Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
  • C08F4/32—Organic compounds
  • C08F4/34—Per-compounds with one peroxy-radical
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
  • C08F4/32—Organic compounds
  • C08F4/38—Mixtures of peroxy-compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica

Definitions

• the present invention relates to a composition
• a composition comprising at least one (meth) acrylic monomer, optionally at least one (meth) acrylic polymer (in particular a copolymer.
• the invention also relates to the use of at least one organic peroxide chosen from hemi-peroxyacetals for the polymerization of a composition comprising at least one acrylic monomer and optionally at least one acrylic polymer (in particular one. acrylic copolymer).
• the invention also relates to the use of the composition, as defined above, for the manufacture of acrylic or methacrylic, thermoplastic, thermoset or composite resins.
• the present invention also relates to a process for manufacturing thermoplastic, thermoset or composite parts from the polymerization of the composition as defined above as well as to the parts obtained themselves.
• (meth) acrylic resins are often used to make molded or cast articles, with or without filler, as well as composites.
• the composition containing the mixture of (meth) acrylic monomers and optionally of (meth) acrylic polymers in the presence of polymerization initiators can be poured into a mold, then polymerized and hardened during a more or less gradual increase. of the temperature. Once the polymerization is complete, a resin is obtained which can then undergo different types of treatment depending on the desired applications.
• the composition may just as well be poured between two molds so as to recover, after polymerization, the corresponding resin.
• the polymerization is conventionally carried out using radical initiators such as azoics, or else organic peroxides. Azo initiators, the most widespread of which is solid, AIBN, give off nitrogen which may be undesirable in films or transparent plates and are liable to release very toxic decomposition products. In addition, they must be stored at controlled temperature.
• organic peroxides regularly used as polymerization initiators, are generally very unstable species when they are heated. In fact, in the event of an uncontrolled rise in temperature, certain organic peroxides can undergo a self-accelerated exothermic decomposition and risk igniting and / or exploding violently. Such behavior therefore proves to be hardly compatible, in particular with the rules in force for the transport and storage of hazardous materials in places intended for the production of resins.
• cold peroxide any composition based on peroxide having a maximum transport temperature as defined above.
• aromatic peroxides of the diacyls or peresters type It has also been proposed to use aromatic peroxides of the diacyls or peresters type.
• alkyl hydroxyperoxides such as tert-butyl hydroperoxide have also been considered.
• one of the objectives of the present invention is to overcome the aforementioned drawbacks, that is to say to substitute the organic peroxides, commonly used during the radical polymerization of acrylic monomers, with other initiators. polymerization which are capable of being stored and transported alone or as a mixture in complete safety without degrading the optical and mechanical properties of the products obtained. [025] In other words, there is a real need to provide other polymerization initiators which are capable of being stored and transported, alone or mixed, under temperature conditions strictly above 20 ° C. while allowing the manufacture of products having good optical and mechanical properties, in particular in terms of transparency, low coloration and wear.
• the present invention relates to a composition
• a composition comprising: a) at least one (meth) acrylic polymer, b) optionally at least one (meth) acrylic monomer, and c) at least one organic peroxide chosen from hemiperoxyacetals, d) at least one additional peroxide, preferably chosen from the group consisting of peroxyacetals.
• the present invention also relates to a composition
• a composition comprising: a) at least one (meth) acrylic polymer, b) optionally at least one (meth) acrylic monomer, and c) at least one organic peroxide chosen from hemiperoxyacetals, d ) at least one additional peroxide, preferably chosen from the group consisting of peroxyacetals, said composition having a dynamic viscosity of between 10 mPa.s and 10,000 mPa.s at 25
• Hemi-peroxyacetals have the advantage of having, alone or as a mixture, with other peroxides and / or phlegmatizers, reactive or not, a maximum transport temperature, also called control temperature, strictly greater than 20 ° C in accordance with the recommendations for the transport of dangerous goods, United Nations (UN), 19th edition of 2015, in section 2.5.3.2.4 relating to organic peroxides.
• a maximum transport temperature also called control temperature
• Hemi-peroxyacetals also have the advantage of being able to be used alone, that is to say in the undiluted state, which makes it possible to dispense, on the one hand, from the use of 'a non-polymerizable solvent, such as oils, imposed for safety reasons and likely to have a negative impact on the optical and mechanical qualities of the resins obtained and, on the other hand, the use of a polymerizable solvent, such as than an acrylic monomer, likely to increase the risks of transport or storage of an onset of polymerization which is not temperature-regulated.
• a non-polymerizable solvent such as oils
• the hemi-peroxyacetals make it possible to dispense with the establishment of any type of storage dedicated to the polymerizable solvent or not on the peroxide production sites (or of a device intended to store a solvent) which leads to significant space savings and reduced maintenance costs.
• the peroxides according to the invention make it possible to overcome any type of problem associated with the use of solvents which may or may not be polymerizable.
• the peroxides according to the invention make it possible to dispense with the usual phlegmatizers of peroxides such as hydrocarbons, such as isododecane, mineral oils, esters such as liquid phthalates, ethylbenzene.
• hydrocarbons such as isododecane, mineral oils, esters such as liquid phthalates, ethylbenzene.
• the hemi-peroxyacetals can be packaged in a greater variety of containers or devices than the conventional thermally unstable peroxides and liable to decompose during an uncontrolled increase in temperature.
• the peroxides envisaged can initiate the polymerization of the (meth) acrylic monomers without necessarily having recourse to systems intended to activate them chemically, such as ferrous ions, which avoids the risks of coloring the resins.
• the products obtained, following the polymerization of a composition comprising one or more (meth) acrylic monomers and / or (meth) acrylic polymers in the presence of one or more hemi-peroxyacetals and a Additional peroxide, in particular a peroxyacetal, exhibit good optical and mechanical properties.
• the products obtained are transparent (in the absence of inorganic filler), weakly colored or even colorless, and are resistant to wear.
• composite is understood to mean a multicomponent material comprising several different phase domains, among which at least one type of phase domain is a continuous phase and in which at least one component is a. polymer.
• the abbreviation "phr” denotes parts per hundred parts of organic composition (that is to say the (meth) acrylic monomer and the possible (meth) acrylic polymer when the latter is present).
• 1 phr of initiator in the composition means that 1 kg of initiator is added to 100 kg of organic composition.
• the abbreviation "ppm” denotes parts by weight per million of organic composition.
• 1000 ppm of a compound in the composition means that 0.1 kg of compound is present in 100 kg of organic composition (that is to say the (meth) acrylic monomer and the possible (meth) acrylic polymer when the latter is present).
• the term "the sum by weight of the (meth) acrylic monomer and of the possible (meth) acrylic polymer” is understood to mean the weight of the (meth) acrylic monomer or monomers when several monomers Different (meth) acrylics are present, to which is added the weight of the (meth) acrylic polymer when it is present.
• thermoplastic is understood to mean an uncrosslinked resin.
• a thermoplastic resin allows repair, remodeling and recycling compared to thermoset resins.
• a thermoplastic resin becomes liquid or less viscous when heated and which can take on new forms by application of heat and pressure.
• thermoset means a crosslinked resin.
• thermosetting resin once hardened, retains a final shape.
• thermosetting means a resin capable of being crosslinked.
• the term “composite” is understood to mean a macroscopic combination of two or more immiscible materials.
• the composite material consists of at least one material which forms the matrix, that is to say a continuous phase which ensures the cohesion of the structure, and a reinforcing material.
• the objective of using a composite material is to obtain performance qualities which cannot be obtained with each of its constituents when used separately.
• the composite material can be thermoplastic or thermoset, preferably is thermoplastic.
• the term “between x to y” means that the upper and lower limits of this range are included, which is equivalent to at least x and up to including. [047]
• the expression “at least one” is equivalent to the expression “one or more”.
• the at least one organic peroxide used in accordance with the present invention is chosen from the group consisting of hemiperoxyacetals.
• hemi-peroxyacetal means a compound of general formula (R3) (R4) C (-OR I ) (- OOR2), in which:
• R 1 represents an alkyl group, linear or branched, preferably C 1- C 12 , preferably C 1- C 4 , more preferably C 1, or a cyclo alkyl group with R2,
• R2 represents an alkyl group, linear or branched, preferably C 1- C 12 , preferably C 4- CI 2 , more preferably C 5 , or a cyclo alkyl group with RI,
• R3 represents a hydrogen or an alkyl group, linear or branched, preferably C1-C12, more preferably C4-C12, or a cycloalkyl group with R 4 ,
• R 4 represents a hydrogen or an alkyl group, linear or branched, preferably C 1- C 12 , more preferably C 4- C 12 , or a cyclo alkyl group with R 3.
• R3 forms a cycloalkyl group with R4.
• R4 is an alkyl group, linear or branched, preferably C 1- C 12 , more preferably C 4- C 12 .
• the organic peroxide is chosen from the group consisting of hemi-peroxyacetals having a half-life temperature at one minute and at atmospheric pressure ranging from 125 ° C to 160 ° C, preferably ranging from 130 ° C to 155 ° C and more preferably ranging from 140 ° C to 150 ° C.
• the term "half-life temperature at one minute” represents the temperature at which half of the organic peroxide has decomposed in one minute and at atmospheric pressure. Conventionally, the "one minute half-life temperature” is measured in n-decane or n-dodecane.
• the organic peroxide according to the invention is chosen from the group consisting of hemi-peroxyacetals corresponding to the following general formula (I):
• - Ri represents an alkyl group, linear or branched, in
• R 2 represents a branched C 4 -C 12 , preferably C 5 , alkyl group
• - n denotes zero or an integer varying from 1 to 3
• R3 represents an alkyl group, linear or branched, C 1- C 3 .
• R 1 represents an alkyl group, linear, in particular in C1-C2, more preferably in Ci.
• R2 represents an alkyl group branched C 4- C 5, more preferably C 5.
• n denotes zero.
• R3 represents a linear or branched, C1-C2, more preferably C1, alkyl group.
• R 1 represents an alkyl group, linear or branched, in C1-C2, R2 represents a branched alkyl group in C4-C5 and n denotes zero.
• RI represents a C1 alkyl group
• R2 represents a branched C 5 alkyl group
• n denotes zero.
• the organic peroxide (s) is or are chosen from the group consisting of 1-methoxy-1-tert-amylperoxycyclohexane (TAPMC), 1-methoxy-lt-butylperoxycyclohexane (TBPMC), l-methoxy -lt-amylperoxy-3,3,5-trimethylcyclohexane, l-methoxy-lt-butylperoxy-3,3,5-trimethylcyclohexane, 1-ethoxy-lt-amylperoxycyclohexane, 1- ethoxy-lt-butylperoxycyclohexane, 1-ethoxy-lt-butyl-3,3,5-peroxycyclohexane, and mixtures thereof.
• TCPMC 1-methoxy-1-tert-amylperoxycyclohexane
• TBPMC 1-methoxy-lt-butylperoxycyclohexane
• TBPMC 1-meth
• the organic peroxide according to the invention is 1-methoxy-1-tert-amylperoxycyclohexane (TAPMC).
• TAPMC 1-methoxy-1-tert-amylperoxycyclohexane
• the half-peroxyacetal (s) present (s) a half-life temperature at 10 hours, denoted HLT 10h, greater than or equal to 60 ° C and less than or equal to 130 ° C.
• the organic peroxide content is between 0.1 phr and 15 phr, preferably between 0.5 and 15 phr, preferably between 0.5 and 10 phr, more preferably between 1 and 5 phr, more preferably between 1.5 and 2.5 phr relative to the sum of the at least one (meth) acrylic monomer and the optional at least one (meth) acrylic polymer.
• organic peroxide content is understood to mean the sum of the content of hemi-peroxyacetal and of additional organic peroxide (s).
• the ratio by weight between the at least one hemiperoxyacetal and the at least one additional organic peroxide is between 99: 1 and 30:70, preferably between 50:50 and 99: 1, more preferably still. between 80:20 and 99: 1.
• composition of the present invention comprises one or more distinct additional organic peroxide (s).
• said additional peroxide (s) is (are) chosen from the group consisting of peroxyacetals.
• the additional peroxide (s) is or are chosen from the group consisting of peroxyacetals corresponding to the following general formula (II):
• R4 to R11 represent a linear, branched or cyclic C1-C6 alkyl group, preferably R7 and R8 together form an optionally substituted ring, more preferably R7 and R8 together form a optionally substituted ring and R4, R5, R6, R9, R10 and R11 represent an alkyl group, linear, branched, or cyclic C1-C6.
• the additional peroxide (s) is or are chosen from the group consisting of 1,1-di (tert-amyl peroxy) cyclohexane, 1 , 1- di (tert-butylperoxy) -3,3,5, trimethylcyclohexane), 2,2-di (4,4- di (tert-butylperoxy) cyclohexyl) propane, 1,1-di (tert-butylperoxy) -cyclohexane and their mixture, preferably is 1,1-di (tert-amyl peroxy) cyclohexane.
• the term “monomer” is understood to mean a molecule which can undergo polymerization.
• the term “at least one monomer” means that at least one chemical species of monomer is present.
• the composition according to the invention comprises at least one chemical species of (meth) acrylic monomers capable of polymerizing.
• the at least one (meth) acrylic monomer is chosen from the group consisting of acrylic acid, methacrylic acid, acrylic alkyl monomers, methacrylic alkyl monomers, acrylic monomers of hydroxyalkyl and hydroxyalkyl methacrylic monomers and mixtures thereof.
• the at least one (meth) acrylic monomer is chosen from the group consisting of acrylic acid, methacrylic acid, acrylic alkyl monomers, methacrylic alkyl monomers, acrylic monomers of hydroxyalkyl and hydroxyalkyl methacrylic monomers and mixtures thereof, the alkyl group containing from 1 to 22 carbons, linear, branched or cyclic, preferably 1 to 12 carbons, linear, branched or cyclic.
• the at least one (meth) acrylic monomer is chosen from the group consisting of methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate , isobornyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate and mixtures thereof.
• At least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight and even more preferably 90% by weight of the monomer (meth) acrylic is methyl methacrylate.
• the (meth) acrylic monomer is methyl methacrylate.
• the at least one (meth) acrylic monomer represents between 40% and 90% by weight, preferably between 45% and 85% by weight of the composition.
• composition according to the present invention comprises at least one second monomer comprising at least two (meth) acrylic functions.
• thermosetting meth (acrylic) resin make it possible to obtain a thermosetting meth (acrylic) resin.
• said at least one second monomer represents between 0.01 and 10 phr, preferably between 0.1 and 5 phr by weight relative to the sum of the (meth) acrylic monomer and of the possible polymer ( meth) acrylic.
• said second (meth) acrylic monomer is chosen from the group consisting of ethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1, 1 diacrylate. 4-butanediol, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, and a mixture thereof.
• composition according to the present invention may comprise at least one (meth) acrylic polymer, preferably chosen from the group consisting of polyalkylacrylates or polymethacrylates of alkyl.
• the (meth) acrylic polymer is poly (methyl methacrylate) (PMMA).
• PMMA denotes a homopolymer or a copolymer of methyl methacrylate (MMA) or their mixtures.
• the homo- or copolymer of methyl methacrylate comprises at least 50%, preferably at least 70%, preferably at least 80%, advantageously at least 90% and more advantageously at least 95% by weight of methyl methacrylate.
• PMMA is a mixture of at least one homopolymer and at least one copolymer of MMA, or a mixture of at least two homopolymers or two copolymers of MMA having a different average molecular weight, or one mixture of at least two MMA copolymers having a different monomer composition.
• the methyl methacrylate (MMA) copolymer comprises from 70% to 99.7% by weight of methyl methacrylate and from 0.3 to 30% by weight of at least one monomer containing at least one ethylenic unsaturation which can be copolymerized with methyl methacrylate.
• these monomers are well known, and mention may in particular be made of acrylic and methacrylic acids and alkyl (meth) acrylates in which the alkyl group contains from 1 to 12 carbon atoms.
• alkyl (meth) acrylates in which the alkyl group contains from 1 to 12 carbon atoms.
• methyl acrylate and ethyl, butyl or 2-ethylhexyl (meth) acrylate methyl acrylate and ethyl, butyl or 2-ethylhexyl (meth) acrylate.
• the comonomer is a alkyl acrylate in which the alkyl group contains 1 to 4 carbon atoms.
• the methyl methacrylate (MMA) copolymer comprises from 80% to 99.7%, advantageously from 90% to 99.7% and more advantageously from 90% to 99.5% by weight of methyl methacrylate, and from 0.3% to 20%, advantageously from 0.3% to 10% and more preferably from 0.5% to 10% by weight of at least one monomer containing at least one unsaturation ethylenic which can be copolymerized with methyl methacrylate.
• the comonomer is chosen from methyl acrylate and ethyl acrylate, and mixtures thereof.
• the average molecular weight of the (meth) acrylic polymer is greater than 50,000 g / mol and preferably greater than 100,000 g / mol.
• the average molecular weight can be measured by size exclusion chromatography (SEC).
• the (meth) acrylic polymer is completely soluble in the composition. This makes it possible to increase the viscosity of the composition.
• the at least one (meth) acrylic polymer represents at least 1% by weight, preferably at least 5% by weight, advantageously at least 10% by weight of the composition.
• the at least one (meth) acrylic polymer represents less than 50% by weight, preferably less than 40% and advantageously less than 30% by weight of the composition.
• composition of the present invention makes it possible to obtain a dynamic viscosity of the appropriate composition.
• This dynamic viscosity makes it possible to preserve the thermoplastic properties of the matrix obtained after polymerization and, where appropriate, good impregnation of the fibrous substrate.
• composition according to the invention makes it possible, after polymerization, to produce products having good optical and mechanical properties.
• composition according to the invention is therefore polymerizable or capable of polymerizing.
• the dynamic viscosity of the composition of the present invention is preferably between 10 mPa.s and 10,000 mPa.s, preferably between 20 mPa.s and 7000 mPa.s and advantageously between 20 mPa.s and 5000 mPa. .s and more advantageously between 20 mPa.s and 2000 mPa.s and even more advantageously between 20 mPa.s and 1000 mPa.s.
• the dynamic viscosity of the composition can easily be measured with a rheometer or viscometer, preferably a Brookfield DV2LVTJ0 apparatus, using ISO 2555. Dynamic viscosity is measured at 25 ° C.
• the dynamic viscosity is independent of the shear in a rheometer or of the speed of the moving body in a viscometer. If the composition has non-Newtonian behavior, meaning that it exhibits shear thinning, the dynamic viscosity is measured at a shear rate of ls ⁇ 1 at 25 ° C.
• composition according to the present invention comprising at least one (meth) acrylic monomer and optionally at least one (meth) acrylic polymer, and at least one organic peroxide chosen from hemi-peroxyacetals is in liquid form if it does not present no charge.
• This composition is generally called a “syrup” or “prepolymer”.
• the dynamic viscosity value of liquid (meth) acrylic syrup is between 10 mPa.s and 10,000 mPa.s.
• the viscosity of the syrup can easily be measured with a rheometer or viscometer. Dynamic viscosity is measured at 25 ° C.
• composition according to the present invention does not contain any additional solvent added voluntarily.
• composition of the present invention can also comprise stabilizers (also called reaction inhibitors). These stabilizers make it possible to prevent spontaneous polymerization of said at least one (meth) acrylic monomer.
• These stabilizers can in particular be chosen from hydroquinone (HQ), hydroquinone of monomethyl ether (MEHQ), 2,6-di-tert-butyl-4-methylphenol (BHT), 2,6-di -tert-butyl-4-methoxyphenol (“Topanol O”) and 2,4-dimethyl-6-tert-butylphenol (“Topanol A”).
• HQ hydroquinone
• MEHQ hydroquinone of monomethyl ether
• BHT 2,6-di-tert-butyl-4-methylphenol
• Topicanol O 2,6-di -tert-butyl-4-methoxyphenol
• Topicanol A 2,4-dimethyl-6-tert-butylphenol
• these stabilizers represent less than 5 parts by weight, advantageously less than 4 parts by weight and, preferably, between 0.3 and 3 parts by weight, per 100 parts by weight of at least one monomer (meth) acrylic and optional at least one (meth) acrylic polymer.
• the (meth) acrylic composition according to the invention can also comprise an inorganic filler.
• the inorganic filler can in particular be chosen from the group consisting of quartz, granite, marble, feldspar, clay, glass, ceramics, mica, graphite, silicates, carbonates, carbides, sulfates, silicates, hydroxides, metal oxides, metals, aluminum trihydrate Al (OH) 3, and mixtures thereof.
• the inorganic filler is in the form of powder.
• Such a powder may, for example, be formed from particles of which at least 50% by number have an average particle size, denoted Do, less than or equal to 50 ⁇ m, advantageously less than or equal to 20 ⁇ m and, preferably, less than or equal to 5pm.
• Do average particle size
• the sulphates are chosen from the group consisting of alkali metal and alkaline earth sulphates, preferably magnesium sulphate, calcium sulphate, strontium sulphate and barium sulphate.
• the metal oxides are chosen from the group consisting of alumina AI2O3, hydrated or not, barium oxide BaO, silica SiC> 2, magnesium oxide MgO and calcium oxide. CaO.
• the metal oxide is silica SiC> 2. This silica can in particular be a crushed crystalline silica or an amorphous silica.
• the carbonates are chosen from the group consisting of calcium carbonate (chalk), magnesium carbonate, sodium carbonate and potassium carbonate.
• the silicates are chosen from the group consisting of calcium silicate, sodium silicate, potassium silicate and magnesium silicate.
• the presence of aluminum trihydrate makes it possible, in particular, to improve the machining of the composite material obtained from the (meth) acrylic composition according to the invention as well as the fire resistance properties of this material.
• the aluminum trihydrate is in the form of particles of which at least 50% by number have an average particle size, denoted D50, less than or equal to 50 ⁇ m, advantageously less than or equal to 20 ⁇ m and, preferably , less than or equal to 5pm.
• D50 average particle size
• the aluminum trihydrate is in the form of particles of which at least 50% by number have an average particle size, denoted D50, less than or equal to 50 ⁇ m, advantageously less than or equal to 20 ⁇ m and, preferably , less than or equal to 5pm.
• the (meth) acrylic composition according to the invention comprises less than 20 parts by weight of inorganic filler, preferably less than 15, more preferably less than 10, more preferably less than 5, more preferably less than 1. part by weight of inorganic filler relative to the sum by weight of (meth) acrylic monomer and / or (meth) acrylic polymer of an inorganic filler.
• the composition comprises at least 0.1 part by weight, preferably at least 0.2 part by weight, more preferably at least 0.5, still more preferably at least 0, 8 part by weight of inorganic filler relative to the sum by weight of the monomer (meth) acrylic and / or (meth) acrylic polymer of an inorganic filler.
• the composition does not include any inorganic filler. This makes it possible to obtain transparent resins.
• composition according to the present invention can also comprise fibers.
• the fibers do not fall within the definition of the inorganic fillers defined above.
• the fibers can be natural or synthetic.
• the fibers can be short or long.
• plant fibers As natural material, mention may be made of plant fibers, wood fibers, animal fibers or mineral fibers.
• Natural fibers are, for example, sisal, jute, hemp, flax, cotton, coconut fibers and banana fibers.
• Animal fibers are, for example, wool or hair.
• polymer fibers chosen from fibers of thermosetting polymers, thermoplastic polymers or mixtures thereof.
• the polymer fibers can consist of polyamide (aliphatic or aromatic), polyester, polyvinyl alcohol, polyolefins, polyurethanes, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins and vinyl esters.
• the mineral fibers can also be chosen from glass fibers, in particular of type E, R or S2, carbon fibers, boron fibers or silica fibers.
• fibers is meant several fibers, unidirectional rovings or a mat of continuous filaments, fabrics, felts or nonwovens which may be in the form of strips, tablecloths, braids, wicks or pieces.
• the fibers have a length to diameter ratio of at least 1000, preferably at least 1500, more preferably at least 2000, preferably at least 3000 and more preferably at least. 5,000, even more preferably at least 6,000, even more preferably at least 7,500 and most preferably at least 10,000.
• the (meth) acrylic composition according to the invention comprises less than 300 parts by weight of fibers, preferably less than 100, more preferably less than 20, preferably less than 15, more preferably less than 10. , more preferably less than 5, still more preferably less than 1 part by weight of inorganic filler relative to the sum by weight of the (meth) acrylic monomer and / or of the (meth) acrylic polymer.
• the composition does not include any fiber. This makes it possible to obtain transparent resins.
• composition according to the present invention may comprise at least one additive making it possible to control the polymerization exotherm, chosen from the group consisting of saturated short-chain aliphatic esters, glycols and short-chain diols, primary amines and secondary and mixtures thereof. These compounds help increase heat dissipation, thereby reducing maximum polymerization exothermicity - reducing the amount of methyl methacrylate (MMA) monomer that boils and results in air voids.
• MMA methyl methacrylate
• said additive represents less than 6% by weight, preferably less than 5% by weight, and preferably between 0.6 and 4% by weight relative to the weight of (meth) acrylic monomer and of l 'optional (meth) acrylic polymer.
• Such contents make it possible not to impact the reaction kinetics or the molecular weight.
• These compounds are particularly desirable due to their low cost, low toxicity and impact. minimal environmental impact.
• they are chemically inert under the conditions of polymerization, which means that there is little or no effect on the curing time or the molecular weight of the product obtained.
• the short-chain aliphatic saturated esters are chosen from those having C6-20 and preferably C8-12 carbon chains. It has been found that the heat dissipation effect decreases as the molecular size increases.
• Useful short chain aliphatic saturated esters include, for example, methyl heptanoate and methyl laurate.
• short chain diol is understood to mean diols having carbon chains of 2 to 6, and preferably of 3 or 4 carbons. Mention may be made, by way of diol, of 1,3-butanediol and 1,4-butanediol. As glycols, mention may be made of glycerol, 1,2 and 1,3-propylene glycol, diethylene glycol and TRITON X-100 (C14H220 (C2H40) n) from Dow Chemical.
• the primary amines are chosen from primary amines having linear and branched C4 to C20 aliphatic alkyl groups and aromatic primary amines.
• the aromatic primary amines are chosen from the group consisting of aniline and o-, m- and p-toluidines.
• the primary hydroxylamines are chosen from the group consisting of ethanolamine and 3-amino-1-propanol.
• the secondary diamines are chosen from the group consisting of secondary diamines having linear and branched C4 to C20 aliphatic alkyl groups and aromatic diamines.
• the present invention also relates to a process for preparing the composition as defined above, comprising the following steps: i) preparation of a mixture of (meth) acrylic polymer and / or (meth) acrylic monomer ii) addition of at least one organic peroxide chosen from hemi-peroxyacetals, and optionally, up to 20 phr with respect to the sum by weight of (meth) acrylic monomer and (meth) acrylic polymer of an inorganic filler to the mixture prepared in step i).
• a (meth) acrylic polymer is present, the latter is added to the (meth) acrylic monomers and dissolved.
• step ii) is carried out at a temperature T add less than 50 ° C, more preferably less than 40 ° C, advantageously less than 30 ° C and more advantageously less than 25 ° C.
• the present invention also relates to the use of at least one organic peroxide chosen from hemi-peroxyacetals as defined above in combination with at least one additional organic peroxide as defined above for the polymerization of a composition comprising at least one (meth) acrylic monomer and an optional at least one (meth) acrylic polymer, in particular an optional at least one (meth) acrylic copolymer as defined above.
• the present invention also relates to the use of the composition as defined above or prepared by the process as defined above, to manufacture acrylic or methacrylic resins, in particular parts, thermoplastics, thermosets. or composites.
• the present invention also relates to a process for manufacturing thermoplastic, thermoset or composite parts comprising the following steps: i) optionally, a step of preparing a composition as defined above, ii) optionally, placing the composition as defined above in a mold, iii) polymerization of said composition.
• Said method may in particular be chosen from the group consisting of vacuum assisted resin infusion (VARI), stretch extrusion, cast molding (by gravity or low pressure injection), bag molding. vacuum, pressure bag molding, autoclave molding, resin transfer molding (RTM) and variations thereof (HP-RTM, C-RTM, I-RTM), injection molding and reaction (RIM), injection and reinforced reaction (R-RIM) and its variants, press molding, compression molding, liquid compression molding (LCM) or prepreg sheet molding (SMC) or bulk prepreg molding (BMC).
• VARI vacuum assisted resin infusion
• stretch extrusion stretch extrusion
• cast molding by gravity or low pressure injection
• bag molding by gravity or low pressure injection
• VARI vacuum, pressure bag molding, autoclave molding, resin transfer molding (RTM) and variations thereof (HP-RTM, C-RTM, I-RTM), injection molding and reaction (RIM), injection and reinforced reaction (R-RIM) and its variants
• RTM resin transfer molding
• RTM resin transfer molding
• RTM
• the mold can in particular be a closed mold or a bath.
• the manufacturing process according to the invention can further comprise a step iv) of postforming.
• this postforming step iv) is carried out after polymerization step iii).
• postforming is meant the bending as well as the change in the shape of the composite part.
• the manufacturing method according to the invention can further comprise a step v) of welding, gluing or lamination.
• the method according to the invention can comprise a step of impregnating the fibrous substrate in a mold with the composition as defined above.
• the impregnation step is carried out during step ii) of placing the composition in a mold.
• the term “sosity of the composition of the present invention at a given temperature” is slightly too high for the impregnation step, it is possible to slightly heat the composition so as to obtain a more liquid composition for sufficient wetting and correct and complete impregnation of the fibrous substrate.
• the term “sosity of the composition of the present invention at a given temperature is slightly too high for the impregnation step, it is possible to slightly heat the composition so as to obtain a more liquid composition for sufficient wetting and correct and complete impregnation of the fibrous substrate.
• Fiber substrate several fibers, unidirectional rovings or a mat of continuous filaments, fabrics, felts or nonwovens which may be in the form of bands, plies, braids, rovings or pieces.
• the polymerization step is carried out at a temperature between 50 ° C and 140 ° C, preferably between 50 ° C and 130 ° C, preferably at a temperature between 70 ° C and 120 ° C, preferably at a temperature between 90 ° C and 110 ° C.
• the present invention also relates to a part obtained by the above manufacturing process.
• Said part can be thermoplastic, thermoset or composite, preferably thermoplastic.
• the part obtained can be postformed after the polymerization of the composition of the invention.
• the part obtained can be welded, glued or laminated.
• the part is chosen from the group consisting of: a part of a motor vehicle, a part of a boat, a part of a bus, a part of a train, a sports article, a part of an airplane or helicopter, space ship or rocket part, photovoltaic module part, construction or building material, for example, composite rebar, studs and frames for civil engineering and high-rise construction, a wind turbine part, for example a wind turbine blade beam spar flange, a piece of furniture, a construction or building part, a telephone or cell phone part, a computer or television room , a part of a printer or copier.
• Composition A according to the invention comprising 1.8 phr of a hemiperoxyacetal and 0.2 phr of peroxyacetal
• a liquid composition A is prepared by dissolving 20% by weight of PMMA (BS520, an MMA copolymer comprising ethyl acrylate as a comonomer) in 80% by weight of methyl methacrylate, which is stabilized with MEHQ (hydroquinone monomethyl ether).
• PMMA BS520, an MMA copolymer comprising ethyl acrylate as a comonomer
• MEHQ hydroquinone monomethyl ether
• Composition B comprising 1.67 phr of a hemiperoxyacetal, 0.19 phr of peroxyacetal and 18.6 phr of an inorganic filler
• quartz flour inorganic filler
• TAPMC + 1,1-di (tert-amyl peroxy) cyclohexane peroxide system are then added to the mixture.
• composition C comprising 2 phr of an organic peroxide of perester type
• Composition D comprising 1.86 phr of an organic peroxide of perester type and 18.6 phr of an inorganic filler
• Molds were made using two glass plates of 20cm * 20cm * 3.85mm assembled in parallel using a transparent PVC seal in a 4.80mm diameter rope, then the ends of the seal were welded to ensure the final sealing of the mussels.
• a programmable oven brand France, XU112, has been set at a temperature of 55 ° C.
• the molds filled with compositions A to D were left at this temperature until complete polymerization of the compositions.
• the oven was then brought to a temperature of 90 ° C., then the molds were heated at this temperature for 1 hour.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polymerization Catalysts (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2019
  • 2019-12-18 FR FR1914808A patent/FR3105228B1/fr active Active
• 2020
  • 2020-12-18 US US17/783,145 patent/US20230055884A1/en active Pending
  • 2020-12-18 WO PCT/FR2020/052571 patent/WO2021123692A1/fr unknown
  • 2020-12-18 EP EP20848962.5A patent/EP4077432A1/de active Pending

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