Patent Application
20250019579
The present invention relates to a composition based on (meth)acrylate monomer.
The invention also relates to the use of said composition in the repair and/or the semi-structural or structural adhesive bonding of materials in the transportation, marine, assembly, electronics or construction field.
Acrylic compositions are known reactive systems which crosslink by radical polymerization. They are used as adhesives, mastics and coatings. Radical polymerization is typically initiated by a redox system which, by means of an oxidation-reduction reaction, results in the production of radicals.
Most acrylic systems are two-component systems. The first component conventionally contains the reducing agent and the reactive monomers, and the second component contains the oxidizing agent. Once the two components have been mixed, the reducing agent induces cleavage of the O—O bond of the organic peroxide for example, and initiates polymerization.
Typically, (meth)acrylic compositions comprise a peroxide (oxidizing agent)/tertiary amine (reducing agent) redox system. However, these systems may present storage stability problems in the presence of (meth)acrylate monomer.
There is a need for novel (meth)acrylic compositions which allow a good compromise between reactivity and storage stability.
In addition, there is also a need for novel (meth)acrylic compositions with good adhesive properties.
The present invention relates to a crosslinkable two-component composition comprising:
In the context of the invention, the term “alkyl” is understood to mean a linear or branched hydrocarbon radical preferably comprising from 1 to 20 carbon atoms. Mention may be made, for example, of methyl, ethyl and propyl.
In the context of the invention, the term “C4 to C20 alkyl” is understood to mean a linear or branched alkyl comprising from 4 to 20 carbon atoms.
In the context of the invention, the term “alkenyl” is understood to mean a linear or branched hydrocarbon radical comprising at least one double bond, said radical preferably comprising from 2 to 20 carbon atoms. By way of example, mention may be made of propenyl, butenyl.
In the context of the invention, the term “alkynyl” means a linear or branched hydrocarbon radical including at least one triple bond, said radical preferably comprising from 2 to 20 carbon atoms.
In the context of the invention, the term “aryl” is understood to mean a monocyclic or bicyclic aromatic radical preferably comprising from 6 to 12 carbon atoms. Mention may be made, for example, of phenyl.
In the context of the invention, the term “arylalkyl” is understood to mean an alkyl group substituted with an aryl group, the arylalkyl group preferably comprising from 7 to 20 carbon atoms. As an arylalkyl group, mention may be made, for example, of benzyl.
In the context of the invention, the term “alkylaryl” means an aryl group substituted with an alkyl group, said alkylaryl group preferably comprising from 7 to 20 carbon atoms.
In the context of the invention, the term “heteroaryl” is understood to mean a monocyclic or bicyclic aromatic radical comprising at least one heteroatom such as for example O, S or N, and preferably comprising from 4 to 12 carbon atoms. Examples that may be mentioned include furanyl, thiophenyl, pyrrolyl, pyridinyl, indolyl or imidazolyl radicals.
In the context of the invention, the term “cycloalkyl” is understood to mean a saturated, monocyclic or polycyclic, preferably monocyclic or bicyclic, system preferably comprising from 3 to 12 carbon atoms, the rings possibly being bridged or fused in pairs, such as the cyclopropyl, cyclopentyl, cyclohexyl or else norbornyl groups.
In the context of the invention, the term “heterocycloalkyl” is understood to mean a saturated, monocyclic or polycyclic, preferably monocyclic or bicyclic, system preferably comprising from 3 to 12 carbon atoms and at least one heteroatom such as for example O or N, the rings possibly being bridged or fused in pairs.
In the context of the invention, the term “cycloalkenyl” means a monocyclic or polycyclic system comprising at least one double bond, preferably including from 3 to 12 carbon atoms, the rings possibly being fused or bridged in pairs.
In the context of the invention, the term “alkoxy” means an —O-alkyl radical.
Compound of formula (Ia) or (Ib)
Component A comprises a compound of formula (Ia) or (Ib) as defined above.
The anion X may be chosen from the group consisting of FSO3−, CF3SO3−, CF2HSO3−, Cl−, Br−, BF4−, BF3Cl−, PF6− and (F5 Ph)4B−.
In the abovementioned formulae (Ia) or (Ib), Rf may represent a haloalkyl. It may, for example, be a fluoroalkyl radical, for instance CHF2 or CH2F.
Preferably, in formulae (Ia) or (Ib), Rf represents a perfluoroalkyl, and even more preferentially CF3, C2F5, C3F7 or C4F9. According to a particularly preferred embodiment, Rf represents CF3.
The compound of formula (Ia) or (Ib) may be chosen from those wherein:
According to a preferred embodiment, component A comprises a compound of formula (Ia), in particular chosen from the group consisting of:
and even more preferentially from one of the following compounds:
The compounds of formula (Ia) may be prepared as described in WO 2016/107578. The compounds of formula (Ib) may be prepared as described in WO 2011/013307.
The total content of compound(s) of formula (Ia) or (Ib) may range from 0.05% to 5.00% by weight, preferably from 0.10% to 3.00% by weight, even more preferentially from 0.25% to 1.50% by weight relative to the total weight of the crosslinkable two-component composition.
Component A comprises at least one (meth)acrylate monomer M1 having one of the formulae (II), (III), (IV) or (V) as defined above;
In the abovementioned formula (II), G is preferably chosen from the group consisting of C4 to C20 alkyls, cycloalkyls or aryls, said alkyls, cycloalkyls and aryls being optionally substituted with an alkyl group, said group G being characterized in that it does not comprise a heteroatom. Even more preferably, G is chosen from cycloalkyls.
Among the cycloalkyls, mention may be made, for example, of isobornyl, tert-butyl cyclohexyl, trimethylcyclohexyl, dicyclopentenyl and tricyclodecyl.
Among the monomers of formula (II), mention may be made, for example, of 2-ethylhexyl (meth)acrylate, n-butyl (meth)acrylate, heptyl (meth)acrylate, 2-tert-butylheptyl (meth)acrylate, octyl (meth)acrylate, 3-isopropylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, 5-methylundecyl (meth)acrylate, dodecyl (meth)acrylate, 2-methyldodecyl (meth)acrylate, tridecyl (meth)acrylate, 5-methyltridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, 2-methylhexadecyl (meth)acrylate, heptadecyl (meth)acrylate, 5-isopropylheptadecyl (meth)acrylate, 4-tert-butyloctadecyl (meth)acrylate, 5-ethyloctadecyl (meth)acrylate, 3-isopropyloctadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, bornyl (meth)acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth)acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, and mixtures thereof.
The preferred monomers of formula (II) are the following:
Among the abovementioned monomers M1 of formula (III), mention may be made, for example, of the following monomers:
Among the abovementioned monomers M1 of formula (IV), mention may be made, for example, of the following monomers:
Among the monomers M1 of formulae (III) or (IV), the following monomers and mixtures thereof are preferred:
The total content of (meth)acrylate monomer(s) M1 in component A may be greater than or equal to 20% by weight, preferably greater than or equal to 50% by weight, and even more preferentially greater than or equal to 70% by weight relative to the total weight of said component A.
The content of (meth)acrylate monomer(s) M1 in the crosslinkable two-component composition according to the invention may range from 20% to 99% by weight, preferably from 50% to 99% by weight and even more preferentially from 75% to 99% by weight relative to the total weight of said crosslinkable two-component composition.
When component A comprises a monomer M1 having the abovementioned formula (II), and component B comprises an amine compound chosen from dihydropyridine compounds, in particular dihydropyridines having one of the formulae (VI) to (X) as defined in the present application, then component A further comprises an organic or mineral acid having a pKa or a pKa1 ranging from 0.3 to 5.0, measured in water at 25° C.
When component A comprises a monomer M1 having one of the formulae (III), (IV) or (V), and component B comprises an amine compound chosen from polyamines, then component A preferably further comprises an organic or mineral acid having a pKa or a pKa1 ranging from 0.3 to 5.0, measured in water at 25° C.
The pKa (or acidity constant) is defined by pKa=−log 10 Ka, where Ka is the acid dissociation constant which is measured in the standard manner at 25° C. The standard measurement method recommended for pKa is in particular potentiometry, and more precisely pH-metry, as described for example in Techniques de l'ingénieur [Engineering Techniques] (ref. K695 v1). This method is the most used for the determination of pKa.
The pKa1 is defined by pKa1=−log10 Ka1, where Ka1 is the acid dissociation constant of the first strongest acidity of the polyacids. Ka2 is the acid dissociation constant of the second acidity of the polyacids (where appropriate) and Ka3 is the acid dissociation constant of the third weakest acidity of the polyacids (where appropriate). Each successive acidity of a polyacid pKa1, pKa2 or pKa3 corresponds notably to decreasing values of the acidity constants Ka1, Ka2 and Ka3. The same standard potentiometric measurement indicated previously is used to measure them.
Among the organic acids, mention may be made, for example, of carboxylic acids that are optionally halogenated, phosphorus-based acids, and mixtures thereof.
Among the carboxylic acids that are optionally halogenated, mention may be made, for example, of formic acid, acetic acid, monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid, propionic acid, malic acid, fumaric acid, malonic acid, succinic acid, maleic acid, fumaric acid, citric acid, acrylic acid, methacrylic acid, cyanoacetic acid, salicylic acid, itaconic acid, benzoic acid, glycolic acid, thioglycolic acid, pyruvic acid, cinnamic acid, and mixtures thereof.
Among the mineral acids, mention may be made, for example, of phosphoric acid, phosphorous acid, methylphosphonic acid, hypophosphorous acid and mixtures thereof.
According to one embodiment, the acid has a pka or pka1 ranging from 2 to 5, and notably from 4 to 5.
According to a preferred embodiment, the acid having a pKa or pka1 ranging from 0.3 to 5 is an organic acid chosen from carboxylic acids that are optionally halogenated, and even more preferentially chosen from acrylic acid, methacrylic acid, itaconic acid, salicylic acid, benzoic acid, monochloroacetic acid, monofluoroacetic acid, dichloroacetic acid, difluoroacetic acid and mixtures thereof. Even more preferably, it is dichloroacetic acid or difluoroacetic acid.
When the two-component composition comprises one or more acids, the total content of acid(s) having a pKa or pKa1 ranging from 0.3 to 5 may range from 0.5% to 20% by weight, preferably from 0.5% to 10% by weight, more preferably from 0.5% to 5%, and even more preferentially from 0.5% to 2% by weight relative to the total weight of the crosslinkable two-component composition according to the invention.
Component A may comprise a photoinitiator P1.
The photoinitiator may be any photoinitiator known to those skilled in the art. Under the action of UV/visible radiation, the photoinitiator typically generates radicals which will be responsible for the initiation of the photopolymerization reaction, and makes it possible in particular to increase the efficiency of the photopolymerization reaction. This is, of course, chosen as a function of the light source used, according to its ability to efficiently absorb the radiation selected. It will be possible, for example, to choose the appropriate photoinitiator from its UV/visible absorption spectrum. Advantageously, the photoinitiator is appropriate for working with irradiation sources emitting in the near zone ranging from 300 to 420 nm. Advantageously, the source of UV or visible radiation may be an LED.
The photoinitiator P1 may be chosen from the group consisting of:
According to a preferred embodiment, the photoinitiator P1 is chosen from:
The total content of photoinitiator P1 may range from 0% to 5% by weight, preferably from 0% to 2% by weight, and even more preferentially from 0% to 1% by weight relative to the total weight of the crosslinkable two-component composition according to the invention.
Component B comprises at least one amine compound chosen from polyamines, dihydropyridine compounds and mixtures thereof.
The polyamines may be chosen from:
Among the polyamines comprising at least one primary amine group (B1), mention may be made of:
vi) polyamines comprising a primary amine group (—NH2) and a secondary amine group (—NHR, R being other than H) such as, for example, N-butyl-1,2-ethanediamine; N-hexyl-1,2-ethanediamine; N-cyclohexyl-1,2-ethanediamine; 4-aminomethylpiperidine; N-(2-aminoethyl) piperazine; N-methyl-1,3-propanediamine; N-butyl-1,3-propanediamine; N-(2-ethylhexyl)-1,3-propanediamine; N-cyclohexyl-1,3-propanediamine; 3-methylamino-1-pentylamine; 3-ethylamino-1-pentylamine; 3-cyclohexylamino-1-pentylamine; and mixtures thereof;
The polyamines (B1) are preferably chosen from
Among the polyamines not comprising a primary amine group (B2), mention may be made, for example, of polyamines comprising one or more secondary amine groups (—NHR, R being other than H) and/or one or more tertiary amine groups (—NR2, R being other than H).
The polyamines B2 may be chosen from the group consisting of N,N,N′,N′-tetraalkyl alkylenediamines, such as, for example, N,N,N′,N′-tetramethylethylenediamine (TEMED, CAS No.: 110-18-9), N,N,N′,N′-tetramethyl-2,2′-oxybis(ethylamine) (CAS No.: 3033-62-3), N,N,N′,N′-tetramethyltrimethylenediamine (CAS No.: 110-95-2) and N,N,N′,N′-tetramethylhexamethylenediamine (CAS No.: 111-18-2).
When the amine compound is a polyamine, then the total content of polyamine(s) may range from 0.2% to 5.0% by weight, preferably from 0.3% to 3.0% by weight, and even more preferentially from 0.4% to 1.5% by weight relative to the total weight of the crosslinkable two-component composition according to the invention.
The dihydropyridine compounds are preferably chosen from the dihydropyridines of formulae (VI) to (X) below:
The dihydropyridine compound may be chosen from those of formulae (VI) to (X) wherein:
According to a preferred embodiment, the dihydropyridine compound has the formula (VI) or (VII) as defined previously.
The dihydropyridine compound may be chosen from the following compounds:
According to a preferred embodiment, the dihydropyridine is the following compound:
The dihydropyridines may be commercially available, for instance Vanax 808 HP sold by Vanderbilt Chemicals, or may be synthesized as described, for example, in WO 2006/086602.
When the amine compound is a dihydropyridine compound, then the total content of dihydropyridine compound(s), having in particular one of the formulae (VI) to (X) as defined above may range from 0.25% to 5.0% by weight, preferably from 0.3% to 3.0% by weight, and even more preferentially from 0.4% to 1.5% by weight relative to the total weight of the crosslinkable two-component composition according to the invention.
Component B may comprise one or more (meth)acrylate monomer(s) M1 having one of the formulae (II), (III), (IV) or (V) as defined for component A.
Preferably, component B comprises the same (meth)acrylate monomer M1 as in component A.
Component B may comprise more than 50% by weight of monomer(s) M1, preferably more than 70% by weight, and even more preferentially more than 90% by weight, relative to the total weight of said component B.
Component B may in particular comprise from 60% to 99.9% by weight of monomer(s) M1, and preferably from 80% to 99.5% by weight, relative to the total weight of said component B.
The crosslinkable two-component composition according to the invention may comprise at least one additive chosen from the group consisting of catalysts, fillers, antioxidants, light stabilizers/UV absorbers, metal deactivators, antistatic agents, film-preventing agents, foaming agents, biocides, plasticizers, lubricants, emulsifiers, dyes, pigments, rheological agents, impact modifiers, adhesion promoters, accelerators, optical brighteners, flame retardants, anti-sweating agents, nucleating agents, solvents, and mixtures thereof.
These additives can be present in component A and/or component B of the composition according to the invention.
By way of example of an accelerator, saccharin may be mentioned, for example.
As examples of plasticizers that may be used, mention may be made of any plasticizer normally used in the field of adhesives, for instance epoxy resins, phthalates, benzoates, trimethylolpropane esters, trimethylolethane esters, trimethylolmethane esters, glycerol esters, pentaerythritol esters, naphthenic mineral oils, adipates, cyclohexyldicarboxylates, paraffinic oils, natural oils (optionally epoxidized), polypropylenes, polybutylenes, hydrogenated polyisoprenes, and mixtures thereof.
Use may be made, for example, of:
As examples of (thixotropic) rheological agent(s) that may be used, mention may be made of any rheological agent customarily used in the field of adhesive compositions.
Preferably, the thixotropic agents are chosen from:
The composition according to the invention may also comprise at least one organic and/or mineral filler.
The mineral filler(s) that may be used is (are) advantageously chosen so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.
As examples of mineral filler(s) that may be used, use may be made of any mineral filler(s) usually used in the field of adhesive compositions. These fillers are typically in the form of particles of diverse geometry. They may be, for example, spherical or fibrous or may have an irregular shape.
Preferably, the filler(s) is (are) chosen from the group consisting of clay, quartz, carbonate fillers, kaolin, gypsum, clays and mixtures thereof; preferentially, the filler(s) is (are) chosen from carbonate fillers, such as alkali metal or alkaline-earth metal carbonates, and more preferentially calcium carbonate or chalk.
These fillers can be untreated or treated, for example treated using an organic acid, such as stearic acid, or a mixture of organic acids predominantly consisting of stearic acid.
Use may also be made of hollow mineral microspheres, such as hollow glass microspheres, and more particularly of those made of calcium sodium borosilicate or of aluminosilicate.
The composition according to the invention may also comprise at least one adhesion promoter, preferably chosen from silanes, such as aminosilanes, epoxysilanes or acryloyl silanes, or adhesion promoters based on a phosphate ester, such as for example the 2-hydroxyethyl methacrylate phosphate ester, 2-methacryloyloxyethyl phosphate, bis(2-methacryloyloxyethyl phosphate), 2-acryloyloxyethyl phosphate, bis(2-acryloyloxyethyl phosphate), methyl-(2-methacryloyloxyethyl phosphate), ethyl-(2-methacryloyloxyethyl phosphate), a mixture of 2-hydroxyethyl methacrylate mono- and diphosphate esters.
When a pigment is present in the composition, its content is preferably less than or equal to 3% by weight, more preferably less than or equal to 2% by weight, relative to the total weight of the composition. When it is present, the pigment can, for example, represent from 0.1% to 3% by weight or from 0.4% to 2% by weight, of the total weight of the composition. The pigments may be organic or inorganic pigments.
For example, the pigment is TiO2, in particular Kronos® 2059 sold by Kronos.
The composition can comprise an amount of from 0.1% to 3%, preferably from 1% to 3%, by weight of at least one UV stabilizer or antioxidant. These compounds are typically introduced to protect the composition from degradation resulting from a reaction with oxygen which is liable to be formed by the action of heat or light. These compounds may include primary antioxidants which trap free radicals. The primary antioxidants may be used alone or in combination with other secondary antioxidants or UV stabilizers.
Mention may be made, for example, of Irganox® 1010, Irganox® B561, Irganox® 245, Irgafos® 168, Tinuvin® 328 or Tinuvin™ 770, which are sold by BASF.
According to a preferred embodiment, the two-component composition according to the invention does not comprise any peroxide.
In the composition according to the invention, the component A/component B volume ratio may range from 20/1 to 1/1, preferentially from 10/1 to 1/1.
The present invention also relates to a ready-to-use kit, comprising both component A as defined above and component B as defined above, packaged in two separate compartments. It can, for example, be a two-component cartridge.
Indeed, the composition according to the invention can be in a two-component form, for example within a ready-to-use kit, comprising both component A in a first compartment or drum and component B in a second compartment or drum, in proportions suitable for direct mixing of the two components, for example using a metering pump.
According to one embodiment of the invention, the kit additionally comprises one or more means for mixing components A and B. Preferably, the mixing means are chosen from metering pumps or static mixers with a diameter suited to the amounts used.
The present invention also relates to the use of a crosslinkable two-component composition as defined above as adhesive, mastic or coating, preferably as adhesive.
The invention also relates to the use of said composition in the repair and/or the structural or semi-structural adhesive bonding of materials in the transportation, motor vehicle (car, bus or truck), assembly, marine, electronics or construction field.
The present invention relates to a process for assembling two substrates by adhesive bonding, involving:
The crosslinking step can be carried out at a temperature of between 0° C. and 200° C., preferably between 10° C. and 150° C., preferably between 23° C. and 80° C. and in particular between 20° C. and 25° C.
The appropriate 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; substrates made of metal and composites coated with paint.
The crosslinking may be performed under electromagnetic irradiation, for instance with a UV radiation source or an LED. Electromagnetic irradiation may be performed on the adhesive bonding wafers in the case of an opaque substrate, or directly through the substrate in the case of a transparent substrate.
The crosslinking step under electromagnetic irradiation may be performed at a wavelength greater than 300 nm, preferably ranging from 360 nm to 680 nm, and even more preferentially from 360 nm to 420 nm.
The compositions according to the invention are advantageously stable on storage.
The compositions according to the invention advantageously allow a good compromise between stability on storage and high reactivity.
The compositions according to the invention advantageously exhibit, after crosslinking, good adhesive properties.
In addition, the surface of the crosslinked compositions advantageously dries rapidly and may be tack-free, thereby notably making it possible to increase the productivity of industrial processes.
All the embodiments described above may be combined with each other. In particular, the various abovementioned constituents of the composition, and notably the preferred embodiments of the composition, may be combined with each other.
In the context of the invention, the term “of between x and y” or “ranging from x to y” is understood to mean an interval within which the limits x and y are included. For example, the range “between 0% and 25%” notably includes the values 0% and 25%.
The invention is now described in the following implementation examples, which are given purely by way of illustration and should not be interpreted in order to limit the scope thereof.
The following ingredients were used:
The ingredients of component A are mixed in the proportions shown in the following table, at a temperature of 23° C., in a continuously stirred mixer and under air.
The various ingredients constituting component B are mixed in the proportions shown in the following table, at a temperature of 23° C., in a continuously stirred mixer and under air.
Component A and component B are mixed, in a volume ratio of 1:1 using a Sulzer® Mixpac mixer at ambient temperature of 23° C.
The ingredients of component A are mixed in the proportions shown in the following table, at a temperature of 23° C., in a continuously stirred mixer and under air.
The various ingredients constituting component B are mixed in the proportions shown in the following table, at a temperature of 23° C., in a continuously stirred mixer and under air.
Component A and component B are mixed, in a volume ratio of 1:1 using a Sulzer® Mixpac mixer at ambient temperature of 23° C.
The ingredients of component A are mixed in the proportions shown in the following table, at a temperature of 23° C., in a continuously stirred mixer and under air.
The various ingredients constituting component B are mixed in the proportions shown in the following table, at a temperature of 23° C., in a continuously stirred mixer and under air.
Component A and component B are mixed, in a volume ratio of 1:1 using a Sulzer® Mixpac mixer at ambient temperature of 23° C.
The exotherm is analyzed continuously using a pyrometer and by thermal imaging.
The peak time is the time required to reach the peak temperature (maximum exotherm observed during polymerization), unlike the gel time (or lag time), which is the time it takes for the sample to start polymerizing.
The time/temperature profiles were produced using an Omega OS552-V1-6 industrial infrared thermometer (Omega Engineering®, Inc., Stamford, CT) accurate to +1° C. for 2 g (about 4.0 mm height) and 0.25 g (1.4 mm height) of polymerization.
Application of composition No. 1 or No. 2 or No. 3 (obtained, respectively, in examples 1, 2, 3 by mixing components A and B using a Sulzer® Mixpac mixer) on a first glass microscope slide (25×76 mm);
The time from which it is no longer possible to separate the two slides is recorded; this is the adhesive bonding time.
As emerges from this table, compositions No. 1, No. 2 and No. 3 (according to the invention) advantageously polymerize quickly (after mixing components A and B), in view of their short peak times (24, 22 and 34 seconds, respectively).
In addition, compositions No. 1 and No. 2 and No. 3 advantageously lead to adhesive bonding having fast setting times.
Finally, it was observed that the polymer obtained after crosslinking is advantageously dry at the surface (tack free).
| Number | Date | Country | Kind |
|---|---|---|---|
| FR2112306 | Nov 2021 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/FR2022/000115 | 11/18/2022 | WO |
