Liquid composition comprising three initiators, its process of polymerization, use and material or composition obtained following polymerization of composition

Abstract

To provide a liquid composition comprising an initiator that enables fast polymerization with high conversion efficiency.SOLUTION: A liquid composition comprises, a) a (meth)acrylic polymer (P1), b) a (meth)acrylic monomer (M1), and c) three initiators (Ini1), (Ini2) and (Ini3), the liquid composition having a dynamic viscosity of between 10 mPa*s and 10,000 mPa*s at 25°C.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a liquid composition comprising a monomer, a (meth)acrylic polymer, and at least three initiators.

[0002] In particular, the invention relates to a liquid composition comprising a monomer, a (meth)acrylic polymer, and at least three initiators with different half-lives. The liquid composition can be used as a syrup, in particular as a syrup for impregnation of fibers or fibrous materials. It also relates to a thermoplastic material obtained after polymerization of the liquid composition. The invention also relates to a process for producing such a liquid composition. The invention also relates to a process for impregnating a fibrous substrate of long fibers with said liquid composition. The invention also relates to a fibrous substrate impregnated with said liquid composition, useful for the manufacture of composite parts.

[0003] The invention also relates to a process for manufacturing a mechanical part or a structural element made of a composite material, as well as to a mechanical part or a structural element made of a composite material obtainable by a process using such a liquid composition. [Background technology]

[0004] Thermoplastic polymers are materials widely used in several sectors and applications, for example in the construction, aviation, automotive or railway sectors, and are part of machine components.

[0005] These mechanical parts, which must withstand high stresses during use, are widely manufactured from composite materials. A composite material is a macroscopic combination of two or more immiscible materials. It consists of at least one material that forms the matrix, i.e. the continuous phase that ensures the bond of the structure, and a reinforcing material.

[0006] The purpose of composite materials is to obtain performance qualities that are not available from each of their components when used separately. As a result, composite materials are widely used in several industrial sectors, e.g., construction, automotive, aerospace, transportation, leisure, electronics, sports, etc., due to their good mechanical performance (higher tensile strength, higher tensile modulus, higher fracture toughness) and lower density compared to homogeneous materials.

[0007] It is also preferred to use thermoplastic polymers in composite materials to allow for thermoforming and recycling.

[0008] Thermoplastic polymers consist of linear or branched polymers that are usually not crosslinked. They are heated to mix the components required for the production of the composite and cooled to harden the final shape. The problem with these molten thermoplastic polymers is that they are very viscous. To prepare polymer composites based on thermoplastic polymers, a thermoplastic polymer resin, commonly known as a "syrup", is used to impregnate a reinforcing material, such as a fibrous substrate. Once polymerized, the thermoplastic polymer syrup constitutes the matrix of the composite.

[0009] During impregnation, when preparing a polymer composite, the viscosity of the impregnation syrup must be controlled and adapted so that it is not too fluid or too viscous, in order to properly impregnate each fiber of the fibrous substrate. Depending on whether the syrup is too fluid or too viscous, if the wetting is partial, "bare" zones, i.e. non-impregnated zones, and zones where droplets of polymer form on the fibers, which are responsible for the generation of air bubbles, respectively, appear. These "bare" zones and these air bubbles give rise to the appearance of defects in the final composite, which are responsible, among other things, for the loss of mechanical strength of the final composite.

[0010] Even when used without impregnation, it is desirable to obtain a liquid composition that polymerizes quickly with good conversion in order to increase productivity.

[0011] Liquid compositions or syrups comprising (meth)acrylic monomers and (meth)acrylic polymers are described in WO 2013 / 056845 and WO 2014 / 013028. Polymerization of the monomer(s) in both documents is achieved using an initiation system comprising a radical-generating initiator(s) or a radical-generating initiator system(s). Both documents use benzoyl peroxide in the examples.

[0012] WO 2014 / 174098 discloses a liquid (meth)acrylic syrup. The syrup comprises an initiator 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 tens of minutes.

[0013] WO 2015 / 110534 discloses an impregnation process for fibrous substrates, a liquid monomer syrup for the impregnation process, a polymerization method thereof, and structural articles obtained therefrom. The document only discloses a list of initiators in a general form and discloses that a combination of two of them can be used.

[0014] WO 2013 / 056845 discloses composites by in situ polymerization of thermoplastic (meth)acrylic resins. The document only discloses a list of initiators in a general form and that combinations of two of them can be used.

[0015] US Patent No. 4,328,329 discloses a process for polymerizing methyl methacrylate syrup using a dual initiator system. The process involves a cast sheet process with cycle times of several tens of minutes, with a temperature profile during polymerization from 80° C. to 135° C. One of the initiators used is always 2,2′-azobis(isobutyronitrile).

[0016] U.S. Patent No. 4,605,717 discloses the preparation of acrylic polymer sheets using a ternary peroxide initiator system. The process uses two temperature ranges: 45° C. to 90° C. for the first two initiators, and 110° C. to 140° C. for the final cure with the third initiator.

[0017] EP 0189930 A1 discloses a process for preparing acrylic polymers using a dual peroxide initiator system, using two temperature ranges: 45°C to 90°C for 10 to 100 minutes with the first initiator, and 110°C to 140°C for 5 to 60 minutes for the final cure with the second initiator.

[0018] US Patent No. 5,151,482 discloses a process for making methacrylic resin sheets. The process uses two initiators. The process also includes different temperature ramps, including heating and cooling ramps, and a final high temperature cure.

[0019] US Patent No. 4,211,742 discloses a process for continuous casting of liquid polymerizable compositions. Even with a sheet thickness of 3 mm, the polymerization time is at least 15 minutes. The process also includes different temperature ramps and a final high temperature cure.

[0020] French patent application FR 1 663 063 discloses a liquid composition comprising a monomer, a (meth)acrylic polymer, and at least two initiators, the two initiators having different half-lives.

[0021] Korean Patent Application Publication No. 2004 / 0014252 discloses impact-resistant methacrylic moldings and their manufacturing method. The process uses a ternary peroxide initiator system and a wide temperature range from 46°C to 120°C for several hours.

[0022] None of these documents suggests that the incorporation of three initiators in a liquid composition would allow rapid and complete polymerization, especially in processes using simple temperature profiles, especially with short cycle times of less than 15 minutes and low residual monomer contents. Summary of the Invention

[0023] It is therefore an object of the present invention to ameliorate at least one of the disadvantages of the prior art.

[0024] The object of the present invention is to obtain a liquid composition comprising a monomer, a (meth)acrylic polymer, and an initiator to have a composition that can be polymerized quickly and with good conversion. By good conversion, it is understood that at least 95%, preferably at least 99% of the monomer is polymerized. By fast, it is understood that the polymerization takes place in less than 15 minutes, preferably less than 10 minutes, even more preferably less than 5 minutes, advantageously less than 3 minutes.

[0025] It is also an object of the present invention to obtain a process for rapid polymerization of a liquid composition comprising a monomer, a (meth)acrylic polymer, and an initiator for good conversion and easy demolding.

[0026] Yet another object of the present invention is to use a liquid composition comprising monomers, (meth)acrylic polymers and initiators for rapid polymerization and good conversion with less than 1% residual monomer based on the amount of monomers initially used.

[0027] The present invention is also directed to complete, precise and uniform wetting of fibrous substrates during impregnation, as defects in fiber wetting, for example due to air bubbles and voids, reduce the mechanical performance of the manufactured mechanical or structured parts or articles, or the final composite part.

[0028] Another object of the present invention is to propose a process that can be carried out at low cost and allows industrial-scale production of mechanical parts or structural elements made of thermoplastic polymers or thermoplastic composites.In addition, the process must be easy and simple to carry out, using commercially available compounds.The production of composite parts must also be reproducible and rapid, which means short cycle times of less than 15 minutes, preferably less than 10 minutes, even more preferably less than 5 minutes, advantageously less than 3 minutes.

[0029] Surprisingly, a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) Including, It has been found that said liquid compositions, wherein said liquid (meth)acrylic syrup has a kinematic viscosity between 10 mPa*s and 10,000 mPa*s at 25°C, produce a thermoplastic polymer composition after polymerization of said (meth)acrylic monomer (M1), said thermoplastic polymer composition having faster kinetics and higher conversion of (meth)acrylic monomer (M1) compared to compositions comprising only one initiator (Ini1) or (Ini2), or a mixture of (Ini1) and (Ini2).

[0030] 1. A liquid composition comprising: a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2) and (Ini3) Including, It has also been found that a liquid composition, wherein the liquid (meth)acrylic syrup has a dynamic viscosity at 25° C. between 10 mPa*s and 10,000 mPa*s, can be used to produce a thermoplastic polymer composition after polymerization of the (meth)acrylic monomer (M1), said thermoplastic polymer composition having a lower content of residual monomers compared to a composition comprising only one initiator (Ini1) or (Ini2), or a mixture of (Ini1) and (Ini2).

[0031] 1. A liquid composition comprising: a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2) and (Ini3) Including, It has also been found that using liquid compositions, said liquid (meth)acrylic syrup having a dynamic viscosity between 10 mPa*s and 10,000 mPa*s at 25° C., a thermoplastic polymer composition can be produced much faster after polymerization of said (meth)acrylic monomer (M1), said thermoplastic polymer composition having a lower content of residual monomers compared to compositions comprising only one initiator (Ini1) or (Ini2), or a mixture of (Ini1) and (Ini2).

[0032] A liquid (meth)acrylic composition for impregnating a fibrous substrate, the fibrous substrate comprising long fibers, a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2) and (Ini3) Including, The liquid (meth)acrylic syrup has a dynamic viscosity of between 10 mPa*s and 10,000 mPa*s at 25° C., It has also been found to provide complete and accurate impregnation of the fibrous substrate.

[0033] The Applicant has also surprisingly found that an impregnation process for impregnating a fibrous substrate, said fibrous substrate consisting of long fibers, comprising a step of impregnating said fibrous substrate with said liquid composition or with a liquid (meth)acrylic impregnation syrup, gives complete and accurate impregnation of the fibrous substrate, allowing a rapid and complete polymerization with good conversion, compared to a composition comprising only the initiators (Ini1) or (Ini2) or a mixture of (Ini1) and (Ini2).

[0034] Surprisingly, there is provided a process for manufacturing a composite part, comprising the steps of: i) a fibrous substrate; a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) impregnating with such a liquid composition or (meth)acrylic syrup, ii) polymerizing the liquid (meth)acrylic syrup impregnated into the fibrous substrate; It has also been found that a thermoplastic composite part can be obtained with significantly improved productivity by a process comprising:

[0035] Moreover, it has been found that the composite parts obtained by the manufacturing process have a significantly improved residual monomer content, due to a better conversion of the monomers, which is less than 5% relative to the amount of monomer used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0036] According to a first aspect, the present invention provides a method for producing a composition comprising: a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) A liquid composition comprising: The liquid composition has a kinematic viscosity at 25°C between 10 mPa*s and 10,000 mPa*s.

[0037] According to a second aspect, the present invention relates to a liquid composition for impregnating a fibrous substrate, said fibrous substrate consisting of long fibres, said liquid composition comprising: a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) The present invention is characterized in that it comprises The liquid (meth)acrylic syrup has a dynamic viscosity at 25° C. between 10 mPa*s and 10,000 mPa*s.

[0038] According to a third aspect, the present invention relates to a process for preparing a liquid composition, said liquid composition comprising: a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) The present invention is characterized in that it comprises The liquid (meth)acrylic syrup is i) preparing a liquid mixture of a (meth)acrylic polymer (P1) and a (meth)acrylic monomer (M1); ii) adding initiators (Ini1), (Ini2) and (Ini3) together or sequentially to the mixture prepared in the previous step; The composition has a kinematic viscosity of between 10 mPa*s and 10,000 mPa*s at 25°C by a process including

[0039] 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 fibres, said liquid composition comprising: a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) The present invention is characterized in that it comprises The liquid (meth)acrylic syrup has a dynamic viscosity at 25° C. between 10 mPa*s and 10,000 mPa*s.

[0040] According to a fifth aspect, the present invention relates to the use of a liquid composition for producing a thermoplastic part or for producing a composite part, said liquid composition comprising a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) The present invention is characterized in that it comprises The liquid (meth)acrylic syrup has a dynamic viscosity at 25° C. between 10 mPa*s and 10,000 mPa*s.

[0041] According to a sixth aspect, the present invention relates to a process for producing a thermoplastic part, comprising: i) preparing a liquid mixture of a (meth)acrylic polymer (P1) and a (meth)acrylic monomer (M1); ii) adding initiators (Ini1), (Ini2) and (Ini3) together or sequentially to the mixture prepared in the previous step; iii) placing the liquid (meth)acrylic composition prepared in i) and ii) in a means for polymerization, said composition comprising: a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) The present invention is characterized in that it comprises the liquid (meth)acrylic syrup having a kinematic viscosity of between 10 mPa*s and 10,000 mPa*s at 25° C. iv) polymerizing The present invention relates to a process for manufacturing a thermoplastic part by a process comprising:

[0042] According to a seventh aspect, the present invention relates to a process for manufacturing a composite part, comprising: i) preparing a mixture of a (meth)acrylic polymer (P1) and a (meth)acrylic monomer (M1) ii) adding initiators (Ini1), (Ini2) and (Ini3) together or sequentially to the mixture prepared in the previous step; iii) impregnating a fiber or fibrous substrate with the liquid (meth)acrylic composition prepared in i) and ii), said composition comprising: a) (meth)acrylic polymer (P1), b) (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) The present invention is characterized in that it comprises the liquid (meth)acrylic syrup having a kinematic viscosity of between 10 mPa*s and 10,000 mPa*s at 25° C. iv) polymerizing The present invention relates to a process for manufacturing a composite part by a process comprising:

[0043] The term "fibrous substrate" as used refers to a mat, woven, felt, or nonwoven fabric of several fibers, unidirectional rovings, or continuous filaments, which may be in the form of strips, wraps, braids, locks, or pieces.

[0044] The term "(meth)acrylic" as used refers to any type of acrylic or methacrylic monomer.

[0045] The term "PMMA" as used refers to homopolymers and copolymers of methyl methacrylate (MMA), the weight ratio of MMA in PMMA being at least 70% by weight for MMA copolymers.

[0046] The term "monomer" as used refers to a molecule that can undergo polymerization.

[0047] The term "polymerization" as used refers to the process of converting a monomer or mixture of monomers into a polymer.

[0048] The term "thermoplastic polymer" as used refers to a polymer that when heated turns into a liquid or becomes more liquid or less viscous and softer and can assume new shapes through the application of heat and pressure. This also applies to lightly crosslinked thermoplastic polymers that can be thermoformed when heated above their softening temperature.

[0049] The term "polymer composite" as used refers to a multicomponent material that includes several distinct phase domains, in which at least one type of phase domain is a continuous phase and at least one component is a polymer.

[0050] The term "initiator" as used refers to a compound capable of starting / initiating the polymerization of one or more monomers.

[0051] The term "half-life", t1 / 2, is used to refer to the time required to reduce the concentration by half relative to the initial amount of initiator. This time is a function of temperature.

[0052] The abbreviation "phr" means parts by weight per 100 parts of composition. For example, 1 phr of initiator in a composition means that 1 kg of initiator is added to 100 kg of the composition.

[0053] The abbreviation "ppm" means parts per million by weight of a composition. For example, 1000 ppm of a compound in a composition means that 0.1 kg of the compound is present in 100 kg of the composition.

[0054] In the present invention, a range from x to y includes the upper and lower limits of the range, and corresponds to at least x and up to y.

[0055] In the present invention, a range between x and y means that the upper and lower limits of the range are excluded, which corresponds to greater than x and less than y.

[0056] The liquid composition or (meth)acrylic syrup according to the present invention comprises a (meth)acrylic monomer (M1) or a mixture of (meth)acrylic monomers (M1) and (M1+x), a (meth)acrylic polymer (P1) and at least three initiators (Ini1), (Ini2) and (Ini3).

[0057] The dynamic viscosity of the liquid composition or (meth)acrylic syrup ranges from 10 mPa*s to 10000 mPa*s, preferably from 20 mPa*s to 7000 mPa*s, advantageously from 20 mPa*s to 5000 mPa*s, advantageously from 20 mPa*s to 2000 mPa*s, and even more advantageously between 20 mPa*s and 1000 mPa*s. The viscosity of the syrup can be easily measured with a rheometer or viscometer. The dynamic viscosity is measured at 25°C. If the liquid (meth)acrylic syrup has Newtonian behavior and is not shear thinning, the dynamic viscosity is independent of the shear of the rheometer or the mobile speed of the viscometer. If the liquid composition has non-Newtonian behavior and is shear thinning, the dynamic viscosity is measured at 25°C for 1 s. -1 The shear rate is measured.

[0058] The liquid composition or (meth)acrylic syrup according to the invention for impregnating fibrous substrates comprises, inter alia, a (meth)acrylic monomer or a mixture of a (meth)acrylic monomer, a (meth)acrylic polymer and at least three initiators (Ini1), (Ini2) and (Ini3).

[0059] The liquid composition of the present invention comprises a (meth)acrylic monomer (M1), a (meth)acrylic polymer (P1), and at least three initiators (Ini1), (Ini2), and (Ini3). Once polymerized, the (meth)acrylic monomer (M1) is converted into a (meth)acrylic polymer (P2) comprising monomer units of the (meth)acrylic monomer (M1).

[0060] The combined amount of the three initiators (Ini1), (Ini2) and (Ini3) in the composition is at least 0.1 phr relative to the sum of the (meth)acrylic monomer (M1) and the (meth)acrylic polymer (P1). Preferably, the combined amount of the three initiators (Ini1), (Ini2) and (Ini3) in the composition is at least 0.2 phr, more preferably at least 0.5 phr, even more preferably at least 0.75 phr, advantageously at least 1 phr relative to the sum of the (meth)acrylic monomer (M1) and the (meth)acrylic polymer (P1).

[0061] The combined amount of the three initiators (Ini1), (Ini2) and (Ini3) in the composition is at most 15 phr, relative to the sum of the (meth)acrylic monomer (M1) and the (meth)acrylic polymer (P1). Preferably, the combined amount of the two initiators (Ini1) and (Ini2) in the composition is at most 12 phr, more preferably at most 10 phr, even more preferably at most 8 phr, advantageously at most 5 phr, relative to the sum of the (meth)acrylic monomer (M1) and the (meth)acrylic polymer (P1).

[0062] The combined amount of the three initiators (Ini1), (Ini2) and (Ini3) in the composition is between 0.1 and 15 phr, relative to the sum of the (meth)acrylic monomer (M1) and the (meth)acrylic polymer (P1). Preferably, the combined amount of the three initiators (Ini1), (Ini2) and (Ini3) in the composition is between 0.2 and 12 phr, more preferably between 0.5 and 10 phr, even more preferably between 0.75 and 8 phr, advantageously at most between 1 and 5 phr, relative to the sum of the (meth)acrylic monomer (M1) and the (meth)acrylic polymer (P1).

[0063] As regards the (meth)acrylic monomer (M1), said monomer is selected from acrylic acid, methacrylic acid, alkyl acrylate monomers, alkyl methacrylate monomers, hydroxyalkyl acrylate monomers and hydroxyalkyl methacrylate monomers, and mixtures thereof.

[0064] Preferably, the (meth)acrylic monomer (M1) is selected from acrylic acid, methacrylic acid, hydroxyalkyl acrylate monomers, hydroxyalkyl methacrylate monomers, alkyl acrylate monomers, alkyl methacrylate 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.

[0065] Advantageously, the (meth)acrylic monomer (M1) 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.

[0066] According to a preferred embodiment, at least 50% by weight, preferably at least 60% by weight, of the (meth)acrylic monomers (M1) is methyl methacrylate.

[0067] According to a first more preferred embodiment, at least 50% by weight, preferably at least 60% by weight, even more preferably at least 70% by weight, advantageously at least 80% by weight and even more advantageously at least 90% by weight of the monomers (M1) is a mixture of methyl methacrylate and optionally at least one other monomer.

[0068] According to a second more preferred embodiment, the liquid composition or (meth)acrylic syrup comprises between 0.01 and 10 phr by weight of a monomer (M2) relative to the sum of the (meth)acrylic monomer (M1) and the (meth)acrylic polymer (P1), said (meth)acrylic monomer (M2) comprising at least two (meth)acrylic functionalities, advantageously between 0.1 and 5 phr by weight of said (meth)acrylic monomer (M2).

[0069] The (meth)acrylic monomer (M2) may be selected from ethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol (glucol) diacrylate, 1,3-butylene glycol (glucol) methacrylate.

[0070] As regards the (meth)acrylic polymer (P1), mention may be made of polyalkyl methacrylates or polyalkyl acrylates. According to a preferred embodiment, the (meth)acrylic polymer is polymethyl methacrylate (PMMA).

[0071] The term "PMMA" refers to homopolymers or copolymers of methyl methacrylate (MMA), or mixtures thereof.

[0072] According to one embodiment, the homopolymer or copolymer of methyl methacrylate (MMA) comprises at least 70%, preferably at least 80%, advantageously at least 90% and even more advantageously at least 95% by weight of methyl methacrylate.

[0073] According to another embodiment, the PMMA is a mixture of at least one homopolymer and at least one copolymer of MMA, or of at least two homopolymers or two copolymers of MMA having different average molecular weights, or of at least two copolymers of MMA having different monomer compositions.

[0074] Copolymers of methyl methacrylate (MMA) contain 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 that can be copolymerized with methyl methacrylate.

[0075] These monomers are well known and may include, inter alia, acrylic and methacrylic acid, and alkyl (meth)acrylates, the alkyl group of which contains from 1 to 12 carbon atoms. By way of example, mention may be made of methyl and ethyl acrylate, butyl (meth)acrylate or 2-ethylhexyl (meth)acrylate. Preferably, the comonomer is an alkyl acrylate, the alkyl group of which contains from 1 to 4 carbon atoms.

[0076] According to a first preferred embodiment, the copolymer of methyl methacrylate (MMA) comprises from 80% to 99.7%, advantageously from 90 to 99.7%, more advantageously from 90 to 99.5% by weight of methyl methacrylate and from 0.3 to 20%, advantageously from 0.3 to 10%, more advantageously from 0.5 to 10% by weight of at least one monomer containing at least one ethylenic unsaturation that can be copolymerized with methyl methacrylate. Preferably, the comonomer is chosen from methyl acrylate and ethyl acrylate, and mixtures thereof.

[0077] The weight average molecular weight of the (meth)acrylic polymer (P1) must be high, meaning more than 50,000 g / mol, preferably more than 100,000 g / mol.

[0078] The weight average molecular weight can be measured by size exclusion chromatography (SEC).

[0079] The (meth)acrylic polymer dissolves completely in the (meth)acrylic monomer or mixture of (meth)acrylic monomers, thereby increasing the viscosity of the (meth)acrylic monomer or mixture of (meth)acrylic monomers. The resulting solution is generally called a "syrup material" or "prepolymer". The dynamic viscosity value of liquid (meth)acrylic syrups is between 10 mPa.s and 10,000 mPa.s. The viscosity of the syrups can be easily measured with a rheometer or viscometer. The dynamic viscosity is measured at 25°C.

[0080] Advantageously, the liquid (meth)acrylic syrup does not contain additional voluntary added solvents.

[0081] With regard to the three initiators (Ini1), (Ini2) and (Ini3), the initiators generate radicals that initiate the monomer(s) to initiate the radical polymerization of the monomer(s) to form a polymer chain by propagation.

[0082] Preferably, the initiators (Ini1), (Ini2) and (Ini3) are activated by heat.

[0083] The thermally activated initiators (Ini1), (Ini2) and (Ini3) are preferably radical initiators.

[0084] The radical initiators (Ini1), (Ini2), and (Ini3) can be selected from peroxy group-containing compounds or azo group-containing compounds, preferably from peroxy group-containing compounds.

[0085] Preferably, the peroxy group-containing compound contains from 2 to 30 carbon atoms.

[0086] Preferably, the peroxy group-containing compound is selected from diacyl peroxides, peroxy esters, peroxy dicarbonates, dialkyl peroxides, peroxy acetals, hydroperoxides or peroxy ketals.

[0087] Preferably, the two initiators (Ini1), (Ini2) and (Ini3) have different half-lives t at a given temperature T1. 1 / 2 has.

[0088] Even more preferably, the third initiator (Ini3) has a half-life t 1 at a given temperature T1 that is longer than the half-life t 2 of the second initiator (Ini2) at T1. 1 / 2 More important than half-life t 1 / 2 The second initiator (Ini2) has a half-life t 1 / 2 More important than half-life t 1 / 2 has.

[0089] Even more preferably, the second initiator (Ini2) has a half-life t 1 / 2 At least twice the half-life t 1 / 2 Even more preferably, the second initiator (Ini2) has a half-life t 1 / 2 At least three times the half-life t 1 / 2 has.

[0090] Even more preferably, the third initiator (Ini3) has a half-life t 1 / 2 At least twice the half-life t 1 / 2 Even more preferably, the third initiator (Ini3) has a half-life t 1 / 2 At least three times the half-life t 1 / 2 have 。

[0091] Preferably, the temperature T1 is between 40°C and 160°C, even better between 40°C and 140°C and advantageously between 50°C and 130°C.

[0092] More preferably, the first initiator (Ini1) has a half-life t of 1 hour at a temperature between 40° C. and 90° C., even more preferably between 45° C. and 80° C., even more preferably between 50° C. and 75° C. 1 / 2 has.

[0093] More preferably, the second initiator (Ini2) has a half-life t of 1 hour at a temperature of at least 70° C., and even more preferably at least 75° C. 1 / 2 has.

[0094] More preferably, the second initiator (Ini2) has a half-life t of 1 hour at a temperature between 70° C. and 100° C., even more preferably between 70° C. and 90° C., even more preferably between 75° C. and 85° C. 1 / 2 has.

[0095] More preferably, the third initiator (Ini3) has a half-life t of 1 hour at a temperature of at least 75° C., even more preferably at least 80° C., even more preferably at least 85° C. 1 / 2 has.

[0096] More preferably, the third initiator (Ini3) has a half-life t of 1 hour at a temperature between 75° C. and 160° C., even more preferably between 80° C. and 140° C., even more preferably between 85° C. and 130° C. 1 / 2 has.

[0097] Preferably, the temperature difference between the initiators (Ini3), (Ini2) and (Ini1) at a given half-life is at least 5 K. This is equivalent to a half-life of 1 hour t 1 / 2 When the temperature of (Ini1) in is 75°C, the half-life of 1 hour is t 1 / 2 The temperature of (Ini2) at is at least 80° C. and the half-life t 1 / 2 This means that the temperature of (Ini3) at is at least 85°C.

[0098] Preferably, the temperature difference between the initiators (Ini3), (Ini2) and (Ini1) at a given half-life is at most 50 K. This corresponds to a half-life of 1 hour t 1 / 2 If the temperature of (Ini1) at 50°C, the half-life of 1 hour is t 1 / 2 This means that the temperature of (Ini3) at is 100°C at most.

[0099] More preferably, the temperature difference at a given half-life between initiators (Ini2) and (Ini1) is between 5K and 50K, more preferably between 6K and 40K, even more preferably between 7K and 30K.

[0100] More preferably, the temperature difference at a given half-life between initiators (Ini3) and (Ini1) is between 10K and 50K, more preferably between 15K and 40K, even more preferably between 20K and 40K.

[0101] Initiators (Ini3), (Ini2), and (Ini1) are diisobutyryl peroxide, cumyl peroxyneodecanoate, di(3-methoxybutyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneoheptanoate, di-n-propyl peroxydicarbonate, tert-amyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-t ert-butylcyclohexyl)peroxydicarbonate, di-(2-ethylhexyl)-peroxydicarbonate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, di-n-butyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate peroxypivalate, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)-hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert -butylperoxydiethyl acetate, tert-butylperoxyisobutyrate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, tert-amylperoxy-2-ethylhexyl carbonate, tert-amylperoxyacetate, tert-butylperoxy-3,5,5-trimethylhexanoate, 2,2-di-(tert-butylperoxy)-butane, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butylperoxyacetate, butyl 4,4-di(tert-butylperoxy)valerate, tert-butylperoxybenzoate, 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) Ini3), (Ini2), and (Ini1) are selected from the group consisting of 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-(2-methylbutyronitrile), azobisisobutyramide, 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azodi(hexahydrobenzonitrile), and 4,4'-azobis(4-cyanopentanoic acid), and the selection of the three initiators (Ini3), (Ini2), and (Ini1) is made taking into consideration the above-mentioned characteristics of the three initiators (Ini3), (Ini2), and (Ini1).

[0102] Preferably, the initiator (Ini1) is cumyl peroxyneodecanoate, di(3-methoxybutyl)peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneoheptanoate, di-n-propyl peroxydicarbonate, tert-amyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, di-(2-ethylhexyl)-peroxydicarbonate, tert-amyl peroxyneodecanoate, tert-butyl peroxyne decanoate, di-n-butyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)-hexane or 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate.

[0103] Preferably, the initiator (Ini2) is selected from the group consisting of tert-amyl peroxypivalate, tert-butyl peroxypivalate, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)-hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, dibenzoylperoxypival ... peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxydiethyl acetate, tert-butylperoxyisobutyrate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, tert-amylperoxy-2-ethylhexyl carbonate, tert-amylperoxyisobutyrate, tert-butyl ... peroxyacetate, tert-butylperoxy-3,5,5-trimethylhexanoate, 2,2-di-(tert-butylperoxy)-butane, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, tert-amylperoxybenzoate, tert-butylperoxyacetate, butyl 4,4-di(tert-butylperoxy)valerate, tert-butylperoxybenzoate, 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-1,4,7-triperoxonane.

[0104] Preferably, the initiator (Ini3) is tert-butyl peroxypivalate, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)-hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert- Butylperoxy-2-ethylhexanoate, tert-butylperoxydiethyl acetate, tert-butylperoxyisobutyrate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, tert-amylperoxy-2-ethylhexyl carbonate, tert-amylperoxyacetate tert-butylperoxy-3,5,5-trimethylhexanoate, 2,2-di-(tert-butylperoxy)-butane, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, tert-amylperoxybenzoate, tert-butylperoxyacetate, butyl 4,4-di(tert-butylperoxy)valerate, tert-butylperoxybenzoate, di-tert t-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-1,4,7-triperoxonane.

[0105] The weight ratio between each two of the three initiators (Ini3), (Ini2) and (Ini1) is between 1 / 10 and 10 / 1, preferably between 1 / 5 and 5 / 1, and more preferably between 1 / 4 and 4 / 1.

[0106] Preferably, the initiator (Ini1) is selected from peroxydicarbonates. Preferably, the initiator (Ini1) has a maximum storage temperature of less than or equal to 20° C.

[0107] More preferably, the initiator (Ini1) has the following general formula (1): TIFF2024174878000001.tif17170

[0108] wherein R1 and R2 are each present and are alkyl groups, which may be linear, branched, or cyclic, or a combination of the three, and have at least 6 carbon atoms, preferably 8 carbon atoms, and more preferably at least 10 carbon atoms. Advantageously, each of the R1 and R2 groups has between 10 and 30 carbon atoms, and more advantageously between 10 and 20 carbon atoms. The R1 and R2 groups may be different or the same.

[0109] Even more preferably, the initiator (Ini1) is selected from di(4-tert-butylcyclohexyl)peroxydicarbonate, dicetyl peroxydicarbonate, and dimyristyl peroxydicarbonate, the initiator (Ini2) is selected from benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, dilauroyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, and didecanoyl peroxide, and the initiator (Ini3) is selected from benzoyl peroxide or t-butylperoxy 2-ethylhexanoate or 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane.

[0110] In a first even more preferred embodiment, the initiator (Ini1) is selected from di(4-tert-butylcyclohexyl)peroxydicarbonate.

[0111] The initiator (Ini2) in this first even more preferred embodiment is selected from dilauroyl peroxide and didecanoyl peroxide.

[0112] The initiator (Ini3) in this first even more preferred embodiment is selected from benzoyl peroxide or t-butyl peroxy 2-ethylhexanoate or 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane.

[0113] In a second even more preferred embodiment, the initiator (Ini1) is selected from dicetyl peroxydicarbonate.

[0114] The initiator (Ini2) in this second even more preferred embodiment is selected from dilauroyl peroxide and didecanoyl peroxide.

[0115] The initiator (Ini3) in this second even more preferred embodiment is selected from benzoyl peroxide or t-butyl peroxy 2-ethylhexanoate or 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane.

[0116] In a third even more preferred embodiment, the initiator (Ini1) is selected from dimyristyl peroxydicarbonate.

[0117] The initiator (Ini2) in this third even more preferred embodiment is selected from dilauroyl peroxide and didecanoyl peroxide.

[0118] The initiator (Ini3) in this third even more preferred embodiment is selected from benzoyl peroxide or t-butyl peroxy 2-ethylhexanoate or 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane.

[0119] In order to maintain the dynamic viscosity of the liquid composition or (meth)acrylic syrup so as to allow good impregnation of the fibrous substrate as required, and in order to maintain the thermoplastic properties of the matrix obtained after polymerization of the fibrous substrate previously impregnated with the syrup, the compounds of the syrup are incorporated in the following weight percentages:

[0120] The (meth)acrylic monomer(s) (M1) in the liquid composition or in the (meth)acrylic syrup are present in a proportion of between 40% and 90% by weight, preferably between 45% and 85% by weight, of the composition comprising the (meth)acrylic monomer(s) (M1) and the (meth)acrylic polymer (P1).

[0121] The (meth)acrylic polymer(s) (P1) in the liquid composition or in 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) (M1) and the (meth)acrylic polymer (P1).

[0122] The (meth)acrylic polymer(s) (P1) in the liquid (meth)acrylic syrup is present in a proportion of less than or equal to 50% by weight, preferably less than or equal to 40% and advantageously less than or equal to 30% by weight of the composition comprising the (meth)acrylic monomer(s) (M1) and the (meth)acrylic polymer (P1).

[0123] All optional additives and fillers are added to the liquid (meth)acrylic syrup prior to impregnation and / or polymerization.

[0124] As regards the process for producing a liquid composition or (meth)acrylic syrup, the first step consists of preparing a first syrup comprising a (meth)acrylic monomer (M1) or a mixture of (meth)acrylic monomers and a (meth)acrylic polymer (P1). Then, initiators (Ini3), (Ini2) and (Ini1) are added to the syrup in the above ratios to maintain a dynamic viscosity at 25° C. between 10 mPa*s and 10,000 mPa*s.

[0125] Preferably, the (meth)acrylic polymer (P1) is added to the (meth)acrylic monomer to solubilize it.

[0126] The initiators (Ini3), (Ini2) and (Ini1) may be added together or separately, in which case the order is not important.

[0127] Preferably, the initiators (Ini3), (Ini2) and (Ini1) are reacted at a temperature T of less than 50 ° C, more preferably less than 40 ° C, advantageously less than 30 ° C and even more advantageously less than 25 ° C. add It can be added with.

[0128] The liquid composition according to the invention detailed in the previous paragraphs can be used for impregnating fibers or fibrous substrates or for producing thermoplastic parts or for producing composite parts.

[0129] The process for impregnating the fibers or fibrous substrate comprises the step of impregnating the fibrous substrate with a liquid composition or a (meth)acrylic syrup.

[0130] This impregnation step can be carried out in a mold or in a closed mold or in a bath.

[0131] If the viscosity of the liquid (meth)acrylic syrup at a given temperature is slightly too high for the impregnation process, it is possible to heat the syrup to obtain a more liquid syrup in order to adequately wet and accurately and completely impregnate the fibrous substrate.

[0132] With regard to fibrous substrates, there are mentioned those made of several fibers, unidirectional rovings, or mats of continuous filaments, woven fabrics, felts, or nonwoven fabrics, which may be in the form of strips, wraps, braids, locks, or pieces. Fibrous materials can have various forms and dimensions, either one-dimensional, two-dimensional, or three-dimensional. Fibrous substrates include an assembly of one or more fibers. When the fibers are continuous, the assembly forms a woven fabric.

[0133] The one-dimensional form corresponds to long linear fibers. The fibers may be discontinuous or continuous. The fibers may be arranged randomly or parallel to each other in the form of continuous filaments. The fibers are defined by the aspect ratio, which is the ratio of the length to the diameter of the fiber. The fibers used in the present invention are long or continuous fibers. The fibers have an aspect ratio of at least 1000, preferably at least 1500, more preferably at least 2000, advantageously at least 3000, even more advantageously at least 5000, even more advantageously at least 6000, even more advantageously at least 7500, and most advantageously at least 10,000.

[0134] A two-dimensional form corresponds to a nonwoven or woven mat or a reinforcement or a bundle of fibers, which may also be braided. Even if a two-dimensional form has a certain thickness and is therefore three-dimensional in principle, it is still considered two-dimensional according to the invention.

[0135] Three-dimensional forms correspond, for example, to nonwoven mats or reinforcements or to bundles of stacked or folded fibers or mixtures thereof that are an assembly of two-dimensional forms in the third dimension.

[0136] The source of the fibrous material can be natural or synthetic. Natural materials can include vegetable, wood, animal, or mineral fibers.

[0137] Natural fibres are for example sisal, jute, hemp, flax, cotton, coconut fibre and banana fibre. Animal fibres are for example wool or hair.

[0138] The synthetic material may include polymer fibers selected from fibers of a thermoset polymer, a thermoplastic polymer, or mixtures thereof.

[0139] The polymeric fibers may be composed of polyamides (aliphatic or aromatic), polyesters, polyvinyl alcohol, polyolefins, polyurethanes, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins, and vinyl esters.

[0140] The mineral fibres may also be chosen from glass fibres, especially of type E, R or S2, carbon fibres, boron fibres or silica fibres.

[0141] The fibrous substrate of the present invention is selected from vegetable fibers, wood fibers, animal fibers, mineral fibers, synthetic polymer fibers, glass fibers, and carbon fibers, and mixtures thereof.

[0142] Preferably, the fibrous substrate is selected from mineral fibers.

[0143] The fibers of the fibrous substrate have a diameter between 0.005 μm and 100 μm, preferably between 1 μm and 50 μm, more preferably between 5 μm and 30 μm, advantageously between 10 μm and 25 μm.

[0144] Preferably, the fibers of the fibrous substrate of the present invention are selected from continuous fibers in one-dimensional form (meaning that in the case of long fibers the aspect ratio does not necessarily apply) or from long or continuous fibers in two- or three-dimensional form of the fibrous substrate.

[0145] According to another additional aspect, the present invention relates to a polymer composite comprising a thermoplastic (meth)acrylic matrix and a fibrous substrate used as reinforcement, wherein the fibrous substrate consists of long fibers, said composite being characterized in that after polymerization of said fibrous substrate previously impregnated with said liquid composition or with a (meth)acrylic syrup according to the invention, a thermoplastic (meth)acrylic matrix is ​​obtained.

[0146] Another aspect of the present invention is a method for producing a i) impregnating a fibrous substrate with a liquid composition according to the invention or a (meth)acrylic syrup, ii) polymerizing the liquid composition or (meth)acrylic syrup impregnated into the fibrous substrate; A process for manufacturing a mechanical or structured part or product comprising:

[0147] During the process for manufacturing mechanical or structured parts or products, during the polymerization step in all embodiments of the present invention, the polymerization of the liquid composition or (meth)acrylic syrup impregnated into the fibrous substrate is carried out at temperatures between 80°C and 140°C, preferably between 90°C and 130°C, and even more preferably between 100°C and 125°C. The polymerization step in all embodiments of the present invention is isothermal. Isothermal means in the present invention that the temperature during polymerization is kept in an interval of ΔT of 20K of the polymerization temperature and does not include a temperature ramp, where the temperature is, for example, lowered during the polymerization or raised at the end, the difference in temperature during the polymerization being 20K or more. The temperature during polymerization is also called the polymerization temperature. For example, the impregnated fibrous substrate is heated to 100°C, and the temperature at the end does not exceed 125°C, or preferably 120°C. Or, for example, the impregnated fibrous substrate is heated to 115°C and the temperature during the polymerization step remains within an interval of 20K, such as between 105°C and 125°C, or between 100°C and 120°C.

[0148] Preferably, the polymerization temperature is kept in a ΔT interval of 18K, more preferably 16K, even more preferably 14K, even more preferably 12K, most preferably 10K.

[0149] As regards the processes for manufacturing composite parts, but also mechanical or structured parts or products, different processes can be used to prepare these parts: Vacuum Assisted Resin Infusion (VARI), pultrusion, vacuum bag molding, pressure bag molding, autoclave molding, Resin Transfer Molding (RTM) and its variations (HP-RTM, C-RTM, I-RTM), Reaction Injection Molding (RIM), Reinforced Reaction Injection Molding (R-RIM) and its variants, press molding, compression molding, liquid compression molding (LCM) or sheet molding compound (SMC) or bulk molding compound (BMC).

[0150] A first preferred manufacturing process for producing composite parts is one in which the liquid composition is transferred to the fibrous substrate by impregnating the latter with a mould. The above processes requiring a mould include the term moulding.

[0151] A second preferred manufacturing process for producing composite parts is one in which a liquid composition is used in a pultrusion process. Fibers are guided through a resin batch containing the composition according to the invention. The fibers as fibrous substrates are, for example, in the form of unidirectional rovings or continuous filament mats. After being impregnated with a resin bath, the wet fibers are pulled through a heated die where polymerization takes place.

[0152] A third preferred manufacturing process is Vacuum Assisted Resin Infusion (VARI).

[0153] A fourth preferred manufacturing process is Resin Transfer Molding (RTM) and its variations (HP-RTM, C-RTM, I-RTM), and more preferably Compression Resin Transfer Molding (C-RTM).

[0154] The process for manufacturing composite parts, as well as mechanical or structured parts or products, can further include a post-forming step, which includes bending to change the shape of the composite part.

[0155] The process for manufacturing composite parts, but also mechanical or structured parts or products, may further include welding or gluing or laminating steps.

[0156] The thermoplastic composite parts resulting from the process according to the invention can be post-molded after polymerization of the liquid composition of the invention, including bending to change the shape of the composite.

[0157] The thermoplastic parts or the composite parts produced obtained after polymerization of the liquid composition of the invention and / or resulting from the process according to the invention can be welded, glued or laminated.

[0158] Uses of mechanical parts made from the composite materials thus produced include automotive applications, transport applications such as buses or lorries, marine applications, railway applications, sports, aviation and aerospace applications, solar power applications, computer related applications, construction and building applications, communications applications, and wind energy applications.

[0159] Mechanical parts made of composite materials are, inter alia, automobile parts, boat parts, bus parts, train parts, sporting goods, airplane or helicopter parts, spacecraft or rocket parts, photovoltaic module parts, construction or building materials (e.g. composite rebar, dowels, and stirrups for civil engineering and high rise construction), wind turbine parts (e.g. spar caps for girders of wind turbine blades), furniture parts, construction or building parts, telephone or mobile phone parts, computer or television parts, or printer or copier parts.

[0160] In a first preferred embodiment, the machine parts made of composite materials are inter alia construction or building materials, such as, for example, composite rebars, dowels and stirrups for civil engineering and high rise construction.

[0161] In a second preferred embodiment, the machine part made of composite material is especially a wind turbine part, such as for example a spar cap of a girder of a wind turbine blade. EXAMPLES

[0162] First step: Preparation of the liquid composition or (meth)acrylic syrup

[0163] A liquid composition is prepared by dissolving 20 wt. % PMMA (BS520, a copolymer of MMA with ethyl acrylate as comonomer) as (P1) in 80 wt. % methyl methacrylate as (M1), which is stabilized with HQME (hydroquinone monomethyl ether).

[0164] To this liquid composition, different initiators are added as a mixture of two or three different initiators (Ini1) and (Ini2) or (Ini1), (Ini2), and (Ini3). As initiators (Ini1) or (Ini2) or (Ini3) di(4-tert-butylcyclohexyl)peroxydicarbonate (P16 - Perkadox® 16 from Akzo Nobel), benzoyl peroxide (BPO - Perkadox® CH50X from Akzo Nobel), dilauroyl peroxide (LP - Luperox® LP from Arkema), and didecanoyl peroxide (DEC - Luperox® DEC from Arkema), and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane (Tx141 - Trigonox® 141 from Akzo Nobel) are used.

[0165] The comparative example does not have a mixture of the three initiators (Ini1), (Ini2) and (Ini3) according to the invention.

[0166] Second step: Polymerization of the liquid composition or (meth)acrylic syrup

[0167] The polymerization of each composition is carried out by adding an initiator to 100 parts by weight of the liquid composition (based only on (M1) and (P1)), as shown in Table 1. The liquid composition is used to impregnate a fibrous substrate. Each composition is placed in a metal press as a mold and heated to various temperatures from 100° C. to 115° C. under a pressure of 10 bar.

[0168] With the aid of a thermocouple, the slight temperature rise within the composition is measured over time to a maximum peak. The time to maximum peak for each sample at various temperatures of the press was measured and is shown for each composition in Table 2. TIFF2024174878000002.tif87170TIFF2024174878000003.tif55170TIFF2024174878000004.tif55170The symbols in Table 3 have the following meanings: + Easy release from the press without any problems 0 Difficult to release, soft, sticky samples * Incomplete polymerization

[0169] Table 2 shows that the polymerization time of the examples and comparative examples decreases with increasing mold temperature, which means better kinetics, faster polymerization, while only the examples can be easily demolded at higher temperatures, which means they have good conversion properties.

Claims

1. 1. A liquid composition comprising: a) (meth)acrylic polymer (P1), b) a (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) Including, having a kinematic viscosity of between 10 mPa*s and 10,000 mPa*s at 25°C; liquid composition.

2. 2. The liquid composition according to claim 1, characterized in that the combined amount of the three initiators (Ini1), (Ini2) and (Ini3) in the composition is between 0.1 phr and 15 phr relative to the sum of the (meth)acrylic monomer (M1) and the (meth)acrylic polymer (P1).

3. 2. The liquid composition according to claim 1, characterized in that the combined amount of the three initiators (Ini1), (Ini2) and (Ini3) in the composition is between 1 phr and 5 phr relative to the sum of the (meth)acrylic monomer (M1) and the (meth)acrylic polymer (P1).

4. Three initiators (Ini1), (Ini2), and (Ini3) are heated at a given temperature T １ Different half-lives t １／２ The liquid composition according to any one of claims 1 to 3, characterized in that it has

5. The third initiator (Ini3) is reacted at a given temperature T １ In the above, １ The half-life t of the second initiator (Ini2) at １／２ Half-life t １／２ and the second initiator (Ini2) is heated to a given temperature T １ In the above, １ The half-life t of the first initiator (Ini1) at １／２ Half-life t １／２5. The liquid composition according to claim 1 , wherein the liquid composition comprises:

6. The second initiator (Ini2) is reacted at a given temperature T １ In the first initiator (Ini1), the half-life t １／２ At least twice the half-life t １／２ 6. The liquid composition according to claim 1 , wherein the liquid composition comprises

7. The third initiator (Ini3) is reacted at a given temperature T １ In the second initiator (Ini2), the half-life t １／２ At least twice the half-life t １／２ 7. The liquid composition according to claim 1, characterized in that it has

8. Temperature T １ 8. A liquid composition according to claim 5, characterized in that the temperature is between 40°C and 160°C, more preferably between 40°C and 140°C, advantageously between 50°C and 130°C.

9. The first initiator (Ini1) has a half-life t １／２ 9. The liquid composition according to claim 1 , characterized in that it has

10. The first initiator (Ini1) has a half-life t １／２ 9. The liquid composition according to claim 1 , characterized in that it has

11. The second initiator (Ini2) has a half-life t １／２ 9. The liquid composition according to claim 1 , characterized in that it has

12. The second initiator (Ini2) has a half-life t １／２ 9. The liquid composition according to claim 1 , characterized in that it has

13. The third initiator (Ini3) has a half-life t １／２ 9. The liquid composition according to claim 1 , characterized in that it has

14. The third initiator (Ini3) has a half-life t １／２ 9. The liquid composition according to claim 1 , characterized in that it has

15. 15. A liquid composition according to any one of claims 1 to 14, characterized in that the temperature difference at a given half-life between the initiators (Ini3), (Ini2) and (Inil) is at least 5 K.

16. 16. A liquid composition according to any one of claims 1 to 15, characterized in that the temperature difference at a given half-life between initiators (Ini3) and (Ini1) is at most 50 K.

17. 17. A liquid composition according to any one of claims 1 to 16, characterized in that the temperature difference at a given half-life between initiators (Ini3) and (Ini1) is between 10K and 50K.

18. 17. A liquid composition according to any one of claims 1 to 16, characterized in that the temperature difference at a given half-life between initiators (Ini3) and (Ini1) is between 20K and 40K.

19. 17. A liquid composition according to any one of claims 1 to 16, characterized in that the temperature difference at a given half-life between initiators (Ini2) and (Ini1) is between 6K and 40K, and even more preferably between 7K and 30K.

20. 20. The liquid composition according to any one of claims 1 to 19, characterized in that the initiators (Ini1), (Ini2) and (Ini3) can be selected from peroxy group-containing compounds or azo group-containing compounds, preferably from peroxy group-containing compounds.

21. Initiators (Ini3), (Ini2), and (Ini1) are diisobutyryl peroxide, cumyl peroxyneodecanoate, di(3-methoxybutyl)peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneoheptanoate, di-n-propyl peroxydicarbonate, tert-amyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-t tert-butylcyclohexyl) peroxydicarbonate, di-(2-ethylhexyl)-peroxydicarbonate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, di-n-butyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate ester, tert-butyl peroxypivalate, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)-hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert -butylperoxydiethyl acetate, tert-butylperoxyisobutyrate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, tert-amylperoxy-2-ethylhexyl carbonate, tert-amylperoxyacetate, tert-butylperoxy-3,5,5-trimethylhexanoate, 2,2-di-(tert-butylperoxy)-butane, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butylperoxyacetate, butyl 4,4-di(tert-butylperoxy)valerate, tert-butylperoxybenzoate, 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, The liquid composition according to any one of claims 1 to 20, characterized in that the azobis(4-cyanopentanoic acid) is selected from 5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butylperoxide, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azodi-(2-methylbutyronitrile), azobisisobutyramide, 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azodi(hexahydrobenzonitrile), or 4,4'-azobis(4-cyanopentanoic acid).

22. Initiator (Ini1) is cumyl peroxyneodecanoate, di(3-methoxybutyl)peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, cumyl peroxyneoheptanoate, di-n-propylperoxydicarbonate, tert-amylperoxyneodecanoate, di-sec-butylperoxydicarbonate, diisopropylperoxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, di-(2-ethylhexyl)-peroxydicarbonate, tert-amylperoxyneodecanoate, tert-butylperoxyneodecanoate, di-n-butylperoxy 22. The liquid composition according to claim 1, characterized in that the peroxydicarbonate is selected from the group consisting of 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)-hexane, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate.

23. Initiator (Ini2) is tert-amyl peroxypivalate, tert-butyl peroxypivalate, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)-hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert -butylperoxy-2-ethylhexanoate, tert-butylperoxy diethyl acetate, tert-butylperoxy isobutyrate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, tert-amylperoxy-2-ethylhexyl carbonate, tert-amylperoxy acetate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 2,2-di-(tert-butylperoxy)-butane, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, tert-amylperoxybenzoate, tert-butylperoxyacetate, butyl 4,4-di(tert-butylperoxy)valerate, tert-butylperoxybenzoate, di-tert-amyl peroxide, dicumylperoxy 23. The liquid composition according to claim 1, characterized in that the peroxy group is selected from the group consisting of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl 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, and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane.

24. Initiator (Ini3) is tert-butyl peroxypivalate, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)-hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butylperoxy-2-ethyl peroxyhexanoate, tert-butylperoxydiethyl acetate, tert-butylperoxyisobutyrate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, tert-amylperoxy-2-ethylhexyl carbonate, tert-amylperoxy acetate, tert-butylperoxy-3,5 ,5-trimethylhexanoate, 2,2-di-(tert-butylperoxy)-butane, tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexyl carbonate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, butyl 4,4-di(tert-butylperoxy)valerate, tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, di-( 24. The liquid composition according to any one of claims 1 to 23, characterized in that the peroxy group is selected from 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-1,4,7-triperoxonane.

25. 22. The liquid composition according to any one of claims 1 to 21, characterized in that the initiator (Ini1) is selected from di(4-tert-butylcyclohexyl)peroxydicarbonate, dicetyl peroxydicarbonate and dimyristyl peroxydicarbonate, the initiator (Ini2) is selected from benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, dilauroyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane and didecanoyl peroxide, and the initiator (Ini3) is selected from benzoyl peroxide or t-butylperoxy 2-ethylhexanoate or 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane.

26. 22. A liquid composition according to any one of claims 1 to 21, characterized in that the initiator (Ini1) is selected from di(4-tert-butylcyclohexyl)peroxydicarbonate, the initiator (Ini2) is selected from dilauroyl peroxide and didecanoyl peroxide, and the initiator (Ini3) in this first even more preferred embodiment is selected from benzoyl peroxide or t-butylperoxy 2-ethylhexanoate or 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane.

27. 22. A liquid composition according to any one of claims 1 to 21, characterized in that the initiator (Ini1) is selected from dicetyl peroxydicarbonate, the initiator (Ini2) is selected from dilauroyl peroxide and didecanoyl peroxide, and the initiator (Ini3) is selected from benzoyl peroxide or t-butyl peroxy 2-ethylhexanoate or 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane.

28. 22. A liquid composition according to any one of claims 1 to 21, characterized in that the initiator (Ini1) is selected from dimyristyl peroxydicarbonate, the initiator (Ini2) in this third even more preferred embodiment is selected from dilauroyl peroxide and didecanoyl peroxide, and the initiator (Ini3) is selected from benzoyl peroxide or t-butylperoxy 2-ethylhexanoate or 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane.

29. 29. The liquid composition according to any one of claims 1 to 28, characterized in that the (meth)acrylic polymer (P1) comprises at least 50% by weight of methyl methacrylate (MMA).

30. 30. The liquid composition according to any one of claims 1 to 29, characterized in that the (meth)acrylic monomers are selected 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, and isobornyl methacrylate, and mixtures thereof.

31. 31. A liquid composition according to any one of the preceding claims, characterized in that the (meth)acrylic monomer(s) (M1) in the liquid composition or in the (meth)acrylic syrup is present in a proportion of between 40% and 90% by weight of the composition comprising the (meth)acrylic monomer(s) (M1) and the (meth)acrylic polymer (P1).

32. 31. A liquid composition according to any one of the preceding claims, characterized in that the (meth)acrylic monomer(s) (M1) in the liquid composition or in the (meth)acrylic syrup is present in a proportion of between 45% and 85% by weight of the composition comprising the (meth)acrylic monomer(s) (M1) and the (meth)acrylic polymer (P1).

33. A process for preparing a liquid composition according to any one of claims 1 to 32, comprising the steps of: i) preparing a mixture of a (meth)acrylic polymer (P1) and a (meth)acrylic monomer (M1) ii) adding initiators (Ini1), (Ini2) and (Ini3) together or sequentially to the mixture prepared in the previous step; The process includes:

34. The initiators (Ini3), (Ini2) and (Ini1) are reacted at a temperature T ａｄｄ 34. The process of claim 33, wherein the compound is added at

35. The initiators (Ini3), (Ini2) and (Ini1) are reacted at a temperature T ａｄｄ 34. The process of claim 33, wherein the compound is added at

36. 36. Use of a liquid composition according to any one of claims 1 to 32 or prepared by the process according to any one of claims 33 to 35 for producing a thermoplastic part or for producing a composite part.

37. 36. Use of a liquid composition according to any one of claims 1 to 32, or a liquid composition prepared by a process according to any one of claims 33 to 35, for impregnating fibres or fibrous substrates, wherein the fibres or fibrous substrates consist of long fibres.

38. 38. Use according to claim 37, characterised in that the long fibres are continuous fibres or that the fibres have an aspect ratio of at least 1000.

39. 33. An impregnation process for impregnating a fibrous substrate, said fibrous substrate being comprised of long fibers, said process comprising the step of impregnating said fibrous substrate with a liquid composition according to any one of claims 1 to 32.

40. 40. The impregnation process according to claim 39, characterized in that the long fibers are continuous fibers or the fibers have an aspect ratio of at least 1000.

41. 1. A process for manufacturing a thermoplastic part, comprising: i) preparing a liquid mixture of a (meth)acrylic polymer (P1) and a (meth)acrylic monomer (M1) ii) adding initiators (Ini1), (Ini2) and (Ini3) together or sequentially to the mixture prepared in the previous step; iii) placing the liquid composition prepared in i) and ii) in a means for polymerization, said composition comprising: a) (meth)acrylic polymer (P1), b) a (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) Including, The liquid (meth)acrylic syrup has a dynamic viscosity of between 10 mPa*s and 10,000 mPa*s at 25° C. as described in any one of claims 1 to 13. The steps are characterized by: iv) polymerizing A process for manufacturing a thermoplastic part by a process comprising:

42. 1. A process for manufacturing a composite part, comprising: iii) impregnating a fiber or fibrous substrate with a liquid composition according to any one of claims 1 to 32; iv) polymerizing 23. A process for manufacturing a composite part, comprising:

43. 1. A process for manufacturing a composite part, comprising: i) preparing a mixture of a (meth)acrylic polymer (P1) and a (meth)acrylic monomer (M1) ii) adding initiators (Ini1), (Ini2) and (Ini3) together or sequentially to the mixture prepared in the previous step; iii) impregnating a fiber or fibrous substrate with the liquid composition prepared in i) and ii), said composition comprising: a) (meth)acrylic polymer (P1), b) a (meth)acrylic monomer (M1), and c) Three initiators (Ini1), (Ini2), and (Ini3) Including, The liquid (meth)acrylic syrup has a kinetic viscosity of between 10 mPa*s and 10,000 mPa*s at 25° C. The method comprises the steps of: iv) polymerizing 23. A process for manufacturing a composite part, comprising:

44. 44. The process according to claim 42 or 43, carried out by vacuum assisted resin infusion (VARI), pultrusion, vacuum bag molding, pressure bag molding, autoclave molding, resin transfer molding (RTM) and its variations (HP-RTM, C-RTM, I-RTM), reaction injection molding (RIM), reinforced reaction injection molding (R-RIM) and its variations, press molding, compression molding, liquid compression molding (LCM) or sheet molding compound (SMC) or bulk molding compound (BMC).

45. 44. The process of claim 42 or 43, characterized in that the liquid composition is transferred to the fibrous substrate by impregnating the fibrous substrate with a mould.

46. 44. The process of claim 42 or 43 carried out by pultrusion.

47. 44. The process of claim 42 or 43, carried out by vacuum assisted resin infusion (VARI).

48. 44. Process according to claim 42 or 43, carried out by Resin Transfer Molding (RTM) and its variations (HP-RTM, C-RTM, I-RTM).

49. 49. The process according to any one of claims 41 to 48, characterized in that the polymerization step is carried out at a temperature between 80°C and 140°C, preferably between 90°C and 130°C.

50. 49. The process according to any one of claims 41 to 48, characterized in that the polymerization step is carried out at a temperature between 100°C and 125°C.

51. 49. The process according to any one of claims 41 to 48, characterized in that the polymerization step in all embodiments of the present invention is isothermal.

52. 51. The process according to claim 49 or 50, characterized in that the temperature during the polymerization is kept in an interval ΔT of 20 K of the polymerization temperature.

53. 51. The process according to claim 49 or 50, characterized in that the temperature during the polymerization is kept at an interval ΔT of 10 K of the polymerization temperature.

54. 33. A polymer composite comprising a thermoplastic (meth)acrylic matrix and a fibrous substrate used as reinforcement, the fibrous substrate consisting of long fibers, characterized in that the thermoplastic (meth)acrylic matrix is ​​obtained after polymerization of a liquid composition, the fibrous substrate being pre-impregnated with a liquid composition according to any one of claims 1 to 32.

55. A machine part or structural element made of a composite material as claimed in claim 54 or obtained by the process according to any one of claims 42 to 53.

56. 56. The part of claim 55, wherein the part is an automobile part, a boat part, a train part, a sporting item, an airplane or helicopter part, a spacecraft or rocket part, a photovoltaic module part, a construction or building material (e.g., composite rebar, dowels, and stirrups for civil engineering and high rise construction), a wind turbine part (e.g., spar caps for girders of wind turbine blades), a furniture part, a construction or building part, a telephone or mobile phone part, a computer or television part, a printer or copier part.

57. 56. The part of claim 55, wherein the part is a construction or building material, for example composite rebar, dowels, and stirrups for civil engineering and high rise construction.

58. 56. The component of claim 55, wherein the component is a wind turbine component, for example a spar cap of a girder of a wind turbine blade.

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