-bis (4- aminophenyl) fluorene (BAFL), diethyltoluenediamine (DETDA), dimethyl thiotoluenediamine (DMTDA), 4,4'-methylenebis (2-ethylaniline) (MOEA), m-xylenediamine, m-phenylenediamine (MPDA) , or 4,4'-diaminodiphenylmethane,

- triamines, in particular diethlyene triamine (DTA),

- tetramines, in particular triethylenetetramine,

- pentamines, in particular tetraethylenepentamine,

- dimeric fatty acid diamines, in particular Priamine ® 1074 from Croda,

- polyetheramines, in particular poly (oxypropylene) diamine (Jeffamine® D-230 from Huntsman Petrochemical, LLC), or poly (oxypropylene) triamine (Jeffamine® T-403 from Huntsman Petrochemical, LLC), or

- any other polyamine, in particular polyethylene imine (e.g. Lupasol ® FG from BASF), dipropenediamine, diethylaminopropylamine, N-aminoethylpiperazine, dicyandiamide (Dicy),

- or a mixture of these.

[64] In a particular embodiment, the hardener (D) is chosen from diamines, in particular linear aliphatic diamines, cyclic aliphatic diamines or aromatic diamines. In particular, the hardener (D) is chosen from 4,4'-methylenebis (2,6-diethylaniline) (MDEA), isophorone diamine (IPDA), 4,4'-diaminodicyclohexylmethane (PACM), 1 , 2-diaminocyclohexane (DACH), 4,4'-diaminodiphenylsulphone (DDS), 9,9-bis (4-aminophenyl) fluorene (BAFL), or m-phenylenediamine (MDPA). More particularly, the hardener (D) is chosen from 4,4'-methylenebis (2,6-diethylaniline) (MDEA), 4,4'-diaminodicyclohexylmethane (PACM), 1,2-diaminocyclohexane (DACH), 4,4'-diaminodiphenylsulphone (DDS), 9,9-bis (4-aminophenyl) fluorene (BAFL) or m-phenylenediamine (MDPA).

[65] The equivalent weight of -NH functions in the hardener (C) can be between 15 and 150 g / eq., More particularly between 20 and 120 g / eq., More particularly still between 25 and 90 g / eq. [66] The epoxy / amine system formed by the curable composition according to the invention can be stoichiometric or contain an excess of amine functions or an excess of epoxy functions.

[67] The ratio between the number of -NH groups of the hardener (D) on the number of epoxy groups of the composition of epoxy prepolymers can thus be between 1: 2 and 2: 1, in particular between 2: 3 and 3 : 2, more particularly is equal to 1: 1.

[68] After bringing the composition of epoxy prepolymers according to the invention into contact with the hardener (D), the epoxides (A) and (B), and optionally the diluent (C), present in the composition of epoxy prepolymers according to the invention react with the hardener (D) so as to crosslink the composition of epoxy prepolymers and obtain a cured epoxy resin.

[69] Thus, the invention also relates to an epoxy resin obtained by crosslinking the curable composition according to the invention.

[70] The initiation of crosslinking can occur spontaneously or require heating or the presence of a catalyst in the curable composition.

[71] In particular, the curable composition according to the invention can be crosslinked at a temperature between 5 ° C and 260 ° C.

[72] More particularly, the curable composition according to the invention can be subjected to a curing cycle optionally comprising a period at room temperature followed by one or more periods of heating at increasing temperatures and between 30 ° C and 260 °. vs.

[73] This curing cycle can optionally be carried out in the presence of a catalyst of Lewis acid, tertiary amine or imidazole type in order to initiate and / or accelerate the crosslinking.

[74] The cured epoxy resin thus obtained from the curable composition according to the present invention exhibits a high glass transition temperature (Tg), that is to say greater than or equal to 90 ° C, in particular between 90 ° C. ° C and 210 ° C, more particularly between 90 ° C and 200 ° C. [75] The glass transition temperature of the cured epoxy resin can be determined by techniques known to those skilled in the art, in particular by differential scanning calorimetry (DSC), for example by means of a DSC Q20 apparatus in a crucible. opened with a temperature cycle from 0 ° C to 200 ° C at 10 ° C / min, or by dynamic mechanical analysis (DMA), for example by means of an MCR 501 Anton Paar rheometer equipped with torsion jaws at a regulated temperature of 25 ° C to 250 ° C at 5 ° C / min and a frequency of 1 Hz.

[76] Furthermore, the hardened epoxy resin thus obtained from the curable composition according to the present invention exhibits low water uptake, that is to say less than or equal to 10%, in particular between 0.1 % and 10%, more particularly between 0.5% and 9.5%, preferably between 1% and 9%, more particularly between 1.5% and 8.5%, even more particularly between 2% and 8%.

[77] The water uptake of the cured epoxy resin can be determined by techniques known to those skilled in the art, in particular by measuring the rate of swelling of the sample immersed in water at room temperature.

[78] These characteristics give the cured epoxy resin obtained an improved chemical and mechanical resistance compared to the materials obtained with the bis-anhydrohexitol ethers according to the prior art.

[79] Thus, according to another aspect, the invention relates to the use of an epoxide comprising at least 2 epoxy functions in a composition of epoxy prepolymers comprising an isosorbide epoxide of formula (I):

[80] [Chem. 3]

where n is an integer from 0 to 300, to decrease the water uptake of an epoxy resin obtained from said composition of epoxy prepolymers comprising an isosorbide epoxide of formula (I).

[81] The epoxy resin according to the invention can thus be used for the manufacture of composite materials, in particular composite materials of the resin / fiber type, the fibers of which are glass fibers, carbon fibers, basalt fibers, natural (flax, hemp ) and various minerals.

[82] Composite materials made with the epoxy resin according to the invention have the particularity of being biobased and of having equivalent, or even improved, impact resistance compared to composite materials made with non-biobased epoxy resins. [83] The composite materials according to the invention can be useful for producing high-performance structural parts, such as, for example, in the automotive field, the nautical field, the aeronautical field or in the field of sports and recreation.

Examples [84] Abbreviations:

AHEW: equivalent weight of -NH BAFL functions: 9,9-bis (4-aminophenyl) fluorene DACH: 1,2-diaminocyclohexane DDS: 4,4'-diaminodiphenylsulphone DGEBA: diglycidyl ether of bisphenol A DGEISO: diglycidyl ether of isosorbide DSC: differential scanning calorimetry EEW: equivalent weight of epoxy functions IPDA: isophorone diamine MDEA '-methylenebis (2,6-diethylaniline)

MPDA: m-phenylenediamine PACM: 4,4'-diaminodicyclohexylmethane Tg: Glass transition temperature TGETMP: trimethylolpropane triglycidyl ether

[85] Production of epoxy resins from compositions according to the prior art. Epoxy resins have been prepared from compositions of isosorbide diglycidyl ethers crosslinked in the presence of an amine hardener.

The amount of hardener introduced is calculated so that the ratio of the number of -NH groups to the number of epoxy groups is equal to 1.

[86] Counter-example 1 5g of isosorbide epoxy (EEW = 180g / eq) are mixed with 2.15g of MDEA (AHEW = 77.62g / eq) before following the following cooking cycle of 1 h at 80 ° C then 2 hours at 180 ° C.

[87] Counterexample 2

5g of isosorbide epoxy (EEW = 180g / eq) are mixed with 1.18g of IPDA (AHEW = 42.5g / eq) before following the following cooking cycle of 1 hour at 80 ° C then

2h at 180 ° C.

[88] Counterexample 3

5g of isosorbide epoxy (EEW = 180g / eq) are mixed with 1.46g of PACM (AHEW = 52.59g / eq) before following the following cooking cycle of 1 h at 80 ° C then 2 h at 180 ° C. [89] Counterexample 4

5g of isosorbide epoxy (EEW = 180g / eq) are mixed with 0.79g of DACH (AHEW = 28.55g / eq) before following the following cooking cycle of 1 h at 80 ° C then 2 h at 180 ° C. [90] Counterexample 5

5g of isosorbide epoxy (EEW = 180g / eq) are mixed with 1.72g of DDS (AHEW = 62g / eq) before following the following cooking cycle of 1 h at 80 ° C then 2 h at 180 ° C .

[91] Counter-example 6 5g of isosorbide epoxy (EEW = 180g / eq) are mixed with 2.42g of BAFL (AHEW = 87.12g / eq) before following the following cooking cycle from 1 h to 80 ° C then 2 hours at 180 ° C.

[92] Counterexample 7

5g of isosorbide epoxy (EEW = 180g / eq) are mixed with 0.75g of MPDA (AHEW = 27g / eq) before following the following cooking cycle of 1 h at 80 ° C then 2 h at 180 ° vs.

[93] The epoxy resins obtained were characterized, in particular by determining their rate of swelling in water and their glass transition temperature. [94] The swelling rates in water are determined by measuring the swelling rate of the sample immersed for 96 hours in water at room temperature, according to the following formula:

[95] [Math. 1]

[96] Glass transition temperatures (Tg) determined by differential scanning calorimetry (DSC) under the following conditions:

Camera: DSC Q20

Between 10 and 20 mg of product are placed in an open crucible. A Heat / Cool / Heat Cycle is carried out from 0 ° C to 200 ° C at 10 ° C / min. [97] The characterizations of counter-examples 1 to 6 are presented in Table 1.

[98] [Table 1]

[99] Production of epoxy resins from compositions according to the invention Epoxy resins have been prepared from compositions of epoxy prepolymers according to the invention comprising isosorbide glycidyl ether, an epoxide comprising at least 2 epoxy functions and optionally a reactive diluent, crosslinked in the presence of a polyamine-type hardener.

[100] Example 1 1, 75g of isosorbide epoxy (EEW = 180g / eq), 3g of trimethylolpropane triglycidyl ether (EEW = 160g / eq) and 0.25g of C12-C14 are mixed with 2.29g of MDEA (AHEW = 77.62g / eq) before following the following cooking cycle of 1 h at RT + 1 h at 80 ° C + 1 h at 130 ° C + 1 h at 160 ° C + 2 h at 200 ° C .

[101] Example 2 1, 75g of isosorbide epoxy (EEW = 180g / eq) and 3.25g of trimethylolpropane triglycidyl ether (EEW = 160g / eq) are mixed with 0.84g of DACH (AHEW = 28.55g / eq) before following the following cooking cycle of 2h at RT + 1 h at 80 ° C + 1 h at 130 ° C + 2h at 160 ° C. [102] Example 3

1.75g of isosorbide epoxy (EEW = 180g / eq), 3g of trimethylolpropane triglycidyl ether (EEW = 160g / eq) and 0.25g of C12-C14 are mixed with 1.83g of DDS (AHEW = 62g / eq) before following the following cooking cycle of 1 h at 130 ° C + 1 h at 160 ° C + 3 h at 180 ° C.

[103] Example 4

1.75g of isosorbide epoxy (EEW = 180g / eq), 3g of trimethylolpropane triglycidyl ether (EEW = 160g / eq) and 0.25g of C12-C14 are mixed with 2.57g of BAFL (AHEW = 87, 12g / eq) before following the following cooking cycle of 1 h at 140 ° C + 1 h at 180 ° C.

[104] Example 5

1.75g of isosorbide epoxy (EEW = 180g / eq), 3g of trimethylolpropane triglycidyl ether (EEW = 160g / eq) and 0.25g of C12-C14 are mixed with 1.56g of PACM (AHEW = 53g / eq) before following the following cooking cycle of 1 h at 140 ° C + 1 h at 180 ° C.

[105] Example 6

1.75g of isosorbide epoxy (EEW = 180g / eq), 3g of trimethylolpropane triglycidyl ether (EEW = 160g / eq) and 0.25g of C12-C14 are mixed with 0.80g of MPDA (AHEW = 27g / eq) before following the following cooking cycle of 1 h at 140 ° C + 1 h at 180 ° C.

[106] The epoxy resins obtained were characterized, in particular by determining their rate of swelling in water and their glass transition temperature.

[107] The swelling rates in water are determined by measuring the swelling rate of the sample immersed for 96 hours in water at room temperature, according to the formula presented above.

[108] Glass transition temperatures (Tg) determined by differential scanning calorimetry (DSC) under the following conditions:

Camera: DSC Q20 Between 10 and 20 mg of product are placed in an open crucible. A Heat / Cool / Heat Cycle is carried out from 0 ° C to 200 ° C at 10 ° C / min.

[109] The characterizations of Examples 1 to 4 according to the invention are presented in Table 2. [110] [Table 2]

[111] These results show that the epoxy resins obtained from the compositions of epoxy prepolymers according to the invention exhibit, on the one hand, glass transition temperatures higher or equivalent to those of the resins obtained from the compositions of epoxy prepolymers according to the invention. the prior art, and on the other hand, water swelling rates lower than those of the resins obtained from the epoxy prepolymer compositions according to the prior art.

Claims

[Claim 1] A composition of epoxy prepolymers comprising: - (A) an isosorbide epoxide of formula (I): [Chem. 3]

where n is an integer from 0 to 300,

- (B) an epoxy comprising at least 3 epoxy functions.

[Claim 2] Composition according to Claim 1, characterized in that the equivalent weight of epoxy functions in the isosorbide epoxide (A) is between 120 and 1500 g / eq, in particular between 150 and 300 g / eq. , more particularly between 160 and 250 g / eq.

[Claim 3] Composition according to any one of claims 1 and 2, characterized in that the proportion of epoxy (A) in the epoxy resin composition is between 15% and 75% by weight, in particular between 20% and 65% by weight, more particularly between 25% and 55% by weight, more particularly between 30% and 50% by weight, even more particularly between 35% and 45% by weight, relative to the total weight of the composition .

[Claim 4] Composition according to any one of claims 1 to 3, characterized in that the epoxy (A) has a Brookfield viscosity measured at 25 ° C of between 500 mPa.s and 10,000 mPa.s, in particular between 1000 mPa.s and 8000 mPa.s, more particularly between 2000 mPa.s and 6000 mPa.s, more particularly between 3000 mPa.s and 5000 mPa.s.

[Claim 5] Composition according to any one of claims 1 to 4, characterized in that the epoxide (B) is chosen from polyglycidyl ethers, in particular from triglycidyl ethers or tetraglycidyl ethers.

[Claim 6] Composition according to any one of claims 1 to 5, characterized in that the equivalent weight of epoxy functions in the epoxide (B) is between 120 and 500 g / eq., Preferably between 130 and 350. g / eq., more preferably between 140 and 250 g / eq.

[Claim 7] Composition according to any one of claims 1 to 6, characterized in that the proportion of epoxy (B) in the epoxy resin composition is between 25% and 85% by weight, more particularly between 30% and 80% by weight, more particularly between 35% and 75% by weight, more particularly between 40% and 70% by weight, more particularly between 50% and 70% by weight, relative to the total weight of the composition.

[Claim 8] Composition according to any one of claims 1 to 7, characterized in that the mass ratio of the epoxide (A) to the epoxide (B) is between 0.3 and 1.0, in particular between 0.3 and 0.8, more particularly between 0.4 and 0.7, more particularly still between 0.5 and 0.6.

[Claim 9] Composition according to any one of claims 1 to 8, characterized in that it further comprises a reactive diluent (C) chosen from mono-epoxides.

[Claim 10] Composition according to any one of claims 1 to 9, characterized in that the reactive diluent (C) is chosen from mono glycidyl ethers, in particular alkyl glycidyl ethers, aryl glycidyl ethers or glycidyl ethers of carboxylic acid.

[Claim 11] Composition according to any one of claims 1 to 10, characterized in that the proportion of diluent (C) in the epoxy resin composition is between 0% and 10% by weight, in particular between 1% and 9% by weight, more particularly between 2% and 8% by weight, more particularly between 3% and 7% by weight, relative to the total weight of the composition.

[Claim 12] Composition according to any one of claims 1 to 11, characterized in that it further comprises one or more additives, chosen from coloring agents, in particular pigments or soluble dyes, or from catalysts, such as catalysts of the Lewis acid, tertiary amine or imidazole type.

[Claim 13] A curable composition comprising the epoxy prepolymer composition according to any one of claims 1 to 12 and a hardener (D) selected from polyamines.

[Claim 14] A curable composition according to claim 13, characterized in that the hardener (D) is chosen from:

- aromatic diamines, in particular 4,4'-methylenebis (2,6-diethylaniline) (MDEA), 4,4'-diaminodiphenylsulphone (DDS), 9,9-bis (4-aminophenyl) fluorene (BAFL) ), diethyltoluenediamine (DETDA), dimethyl thiotoluenediamine (DMTDA), 4,4'-methylenebis (2-ethylaniline) (MOEA), m-xylenediamine, m-phenylenediamine (MPDA), or 4, 4'- diaminodiphenylmethane,

- triamines, in particular diethlyene triamine (DTA),

- tetramines, in particular triethylenetetramine,

- pentamines, in particular tetraethylenepentamine,

- dimeric fatty acid diamines, in particular Priamine ® 1074 from Croda,

- polyetheramines, in particular poly (oxypropylene) diamine (Jeffamine® D-230 from Huntsman Petrochemical, LLC), or poly (oxypropylene) triamine (Jeffamine® T-403 from Huntsman Petrochemical, LLC), or - any other polyamine, in particular polyethylene imine (eg Lupasol ® FG from BASF), dipropenediamine, diethylaminopropylamine, N-aminoethylpiperazine, or dicyandiamide (Dicy),

- or a mixture of these.

[Claim 15] A curable composition according to any one of claims 13 and 14, characterized in that the hardener (D) is chosen from diamines, in particular linear aliphatic diamines, cyclic aliphatic diamines and aromatic diamines, more particularly 4,4'-methylenebis (2,6-diethylaniline) (MDEA), isophorone diamine (IPDA), 4,4'-diaminodicyclohexylmethane (PACM), 1, 2-diaminocyclohexane (DACH), 4, 4'-diaminodiphenylsulphone (DDS), 9,9-bis (4-aminophenyl) fluorene (BAFL) or m-phenylenediamine (MDPA).

[Claim 16] Curable composition according to any one of claims 13 to 15, characterized in that the equivalent weight of - NH functions in the hardener (D) is between 15 and 150 g / eq., More particularly between 20 and 120 g / eq., More particularly still between 25 and 90 g / eq.

[Claim 17] Curable composition according to any one of claims 13 to 16, characterized in that the ratio between the number of groups - NH of the hardener (D) on the number of epoxy groups of the composition of epoxy prepolymers is between 1: 2 and 2: 1, in particular between 2: 3 and 3: 2, more particularly equal to 1: 1.

[Claim 18] An epoxy resin obtained by crosslinking the curable composition according to any one of claims 13 to 17.

[Claim 19] Epoxy resin according to claim 18, characterized in that the crosslinking is carried out at a temperature between 5 ° C and 260 ° C.

[Claim 20] Use of an epoxy comprising at least 2 epoxy functions in a composition of epoxy prepolymers comprising an isosorbide epoxide of formula (I):

[Chem. 3]