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    • 专利摘要:
    The present invention relates to a liquid composition comprising a monomer, a (meth) acrylic polymer and at least two initiators. In particular, the present invention relates to a liquid composition comprising a monomer, a (meth) acrylic polymer and at least two initiators which have different half-life times. This liquid composition can be used in the form of a syrup and in particular in the form of a syrup for the impregnation of fibers or fibrous material. The invention further relates to a thermoplastic material obtained after polymerization of the liquid composition. The invention further relates to a method of manufacturing such a liquid composition. The invention further relates to a method of impregnating a fibrous substrate of long fibers with said liquid composition. The invention further relates to a fibrous substrate impregnated with said liquid composition which is useful for making composite parts. The present invention further relates to a method of manufacturing mechanical parts or structural elements made of composite material and mechanical parts or structural elements made of composite material obtained by a method using such a liquid composition.
    公开号:FR3060577A1
    申请号:FR1663063
    申请日:2016-12-21
    公开日:2018-06-22
    发明作者:Pierre Gerard；Pierre ESCALE；Alexander Zoller
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [Field of the invention] The present invention relates to a liquid composition comprising a monomer, a (meth) acrylic polymer and at least two initiators.
    In particular, the present invention relates to a liquid composition comprising a monomer, a (meth) acrylic polymer and at least two initiators which have different half-life times. This liquid composition can be used in the form of a syrup and in particular, in the form of a syrup for the impregnation of fibers or fibrous material. The invention further relates to a thermoplastic material obtained after polymerization of the liquid composition. The invention further relates to a method of manufacturing such a liquid composition. The invention further relates to a method of impregnating a fibrous substrate of long fibers with said liquid composition. The invention further relates to a fibrous substrate impregnated with said liquid composition which is useful for manufacturing composite parts.
    The present invention further relates to a method of manufacturing mechanical parts or structural elements made of composite material and mechanical parts or structural elements made of composite material obtained by a process using such a liquid composition.
    [Prior art] [004] Thermoplastic polymers are materials which are widely used today in several fields and applications, for example in the construction, aeronautics, automotive or railways sectors, in which they are part of mechanical parts.
    These mechanical parts which have to withstand high stresses during their use are generally made from composite materials. A composite material is a macroscopic combination of two or more of two 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 of a reinforcement material.
    The objective of using a composite material to obtain performance qualities which are not available from each of its constituents when used separately. Consequently, composite materials are widely used in pure industrial sectors, for example construction, automotive, aerospace, transport, leisure, electronics and sports, in particular because of their better mechanical performance (resistance to higher tensile, higher tensile modulus, higher toughness) and their low density, compared to homogeneous materials.
    In order to allow thermoforming and recycling, it is preferable to also use thermoplastic polymers in composite materials.
    Thermoplastic polymers consist of linear or branched polymers which are not generally crosslinked. The thermoplastic polymers are heated to mix the constituents necessary to make the composite material and are cooled to harden into the final form. The problem with these molten thermoplastic polymers is their very high viscosity. In order to prepare a polymer composite material based on thermoplastic polymers, a thermoplastic polymer resin, commonly called “syrup”, is used to impregnate the reinforcing material, for example a fibrous substrate. Once polymerized, the thermoplastic polymer syrup constitutes the matrix of the composite material.
    [009] During the impregnation, during the preparation of polymer composites, the viscosity of the impregnation syrup must be regulated and adapted so as not to be too fluid or too viscous, in order to correctly impregnate each fiber of the fibrous substrate. .
    When the wetting is partial, either because the syrup is too fluid or too viscous, “bare” zones, that is to say non-impregnated zones, and zones in which drops of polymer form on the fibers , which are the cause of the formation of bubbles, respectively, appear. These “bare” zones and these bubbles lead to the appearance of defects in the final composite material, which are the cause, inter alia, of a loss of mechanical strength of the final composite material.
    In addition, when used without impregnation, it is desirable to have a liquid composition which polymerizes quickly with good conversion in order to increase productivity.
    [011] A liquid composition or a syrup comprising a (meth) acrylic monomer and a (meth) acrylic polymer is described in WO 2013/056845 and WO 2014/013028. The polymerization of the monomer (s) in the two documents is obtained with one or more initiator (s) or radical generation initiation systems comprising one or more radical generation initiator system (s). For both documents, benzoyl peroxide is used in the examples.
    Document WO2014 / 174098 describes a liquid (meth) acrylic syrup. The syrup comprises an initiation system comprising an accelerator, an organic aldehyde, a peracid and a liquid peroxy compound. The polymerization time in the examples of this document is several hours or several dozen minutes. It is not suggested in any of these documents that the incorporation of two initiators in a liquid composition allows rapid and total polymerization.
    [TECHNICAL PROBLEM] [014] the objective of the invention is, therefore, to remedy at least one of the drawbacks of the prior art.
    An objective of the present invention is to have a liquid composition comprising a monomer, a (meth) acrylic polymer and at least two initiators to obtain a composition which can be polymerized quickly and with good conversion. Good conversion means that at least 95% of the monomers have been polymerized.
    [016] An objective of the present invention is also to have a process for rapidly polymerizing a liquid composition comprising a monomer, a (meth) acrylic polymer and at least two initiators with good conversion.
    Another additional objective of the present invention is to use a liquid composition comprising a monomer, a (meth) acrylic polymer and at least two initiators to obtain rapid polymerization and good conversion.
    The invention further relates to the complete, correct and uniform wetting of the fibrous substrate during the impregnation. Possible defects in the wetting of the fibers, for example by bubbles and voids, reduce the mechanical performance of the mechanical or structured parts or articles or of the final composite part. Another object of the present invention is to provide a process which can be carried out at low cost and which allows the manufacturing on an industrial scale of mechanical parts or structural elements made of thermoplastic polymer or of thermoplastic composite material. In addition, the process should be easy and simple to carry out using commercially available compounds. The manufacturing of the composite parts must also be reproducible and rapid, which means short cycle times.
    [BRIEF DESCRIPTION OF THE INVENTION] It has been unexpectedly discovered that a liquid composition comprising
    a) a (meth) acrylic polymer (Pl),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity between 10 mPa * s and 10,000 mPa * s at 25 ° C, produces a thermoplastic polymer composition after polymerization of said (meth) acrylic monomer (Ml), said polymer composition thermoplastic with rapid kinetics and high conversion of the (meth) acrylic monomer (Ml), compared to a composition comprising only the initiator (Inil).
    [021] It has also been discovered that a liquid composition comprising
    a) a (meth) acrylic polymer (PI),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C, can be used to produce a thermoplastic polymer composition after polymerization of said (meth) acrylic monomer (Ml), said thermoplastic polymer composition having a low residual monomer content, compared to a composition comprising a single initiator as (Inil).
    [022] It has also been discovered that a liquid composition comprising
    a) a (meth) acrylic polymer (PI),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C, can be used to produce a thermoplastic polymer composition after polymerization of said (meth) acrylic monomer (Ml), much faster compared to a composition comprising a single initiator as (Ini2).
    [023] It has also been discovered that a liquid (meth) acrylic composition for impregnating a fibrous substrate, said fibrous substrate consisting of long fibers, said composition being characterized in that it comprises:
    a) a (meth) acrylic polymer (PI),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C;
    produces a complete and correct impregnation of the fibrous substrate.
    The applicant has also unexpectedly discovered that an impregnation method for impregnating a fibrous substrate, said fibrous substrate consisting of long fibers and said method comprising a step of impregnating said fibrous substrate with said liquid composition or liquid (meth) acrylic impregnation syrup, produces a complete and correct impregnation of the fibrous substrate and allows total and rapid polymerization with good conversion, compared to a composition comprising only initiators (Inil).
    [025] It has also been discovered, unexpectedly, that a process for manufacturing composite parts, comprising the following steps:
    i) impregnation of a fibrous substrate with such a liquid composition or such a (meth) acrylic syrup, ii) polymerization of the liquid (meth) acrylic syrup impregnating said fibrous substrate, makes it possible to obtain thermoplastic composite parts with significantly improved productivity .
    [026] In addition, it was also discovered that a composite part obtained by the manufacturing process has a significantly improved residual monomer content, due to better conversion of the monomer. The content of residual monomer is less than 5% relative to the amount of the monomer used.
    [DETAILED DESCRIPTION] [027] According to a first aspect, the present invention relates to a liquid composition comprising:
    a) a (meth) acrylic polymer (PI),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2), said liquid composition having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C.
    [028] According to a second aspect, the present invention relates to a liquid composition for impregnating a fibrous substrate, said fibrous substrate consisting of long fibers, and said liquid composition being characterized in that it comprises:
    a) a (meth) acrylic polymer (Pl),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C.
    [029] According to a third aspect, the present invention relates to a process for preparing a liquid composition, said liquid composition being characterized in that it comprises:
    a) a (meth) acrylic polymer (Pl),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C, by a process comprising the following steps:
    i) preparation of a liquid mixture of (meth) acrylic polymer (Pl) and (meth) acrylic monomer (Ml) ii) addition of initiators (Inil) and (Ini2) jointly or one after the other mixture prepared in the previous step.
    [030] According to a fourth aspect, the present invention relates to the use of a liquid composition for impregnating a fibrous substrate, said fibrous substrate consisting of long fibers, and said liquid composition being characterized in that it comprises:
    a) a (meth) acrylic polymer (Pl),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C.
    [031] According to a fifth aspect, the present invention relates to the use of a liquid composition for manufacturing thermoplastic parts or for manufacturing composite parts, and said liquid composition being characterized in that it comprises:
    a) a (meth) acrylic polymer (Pl),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C.
    [032] According to a sixth aspect, the present invention relates to a method for manufacturing thermoplastic parts by a method comprising the following steps:
    i) preparation of a liquid mixture of (meth) acrylic polymer (Pl) and (meth) acrylic monomer (Ml) ii) addition of initiators (Inil) and (Ini2) jointly or one after the other mixture prepared in the previous step.
    iii) placing the liquid (meth) acrylic composition prepared in i) and ii) in polymerization means, said composition being characterized in that it comprises:
    a) a (meth) acrylic polymer (Pl),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C, iv) polymerization.
    [033] According to a seventh aspect, the present invention relates to a method of manufacturing composite parts by a method comprising the following steps:
    i) preparation of a mixture of (meth) acrylic polymer (Pl) and (meth) acrylic monomer (Ml) ii) addition of initiators (Inil) and (Ini2) jointly or one after the other to the mixture prepared in the previous step.
    iii) impregnating fibers or a fibrous substrate with the liquid (meth) acrylic composition prepared in i) and ii), said composition being characterized in that it comprises:
    a) a (meth) acrylic polymer (PI),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C, iv) polymerization.
    [034] The term “fibrous substrate”, in the present context, designates several fibers, unidirectional rovings or a continuous filament mat, fabrics, felts or nonwovens which can be in the form of strips, sheets, braids, locks or parts.
    The term "(meth) acrylic", in the present context, designates any type of acrylic or methacrylic monomer. The term “PMMA”, in the present context, designates homoet copolymers of methyl methacrylate (MMA), the weight ratio of MMA in PMMA being at least 70% by weight for the MMA copolymer.
    The term "monomer", in the present context, designates a molecule which can undergo polymerization.
    The term “polymerization”, in the present context, designates the process for converting a monomer or a mixture of monomers in a polymer.
    [039] The term "thermoplastic polymer", in the present context, designates a polymer which becomes liquid or becomes more liquid or less viscous when heated and which can take new forms by the application of heat and pressure. This also applies to lightly crosslinked thermoplastic polymers which can be thermoformed when heated above the softening temperature.
    The term “polymer composite”, in the present context, designates 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. .
    ίο [041] The term “initiator”, in the present context, designates a compound which can start / initiate the polymerization of a monomer or monomers.
    The term "half-life time" tl / 2, in the present context, designates the time necessary for an initial quantity of initiator to decrease in concentration by half. This time is a function of the temperature.
    [043] The abbreviation "phr" designates parts by weight per hundred parts of composition. For example 1 phr of initiator in the composition means that 1 kg of initiator is added to 100 kg of composition.
    [044] The abbreviation "ppm" designates parts by weight per million parts of composition. For example, 1000 ppm of a compound in the composition means that 0.1 kg of compound is present in 100 kg of composition.
    The liquid composition or the (meth) acrylic syrup according to the invention comprises a (meth) acrylic monomer (Ml) or a mixture of (meth) acrylic monomers (Ml) and (Ml + x), a polymer (meth ) acrylic (PI) and at least two initiators (Inil) and (Ini2). [046] The dynamic viscosity of the liquid composition or of the (meth) acrylic syrup is in a range of 10 mPa * s to 10,000 mPa * s, preferably from 20 mPa * s to 7000 mPa * s and advantageously from 20 mPa * s at 5000 mPa * s. The viscosity of the syrup can be easily measured with a rheometer or a viscometer. The dynamic viscosity is measured at 25 ° C. If the liquid (meth) acrylic syrup exhibits Newtonian behavior, that is to say without shear thinning, the dynamic viscosity is independent of the shear in a rheometer or the speed of the mobile in a viscometer. If the liquid composition exhibits a non-Newtonian behavior, that is to say with shear thinning, the dynamic viscosity is measured at a shear rate of ls _1 at 25 ° C.
    [047] The liquid composition or the (meth) acrylic syrup according to the invention, for impregnating the fibrous substrate, comprises in particular a (meth) acrylic monomer or a mixture of (meth) acrylic monomers, a (meth) acrylic polymer and at least two initiators (Inil) and (Ini2).
    [048] As regards the liquid composition of the invention, this comprises a (meth) acrylic monomer (Ml), a (meth) acrylic polymer (PI) and at least two initiators (Inil) and (Ini2) . Once polymerized, the (meth) acrylic monomer (Ml) is transformed into a (meth) acrylic polymer (P2) comprising the monomer units of (meth) acrylic monomer (Ml).
    [049] The amount of two initiators (Inil) and (Ini2) together in the composition is at least 0.1 phr relative to the sum of the (meth) acrylic monomer (Ml) and the (meth) acrylic polymer ( PI). Preferably, the amount of the two initiators (Inil) and (Ini2) together in the composition is at least 0.2 phr, more preferably at least 0.5 phr, even more preferably at least 0.75 phr and advantageously at least. minus 1 phr from the sum of the (meth) acrylic monomer (Ml) and the (meth) acrylic polymer (PI).
    The amount of the two initiators (Inil) and (Ini2) together in the composition is at most 15 phr relative to the sum of the (meth) acrylic monomer (Ml) and the (meth) acrylic polymer (PI) . Preferably, the amount of the two initiators (Inil) and (Ini2) together in the composition is at most 12 phr, more preferably at most 10 phr, even more preferably at most 8 phr and advantageously at most 5 phr relative to the sum of the (meth) acrylic monomer (Ml) and the (meth) acrylic polymer (PI).
    [051] The amount of the two initiators (Inil) and (Ini2) together in the composition is between 0.1 phr and 15 phr relative to the sum of the (meth) acrylic monomer (Ml) and the (meth) acrylic polymer (PI). Preferably, the amount of the two initiators (Inil) and (Ini2) together in the composition is between 0.2 phr and 12 phr, more preferably between 0.5 phr and 10 phr, even more preferably between 0.75 phr and 8 phr and advantageously, at most between 1 phr and 5 phr relative to the sum of the (meth) acrylic monomer (Ml) and the (meth) acrylic polymer (PI).
    As regards the (meth) acrylic monomer (Ml), the monomer is chosen from acrylic acid, methacrylic acid, alkyl acrylic monomers, alkyl methacrylic monomers, hydroxyalkyl acrylic acryl monomers and hydroxyalkyl methacrylic monomers, and mixtures of these.
    [053] Preferably, the (meth) acrylic monomer (Ml) is chosen from acrylic acid, methacrylic acid, hydroxyalkylacrylic monomers, hydroxyalkylmethacrylic monomers, alkylacrylic monomers, alkylmethacrylic monomers and mixtures thereof , the alkyl group containing from 1 to 22 linear, branched or cyclic carbons; the alkyl group preferably containing from 1 to 12 linear, branched or cyclic carbons.
    [054] Advantageously, the (meth) acrylic monomer is chosen from 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.
    [055] According to a preferred embodiment, at least 50% by weight and preferably at least 60% by weight of the (meth) acrylic monomer is methyl methacrylate.
    [056] According to a first more preferred embodiment, at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, advantageously at least 80% by weight and even more advantageously 90% by weight of the monomer is a mixture of methyl methacrylate with optionally at least one other monomer.
    [057] As regards the (meth) acrylic polymer (Pl), there may be mentioned polyalkyl methacrylates or polyalkyl acrylates. According to a preferred embodiment, the (meth) acrylic polymer is poly (methyl methacrylate) (PMMA).
    [058] The term "PMMA" denotes a homopolymer or copolymer of methyl methacrylate (MMA) or mixtures thereof.
    [059] According to one embodiment, the methyl methacrylate (MMA) homo- or copolymer comprises at least 70%, preferably at least 80%, advantageously at least 90% and more advantageously at least 95% by weight of methyl methacrylate.
    According to another embodiment, the PMMA is a mixture of at least one homopolymer and at least one MMA copolymer, or a mixture of at least two homopolymers or two MMA copolymers with a different average molecular weight, or a mixture of at least two MMA copolymers having a different composition of monomers.
    [061] 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 copolymerize with methyl methacrylate.
    [062] These monomers are well known and it may be particularly mentioned acrylic and methacrylic acids and alkyl (meth) acrylates in which the alkyl group contains from 1 to 12 carbon atoms. By way of examples, there may be mentioned methyl acrylate and ethyl, butyl or 2-ethylhexyl (meth) acrylate. Preferably, the comonomer is an alkyl acrylate in which the alkyl group contains from 1 to 4 carbon atoms.
    [063] According to a first preferred embodiment, 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 advantageously from 0.5% to 10% by weight of at least one monomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate. Preferably, the comonomer is chosen from methyl acrylate and ethyl acrylate, and mixtures of these.
    The weight average molecular weight of the (meth) acrylic polymer (PI) must be high, that is to say greater than 50,000 g / mol and preferably greater than 100,000 g / mol.
    [065] The weight average molecular weight can be measured by exclusion chromatography (SEC).
    [066] The (meth) acrylic polymer is completely soluble in the (meth) acrylic monomer or in the mixture of (meth) acrylic monomers. It allows the viscosity of the (meth) acrylic monomer or of the mixture of (meth) acrylic monomers to be increased. The solution obtained is generally called "syrup" or "prepolymer". The dynamic viscosity value of the liquid (meth) acrylic syrup is between 10 mPa.s and 10 000 mPa.s. The viscosity of the syrup can be easily measured with a rheometer or a viscometer. The dynamic viscosity is measured at 25 ° C.
    [067] Advantageously, the liquid (meth) acrylic syrup does not contain any additional solvent added voluntarily.
    [068] As regards the two initiators (Inil) and (Ini2), the initiators generate radicals which initiate the monomer (s) to start radical polymerization of the monomer in order to form the polymer chains by propagation.
    [069] Preferably, the initiators (Inil) and (Ini2) are activated by heat.
    The heat activated initiators (Inil) and (Ini2) are preferably radical initiators.
    The radical initiators (Inil) and (Ini2) can be chosen from a compound comprising a peroxy group or compounds comprising an azo group and, preferably, from a compound comprising a peroxy group.
    [072] Preferably, the compound comprising a peroxy group comprises from 2 to 30 carbon atoms.
    Preferably, the compound comprising a peroxy group is chosen from diacyl peroxides, peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyacetals, a hydroperoxide or a peroxyketal.
    [074] Preferably, the two initiators (Inil) and (Ini2) have, at any given temperature T1, different half-life times ti / 2.
    [075] Even more preferably, the second initiator (Ini2) has, at a given temperature Ti, a half-life time ti / 2 which is at least twice the half-life time ti / 2 of the first initiator (Inil) . Even more preferably, the second initiator (Ini2) exhibits, at a given temperature T1, a half-life time ti / 2 which is at least three times, advantageously four times, more advantageously five times, even more advantageously six times the time of half-life ti / 2 of the first initiator (Inil).
    [076] Preferably, the temperature Ti is between 20 ° C and 160 ° C, more preferably between 40 ° C and 140 ° C and advantageously between 50 ° C and 130 ° C.
    [077] More preferably, the first initiator (Inil) has a half-life time ti / 2 of 1 hour at a temperature between 40 ° C and 90 ° C, even more preferably between 45 ° C and 80 ° C and even more preferably between 50 ° C and 75 ° C.
    [078] More preferably, the second initiator (Ini2) has a half-life time ti / 2 of 1 hour at a temperature of at least 70 ° C, even more preferably of at least 75 ° C.
    [079] More preferably, the second initiator (Ini2) has a half-life time ti / 2 of 1 hour at a temperature between 70 ° C and 150 ° C, even more preferably between 75 ° C and 140 ° C and even more preferably between 75 ° C and 130 ° C.
    [080] Preferably, the temperature difference for a given half-life time between the initiator (Ini2) and (Inil) is at least 5 K. This means that if, for a half-life time ti / 2 of 1 hour, the temperature of (Inil) is 75 ° C, the temperature of (Ini2) for a half-life time ti / 2 of 1 hour is at least 80 ° C.
    [081] Preferably, the difference in temperature for a given half-life time between the initiator (Ini2) and (Inil) is at most 50 K. This means that if, for a half-life time ti / 2 of 1 hour, the temperature of Inil is 50 ° C, the temperature of Ini2 for a half-life time ti / 2 of 1 hour is at most 100 ° C.
    [082] More preferably, the temperature difference for a given half-life time between the initiators (Ini2) and (Inil) is between 5 K and 50 K and, more preferably, between 6 K and 40 K and, again more preferably, between 7 K and 30 K.
    [083] The initiators (Ini2) and (Inil) are chosen from diisobutyryl peroxide, cumyl peroxynodeodecanoate, di (3-methoxybutyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxynodeodecanoate, cumyl peroxyneoheptanoate, peroxide di-n-propyl, tertamyl peroxynodeodecanoate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di- (2-ethylhexyl) peroxydicarbonate, tert-butyl peroxicodecanate di-n-butyl peroxydicarbonate, diketyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxynoheptanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, di-peryl peroxide (3,5,5-trimethylhexanoyl), dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di (2éthylhexanoylperoxy) -hexane, peroxy-2-ethylhexanoate 1,1,3,3tetramethylbutyl, peroxy -2-tert-ethylhexanoate amyl, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxyisobutyrate, 1,1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1di ( tert-amylperoxy) cyclohexane, 1,1-di- (tert-butylperoxy) cyclohexane, tert-amyl peroxy-2-ethylhexylcarbonate, tert-amyl peroxyacetate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 2 , 2-di- (tert-butylperoxy) -butane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxy-2ethylhexylcarbonate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, 4,4-di (tert-butylperoxy) valerate butyl, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di- (2-tert-butyl-peroxyisopropyl) -benzene, 2,5-dimethyl-2,5-di- (tert- butylperoxy) -hexane, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, di-tert-butyl peroxide, 3,6,9-triethyl-3,6,9 -trimethyl-1,4,7-triperoxonane, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azodi- (2methylbutyronitrile), azobisiso-butyramide, 2,2'-azobis (2,4dimethylvaleronitrile), 1,1'-azodi (hexahydrobenzonitrile) or 4,4'azobis (4-cyanopentanoic).
    [084] Preferably, the initiator (Inil) is chosen from cumyl peroxyneodecanoate, di (3-methoxybutyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxynodeodecanoate, cumyl peroxyneoheptanoate, di-n-propyl peroxydicarbonate , tert-amyl peroxynodeodecanoate, di-secbutyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, di- (2ethylhexyl) peroxydicarbonate, tert-butyl peroxynodeodecanoate, di-butyl peroxydicarbonate diketyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxynoheptanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, di- (3,5,5trimethylhexanoyl) peroxide dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) -hexane or 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate.
    [085] Preferably, the initiator (Ini2) is chosen from tert-amyl peroxypivalate, tert-butyl peroxypivalate, di- (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di (2ethylhexanoylperoxy) -hexane, 1,1,3,3tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, 2-peroxyethylhexanoate tert-butyl, tert-butyl peroxydiethylacetate, tert-butyl peroxyisobutyrate, 1,1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1di (tert-amylperoxy) cyclohexane - (tert-butylperoxy) cyclohexane, tert-amyl peroxy-2-ethylhexylcarbonate, tert-amyl peroxyacetate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 2,2-di- (tert-butylperoxy) - butane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxy-2ethylhexylcarbonate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, 4,4-di (tert-butylperoxy) butyl pererybenzoate tert-butyl, di-tert-amyl peroxide, dicumyl peroxide, di- (2-tert-butyl-peroxyisopropyl) -benzene, 2,5-dimethyl-2,5-di- (tert-butylperoxy) -hexane, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, di-tert-butyl peroxide or 3,6,9-triethyl-3,6,9-trimethyl-1, 4.7triperoxonane.
    The ratio between the two initiators (Ini2) and (Inil) is between 1/10 and 10/1, preferably between 1/5 and 5/1 and more preferably between 1/4 and 4/1.
    [087] In a first preferred embodiment, the initiator (Inil) is chosen from di (4-tertbutylcyclohexyl) peroxydicarbonate.
    The initiator (Ini2) in this first preferred embodiment is chosen from benzoyl peroxide, t-butyl peroxy-2ethylhexanoate, dilauroyl peroxide and didecanoyl peroxide.
    [089] In a second preferred embodiment, the initiator (Inil) is chosen from diketyl peroxydicarbonate.
    The initiator (Ini2) in this second preferred embodiment is chosen from benzoyl peroxide, t-butyl peroxy-2ethylhexanoate, dilauroyl peroxide and didecanoyl peroxide.
    [091] In a third preferred embodiment, the initiator (Inil) is chosen from dimyristyl peroxydicarbonate.
    [092] The initiator (Ini2) in this third preferred embodiment is chosen from benzoyl peroxide, t-butyl peroxy-2ethylhexanoate, dilauroyl peroxide and didecanoyl peroxide.
    In order to maintain a dynamic viscosity of the liquid composition or of the (meth) acrylic syrup, in addition to the fact that this allows good impregnation of the fibrous substrate, if necessary, and to preserve the thermoplastic properties of the matrix obtained after polymerization of the fibrous substrate pre-impregnated with syrup, the syrup compounds are incorporated in the following mass percentages:
    [094] The (meth) acrylic monomer (s) (Ml) in the liquid composition or the (meth) acrylic syrup are present in proportions of between 40% and 90% by weight and preferably between 45 % and 85% by weight of the composition comprising the (meth) acrylic monomer (s) (Ml) and the (meth) acrylic polymer (Pl).
    [095] The (meth) acrylic polymer (s) (Pl) in the liquid composition or the (meth) acrylic syrup are present in a proportion of at least 1% by weight, preferably at least 5% and advantageously at least 10% by weight of the composition comprising the (meth) acrylic monomer (s) (Ml) and the (meth) acrylic polymer (Pl).
    [096] The (meth) acrylic polymer (s) (Pl) in the liquid (meth) acrylic syrup are present in a proportion of not more than 50% by weight, preferably not more than 40% and advantageously not more than 30% by weight of the composition comprising the (meth) acrylic monomer (s) (Ml) and the (meth) acrylic polymer (P1).
    [097] All of the optional additives and fillers are added to the liquid (meth) acrylic syrup before impregnation and / or polymerization.
    [098] The liquid composition according to the invention can also comprise, optimally, an activator for the polymerization. The polymerization activator or accelerator is chosen from tertiary amines such as N, N-dimethyl-p-toluidine (DMPT), N, N-dihydroxyethyl-p-toluidine (DHEPT), metal catalysts of transition soluble in organic medium or mixtures thereof.
    Advantageously, the liquid (meth) acrylic composition does not contain any metal-based catalyst. No additive comprising a metal as activators for catalytically accelerating the polymerization reaction is added to the liquid (meth) acrylic composition according to the invention. This relates, in particular, to tin-based compounds such as tin chloride.
    The content of the activator relative to the (meth) acrylic monomer (Ml) of the liquid (meth) acrylic composition is from 100 ppm to 10,000 ppm (by weight), preferably from 200 ppm to 7000 ppm by weight and advantageously, from 300 ppm to 4000 ppm.
    As regards the process for manufacturing the liquid or su (meth) acrylic syrup composition, a first step consists in preparing a first syrup comprising the (meth) acrylic monomer (Ml) or a mixture of (meth) monomers acrylics and a (meth) acrylic polymer (PI). The initiators (Ini2) and (Inil) are then added to the syrup, in the proportions indicated above to maintain a dynamic viscosity between 10 mPa * s and 10,000 mPa * s, at 25 ° C.
    The initiators (Ini2) and (Inil) can be added jointly or separately one after the other. If added separately, the order does not matter.
    Preferably, the initiators (Ini2) and (Inil) are added at a temperature T add of less than 50 ° C, more preferably less than 40 ° C, advantageously less than 30 ° C and more advantageously less than 25 ° C .
    The liquid composition according to the invention, detailed in the preceding paragraphs, can be used for impregnating fibers or a fibrous substrate or for manufacturing thermoplastic parts or manufacturing composite parts.
    As regards the process for impregnating the fibers or the fibrous substrate, this comprises a step of impregnating the fibrous substrate with the liquid composition or the (meth) acrylic syrup.
    This impregnation step can be carried out in a mold or a closed mold or a bath.
    If the viscosity of the (meth) acrylic syrup liquid at a given temperature is slightly too high for the impregnation process, it is possible to heat the syrup so as to obtain a more liquid syrup for sufficient wetting and impregnation correct and complete fiber substrate.
    With regard to the fibrous substrate, it may be mentioned several fibers, unidirectional rovings or a mat with continuous filament, fabrics, felts or nonwovens which can be in the form of strips, plies, braids , wicks or parts. The fibrous material can have different shapes and dimensions, one-dimensional, two-dimensional or three-dimensional. A fibrous substrate comprises an assembly of one or more fibers. When the fibers are continuous, their assembly forms fabrics.
    The one-dimensional shape corresponds to long linear fibers. The fibers can be discontinuous or continuous. The fibers can be arranged randomly or parallel to each other, in the form of a continuous filament. A fiber is defined by its form factor, which is the ratio between the length and the diameter of the fiber. The fibers used in the present invention are long fibers or continuous fibers. The fibers have a form factor of at least 1000, preferably at least 1500, more preferably at least 2000, advantageously at least 3000 and more advantageously at least 5000, even more advantageously at least 6000, even more advantageously at least 7500 and most advantageously at least
    000.
    The two-dimensional shape corresponds to mats or non-woven or woven fibrous reinforcements or bundles of fibers, which can also be braided. Even if the two-dimensional shape has a certain thickness and, therefore, in principle a third dimension, it is considered to be two-dimensional according to the present invention.
    The three-dimensional shape corresponds, for example, to non-woven fiber mats or reinforcements or bundles stacked or folded of fibers or mixtures thereof, an assembly of the two-dimensional shape in the third dimension.
    The origins of the fibrous material can be natural or synthetic. As natural material, vegetable fibers, wood fibers, animal fibers or mineral fibers can be mentioned.
    Natural fibers are, for example, sisal fibers, jute, hemp, flax, cotton, coconut, and banana fibers. Animal fibers are, for example, wool or hair.
    As synthetic material, it may be mentioned 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.
    The fibrous substrate of the present invention is chosen from plant fibers, wood fibers, animal fibers, mineral fibers, synthetic polymer fibers, glass fibers and carbon fibers, and mixtures of those -this.
    Preferably, the fibrous substrate is chosen from mineral fibers.
    The fibers of the fibrous substrate have a diameter between 0.005 pm and 100 pm, preferably between 1 pm and 50 pm, more preferably between 5 pm and 30 pm and advantageously, between 10 pm and 25 pm.
    Preferably, the fibers of the fibrous substrate of the present invention are chosen from continuous fibers (which means that the form factor does not necessarily apply as for long fibers) for the one-dimensional shape, or for long or continuous fibers for the two-dimensional or three-dimensional shape of the fibrous substrate.
    According to another additional aspect, the invention relates to a polymer composite material comprising a thermoplastic (meth) acrylic matrix and a fibrous substrate used as a reinforcement, in which the fibrous substrate consists of long fibers, said composite material being characterized in that the thermoplastic (meth) acrylic matrix is obtained after polymerization of said fibrous substrate prepreg with said liquid composition according to the invention or the (meth) acrylic syrup.
    Another aspect of the present invention is a process for manufacturing mechanical or structured parts or products, comprising the following steps:
    i) impregnation of a fibrous substrate with the liquid composition or (meth) acrylic syrup according to the invention, ii) polymerization of the liquid composition or of (meth) acrylic syrup impregnating said fibrous substrate.
    With regard to the method of manufacturing composite parts, but also of mechanical or structured parts or products, different methods can be used to manufacture these parts. Mention may be made of vacuum assisted resin infusion (VARI), pultrusion, vacuum infusion molding, pressure infusion molding, autoclave molding, resin transfer molding (RTM) and variants thereof such as (HP-RTM, C-RTM, I-RTM), reaction injection molding (RIM), enhanced reaction injection molding (R-RIM) and variants thereof -this, press molding, compression molding, liquid compression molding (LCM) or sheet molding (SMC) or bulk molding (BMC).
    A first preferred manufacturing method for manufacturing composite parts is a method according to which the liquid composition is transferred onto the fibrous substrate by impregnation of the fibrous substrate in a mold. The processes requiring a mold are listed above and include the word molding.
    A second preferred manufacturing method for manufacturing composite parts are methods according to which the liquid composition is used in the pultrusion process. The fibers are guided by means of a batch of resin comprising the composition according to the invention. The fibers in the form of a fibrous substrate are, for example, in the form of a unidirectional roving or a continuous filament mat. After impregnation in the resin batch, the wet fibers are drawn through a heated die, where polymerization occurs.
    A third preferred manufacturing process is the vacuum assisted resin infusion (VARI).
    The manufacturing process for composite parts, but also for mechanical or structured parts or products, can also comprise the post-forming step. Post-forming includes bending and modifying the shape of the composite part.
    The method of manufacturing composite parts, but also of mechanical or structured parts or products, may further comprise the step of welding or gluing or rolling.
    The thermoplastic parts obtained by the methods according to the invention can be post-formed after polymerization of the liquid composition of the invention. Forming includes bending and modifying the shape of the composite part.
    The thermoplastic parts or manufactured composite parts obtained after polymerization of the liquid composition of the invention and / or by the methods according to the invention can be welded, glued or laminated.
    With regard to the use of mechanical parts made of composite material manufactured in this way, it may be mentioned applications in the automobile, applications in transport such as buses or trucks, nautical applications, applications railway, sports, aeronautical and aerospace applications, photovoltaic applications, computer applications, construction and building applications, telecommunications applications and wind energy applications. The mechanical part made of composite material is in particular a motor vehicle part, a boat part, a bus part, a train part, a sports article, an airplane or helicopter part. , a spacecraft or rocket part, a photovoltaic module part, a material for construction or building, for example composite reinforcements, dowels and stirrups for civil engineering and high-rise construction, a turbine part wind turbine, for example a soleplate of a wind turbine blade beam, a piece of furniture, a construction or building part, a telephone or cell phone part, a computer or television part, or a part printer or copier.
    In a first preferred embodiment, the mechanical part made of composite material is, in particular, a material for construction or building, for example composite reinforcements, dowels and stirrups for civil engineering and large-scale construction height.
    In a second preferred embodiment, the mechanical part made of composite material is, in particular, a wind turbine part, for example, a sole of the beam spar of the wind turbine blade.
    [Examples] [0136] First Step: Preparation of a Liquid Composition or (Meth) Acrylic Syrup [0137] A liquid composition is prepared by dissolving 25% by weight of PMMA (BS520, an MMA copolymer comprising 1 ' ethyl acrylate as a comonomer) as (P1) in 75% by weight of methyl methacrylate as (Ml), which is stabilized with HQME (hydroquinone monomethyl ether).
    To this liquid composition are added different initiators (Inil) only or mixtures of two different initiators (Inil) and (Ini2). As initiators (Inil) or (Ini2), di (4-tert-butylcyclohexyl) peroxydicarbonate (P16 - Perkadox® 16 from Akzo Nobel), benzoyl peroxide (BPO - Perkadox® CH50X) are used. Akzo Nobel), t-butyl peroxy-2-ethylhexanoate (TBPO - Luperox® 26 from Arkema), dilauroyl peroxide (LP - Luperox® LP from Arkema) and peroxide didécanoyle (DEC Luperox® DEC from Arkema).
    The comparative examples do not include any mixture of two initiators (Inil) and (Ini2) according to the invention.
    Second step: polymerization of a liquid composition or of (meth) acrylic syrup The polymerization of respective compositions is carried out by adding to 100 parts by weight of the liquid composition (on the basis of (Ml) and ( Pl) only) of the initiator or initiators as indicated in Table 1. The respective compositions are heated to 110 ° C. in a metal press under a pressure of 10 bar.
    The time up to 95% conversion of the respective samples is measured and indicated in Table 1 for each composition.
    Table 1. Compositions and results at 110 ° C
    Inil[hr] Ini2[hr] time[s] Examplecomparative1 P162 Nopolymerizationcomplete * Examplecomparative2 LP2 302 Examplecomparative3 P163 Nopolymerizationcomplete * Example 1 P162 BPO1 166 Example 2 P162 DEC1 142 Example 3 P162 LP1 159 Example 4 P162 TBPO1 170 Example 5 P161 DEC2 164 Example 6 P161 LP2 180 Example 7 P161 TBPO2 174
    Conversion less than 50% The reduction in the polymerization time in Table 1 for the examples indicates better kinetics, faster polymerization, while exhibiting good conversion.
    Comparative examples 1 and 3 show a conversion of less than 50% at 110 ° C., and good conversion and faster polymerization are obtained using two initiators (see examples 1 to 7) compared to comparative example 2.
    权利要求:
    Claims (34)
    [1" id="c-fr-0001]
    1. Liquid composition comprising,
    a) a (meth) acrylic polymer (PI),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2), said liquid composition having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C.
    [2" id="c-fr-0002]
    2. Liquid composition according to claim 1, characterized in that the amount of two initiators (Inil) and (Ini2) together in the composition is between 0.1 phr and 15 phr relative to the sum of the (meth) acrylic monomer (Ml) and (meth) acrylic polymer (PI).
    [3" id="c-fr-0003]
    3. Liquid composition according to claim 1 or 2, characterized in that the two initiators (Inil) and (Ini2) have, at any given temperature T1, half-life times ti / 2 different.
    [4" id="c-fr-0004]
    4. Liquid composition according to claim 3, characterized in that the second initiator (Ini2) has, at a given temperature Ti, a half-life time ti / 2 which is at least twice the half-life time ti / 2 of the first initiator (Inil).
    [5" id="c-fr-0005]
    5. Liquid composition according to claim 3 or 4, characterized in that the first initiator (Inil) has a half-life time ti / 2 of 1 hour at a temperature between 40 ° C and 90 ° C.
    [6" id="c-fr-0006]
    6. Liquid composition according to claim 3 or 4, characterized in that the second initiator (Ini2) has a half-life time ti / 2 of 1 hour at a temperature of at least 70 ° C.
    [7" id="c-fr-0007]
    7. Liquid composition according to claim 3 or 4, characterized in that the second initiator (Ini2) has a half-life time ti / 2 of 1 hour at a temperature between 70 ° C and 150 ° C.
    [8" id="c-fr-0008]
    8. Liquid composition according to any one of claims 3 to 7, characterized in that the difference in temperature for a given half-life time between the initiator (Ini2) and (Inil) is at least 5 K .
    [9" id="c-fr-0009]
    9. Liquid composition according to any one of claims 3 to 7, characterized in that the temperature difference for a given half-life time between the initiator (Ini2) and (Inil) is at most 50 K.
    [10" id="c-fr-0010]
    10. Liquid composition according to any one of claims 3 to 7, characterized in that the temperature difference for a given half-life time between the initiator (Ini2) and (Inil) is between 5 K and 50 K .
    [11" id="c-fr-0011]
    11. Liquid composition according to any one of claims 1 to 10, characterized in that the two initiators (Inil) and (Ini2) are chosen from diacyl peroxides, peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyacetals , a hydroperoxide or a peroxyketal.
    methoxybutyl), tetramethylbutyl, tert-butyl, peroxydicarbonate
    [12" id="c-fr-0012]
    12. Liquid composition according to any one of claims 1 to 10, characterized in that the two initiators (Inil) and (Ini2) are chosen from diisobutyryl peroxide, cumyl peroxynodeodecanoate, di peroxydicarbonate (3 peroxynodecanoate , 3,3 cumyl peroxyneoheptanoate, di-n-propyl peroxydicarbonate, tert-amyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, dihexyl peroxydicarbonate ), di-n-butyl, diketyl peroxydicarbonate peroxyneodecanoate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxynoheptanoate, tertamyl peroxypivalate, tert-butyl peroxypivalate, peroxide - (3,5,5trimethylhexanoyl), dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, peroxy-2-ethylhexanoate 1,1,3,3-tetramethylbutyl , peroxy- Tert-amyl 2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxyisobutyrate, 1,1-di- (tertbutylperoxy) -3,3,5- trimethylcyclohexane, 1,1-di (tertamylperoxy) cyclohexane, 1,1-di- (tert-butylperoxy) -cyclohexane, peroxy-2-ethylhexyl tert-amyl, peroxyacetate tert-amyl, peroxy-3,5,5- tert-butyl trimethylhexanoate, 2,2-di- (tert-butylperoxy) -butane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxy-2-ethylhexylcarbonate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate,
    4.4- butyl di (tert-butylperoxy) valerate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di- (2-tert-butyl-peroxyisopropyl) -benzene, 2,5-dimethyl- 2,5di- (tert-butylperoxy) -hexane, tert-butylcumyl peroxide,
    2.5- dimethyl-2,5-di (tert-butylperoxy) hexyne-3, ditert-butyl peroxide, 3,6,9-triethyl-3,6,9-trimethyl-l, 4,7triperoxonane, 2,2 ' -azobisisobutyronitrile (AIBN), 2,2'-azodi (2-methylbutyronitrile), azobisiso-butyramide, 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'azodi (hexahydrobenzonitrile), or 4.4 ' -azobis (4cyanopentanolque).
    [13" id="c-fr-0013]
    13. Liquid composition according to any one of claims 1 to 11, characterized in that the initiator (Inil) is chosen from cumyl peroxynodeodecanoate, di (3-methoxybutyl) peroxicarbonate, 1,1.3 peroxynodecanoate, 3tetramethylbutyl, cumyl peroxynoeheptanoate, di-n-propyl peroxydicarbonate, tertamyl peroxynodeodecanoate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxide dicarbonate) , tert-butyl peroxyneodecanoate, di-n-butyl peroxydicarbonate, diketyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxynoheptanoate, tertamyl peroxypivalate, tert-butyl peroxypivalate , di- (3,5,5trimethylhexanoyl) peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) -hexane or peroxy-2-ethylhexanoate, 3.3-t traméthylbutyle.
    [14" id="c-fr-0014]
    14. Liquid composition according to any one of claims 1 to 11, characterized in that the initiator (Ini2) is chosen from tert-amyl peroxypivalate, tert-butyl peroxypivalate, di- (3,5,5- trimethylhexanoyl), dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di (2ethylhexanoylperoxy) -hexane, peroxy-2-ethylhexanoate
    1,1,3,3-tetramethylbutyl, tertamyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxyisobutyrate, 1,1-di- (tert -butylperoxy) -3.3.5 trimethylcyclohexane, 1,1-di (tert-amylperoxy) cyclohexane, 1,1di- (tert-butylperoxy) -cyclohexane, peroxy-2ethylhexylcarbonate of tert-amyl, peroxyacetate of tert-amyl, peroxy- Tert-butyl 3,5,5-trimethylhexanoate, 2,2-di- (tertbutylperoxy) -butane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxy-2-ethylhexylcarbonate, tert-amyl peroxybenzoate, tert- peroxyacetate butyl, 4,4-di (tertbutylperoxy) butyl valerate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di- (2-tertbutyl-peroxyisopropyl) -benzene, 2,5-dimethyl- 2,5-di- (tertbutylperoxy) -hexane, tert-butylcumyl peroxide, 2,5dimethyl-2,5-di (tert-butylperoxy) hexyne-3, di-tertbutyl peroxide or 3,6,9-triethyl- 3,6,9-trimethyl-1,4,7- triperoxonane.
    [15" id="c-fr-0015]
    15. Liquid composition according to any one of claims 1 to 14, characterized in that the (meth) acrylic polymer (PI) comprises at least 50% by weight of methyl methacrylate (MMA).
    [16" id="c-fr-0016]
    16. Liquid composition according to any one of claims 1 to 15, characterized in that the (meth) acrylic monomer (Ml) is chosen from acrylic acid, methacrylic acid, alkyl acrylic monomers and alkyl methacrylic monomers, and mixtures thereof, the alkyl group containing from 1 to 22 linear, branched or cyclic carbons; the alkyl group preferably containing from 1 to 12 linear, branched or cyclic carbons.
    [17" id="c-fr-0017]
    17. Liquid composition according to any one of claims 1 to 16, characterized in that 50% by weight of the (meth) acrylic monomer (Ml) is methyl methacrylate.
    [18" id="c-fr-0018]
    18. A method of preparing a liquid composition according to any one of claims 1 to 17, said method comprising the following steps:
    i) preparation of a mixture of (meth) acrylic polymer (PI) and of (meth) acrylic monomer (Ml) ii) addition of initiators (Inil) and (Ini2) jointly or one after the other to the mixture prepared in the previous step.
    [19" id="c-fr-0019]
    19. Use of the liquid composition according to any one of claims 1 to 17 or prepared by a process according to claim 18, for manufacturing thermoplastic parts or manufacturing composite parts.
    [20" id="c-fr-0020]
    20. Use of the liquid composition according to any one of claims 1 to 17 or prepared by a process according to claim 18 for impregnating fibers or a fibrous substrate, said fibers or said fibrous substrate being made up of long fibers.
    [21" id="c-fr-0021]
    21. An impregnation method for impregnating a fibrous substrate, said fibrous substrate consisting of long fibers and said method comprising a step of impregnating said fibrous substrate with a liquid composition according to any one of claims 1 to 17.
    [22" id="c-fr-0022]
    22. Method for manufacturing thermoplastic parts by a method comprising the following steps:
    i) preparation of a liquid mixture of (meth) acrylic polymer (Pl) and (meth) acrylic monomer (Ml) ii) addition of initiators (Inil) and (Ini2) jointly or one after the other mixture prepared in the previous step.
    iii) placing the liquid composition prepared in i) and ii) in polymerization means, said composition being characterized in that it comprises:
    a) a (meth) acrylic polymer (Pl),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C, according to any one of claims 1 to 17, iv) polymerization.
    [23" id="c-fr-0023]
    23. Process for manufacturing composite parts by a process comprising the following steps:
    iii) impregnating fibers or a fibrous substrate with the liquid composition according to any one of claims 1 to 17, iv) polymerization.
    [24" id="c-fr-0024]
    24. Process for manufacturing composite parts by a process comprising the following steps:
    i) preparation of a mixture of (meth) acrylic polymer (Pl) and (meth) acrylic monomer (Ml) ii) addition of initiators (Inil) and (Ini2) jointly or one after the other to the mixture prepared in the previous step, iii) impregnating fibers or a fibrous substrate with the liquid composition prepared in i) and ii), said composition being characterized in that it comprises:
    a) a (meth) acrylic polymer (Pl),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C, iv) polymerization.
    [25" id="c-fr-0025]
    25. The method of claim 23 or 24 conducted by vacuum assisted resin infusion (VARI), pultrusion, vacuum infusion molding, pressure infusion molding, autoclave molding, resin transfer molding (RTM) and variants thereof such as (HP-RTM, C-RTM, I-RTM), reaction injection molding (RIM), enhanced reaction injection molding (R-RIM) and variants thereof , press molding, compression molding, liquid compression molding (LCM) or sheet molding (SMC) or bulk molding (BMC).
    [26" id="c-fr-0026]
    26. The method of claim 23 or 24 characterized in that the impregnation step is carried out in a mold.
    [27" id="c-fr-0027]
    27. The method of claim 23 or 24 characterized in that the impregnation step is carried out during a pultrusion process.
    [28" id="c-fr-0028]
    28. Method according to any one of claims 23 to 27 characterized in that the method comprises the additional post-forming step.
    [29" id="c-fr-0029]
    29. Method according to any one of claims 23 to 27 characterized in that the method comprises the additional step of welding or gluing or rolling.
    [30" id="c-fr-0030]
    30. A polymer composite material comprising a thermoplastic (meth) acrylic matrix and a fibrous substrate used as a reinforcement, in which the fibrous substrate consists of long fibers, said composite material being characterized in that the thermoplastic (meth) acrylic matrix is obtained after polymerization of the liquid composition, said fibrous substrate being prepreg with the liquid composition according to any one of claims 1 to 17.
    [31" id="c-fr-0031]
    31. Mechanical part or structural element made up of the composite material according to claim 30, or obtained by the process according to any one of claims 23 to 29.
    [32" id="c-fr-0032]
    32. Part according to claim 31, said part being a motor vehicle part, a boat part, a train part, a sporting article, an airplane or helicopter part, a spacecraft part or rocket, a part of a photovoltaic module, a material for construction or building, for example reinforcements, dowels and composite stirrups for civil engineering and high-rise construction, a part of wind turbine, for example a sole of spar of a wind turbine blade beam, a piece of furniture, a construction or building piece, a telephone or cell phone piece, a computer or television piece, a printer or photocopier piece.
    [33" id="c-fr-0033]
    33. Part according to claim 31, said part being a material for construction or building, reinforcements, pegs and composite stirrups for civil engineering and high-rise construction.
    [34" id="c-fr-0034]
    34. Part according to claim 31, said part being a part of a wind turbine, for example a sole of a beam spar of a wind turbine blade.
    1. Liquid composition comprising,
    a) a (meth) acrylic polymer (PI),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2), said liquid composition having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C.
    2. Liquid composition according to claim 1, characterized in that the amount of two initiators (Inil) and (Ini2) together in the composition is between 0.1 phr and 15 phr relative to the sum of the (meth) acrylic monomer (Ml) and (meth) acrylic polymer (PI).
    3. Liquid composition according to claim 1 or 2, characterized in that the two initiators (Inil) and (Ini2) have, at any given temperature T1, half-life times ti / 2 different.
    4. Liquid composition according to claim 3, characterized in that the second initiator (Ini2) has, at a given temperature Ti, a half-life time ti / 2 which is at least twice the half-life time ti / 2 of the first initiator (Inil).
    5. Liquid composition according to claim 3 or 4, characterized in that the first initiator (Inil) has a half-life time ti / 2 of 1 hour at a temperature between 40 ° C and 90 ° C.
    6. Liquid composition according to claim 3 or 4, characterized in that the second initiator (Ini2) has a half-life time ti / 2 of 1 hour at a temperature of at least 70 ° C.
    7. Liquid composition according to claim 3 or 4, characterized in that the second initiator (Ini2) has a half-life time ti / 2 of 1 hour at a temperature between 70 ° C and 150 ° C.
    8. Liquid composition according to any one of claims 3 to 7, characterized in that the difference in temperature for a given half-life time between the initiator (Ini2) and (Inil) is at least 5 K .
    9. Liquid composition according to any one of claims 3 to 7, characterized in that the temperature difference for a given half-life time between the initiator (Ini2) and (Inil) is at most 50 K.
    10. Liquid composition according to any one of claims 3 to 7, characterized in that the temperature difference for a given half-life time between the initiator (Ini2) and (Inil) is between 5 K and 50 K .
    11. Liquid composition according to any one of claims 1 to 10, characterized in that the two initiators (Inil) and (Ini2) are chosen from diacyl peroxides, peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyacetals , a hydroperoxide or a peroxyketal.
    methoxybutyl), tetramethylbutyl, tert-butyl, peroxydicarbonate
    12. Liquid composition according to any one of claims 1 to 10, characterized in that the two initiators (Inil) and (Ini2) are chosen from diisobutyryl peroxide, cumyl peroxynodeodecanoate, di peroxydicarbonate (1.1 peroxynodecanoate , 3,3 cumyl peroxyneoheptanoate, di-n-propyl peroxydicarbonate, tert-amyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, dihexyl peroxydicarbonate ), di-n-butyl-, diketyl peroxydicarbonate peroxyneodecanoate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxynoheptanoate, tertamyl peroxypivalate, tert-butyl peroxypivalate, di- (3,5,5trimethylhexanoyl), dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, peroxy-2-ethylhexanoate 1,1,3,3- tetramethylbutyl, peroxy Tert-amyl -2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxyisobutyrate, 1,1-di- (tertbutylperoxy) -3,3,5 -trimethylcyclohexane, 1,1-di (tertamylperoxy) cyclohexane, 1,1-di- (tert-butylperoxy) -cyclohexane, peroxy-2-ethylhexyl tert-amylcarbonate, peroxyacetate tert-amyl, peroxy-3,5,5 tert-butyl trimethylhexanoate, 2,2-di- (tert-butylperoxy) -butane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxy-2-ethylhexylcarbonate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate,
    4.4- butyl di (tert-butylperoxy) valerate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di- (2-tert-butyl-peroxyisopropyl) -benzene, 2,5-dimethyl- 2,5di- (tert-butylperoxy) -hexane, tert-butylcumyl peroxide,
    2.5- dimethyl-2,5-di (tert-butylperoxy) hexyne-3, ditert-butyl peroxide, 3,6,9-triethyl-3,6,9-trimethyl-l, 4,7triperoxonane, 2,2 ' -azobisisobutyronitrile (AIBN), 2,2'-azodi (2-methylbutyronitrile), azobisiso-butyramide, 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'azodi (hexahydrobenzonitrile), or 4.4 ' -azobis (4cyanopentanolque).
    13. Liquid composition according to any one of claims 1 to 11, characterized in that the initiator (Inil) is chosen from cumyl peroxynodeodecanoate, di (3-methoxybutyl) peroxicarbonate, 1,1.3 peroxynodecanoate, 3tetramethylbutyl, cumyl peroxynoeheptanoate, di-n-propyl peroxydicarbonate, tertamyl peroxynodeodecanoate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxide dicarbonate) , tert-butyl peroxyneodecanoate, di-n-butyl peroxydicarbonate, diketyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxynoheptanoate, tertamyl peroxypivalate, tert-butyl peroxypivalate , di- (3,5,5trimethylhexanoyl) peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) -hexane or peroxy-2-ethylhexanoate, 3.3-t traméthylbutyle.
    14. Liquid composition according to any one of claims 1 to 11, characterized in that the initiator (Ini2) is chosen from tert-amyl peroxypivalate, tert-butyl peroxypivalate, di- (3,5,5- trimethylhexanoyl), dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di (2ethylhexanoylperoxy) -hexane, peroxy-2-ethylhexanoate
    1,1,3,3-tetramethylbutyl, tertamyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxyisobutyrate, 1,1-di- (tert -butylperoxy) -3,3,5 trimethylcyclohexane, 1,1-di (tert-amylperoxy) cyclohexane, 1,1di- (tert-butylperoxy) -cyclohexane, peroxy-2ethylhexylcarbonate of tert-amyl, peroxyacetate of tert-amyl, peroxy- Tert-butyl 3,5,5-trimethylhexanoate, 2,2-di- (tertbutylperoxy) -butane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxy-2-ethylhexylcarbonate, tert-amyl peroxybenzoate, tert- peroxyacetate butyl, 4,4-di (tertbutylperoxy) butyl valerate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di- (2-tertbutyl-peroxyisopropyl) -benzene, 2,5-dimethyl- 2,5-di- (tertbutylperoxy) -hexane, tert-butylcumyl peroxide, 2,5dimethyl-2,5-di (tert-butylperoxy) hexyne-3, di-tertbutyl peroxide or 3,6,9-triethyl- 3,6,9-trimethyl-1,4,7-t riperoxonane.
    15. Liquid composition according to any one of claims 1 to 14, characterized in that the (meth) acrylic polymer (Pl) comprises at least 50% by weight of methyl methacrylate (MMA).
    16. Liquid composition according to any one of claims 1 to 15, characterized in that the (meth) acrylic monomer (Ml) is chosen from acrylic acid, methacrylic acid, alkyl acrylic monomers and alkyl methacrylic monomers, and mixtures thereof, the alkyl group containing from 1 to 22 linear, branched or cyclic carbons; the alkyl group preferably containing from 1 to 12 linear, branched or cyclic carbons.
    17. Liquid composition according to any one of claims 1 to 16, characterized in that 50% by weight of the (meth) acrylic monomer (Ml) is methyl methacrylate.
    18. A method of preparing a liquid composition according to any one of claims 1 to 17, said method comprising the following steps:
    i) preparation of a mixture of (meth) acrylic polymer (Pl) and (meth) acrylic monomer (Ml) ii) addition of initiators (Inil) and (Ini2) jointly or one after the other to the mixture prepared in the previous step.
    19. Use of the liquid composition according to any one of claims 1 to 17 or prepared by a process according to claim 18, for manufacturing thermoplastic parts or manufacturing composite parts.
    20. Use of the liquid composition according to any one of claims 1 to 17 or prepared by a process according to claim 18 for impregnating fibers or a fibrous substrate, said fibers or said fibrous substrate being made up of long fibers.
    21. An impregnation method for impregnating a fibrous substrate, said fibrous substrate consisting of long fibers and said method comprising a step of impregnating said fibrous substrate with a liquid composition according to any one of claims 1 to 17.
    22. Method for manufacturing thermoplastic parts by a method comprising the following steps:
    i) preparation of a liquid mixture of (meth) acrylic polymer (PI) and of (meth) acrylic monomer (Ml) ii) addition of initiators (Inil) and (Ini2) jointly or one after the other mixture prepared in the previous step.
    iii) placing the liquid composition prepared in i) and ii) in polymerization means, said composition being characterized in that it comprises:
    a) a (meth) acrylic polymer (PI),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C, according to any one of claims 1 to 17, iv) polymerization.
    23. Process for manufacturing composite parts by a process comprising the following steps:
    iii) impregnating fibers or a fibrous substrate with the liquid composition according to any one of claims 1 to 17, iv) polymerization.
    24. Process for manufacturing composite parts by a process comprising the following steps:
    i) preparation of a mixture of (meth) acrylic polymer (PI) and of (meth) acrylic monomer (Ml) ii) addition of initiators (Inil) and (Ini2) jointly or one after the other to the mixture prepared in the previous step, iii) impregnating fibers or a fibrous substrate with the liquid composition prepared in i) and ii), said composition being characterized in that it comprises:
    a) a (meth) acrylic polymer (PI),
    b) a (meth) acrylic monomer (Ml), and
    c) two initiators (Inil) and (Ini2);
    said liquid (meth) acrylic syrup having a dynamic viscosity of between 10 mPa * s and 10,000 mPa * s at 25 ° C, iv) polymerization.
    25. The method of claim 23 or 24 conducted by vacuum assisted resin infusion (VARI), pultrusion, vacuum infusion molding, pressure infusion molding, autoclave molding, resin transfer molding (RTM) and variants thereof such as (HP-RTM, C-RTM, I-RTM), reaction injection molding (RIM), enhanced reaction injection molding (R-RIM) and variants thereof , press molding, compression molding, liquid compression molding (LCM) or sheet molding (SMC) or bulk molding (BMC).
    26. The method of claim 23 or 24 characterized in that the impregnation step is carried out in a mold.
    27. The method of claim 23 or 24 characterized in that the impregnation step is carried out during a pultrusion process.
    28. Method according to any one of claims 23 to 27 characterized in that the method comprises the additional post-forming step.
    29. Method according to any one of claims 23 to 27 characterized in that the method comprises the additional step of welding or gluing or rolling.
    30. A polymer composite material comprising a thermoplastic (meth) acrylic matrix and a fibrous substrate used as a reinforcement, in which the fibrous substrate consists of long fibers, said composite material being characterized in that the thermoplastic (meth) acrylic matrix is obtained after polymerization of the liquid composition, said fibrous substrate being prepreg with the liquid composition according to any one of claims 1 to 17.
    31. Mechanical part or structural element made up of the composite material according to claim 30, or obtained by the process according to any one of claims 23 to 29.
    32. Part according to claim 31, said part being a motor vehicle part, a boat part, a train part, a sporting article, an airplane or helicopter part, a spacecraft part or rocket, a part of a photovoltaic module, a material for construction or building, for example reinforcements, dowels and composite stirrups for civil engineering and high-rise construction, a part of wind turbine, for example a sole of spar of a wind turbine blade beam, a piece of furniture, a construction or building piece, a telephone or cell phone piece, a computer or television piece, a printer or photocopier piece.
    33. Part according to claim 31, said part being a material for construction or building, reinforcements, pegs and composite stirrups for civil engineering and high-rise construction.
    34. Part according to claim 31, said part being a part of a wind turbine, for example a sole of a beam spar of a wind turbine blade.
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    同族专利:
    公开号 | 公开日
    EP3559335A1|2019-10-30|
    CA3044608A1|2018-06-28|
    FR3060577B1|2020-11-06|
    CN110088388A|2019-08-02|
    BR112019011102A2|2019-10-08|
    KR20190091287A|2019-08-05|
    WO2018115342A1|2018-06-28|
    MX2019006506A|2019-08-21|
    JP2020502349A|2020-01-23|
    US20200010639A1|2020-01-09|
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    法律状态:
    2017-11-13| PLFP| Fee payment|Year of fee payment: 2 |
    2018-06-22| PLSC| Publication of the preliminary search report|Effective date: 20180622 |
    2019-11-14| PLFP| Fee payment|Year of fee payment: 4 |
    2020-11-12| PLFP| Fee payment|Year of fee payment: 5 |
    2021-11-15| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1663063A|FR3060577B1|2016-12-21|2016-12-21|LIQUID COMPOSITION COMPRISING TWO INITIATORS, ITS POLYMERIZATION PROCESS, USE AND MATERIAL OR COMPOSITION OBTAINED AFTER POLYMERIZATION OF THE COMPOSITION|
    FR1663063|2016-12-21|FR1663063A| FR3060577B1|2016-12-21|2016-12-21|LIQUID COMPOSITION COMPRISING TWO INITIATORS, ITS POLYMERIZATION PROCESS, USE AND MATERIAL OR COMPOSITION OBTAINED AFTER POLYMERIZATION OF THE COMPOSITION|
    CA3044608A| CA3044608A1|2016-12-21|2017-12-21|Liquid composition comprising two initiators, its process of polymerization, use and material or composition obtained following polymerization of composition|
    KR1020197017704A| KR20190091287A|2016-12-21|2017-12-21|Liquid compositions comprising two initiators, methods of polymerization thereof, uses and materials or compositions obtained after polymerization of the compositions|
    MX2019006506A| MX2019006506A|2016-12-21|2017-12-21|Liquid composition comprising two initiators, its process of polymerization, use and material or composition obtained following polymerization of composition.|
    CN201780079149.5A| CN110088388A|2016-12-21|2017-12-21|Liquid composition comprising two kinds of initiators, its polymerization, purposes and the material or composition obtained after composition polymerization|
    JP2019533527A| JP2020502349A|2016-12-21|2017-12-21|Liquid composition comprising two initiators, its polymerization method, use and materials, or composition obtained after polymerization of the composition|
    PCT/EP2017/084201| WO2018115342A1|2016-12-21|2017-12-21|Liquid composition comprising two initiators, its process of polymerization, use and material or composition obtained following polymerization of composition|
    BR112019011102A| BR112019011102A2|2016-12-21|2017-12-21|liquid composition comprising two initiators, their polymerization process, use and material or composition obtained following composition polymerization|
    EP17818172.3A| EP3559335A1|2016-12-21|2017-12-21|Liquid composition comprising two initiators, its process of polymerization, use and material or composition obtained following polymerization of composition|
    US16/468,003| US20200010639A1|2016-12-21|2017-12-21|Liquid composition comprising two initiators, its process of polymerization, use and material or composition obtainedfollowing polymerization of composition|
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