WO2022152942A1

WO2022152942A1 - Epoxy adhesive composition comprising elastomer nanoparticles, and uses thereof

Info

Publication number: WO2022152942A1
Application number: PCT/EP2022/051035
Authority: WO
Inventors: Guillaume De Combarieu; Lorenzo YEE; Esther CAZARES
Original assignee: Gaztransport Et Technigaz
Priority date: 2021-01-18
Filing date: 2022-01-18
Publication date: 2022-07-21
Also published as: FR3118966B1; KR20230130731A; FR3118966A1; CN117043214A

Abstract

The invention relates to epoxy adhesive compositions comprising low glass transition temperature elastomeric core nanoparticles, a process for the preparation thereof, and uses thereof, in particular at a low temperature.

Description

Title of the invention: Epoxy adhesive composition comprising elastomer nanoparticles, and uses thereof

[0001] The invention relates to the field of storage facilities for liquefied gas comprising a sealed and thermally insulating tank, with membranes. In particular, the invention relates to the field of sealed and thermally insulating tanks for the storage and/or transport of liquefied gas at low temperature, such as tanks for the transport of Liquefied Petroleum Gas (also called LPG) having for example a temperature between -50°C and 0°C, or for the transport of Liquefied Natural Gas (LNG) at around -162°C at atmospheric pressure. These tanks can be installed on land or on a floating structure. In the case of a floating structure, the tank may be intended for the transport of liquefied gas or to receive liquefied gas used as fuel for the propulsion of the floating structure.

The present invention relates in particular to epoxy adhesive compositions comprising nanoparticles with an elastomer core at a low glass transition temperature, their method of preparation, and their uses, in particular at low temperature.

[0003] Epoxy resins are widely used as coatings, adhesives, insulating materials and matrices for composite fibers due to their stiffness, high temperature performance, chemical resistance and adhesive properties.

[0004] However, the fragility inherent in their high crosslinking density is one of the greatest limitations when they are used in demanding industrial applications.

This is why great efforts have been made in modifying epoxy resins to improve their physical properties.

[0006] The currently most widely used technique consists in introducing a low molar mass elastomer, miscible in the reactants corresponding to the epoxy resin to be reinforced. The most widely used reactive elastomer is a 1,4-butadiene- stat-1,2-butadiene-stat-acrylonitrile terminated at each end by a COOH function, designated by CTBN. However, the CTBN technique does not make it possible to effectively reinforce certain epoxy resins whose molar mass between crosslinking points is too low, in particular resins of the DGEBA type, since the improvement in hardness is accompanied by a loss of resistance.

[0007] In any case, the techniques of the prior art do not make it possible to reinforce epoxy resins when they are used at low, or even very low, temperature.

[0008] In fact, the resins reinforced by the techniques of the prior art are used for the adhesion of thermal insulation to the hull of the tanks of LNG carriers, but these resins do not have sufficient mechanical strength characteristics, in particular of the type tensile and shear strength when the outside temperature is very low, typically in an arctic ocean type environment, so as to resist the pressure of the liquefied gas moving in the vessel.

The object of the invention is to allow the preparation of a mastic which avoids the aforementioned drawbacks and which has mechanical characteristics of the tensile (detachment) and shear resistance type, when hot (about 20° C. at approximately 40° C.) and when cold (for example from approximately -25° C. to -60° C.) improved, these characteristics allowing it in particular to be used as a putty for restoring the flatness and adhesion of the elements of thermal insulation on the tanks of LNG carriers or ships using LNG (Liquefied Natural Gas) as fuel, or for all other low temperature applications.

Another object of the invention is to provide a solution which does not or very little modify the thixotropy of the epoxy adhesive to be reinforced, that is to say which allows a direct and identical transposition of the means implementation of state-of-the-art bonding.

[001 1] The mastic thus presents, thanks to the use of core-shell nanoparticles with an elastomer core at a low glass transition temperature, associated with a particular epoxy resin, according to the invention as defined below, and this, surprisingly, particularly advantageous mechanical characteristics of resistance to traction and to hot and cold shearing, allowing it thus to be used as an adhesive for insulation material for LNG carriers or ships using LNG as fuel. The thixotropy of the epoxy adhesive thus reinforced is unchanged.

Thus, according to a first aspect, the invention relates to a composition suitable as an epoxy adhesive composition comprising: a) a first part composition comprising: a1) at least one epoxy resin or a mixture of epoxy resins chosen from the group consisting of bisphenol A diglycidyl ether, optionally brominated, and its oligomers, bisphenol F diglycidyl ether, optionally brominated, and its oligomers, diethylene glycol epoxy and its oligomers, as well as combinations thereof; a2) a reactive diluent chosen from diglycidyl ethers of C4-C12 aliphatic diols; a3) core-shell type nanoparticles, the core comprising or consisting of at least one elastomer having a glass transition temperature (Tg) comprised in a range ranging from -40 to -110°C, preferably between - 70 and -110°C, the shell comprising or being made of an epoxy resin compatibilizer; a4) at least one filler or a mixture of fillers, preferably having a coefficient of thermal contraction at most equal to 50×10′ ⁶ K′ ¹ ; a5) a reactive coupling agent ensuring the chemical bond with the filler on the one hand and the hardener forming the second part on the other hand; b) a second-part composition comprising: b1) a hardener chosen from the group comprising aliphatic polyamines, amido amines, and aliphatic polyamides, in particular the reaction products between an aliphatic polyamine and a fatty acid dicarboxylic acid, in in particular the reaction products between an aliphatic polyamine and an unsaturated C12-C18 fatty acid dimer, or the reaction products between an aliphatic polyamine and a tall oil or a tall oil fatty acid dimer; b2) at least one filler or a mixture of fillers, preferably having a coefficient of thermal contraction at most equal to 50.10' ⁶ K ^-1 ; it being understood that at least one filler among filler a4) or filler b2) has a coefficient of thermal contraction at most equal to 50×10′ ⁶ K′ ¹ ; b3) a reactive coupling agent ensuring the chemical bond with the filler on the one hand and the resin forming the first part on the other hand.

Thus, the combination of core-shell type nanoparticles and at least one filler having a low coefficient of thermal contraction makes it possible to obtain a polymerized material whose coefficient of thermal contraction, also called coefficient of thermal expansion or coefficient of thermal expansion, either as low as possible and so that the variation in volume occupied by the material as a function of temperature is as low as possible.

[0014] It is noted here that the term diglycidyl can also be understood as diglycidyl.

As advantageous examples for the fillers mentioned above in a4) and b2), mention may advantageously be made of silica or glass, in the form of nano or microparticles or solid or hollow microbeads, preferably hollow.

By epoxy adhesive (or epoxy mastic), is meant in particular a composition comprising an epoxy resin (that is to say an organic compound having at least two functional groups of the oxirane type), including all or part of the oxirane groups can be cycle-opened, using a hardener. Once cured, epoxy resin is a thermosetting polymer.

[0017] The expression “chemical bond”, mentioned above, means a covalent bond.

[0018] As regards the core-shell type nanoparticles (a3 above), they are preferably poly-1,4-butadiene but one can also envisage other elastomers having a Tg of between -110°C and -40°C (-1 to 10°C <Tg<-40°C), such as for example silicones, PDMS (polydimethylsiloxane) and polyalkylsiloxane with C1 to C12 alkyl and their copolymers, a poly-1,4butylene adipate , a poly-1,4 butane sebacate, a polyalkylmethacrylate with Cs to linear C12 and their isomers or else a polyalkylacrylate with linear C3 to C6 alkyl and their isomers.

[0019] Concerning the filler or the mixture of fillers (characteristics a4 and b2 above), this filler or these fillers are advantageously hollow to maintain a low apparent density of the mixture of the first or the second part, less than 1, 5 and preferably less than 1.2, and pressure resistant to allow their implementation in a pneumatic or electric metering and static mixing machine from medium to high pressure, i.e. a pressure greater than 10 bars and up to 250 bars, without loss of the integrity of the initial loads (shape and density).

[0020] The first part composition may also be referred to as the "resin part".

[0021] The second part composition may also be referred to as the "hardener part".

Other advantageous features of the invention are briefly presented below:

According to one aspect of the invention, the core-shell type nanoparticles represent from 2 to 20% by mass of the total mass of the first part composition and of the second part composition, in particular from 4 to 18 % by mass, more particularly from 5 to 16% by mass, or from 8 to 12% by mass, for example approximately 10% by mass.

According to one aspect of the invention, the core of all or part of the nanoparticles comprises or consists of at least one elastomer chosen from silicone, polybutadiene, and polystyrene-butadiene, preferably polybutadiene.

According to one aspect of the invention, the ratio of the total mass of the first part composition to the total mass of the second part composition is between 0.5 and 1.5; in particular from 0.6 to 1.4; more particularly from 0.7 to 1.3.

According to one aspect of the invention, the second part composition comprises, in addition to the hardener and the filler, a diluent. According to one aspect of the invention, the epoxy resin compatibilizer is a compound bearing one or more epoxy functions.

According to one aspect of the invention, the reactive diluent is chosen from 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and mixtures thereof.

According to one aspect of the invention, the filler of the first-part and/or second-part composition is chosen from calcium carbonate, in particular ground or precipitated calcium carbonates, and glass microbeads.

The present invention also relates to a method for preparing the composition briefly described above, said method comprising the steps of: a) supplying a first-part composition comprising: a1) at least one epoxy resin or a mixture of epoxy resins chosen from the group comprising optionally brominated diglycidyl ether of bisphenol A and its oligomers, optionally brominated diglycidyl ether of bisphenol F and its oligomers, diethylene glycol epoxy and its oligomers, as well as their combinations; a2) a reactive diluent chosen from diglycidyl ethers of C4-C12 aliphatic diols; a3) core-shell type nanoparticles, the core comprising or consisting of at least one elastomer having a glass transition temperature (Tg) comprised in a range ranging from -40 to -110°C, preferably between - 70 and -110°C, the shell comprising or being made of an epoxy resin compatibilizer; a4) at least one filler or a mixture of fillers, preferably having a coefficient of thermal contraction at most equal to 50.10' ⁶ K ^-1 ; a5) a reactive coupling agent ensuring the chemical bond with the filler on the one hand and the hardener forming the second part on the other hand; b) providing a second part composition comprising: b1) a hardener chosen from the group comprising aliphatic polyamines, amido amines, and aliphatic polyamides, in particular the reaction products between an aliphatic polyamine and a fatty acid dicarboxylic acid, in particular the reaction products between an aliphatic polyamine and an unsaturated C12-C18 fatty acid dimer, or the reaction products between an aliphatic polyamine and a tall oil or a tall oil fatty acid dimer; b2) at least one filler or a mixture of fillers, preferably having a coefficient of thermal contraction at most equal to 50×10′ ⁶ K′ ¹ ; it being understood that at least one filler among filler a4) or filler b2) has a coefficient of thermal contraction at most equal to 50×10′ ⁶ K′ ¹ ; b3) a reactive coupling agent ensuring the chemical bond with the filler on the one hand and the resin forming the first part on the other hand; c) curing the mixture of the first part composition and the second part composition.

[0031] Preferably, the hardening is carried out at room temperature. More particularly at a temperature between 0°C and 35°C.

[0032] Preferably, the time required to obtain this hardening is between 3 and 5 days, and preferably at least 14 days.

Finally, the invention relates to a composition as succinctly defined above, for obtaining a structural adhesive, in particular a structural adhesive capable of being brought to a temperature below 0° C., for example at a temperature below -10°C, -25°C, -50°C or -60°C, in particular for the structural bonding of liquefied gas transport tanks and their thermal insulation.

[0034] More particularly, the composition defined above can be used for the production of beads of mastic making it possible to fix a tank insulation structure to the hull of a ship. Such cords deposited on the insulation structure, before installation on the hull, can have a height of 15 to 40 mm, a width of between 20 and 30 mm, preferably of the order of 25 mm. the putty has a function of repairing the structure of the hull and makes up for the flatness defects of the hull. After the installation of the insulation structure, the mastic bead, crushed between the shell and the insulation structure, has a height of 5-30 mm.

According to a particular embodiment, the core-shell type nanoparticles represent from 2 to 40% by mass of the total mass of the composition of the first part, in particular from 4 to 18% by mass, more particularly from 5 to 16% by mass, or 8 to 12% by mass, for example about 10% by mass.

The glass transition temperature (Tg or Tg) Tg of a material can be measured by any technique well known to those skilled in the art, in particular by differential thermal analysis, or DSC (Differential Scanning Calorimetry) method, which is the most commonly used static technique for this purpose, for example using a DSC Q2000 pattern analyzer supplied by TA Instruments, or by dynamic mechanical analysis, using equipment capable of performing a thermomechanical analysis (by precise measurement of the viscoelastic changes of a sample as a function of temperature, applied stress or strain), for example a Q800 DMA analyzer supplied by TA Instruments.

According to a particular embodiment, the core of all or part of the nanoparticles comprises or consists of at least one elastomer chosen from silicone, polybutadiene, and polystyrene-butadiene, in particular polybutadiene.

According to a more particular embodiment, the core of all or part of the nanoparticles comprises or consists of at least one polybutadiene elastomer, in particular a butadiene homopolymer.

According to a particular embodiment, the epoxy resin compatibilizing agent is a compound grafted onto the nanoparticle and bearing one or more epoxy functions.

According to one possibility offered by the invention, the compatibilizing agent is based on diglycidyl ether of bisphenol A or diglycidyl ether of bisphenol F, in particular diglycidyl ether of bisphenol A. The term diglycidyl can be also understood as diglycidic. [0041] The epoxy resin compatibilizing agent included in or constituting the shell of the nanoparticles is for example grafted onto the core of said nanoparticles, in particular onto the elastomer included in or constituting the core of said nanoparticles.

According to a particular embodiment, the mass content of the core of the nanoparticles is comprised from 20 to 100% of the total mass of the nanoparticles, in particular from 60 to 100%, for example approximately (+/- 5%) 90 %.

According to a particular embodiment, the nanoparticles have an average size of between 50 and 500 nm, preferably between 100 and 300 nm and on average approximately 200 nm.

The size of the fillers or particles, for example core-shell nanoparticles, calcium carbonate particles or glass microbeads, can be measured by any technique well known to those skilled in the art, depending on the size said particles in particular by dynamic light scattering, for example using a device of the Zetasizer type from Malvern, or by granulometry, for example using a device of the Mastersizer 3000 type from Malvern, or else by electron microscopy.

The nanoparticles are, for example, nanoparticles from the Kane Ace MX range from Kaneka, in particular the references MX-154 or MX-150.

According to a particular embodiment, the epoxy resin is chosen from bisphenol A diglycidyl ether and its oligomers, and bisphenol F diglycidyl ether and its oligomers, in particular from bisphenol A diglycidyl ether and its oligomers.

According to a particular embodiment, the diglycidyl ether of bisphenol A (or F) is in the form of a mixture comprising the diglycidyl ether of bisphenol A (or F) and at least one of its oligomers , with for the mixture an average number of hydroxyl groups per molecule n, n being greater than 0 and less than or equal to 3 (0 < n < 3), preferably less than or equal to 0.5, depending on the viscosity of the resin and the desired final mechanical characteristics. This number n can also be illustrated as follows, with the example of bisphenol A diglycidyl ether:

Still by way of example with diglycidyl ether of bisphenol A, a value of n equal to 0 corresponds to a molar mass Mn of 340 g.mol-1.

The diglycidyl ether of bisphenol A is for example marketed by Dow under the trade name DER 331.

[0051] The diglycidyl ether of bisphenol F is for example marketed by Dow under the trade name DER 354.

[0052] The epoxy resin can be found and used alone, or in any suitable combination with other components, for example with a reactive diluent, and/or at least one filler, and/or at least one coupling agent, as described in this description.

According to one embodiment, the reactive diluent is chosen from 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and mixtures thereof.

According to one embodiment, the filler of the first part composition is chosen from calcium carbonate, in particular ground or precipitated calcium carbonates, glass microbeads, and mixtures thereof.

According to a particular embodiment, the calcium carbonate is in the form of a powder comprising or consisting of particles whose average size is less than or equal to 50 μm, in particular less than or equal to 10 μm, more particularly less or equal to 5; 4; 3; 2; 1 or 0.5 µm.

According to a particular embodiment, the glass microbeads have a maximum size of less than 150 μm and an average size by volume of less than or equal to 60 μm. According to a particular embodiment, the first-part composition further comprises one or more pigments, in particular one or more colored pigments.

According to a particular embodiment, the hardener is chosen from the group comprising aliphatic polyamines, amido amines, and aliphatic polyamides, in particular the reaction product between an aliphatic polyamine and a fatty acid dicarboxylic acid, in in particular the reaction products between an aliphatic polyamine and an unsaturated C12-C18 fatty acid dimer, or the reaction products between an aliphatic polyamine and a tall oil or a tall oil fatty acid dimer. According to a particular embodiment, the aliphatic polyamines, in particular cycloaliphatic polyamines alone or in a mixture with the aliphatic polyamines, are chosen from aliphatic polyamines having a molar mass greater than or equal to 200 g. mol ¹ .

As advantageous examples, mention may be made of Jeffamine® D230 = 230 g/mol (gram per mole), D400 = 430 g/mol, T403 = 440 g/mol of polyether amine type, or other amines of the DETA, TETA, etc. type greater than 300 g/mol or other polyamidoamines with a mass greater than 350 g/mol.

Amido amines (or amino amides) are in particular aliphatic organic compounds—which includes cycloaliphatic compounds—carrying one or more amine functions and one or more amide functions.

[0061] The fatty acids of natural oil, in particular of tall ("Tall oil" or tallol) are also known by the abbreviation TOFA (Anglo-Swedish abbreviation of "Tall Oil Fatty Acid" or fatty acid from pine). According to a particular embodiment, the second part composition also comprises a diluent. It should be noted here that if low molar mass polyetheramines are not used, these are very fluid and do not require the additional use of a thinner when they are used as a mixture in the hardener (part 2 above).

According to a more particular embodiment, the diluent is benzyl alcohol.

According to a particular embodiment, the second part composition also comprises one or two fillers. According to a particular embodiment, the filler of the second part composition is chosen from calcium carbonate, in particular ground or precipitated calcium carbonates, and glass microbeads, alone or as a mixture.

According to a particular embodiment, the second part composition comprises, in addition to the hardener, a diluent and one or two fillers.

According to a particular embodiment, the epoxy resin represents from 20% to 80% by mass of the total mass of the first part composition, in particular from 20% to 80% by mass of the total mass of the composition of first part, more particularly from 30% to 60% by mass of the total mass of the first part composition.

According to a particular embodiment, the reactive diluent represents from 1% to 10% by mass of the total mass of the first part composition, in particular from 1.5% to 8% by mass of the total mass of the first part composition, more particularly from 2% to 4% by mass of the total mass of the first part composition.

According to a particular embodiment, the filler represents from 25% to 60% by mass of the total mass of the first part composition, in particular from 30% to 50% by mass of the total mass of the composition of first part, more particularly from 35% to 45% by mass of the total mass of the first part composition.

According to a particular embodiment, the ratio of the total mass of the first part composition to the total mass of the second part composition is between 0.5 and 1.5; in particular from 0.6 to 1.4; more particularly from 0.7 to 1.3.

According to a particular embodiment, the hardener represents from 35% to 75% by mass of the total mass of the second part composition, in particular from 40% to 70% by mass of the total mass of the composition of second part, more particularly from 40% to 60% by mass of the total mass of the second part composition. [0071] According to a particular embodiment, the filler represents from 25% to 70% by mass of the total mass of the second part composition, in particular from 30% to 65% by mass of the total mass of the composition of second part, more particularly from 40% to 60% by mass of the total mass of the second part composition.

According to a particular embodiment, the diluent represents from 0% to 10% by mass of the total mass of the first part composition, in particular from 0% to 8% by mass of the total mass of the composition of first part, more particularly from 0% to 6% by mass of the total mass of the first part composition.

According to another aspect, the present invention relates to a composition as defined above as a first part composition.

[0074] All the embodiments described with regard to the composition are applicable here, alone or in combination.

According to a particular embodiment, this mixture is produced at ambient temperature.

According to a particular embodiment, this mixing is carried out using a static, dynamic and/or manual mixer.

According to a more particular embodiment, when working in the laboratory, this mixing is carried out by alternating mechanical mixing, for example using a planetary mixer (SpeedMixer®), and manual mixing. The mechanical mixtures can be carried out for a period of 10 seconds to 1 minute, for example for about 30 seconds, for example at an angular speed of about 1800 rpm (revolution per minute). The mechanical mixing can be carried out for a period of 1 to 10 minutes, for example for approximately 3 to 5 minutes.

[0078] During an industrial production, a dynamic mixer with an anchor or butterfly rotor or even with a hook is used, possibly associated with a peripheral scraper and/or with a gravity loading of liquids and solids, possibly with a thermoregulated double jacket. so as to be able to heat the components and facilitate their mixing. The hardening of the mixture (step c) can be carried out at room temperature, for example at a temperature between approximately 5 and 40°C, preferably between 15 and 35°C and particularly between 20 and 30°C.

According to a more particular embodiment, the mixing of the first part composition and the second part composition is carried out using a mechanical mixer and/or manually.

[0081] According to a more particular embodiment, this mixing is carried out by alternating mechanical mixing, for example using a planetary mixer, and manual mixing. The last of these mixtures, or even the entire mixture, can be carried out under reduced pressure, for example under a pressure of approximately 10 to approximately 100 mbar (millibars), for example approximately 60 mbar.

The mechanical mixtures can be carried out for a period of 10 seconds to 1 minute, for example for about 30 seconds, for example at an angular speed of about 1800 rpm.

[0083] The total duration of the set of mechanical and manual mixtures is between 1 and 10 minutes, for example for approximately 3 to 5 minutes.

According to another aspect, the present invention relates to the use of a composition as defined above, for obtaining a structural adhesive.

[0085] All the embodiments described with regard to the composition are applicable here, alone or in combination.

According to a particular embodiment, said use relates to obtaining a structural adhesive capable of being brought to a temperature below 0° C., for example at a temperature below -10° C., - 25°C, -50°C or -60°C.

According to a particular embodiment, said use relates to obtaining a structural adhesive for bonding liquefied gas transport tanks, and in particular LNG carrier tanks, and thermal insulators. For wedging, the composition according to the invention serves to restore the flatness of the external load-bearing structure, i.e. the internal hull of the LNG carrier or of the ship using LNG as fuel, or of the self-supporting structure, or exoskeleton, serving as a support for the liquefied natural gas containment and insulation system, and the structural bonding between this same external load-bearing structure and the vat elements allowing containment and insulation thermal insulation of LNG, called insulation panels.

[0088] Definitions:

[0089] As used herein, the term "about" refers to a range of values within ±10% of a specific value. For example, the expression "about 20" includes values of 20 ± 10%, i.e. values from 18 to 22.

[0090] Within the meaning of the present description, the percentages refer to percentages by mass with respect to the total mass of the formulation of each part, unless otherwise indicated.

[0091] As understood here, the value ranges in the form of "x-y" or "from x to y" or "between x and y" include the limits x and y as well as the integers included between these terminals. By way of example, "1-5", or "from 1 to 5", or "between 1 and 5" designates the integers 1, 2, 3, 4 and 5. Preferred embodiments include each integer taken individually in the range of values, as well as any sub-combination of these integers. As an example, preferred values for "1 -5" may include the integers 1 , 2, 3, 4, 5, 1 -2, 1 -3, 1 -4, 1 -5, 2-3, 2 -4, 2-5, etc.

[0092] EXAMPLES

Example 1: preparation of a composition suitable as an epoxy adhesive composition according to the invention

Mixtures of core-shell nanoparticles with a polybutadiene core and a compatibilizing agent shell of epoxy resin and epoxy resin of the DGEBA and/or DGEBF type (for example from the Kaneka Kane Ace MX range, in particular the reference MX-154 or MX-150), were added and mixed with a commercial composition, for example the resin part of reference ULBM100/200 or reference Fastik 15F, comprising DGEBA, diglycidyl ether of 1,6-hexanediol (and optionally diglycidyl ether of 1,4-butanediol), fatty acid ester, calcium carbonate and glass microbeads, for example according to the following protocol:

[0095] ^1st mixing using a planetary mixer, 1 cycle at 1800 rpm, 30 s (second), room temperature; manual mixing (3-5 min);

[0096] 2 ^nd mixture using a planetary mixer, 1 cycle at 1800 rpm, 30 s; manual mixing (3-5 min);

[ ⁰⁰⁹⁷ ] 3rd mixing using a planetary mixer, 1 cycle at 1800 rpm, 30 s.

The mixture thus obtained is itself mixed with a second part composition (hardener part) reference ULBM100/200 or reference Fastik 15F, for example according to the previous protocol. The last planetary mixing was preceded by a step of putting under reduced pressure, the last two steps being thus the following:

^1st cycle: 0 rpm, 2 min, 60 mbar;

^2nd cycle: 1800 rpm, 30 s, 60 mbar.

[0099] The alternation of cycles in the planetary mixer and manual mixing can in particular make it possible to limit the increase in temperature, caused by the dissipation of energy linked to the viscosity of the mixture, and consequently limit the progress of the reaction. of polymerization for use of the final mixture. For example, the temperature at the end of mixing may be below about 40°C.

[0100] Example 2: preparation of an epoxy adhesive (cured)

[0101] For the hardening step (polymerization), a composition as obtained in Example 1 is for example placed in a mold 4 mm (millimeter) thick and left to polymerize at room temperature for at least 3 or 5 days, and preferably at least 10 days.

[0102] The tensile specimens as evaluated below are obtained by water jet cutting.

[0103] For the shear specimens ("lap shear"), two metal supports (25x100mm; roughness Ra 6.3 μm sandblasted) are bonded together with an epoxy adhesive joint according to the invention (bonding surface: 12 ,5x25mm; thickness: approx. 250pm). The mastic is left to polymerize at room temperature for at least 3 or 5 days, and preferably at least 10 days.

[01041 Example 3: Evaluation of the mechanical characteristics of resistance to traction and to hot and cold shearing of mastics of the invention

[0105] Compositions for the preparation of mastic were produced according to Example 1. The composition of the first part (in % of total mass of resin part) and of the second part (in % of total mass of hardener part) for each sample is indicated below:

[0106] Samples A, B, C and M do not include nanoparticles and are controls, outside the invention.

The NP1 and NP2 nanoparticles correspond respectively to reference nanoparticles MX-154 and MX-150 (Kaneka Kane Ace MX range). These are core-shell nanoparticles with a polybutadiene core and a compatibilizing agent shell of epoxy resin based on DGEBA.

The bisphenol A diglycidyl ether (DGEBA) used has a molar mass Mn=340-372 g.mol-1 with optional presence of DGEBA with a molar mass Mn=472 g.mol-1 (samples B and C) .

The amounts of DGEBA indicated above take into account the DGEBA carried by the nanoparticles.

[01 10] Tensile and shear specimens are produced for each sample according to Example 2.

[01 11 ] The results of the tensile and shear tests according to the ISO R527 and ISO 4587 standards respectively are presented for the said samples at three different temperatures:

[01 12] The expression “lapshear” in the result table above means “shear” or even “interlaminar shear” depending on the standard considered.

[01 13] These data show the advantageous characteristics of the mastics of the invention in terms of both tensile and shear resistance, hot and cold, compared to controls without nanoparticles. At -60° C., all the compositions of the invention (E, I, J, K, L, N, O, R, S, T, U and V) exhibit better tensile and shear properties. They have lower moduli than the reference compositions (A, B, C and M), between 3663 and 5157 MPa, vs. 5102 and 7260 MPa; have higher elongation at break, between 0.8 and 1.4%, vs. 0.5 and 0.8%; and they have higher shear stresses than the reference compositions, between 34 to 36.4 MPa, vs. 24 to 26.4 MPa.

[01 14] Among the compositions of the invention, the compositions R, O, N are the best in tension, having the lowest moduli, 3663 MPa, 3734 MPa and 4147 MPa respectively, i.e. a delta of approximately 3600 MPa compared to the reference compositions. Compositions R and O also have the greatest elongations, respectively 1.41 and 1.09%, ie a delta of about 0.9% relative to the reference compositions. Compositions L and J have the best shear breaking stresses, respectively 36 and 36.4 MPa, ie a delta of 12 MPa with respect to the reference compositions. [01 15] The results of the thermal contraction tests are carried out according to the ISO 1 1359-2 standard for the said samples:

[01 16] It can be seen that the addition of hollow glass microbeads added to sample O as defined previously, significantly reduces the value of the coefficient of thermal contraction. For example, an addition of 4% by mass of hollow glass microbeads makes it possible to reduce the coefficient of thermal contraction by 23%. An addition of 12% by mass of hollow glass microbeads makes it possible to reduce the coefficient of thermal contraction by 36%.

[01 17] It should be noted here that the applicant has carried out additional tests in-house, on test specimens of compositions according to the invention, where these compositions are tested under conditions precisely representative of their working environment - i.e. a representative test of a working environment, with a temperature between -20°C and -60°C, of a mastic placed in situ between a generally metallic supporting structure and a storage installation for a cryogenic liquid - and the compositions according to the invention have shown very satisfactory results, much better than the compositions according to the state of the art. Mainly for the sake of clarity and simplicity of apprehension of this application, these additional tests and their results are not presented here.

[01 18] In addition, tests carried out with other core-shell type nanoparticles as defined above gave almost similar results, the tests not being presented here for the sake of clarity and simplification.

Claims

[Claim 1] A composition suitable as an epoxy adhesive composition comprising: a) a first part composition comprising: a1) at least one epoxy resin or a mixture of epoxy resins selected from the group comprising the diglycidyl ether of bisphenol A , optionally brominated, and its oligomers, diglycidyl ether of bisphenol F, optionally brominated, and its oligomers, epoxy diethylene glycol and its oligomers, as well as their combinations; a2) a reactive diluent chosen from diglycidyl ethers of C4-C12 aliphatic diols; a3) core-shell type nanoparticles, the core comprising or consisting of at least one elastomer having a glass transition temperature (Tg) comprised in a range ranging from -40 to -110°C, preferably between - 70 and -110°C, the shell comprising or being made of an epoxy resin compatibilizer; a4) at least one filler or a mixture of fillers, preferably having a coefficient of thermal contraction at most equal to 50×10′ ⁶ K′ ¹ ; a5) a reactive coupling agent ensuring the chemical bond with the filler on the one hand and the hardener forming the second part on the other hand; b) a second-part composition comprising: b1) a hardener chosen from the group comprising aliphatic polyamines, amido amines, and aliphatic polyamides, in particular the reaction products between an aliphatic polyamine and a fatty acid dicarboxylic acid, in in particular the reaction products between an aliphatic polyamine and an unsaturated C12-C18 fatty acid dimer, or the reaction products between an aliphatic polyamine and a tall oil or a tall oil fatty acid dimer;

23 b2) at least one filler or a mixture of fillers, preferably having a coefficient of thermal contraction at most equal to 50.10' ⁶ K ^-1 ; it being understood that at least one filler among filler a4) or filler b2) has a coefficient of thermal contraction at most equal to 50×10′ ⁶ K′ ¹ ; b3) a reactive coupling agent ensuring the chemical bond with the filler on the one hand and the resin forming the first part on the other hand.

[Claim 2] Composition according to Claim 1, in which the core-shell type nanoparticles represent from 2 to 20% by mass of the total mass of the first part composition and of the second part composition, in particular from 4 to 18% by mass, more particularly from 5 to 16% by mass, or from 8 to 12% by mass, for example approximately 10% by mass.

[Claim 3] Composition according to Claim 1 or 2, in which the core of all or part of the nanoparticles comprises or consists of at least one elastomer chosen from silicone, polybutadiene, and polystyrene-butadiene, preferably polybutadiene .

[Claim 4] Composition according to any one of the preceding claims, in which the ratio of the total mass of the first part composition to the total mass of the second part composition is between 0.5 and 1.5; in particular from 0.6 to 1.4; more particularly from 0.7 to 1.3.

[Claim 5] A composition according to any preceding claim, wherein the second part composition comprises, in addition to the hardener and filler, a diluent.

[Claim 6] A composition according to any preceding claim, wherein the epoxy resin compatibilizer is a compound bearing one or more epoxy functions.

[Claim 7] A composition according to any preceding claim, wherein the reactive diluent is selected from 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and mixtures thereof.

[Claim 8] A composition according to any preceding claim, wherein the filler of the first part composition and/or second part is chosen from calcium carbonate, in particular ground or precipitated calcium carbonates, and glass microbeads.

[Claim 9] A method of preparing the composition according to any preceding claim, said method comprising the steps of: a) providing a first part composition comprising: a1) at least one epoxy resin or mixture of resins epoxies chosen from the group consisting of bisphenol A diglycidyl ether, optionally brominated, and its oligomers, bisphenol F diglycidyl ether, optionally brominated, and its oligomers, diethylene glycol epoxy and its oligomers, as well as their combinations; a2) a reactive diluent chosen from diglycidyl ethers of C4-C12 aliphatic diols; a3) core-shell type nanoparticles, the core comprising or consisting of at least one elastomer having a glass transition temperature (Tg) comprised in a range ranging from -40 to -110°C, preferably between - 70 and -110°C, the shell comprising or being made of an epoxy resin compatibilizer; a4) at least one filler or a mixture of fillers, preferably having a coefficient of thermal contraction at most equal to 50×10′ ⁶ K′ ¹ ; a5) a reactive coupling agent ensuring the chemical bond with the filler on the one hand and the hardener forming the second part on the other hand; b) supply of a second part composition comprising: b1) a hardener chosen from the group comprising aliphatic polyamines, amido amines, and aliphatic polyamides, in particular the reaction products between an aliphatic polyamine and a dicarboxylic acid fatty acid, in particular the reaction products between an aliphatic polyamine and an unsaturated C12-C18 fatty acid dimer, or the reaction products between an aliphatic polyamine and a tall oil or a fatty acid dimer of tall; b2) at least one filler or a mixture of fillers, preferably having a coefficient of thermal contraction at most equal to 50.10' ⁶ K ^-1 ; it being understood that at least one filler among filler a4) or filler b2) has a coefficient of thermal contraction at most equal to 50×10′ ⁶ K′ ¹ ; b3) a reactive coupling agent ensuring the chemical bond with the filler on the one hand and the resin forming the first part on the other hand; c) curing the mixture of the first part composition and the second part composition.

[Claim 10] Use of a composition according to any one of Claims 1 to 8, for obtaining a structural adhesive, in particular a structural adhesive capable of being brought to a temperature below 0° C., for example at a temperature below -10°C, -25°C, -50°C or -60°C, in particular for the structural bonding of liquefied gas transport tanks and their thermal insulation.

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