Method for producing shaped thermoplastic composite material, shaped thermoplastic composite material, and system for producing shaped thermoplastic composite material

Abstract

The invention relates to a method (100) for producing a shaped thermoplastic composite material (10), said method comprising a pultrusion process and comprising:-a feeding step (110) providing fibres (12) in a direction A of the pultrusion path,-a step (120) of wetting the fibres (12) comprising passing the fibres through a thermoplastic composition (14),-a heating step (130) for heating the fibres (12) in the direction A of the pultrusion path, the invention relates to a method for producing a thermoplastic composite material (18) comprising polymerizing (131) a thermoplastic composition (14) impregnated with fibres to form a heated thermoplastic composite material (16) having a first section (S1), a forming step (140) passing through a forming device (17) having a second section (S2) and the second section (S2) being smaller than the first section (S1) to provide a heated thermoplastic composite material (18) having the second section (S2), and a cooling step (150) comprising polymerizing (131) a thermoplastic composition (14) impregnated with fibres to form the heated thermoplastic composite material (16) having the first section (S1). In this way, the shaped thermoplastic composite material (10) is produced.

Description

Field of the Invention

[0001] The present invention relates to the field of thermoplastic composite materials and more preferably to the field of reinforcing elements.

[0002] The invention provides a new method for producing a molded thermoplastic composite material, a molded thermoplastic composite material and a system for producing a molded thermoplastic composite material.

[0003] Related technical description

[0004] Reinforcement elements are often used to reinforce structures in various fields, such as automotive, transportation, aviation, aerospace, photovoltaics, building and construction and / or wind energy applications.

[0005] At present, reinforcing elements in the form of composite reinforcing elements are known.

[0006] Typically, composite reinforcing elements comprise a matrix, typically a polymer matrix comprising a thermosetting polymer, and fibers, as a fiber matrix. Such composite reinforcing elements are typically produced by a pultrusion process.

[0007] The conventional pultrusion process involves pulling a fiber bundle through a pultrusion die to allow the fibers to be wetted, impregnating them by passing them through a resin bath or injection box, polymerizing the resin and cooling the impregnated bundle to form a composite profile at the exit of the die.

[0008] The pultrusion process allows to obtain profiles of constant section with high mechanical properties. The profile is fully formed when it leaves the pultrusion die. Moreover, in the case of thermosetting resins, the profile cannot be modified after leaving the die.

[0009] This technology requires a complete tool for each profile section that is to be manufactured, from the impregnation zone to the die exit.

[0010] In addition, thermosetting polymers have other disadvantages, such as long cycle times, high energy consumption, low recyclability of the materials used, toxicity of some components and emissions of volatile organic compounds. Another disadvantage of thermosetting materials is the volume shrinkage after curing, which affects the dimensional stability and surface appearance after molding and requires special treatment.

[0011] It is also known to manufacture reinforcing elements with resins comprising thermoplastic polymers. Advantageously, reinforcing elements with thermoplastic polymers can be heated and cooled continuously to change or modify the geometry of the thermoplastic polymer.

[0012] However, continued heating reduces thermal stability and adversely changes some properties of the reinforcing element, such as bending resistance, flexural strength, and may result in retention and delamination.

[0013] The pultrusion process with thermoplastic polymers can consist of melting the polymer, impregnating the fibers and calibrating by cooling, without polymerization. However, the impregnation of the fibers is low and uneven. In fact, due to the high viscosity of thermoplastic resins, it is currently difficult to achieve a sufficient and uniform impregnation of the fibers. In fact, on the one hand, the viscosity of the resin produces very high pressure levels, which leads to fiber breakage (which may cause mechanical defects, in particular fiber delamination and weaken the final composite material), and on the other hand, poor uniformity (resin-rich areas and fiber-rich areas) leads to the creation of resin flow paths, thereby weakening the composite material. The use of resins with high melting temperatures exacerbates these problems.

[0014] In order to solve this problem, international patent application WO2017219143 proposes a solution for a method of pultruding a beam, which includes a first mold having a tapered channel portion and heated to achieve the desired viscosity, a vacuum chamber to remove air, and a second mold having a tapered channel portion and heated to increase fiber impregnation. However, heating, impregnation and molding are carried out simultaneously. According to this method, many volatile compounds are generated, thereby increasing the porosity of the composite material, and the volatile compounds are still trapped in the composite material. In addition, this method requires feeding a preform containing polymer and fibers without polymerization, and therefore reproduces the same disadvantages mentioned above (mechanical defects, delamination of fibers and weakening of the final composite material).

[0015] Finally, other technologies have been developed, and in particular the reactive pultrusion technology. This technology uses reactive thermoplastic monomers with very low viscosity, which make it possible to impregnate a large number of fibers. In this case, the profile usually comes out according to the final shape of the pultrusion die, incorporating an impregnation zone, followed by a polymerization zone with the desired profile shape, so that the composite leaves the die in its final form, usually in the solid state. The polymerization zone thus also acts as a calibration zone.

[0016] Document FR 3 053 915 discloses a method and a device for obtaining a part made of thermoplastic composite material.

[0017] Document US 2013 / 0134621 discloses a stable preform and a method for forming such a preform, the preform containing fibers and a thermoplastic resin.

[0018] Although these techniques attempt to calibrate composites (thermosets or thermoplastics), composites generally exhibit shrinkage. The polymerization reaction also causes significant shrinkage. Shrinkage causes pressure loss in the pultrusion die during processing. This pressure loss leads to relatively high porosity, which leads to reduced mechanical properties, increased residual monomers, higher water absorption, loss of electrical conductivity and chemical resistance. In fact, there is more gas and air in the composite, which reduces its quality. In addition, some polymers have high water absorption under humid conditions, which can lead to dimensional changes, internal stresses, delamination and significant changes in matrix properties.

[0019] Therefore, there is a need for solutions that can produce molded thermoplastic composites with reduced porosity. Summary of the invention

[0020] In order to provide a basic understanding of the present invention, a simplified overview of selected aspects, embodiments and examples of the present invention is provided below. However, the overview does not constitute a broad overview of all aspects, embodiments and examples of the present invention. The sole purpose of the overview is to present selected aspects, embodiments and examples of the present invention in a concise form, as an introduction to a more detailed description of aspects, embodiments and examples of the present invention after the overview.

[0021] The present invention aims to overcome the disadvantages of the prior art. In particular, the present invention proposes a method for producing a shaped thermoplastic composite material, the method comprising a pultrusion process and comprising:

[0022] - a feeding step by means of a fiber feeding device, said feeding step providing the fibers in the direction of the pultrusion path;

[0023] - a step of wetting the fibers by means of an impregnation device, which comprises passing the fibers through a thermoplastic composition which is a thermoplastic resin or a thermoplastic resin precursor and which contains at least 50% by weight of monomers;

[0024] - a step of heating by means of a heating device, which comprises polymerizing the thermoplastic composition with which the fibers have been impregnated to form a heated thermoplastic composite material having a first section;

[0025] - a step of shaping the heated thermoplastic composite material by pulling the heated thermoplastic composite material through a shaping device, the shaping device having a second section, and the second section being smaller than the first section, to provide the heated thermoplastic composite material having a second section;

[0026] - A step of cooling by a cooling device at a cooling temperature lower than the glass transition temperature of the heated thermoplastic composite material having the second section to produce a molded thermoplastic composite material.

[0027] The advantage of this method is that the porosity of the shaped thermoplastic composite is reduced compared to that obtained with conventional processes to date. In fact, the developed method makes it possible to apply pressure to the thermoplastic composite during production, which allows the porosity to be reduced. Advantageously, this pressure is applied to the heated thermoplastic composite, which facilitates the application of pressure. Thus, the porosity of the shaped thermoplastic composite is reduced, thereby improving its mechanical and chemical properties.

[0028] Furthermore, since the method takes into account both chemical and thermal shrinkage, this further reduces porosity.

[0029] Furthermore, the method improves the surface quality, making the surface smoother and less rough, which facilitates further processing such as coating.

[0030] The process according to the invention thus improves the electrical conductivity, the chemical and / or mechanical resistance of the shaped thermoplastic composite material, while allowing a reduction in water absorption, alkaline attack, dimensional changes and matrix modifications.

[0031] Advantageously, since the process reduces the generation of volatile compounds, they are not trapped in the molded thermoplastic composite.

[0032] According to other optional features of the method of the present invention, it may optionally include one or more of the following features alone or in combination:

[0033] -Pultrusion process is a reactive pultrusion process to improve mechanical and / or chemical properties,

[0034] - performing the feeding step and the wetting step so that the shaped thermoplastic composite material comprises at least 60% by volume of fibers, thereby improving the mechanical and / or chemical properties of the shaped thermoplastic composite material,

[0035] - The cooling step is carried out simultaneously with the forming step, which saves time and takes into account e.g. thermal shrinkage,

[0036] The method comprises a vacuuming step before the shaping step, which allows reducing the porosity and reducing the presence of air and volatile compounds in the heated thermoplastic composite material, thus further reducing the porosity.

[0037] According to another aspect, the present invention also relates to a shaped thermoplastic composite material obtainable, preferably obtained, by the process according to the present invention. The shaped thermoplastic composite material according to the present invention has a reduced porosity, which allows better mechanical and / or chemical properties, better water absorption (better water absorption here means lower water absorption) and better electrical conductivity. Advantageously, the shaped thermoplastic composite material according to the present invention may comprise a porosity less than or equal to 10% based on the total volume of the shaped thermoplastic composite material.

[0038] According to another aspect of the invention, it provides the use of the shaped thermoplastic composite material according to the invention in automotive, transport, marine, railway, sports, aviation, aerospace, photovoltaic, computing, building and construction, telecommunications and / or wind energy applications. In fact, in these fields, shaped thermoplastic composite materials with reduced porosity are of particular interest.

[0039] According to another aspect, the present invention relates to a molding device suitable for reducing a first section of a heated thermoplastic composite material to a second section to form a molded thermoplastic composite material having a second section, the second section being smaller than the first section, and the molded thermoplastic composite material comprising at least 60% by volume of fibers. The molding device according to the present invention allows the porosity of the thermoplastic composite material to be reduced to obtain better quality. Advantageously, the molding device is also adaptable and can be implemented in any pultrusion or reactive pultrusion system for thermoplastics. The molding device according to the present invention may include at least one inlet and at least one outlet, the outlet being smaller than the inlet so as to apply pressure.

[0040] According to another aspect, the present invention relates to a system for producing a shaped thermoplastic composite material, comprising:

[0041] - a fiber feeding device configured to provide fibers in the direction of the pultrusion path,

[0042] - an impregnation device configured to wet the fibers with a thermoplastic composition which is a thermoplastic resin or a thermoplastic resin precursor and which contains at least 50% by weight of monomers,

[0043] a heating device configured to polymerize the thermoplastic composition with which the fibers have been impregnated to form a heated thermoplastic composite material having a first section,

[0044] - a molding device configured to mold the heated thermoplastic composite material into a second section, the molding device having a second section, and the second section is smaller than the first section to provide the heated thermoplastic composite material having the second section, the molding device facing the previous device,

[0045] - A cooling device configured to cool at a temperature below the glass transition temperature of the heated thermoplastic composite material having the second section to produce a shaped thermoplastic composite material.

[0046] The system according to the invention allows the production of shaped thermoplastic composite materials having reduced porosity.

[0047] According to other optional features of the system of the present invention, it may optionally include one or more of the following features alone or in combination:

[0048] - it includes empty space, vacuum or air space,

[0049] - an empty space, a vacuum or an air space is arranged between the heating device and the forming device,

[0050] The shaping device comprises at least one inlet and at least one outlet, the outlet facing the cooling device. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] The foregoing and other objects, features and advantages of the present invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings, in which:

[0053] [ Figure 1 ] Figure 1 Flowchart showing a method according to one embodiment of the invention.

[0054] [ Figure 2 ] Figure 2 A schematic diagram showing a system according to one embodiment of the present invention is shown.

[0055] [ Figure 3 ] Figure 3 Gradient field microscopy images showing molded thermoplastic composites.

[0056] Several aspects of the present invention are disclosed with reference to flowcharts and / or block diagrams of methods and apparatus according to embodiments of the invention.

[0057] In the figures, flow charts and / or block diagrams show the architecture, functions and possible implementations of devices, systems or methods according to several embodiments of the present invention.

[0058] To this end, each block in the flowchart or block diagram may represent a system, a device, or a module, which contains a plurality of executable instructions for implementing the specified logical function(s).

[0059] In some implementations, the functionality associated with the blocks may occur in a different order than shown in the figures.

[0060] For example, two blocks shown in succession may be executed substantially concurrently, or the blocks may sometimes be executed in the reverse order, depending upon the functionality involved.

[0061] Each block in the flowchart or block diagram, and combinations of blocks in the flowchart or block diagram, can be implemented by a dedicated system that performs the specified functions or actions, or a combination of dedicated devices and computer instructions.

[0062] Details

[0063] A description of an exemplary embodiment of the invention follows.

[0064] "Polymer" refers to copolymers or homopolymers or block copolymers. The term "copolymer" refers to a polymer composed of several different monomer units combined together, while the term "homopolymer" refers to a polymer composed of the same monomer units combined together. "Block copolymer" refers to a polymer composed of one or more uninterrupted blocks of different polymer species, which are chemically different from each other and are linked together by covalent bonds. These polymer blocks are also called polymer blocks.

[0065] The expression "polymer composite material" within the meaning of the present invention denotes a multicomponent material comprising at least two immiscible components, wherein at least one component is a polymer and the other component may, for example, be a fiber reinforcement.

[0066] "Fiber reinforcement" or "fibrous substrate" or "fiber" within the meaning of the present invention refers to a plurality of fibers, unidirectional fibers or braids, or continuous filament mats, fabrics, felts or nonwovens, which may be in the form of tapes, webs, braids, core ropes or fragments.

[0067] The term "matrix" may refer to a material that acts as a binder and is capable of transmitting force to a fiber-reinforced material. A "polymer matrix" includes polymers, but may also include other compounds or materials. Thus, a "(meth)acrylic polymer matrix" refers to all types of compounds, polymers, oligomers, copolymers or block copolymers of acrylic and methacrylic systems. However, it does not depart from the scope of the present invention if the (meth)acrylic polymer matrix contains up to 10% by weight, preferably less than 5% by weight, of other non-acrylic monomers, which are selected, for example, from the following group: butadiene, isoprene, styrene, substituted styrenes such as α-methylstyrene or tert-butylstyrene, cyclosiloxanes, vinylnaphthalene and vinylpyridine.

[0068] The term "initiator" or "precursor" within the meaning of the present invention refers to a compound that can start / initiate / continue the polymerization of a monomer or monomers. The term "initiator" preferably refers to a compound that can start / initiate the polymerization of a monomer or monomers.

[0069] The term "polymerization" within the meaning of the present invention may refer to the process of converting a monomer or a mixture of monomers into a polymer.

[0070] The term "monomer" within the meaning of the present invention refers to a molecule that can undergo polymerization.

[0071] For the purposes of the present invention, the term "thermoplastic polymer" may refer to a polymer which is generally solid at room temperature, which may be crystalline, semi-crystalline or amorphous, and which softens during temperature increase, in particular after passing its glass transition temperature (Tg), and flows at higher temperatures and / or can observe a clear melting when passing its so-called melting temperature (Tf) (when it is semi-crystalline) and becomes solid again when the temperature drops to its melting point and below its glass transition temperature. This also applies to thermoplastic polymers which are slightly crosslinked by the presence of polyfunctional monomers or oligomers in a mass percentage of preferably less than 10%, preferably less than 5%, thus preferably less than 2%, and which may be at least 0.5% in a "syrup" (meth)acrylate formulation, which can be thermoformed when heated above the softening temperature.

[0072] The term "thermoplastic composition" may refer to a thermoplastic syrup or a thermoplastic resin or a thermoplastic resin precursor, but may also refer to a mixture of a thermoplastic resin or a thermoplastic resin precursor, respectively, and a monomer. The term "thermoplastic resin precursor" refers to a prepolymer, which contains a plurality of monomers that have been polymerized as monomer units in a prepolymer chain, and the prepolymer can be further polymerized so as to obtain a higher molecular weight after complete polymerization, or in other words, can continue to polymerize.

[0073] The term "thermosetting polymer" may refer to a plastic material that is irreversibly transformed by polymerization.

[0074] The term "(meth)acrylic monomer" may refer to any type of acrylic and methacrylic monomers.

[0075] The term “(meth)acrylic polymer” may refer to a polymer substantially including at least 50 wt % or more of a (meth)acrylic monomer constituting the (meth)acrylic polymer.

[0076] The term "PMMA" within the meaning of the present invention may refer to homopolymers and copolymers of methyl methacrylate (MMA), the weight proportion of MMA in PMMA being preferably at least 70% by weight of the MMA copolymer.

[0077] The expression "reinforcement element" as used may refer to an element used in / with a structure in order to strengthen, support, solidify, consolidate the structure, improve its mechanical properties (reinforcement, tension, stretch, etc.), its thermal, electrical and / or chemical properties.

[0078] The term "rebar" may refer to reinforcing bars used as tensioning devices in reinforced concrete and reinforced masonry structures to strengthen and assist concrete under tension. Rebar significantly increases the tensile strength of concrete or structures.

[0079] The abbreviation "phr" may refer to parts by weight per hundred parts of the composition. For example, 1 phr of initiator in the composition means that 1 kg of initiator is added to 100 kg of the composition.

[0080] The abbreviation "ppm" may refer to 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.

[0081] In the following description, "shape" may refer to a form, preferably a geometric shape, such as circle, tube, cone, pyramid, parallelepiped, rectangle, square, trapezoid, having at least one segment.

[0082] The term "segment" may be defined by a dimension of thickness, diameter, width, slope or by area (eg, area or perimeter) or even volume. For example, a segment may correspond to a shape cut out along a transverse plane.

[0083] The term "about" as used herein can allow for a certain degree of variation in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or limit of a stated range.

[0084] As mentioned above, thermoplastic composites are currently produced without taking into account the porosity and the various shrinkages that occur during polymerization or heating and cooling operations. This results in the production of composite thermoplastics with high porosity, which leads to reduced quality in terms of mechanical and chemical resistance, electrical conductivity and sensitivity to water. A new method is needed to produce molded thermoplastic composites with reduced porosity and better quality.

[0085] According to a first aspect, the present invention relates to a method for producing a shaped thermoplastic composite material, said method comprising a pultrusion process. Preferably, the pultrusion process is a reactive pultrusion process.

[0086] In particular, if Figure 1 and Figure 2 As shown, the method 100 for producing a molded thermoplastic composite material 10 according to the present invention includes the following steps: a feeding step 110 ; a wetting step 120 ; a heating step 130 ; a molding step 140 ; ​​and a cooling step 150 .

[0087] like Figure 1 As shown, the method according to the present invention comprises a feeding step 110. This step is preferably carried out by, for example Figure 2 This is achieved by the fiber feeding device 11 shown in FIG.

[0088] The step 110 of feeding the fibers 12 allows providing the fibers 12 in the direction A of the pultrusion path. The fibers 12 may be made of a plurality of fibers, unidirectional rovings or continuous filament mats, fabrics, felts or nonwovens, which may be in the form of tapes, laps, braids, locks or pieces. The fiber material of the composite material may have a variety of forms and sizes, which may be one-dimensional, two-dimensional or three-dimensional.

[0089] One-dimensional form corresponds to linear long fibers. The fibers can be discontinuous or continuous. The fibers can be randomly arranged in the form of continuous filaments or arranged parallel to each other. The fibers are defined by their aspect ratio, which is the ratio between the length and diameter of the fiber. Preferably, the fibers used in the present invention are long fibers or continuous fibers. The fibers can have an aspect ratio 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, more advantageously at least 7500, and most advantageously at least 10000.

[0090] Two-dimensional forms correspond to nonwoven or woven fiber mats or reinforcements or fiber bundles, which may also be woven. Even if a two-dimensional form has a certain thickness and thus in principle a third dimension, it is considered to be two-dimensional according to the invention.

[0091] The three-dimensional form corresponds to, for example, a nonwoven fiber mat or reinforcement or stacked or folded fiber bundles or a mixture thereof, an aggregate of the two-dimensional form in the third dimension.

[0092] The origin of the fiber material can be natural or synthetic. As natural materials, mention may be made of plant fibers, wood fibers, animal fibers or mineral fibers.

[0093] Natural fibers are, for example, sisal, jute, hemp, flax, cotton, coconut fiber and banana fiber. Animal fibers are, for example, wool, hair.

[0094] As synthetic materials, mention may be made of polymer fibers chosen from thermosetting polymer fibers, thermoplastic polymer fibers, polyamides (aliphatic or aromatic), polyesters, polyvinyl alcohol, polyolefins, polyurethanes, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins and vinyl ester fibers and / or carbon fibers, or mixtures thereof.

[0095] The mineral fibers may also be chosen from glass fibers, especially of type E, R or S2, boron fibers, basalt fibers or silica fibers.

[0096] The fibrous substrate of the present invention may be selected from plant fibers, wood fibers, animal fibers, mineral fibers, synthetic polymer fibers, glass fibers and carbon fibers, and mixtures thereof.

[0097] Preferably, the fiber substrate is selected from mineral fibers. More preferably, the fiber substrate is selected from glass fibers or carbon fibers.

[0098] The fibers of the fibrous substrate may 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 and advantageously between 10 μm and 25 μm.

[0099] Preferably, the fibers of the fibrous substrate of the present invention are selected from continuous fibers (meaning not necessarily applicable to aspect ratios such as long fibers) for one-dimensional forms, or from long fibers or continuous fibers for two-dimensional or three-dimensional forms of the fibrous substrate.

[0100] The method according to the invention may comprise a step 120 of wetting the fibres 12. This step is preferably carried out by means of an impregnation device 13. The wetting step allows the fibres 12 to be impregnated with the thermoplastic composition 14, in other words, the thermoplastic composition penetrates the fibres.

[0101] The step of wetting the fibers may include passing the fibers through the thermoplastic composition 14. For example, the fibers are directed through a bath or injection chamber containing the thermoplastic composition. The thermoplastic composition 14 may be a thermoplastic resin or a thermoplastic resin precursor and include at least 50 weight percent of the monomers of the thermoplastic composite. In the case where the thermoplastic composition 14 includes a thermoplastic resin and at least 50 weight percent of the monomers, the monomers are partially polymerized during the heating step 130 so as to form together a matrix of the thermoplastic resin and the thermoplastic composite of the thermoplastic composition 14 with the impregnated fibers 12. In the case where the thermoplastic composition 14 includes a thermoplastic resin precursor and at least 50 weight percent of the monomers, the monomers are partially polymerized, and as the polymerization continues during the heating step 130, the molecular weight of the thermoplastic resin precursor increases so as to form together a matrix of the thermoplastic composite. The thermoplastic composition 14 may include a polymer and a monomer.

[0102] Preferably, the monomers of the thermoplastic composite are selected from alkyl acrylic monomers, alkyl methacrylic monomers, hydroxyalkyl acrylic monomers and hydroxyalkyl methacrylic monomers, and mixtures thereof.

[0103] Preferably, the polymer of the thermoplastic composite is selected from all types of compounds, polymers, oligomers, copolymers or block copolymers of the acrylic and methacrylic series. However, it does not depart from the scope of the invention if the (meth)acrylic polymer matrix contains up to 10% by weight, preferably less than 5% by weight, of other non-acrylic monomers, for example selected from the group consisting of butadiene, isoprene, styrene, substituted styrenes such as α-methylstyrene or tert-butylstyrene, cyclosiloxanes, vinylnaphthalene and vinylpyridine.

[0104] The thermoplastic composition 14 according to the present invention may contain between 10% and 50% by weight of the (meth)acrylic polymer (PI) and between 50% and 90% by weight of the (meth)acrylic monomer (Ml). Preferably, the thermoplastic composition contains between 10% and 40% by weight of the (meth)acrylic polymer (PI) and between 60% and 90% by weight of the (meth)acrylic monomer (Ml); and more preferably, the thermoplastic composition contains between 10% and 30% by weight of the (meth)acrylic polymer (PI) and between 70% and 90% by weight of the (meth)acrylic monomer (Ml).

[0105] The dynamic viscosity of the thermoplastic composition 14 is between 10 mPa*s and 10000 mPa*s, preferably between 20 mPa*s and 7000 mPa*s, and advantageously between 20 mPa*s and 5000 mPa*s, and more advantageously between 20 mPa*s and 2000 mPa*s, and even more advantageously between 20 mPa*s and 1000 mPa*s. The viscosity of the thermoplastic composition can be easily measured with a rheometer or a viscometer. The dynamic viscosity is measured at 25°C. If the thermoplastic composition has Newtonian behavior, meaning no shear thinning, the dynamic viscosity is independent of the shear in the rheometer or the moving speed in the viscometer. If the thermoplastic composition has non-Newtonian behavior, meaning shear thinning, the dynamic viscosity is the velocity at 25°C in 1 s -1 Measured at a shear rate of .

[0106] Regarding the thermoplastic composition 14 of the present invention, it comprises a (meth)acrylic monomer (M1) and a (meth)acrylic polymer (PI). Once polymerized, the (meth)acrylic monomer (M1) is converted into a (meth)acrylic polymer (P2), which comprises monomer units of the (meth)acrylic monomer (M1) and other possible monomers. Since the thermoplastic composition 14 of the present invention substantially comprises a (meth)acrylic monomer (M1) and a (meth)acrylic polymer (PI), it is also referred to as a (meth)acrylic composition MCI. Since the thermoplastic composition 14 of the present invention is a liquid, it substantially comprises a (meth)acrylic monomer (M1) and a (meth)acrylic polymer (PI), and is therefore also referred to as a (meth)acrylic syrup.

[0107] Preferably, the (meth)acrylic composition MCI also has a dynamic viscosity of 10 to 10000 mPa*s, preferably 20 to 7000 mPa*s, and advantageously 20 to 5000 mPa*s, and more advantageously 20 to 2000 mPa*s, and even more advantageously 20 to 1000 mPa*s.

[0108] As regards the (meth)acrylic polymer (PI), mention may be made of polyalkyl methacrylates or polyalkyl acrylates. According to a preferred embodiment, the (meth)acrylic polymer (PI) is polymethyl methacrylate (PMMA).

[0109] According to one embodiment, the methyl methacrylate (MMA) homopolymer or copolymer comprises at least 70% by weight, preferably at least 80% by weight, advantageously at least 90% by weight and more advantageously at least 95% by weight of methyl methacrylate.

[0110] According to another embodiment, PMMA is a mixture of at least one homopolymer and at least one copolymer of MMA, or a mixture of at least two homopolymers or two copolymers of MMA having different average molecular weights, or a mixture of at least two copolymers of MMA having different monomer compositions.

[0111] The methyl methacrylate (MMA) copolymer comprises 70 to 99.9 weight percent of methyl methacrylate and 0.1 to 30 weight percent of at least one monomer containing at least one ethylenic unsaturation copolymerizable with methyl methacrylate.

[0112] These monomers are well known and mention may be made in particular of acrylic and methacrylic and alkyl (meth) acrylates, in which the alkyl group contains from 1 to 12 carbon atoms. Mention may be made, by way of example, of methacrylate and ethyl (meth) acrylate, butyl (meth) acrylate or 2-ethylhexyl (meth) acrylate. Preferably, the comonomer is an alkyl acrylate, in which the alkyl group contains from 1 to 4 carbon atoms.

[0113] According to a first preferred embodiment, the copolymer of methyl methacrylate (MMA) comprises 80% to 99.9% by weight, advantageously 90% to 99.9% by weight, more advantageously 90% to 99.9% by weight of methyl methacrylate and 0.1% to 20% by weight, advantageously 0.1% to 10% by weight, more advantageously 0.1% to 10% by weight of at least one monomer containing at least one ethylenic unsaturation copolymerizable with methyl methacrylate. Preferably, the comonomer is chosen from methyl acrylate and ethyl acrylate and mixtures thereof.

[0114] The weight average molecular weight of the (meth)acrylic polymer (PI) should be high, which means greater than 50,000 g / mol, preferably greater than 100,000 g / mol.

[0115] The weight average molecular weight can be measured by size exclusion chromatography (SEC).

[0116] The (meth)acrylic polymer (PI) is completely soluble in the (meth)acrylic monomer (Ml) or the (meth)acrylic monomer mixture. It is able to increase the viscosity of the (meth)acrylic monomer (Ml) or the mixture of (meth)acrylic monomers. The resulting solution is a liquid composition generally referred to as a "slurry" or "prepolymer". The dynamic viscosity value of the liquid (meth)acrylic slurry is between 10 mPa.s and 10000 mPa.s. The viscosity of the slurry can be easily measured with a rheometer or a viscometer. The dynamic viscosity is measured at 25°C.

[0117] Advantageously, the liquid (meth)acrylic composition or syrup contains no additional intentionally added solvent.

[0118] As for the (meth)acrylic monomer (M1), the monomer is selected from the group consisting of alkyl acrylic monomers, alkyl methacrylic monomers, hydroxyalkyl acrylic monomers and hydroxyalkyl methacrylic monomers, and mixtures thereof.

[0119] Preferably, the (meth)acrylic monomer (Ml) is selected from hydroxyalkyl acrylic monomers, hydroxyalkyl methacrylic monomers, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof, wherein the alkyl group contains 1 to 22 straight chain, branched or cyclic carbons; the alkyl group preferably contains 1 to 12 straight chain, branched or cyclic carbons.

[0120] More preferably, the (meth)acrylic monomer (M1) is selected from alkyl acrylic monomers or alkyl methacrylic monomers and mixtures thereof, wherein the alkyl group contains 1 to 22 linear, branched or cyclic carbons; the alkyl group preferably contains 1 to 12 linear, branched or cyclic carbons.

[0121] Advantageously, the (meth)acrylic monomer (M1) is 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, isobornyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate, and mixtures thereof.

[0122] More advantageously, the (meth)acrylic monomer (M1) is 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, isobornyl methacrylate, and mixtures thereof.

[0123] According to a preferred embodiment, at least 50% by weight, preferably at least 60% by weight, of the (meth)acrylic monomers (M1) are methyl methacrylate.

[0124] 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 (meth)acrylic monomers (M1) are a mixture of methyl methacrylate and optionally at least one other monomer.

[0125] The thermoplastic composition 14 or the (meth)acrylic composition MCI of the present invention may further comprise a (meth)acrylic monomer (M2). With regard to the (meth)acrylic monomer (M2), the monomer is multifunctional. Preferably, the (meth)acrylic monomer (M2) is selected from compounds comprising at least two (meth)acrylic functional groups. The (meth)acrylic monomer (M2) may also be selected from a mixture of at least two compounds (M2a) and (M2b), each of which comprises at least two (meth)acrylic functional groups.

[0126] The (meth)acrylic monomer (M2) may be selected from 1,3-butylene glycol dimethacrylate; 1,4-butylene glycol dimethacrylate; 1,6-hexanediol diacrylate; 1,6-hexanediol dimethacrylate; diethylene glycol dimethacrylate; dipropylene glycol diacrylate; ethoxylated (10) bisphenol A diacrylate; ethoxylated (2) bisphenol A dimethacrylate; ethoxylated (3) bisphenol A diacrylate; ethoxylated (3) bisphenol A dimethacrylate; ethoxylated (4) bisphenol A diacrylate; ethoxylated (4) bisphenol A dimethacrylate; ethoxylated bisphenol A dimethacrylate; ethoxylated (10) bisphenol dimethacrylate; ethylene glycol dimethacrylate; polyethylene glycol (200) diacrylate; polyethylene glycol (400) diacrylate; polyethylene glycol (400) dimethacrylate; polyethylene glycol (400) dimethacrylate; polyethylene glycol (600) diacrylate; polyethylene glycol (600) dimethacrylate; polyethylene glycol 400 diacrylate; propoxylated (2) neopentyl glycol diacrylate; tetraethylene glycol diacrylate; tetraethylene glycol dimethacrylate; tricyclodecane dimethanol diacrylate; tricyclodecane dimethanol dimethacrylate; triethylene glycol diacrylate; triethylene glycol dimethacrylate; tripropylene glycol diacrylate; ethoxylated (15) trimethylolpropane triacrylate; ethoxylated (3) trimethylolpropane triacrylate; ethoxylated (6) trimethylolpropane triacrylate; ethoxylated (9) trimethylolpropane triacrylate; ethoxylated 5 pentaerythritol triacrylate; ethoxylated (20) trimethylolpropane triacrylate; propoxylated (3) glycerol triacrylate; trimethylolpropane triacrylate; propoxylated (5.5) Glycerol triacrylate; Pentaerythritol triacrylate; Propoxylated (3) glycerol triacrylate; Propoxylated (3) trimethylolpropane triacrylate; Trimethylolpropane triacrylate; Trimethylolpropane trimethacrylate; Tris(2-hydroxyethyl)isocyanurate triacrylate; Di-trimethylolpropane tetraacrylate; Dipentaerythritol pentaacrylate; Ethoxylated (4) pentaerythritol tetraacrylate; Pentaerythritol tetraacrylate; Dipentaerythritol hexaacrylate; 1,10-decanediol diacrylate; 1,3-butylene glycol diacrylate; 1,4-butylene glycol diacrylate; 1,9-nonanediol diacrylate; 2-(2-vinyloxyethoxy)ethyl acrylate; 2-butyl-2-ethyl-1,3-propanediol diacrylate; 2-methyl-1,3-propanediol diacrylate; 2-methyl-1 ,3-propylene glycol ethoxylate; 3-methyl 1,5-pentanediol diacrylate; alkoxylated cyclohexanedimethanol diacrylate; alkoxylated hexanediol diacrylate; cyclohexanedimethanol diacrylate; ethoxylated cyclohexanedimethanol diacrylate; diethylene glycol diacrylate; dioxanediol diacrylate; ethoxylated dipentaerythritol hexaacrylate; ethoxylated glycerol triacrylate; ethoxylated neopentyl glycol diacrylate; hydroxyneopentyl hydroxyneopentyl diacrylate; neopentyl glycol diacrylate; poly(tetramethylene glycol) diacrylate; polypropylene glycol 400 diacrylate; polypropylene glycol 700 diacrylate; propoxylated (6) ethoxylated bisphenol A diacrylate; propoxylated ethylene glycol diacrylate; propoxylated (5) pentaerythritol tetraacrylate; and propoxylated trimethylolpropane triacrylate or mixtures thereof.

[0127] Preferably, the (meth)acrylic monomer (M2) is selected from ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,4-butylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, triethylene glycol dimethacrylate and triethylene glycol diacrylate or a mixture thereof.

[0128] With respect to 100 parts of liquid (meth)acrylic syrup (or (meth)acrylic composition MCI) comprising (meth)acrylic monomer (M1) and (meth)acrylic polymer (PI), (meth)acrylic monomer (M2) may be present in the (meth)acrylic composition MCI at 0.01 to 10 phr by weight, preferably at 0.1 to 9.5 phr, more preferably 0.1 to 9 phr, even more preferably 0.1 to 8.5 phr, and advantageously 0.1 to 8 phr.

[0129] In a first more preferred embodiment, the (meth)acrylic monomer (M2) is present in the (meth)acrylic composition MCI at 0.01 to 9 phr and is chosen from compounds comprising two (meth)acrylic functions.

[0130] In a second more preferred embodiment, the (meth)acrylic monomer (M2) is present in the (meth)acrylic composition MCI at 0.01 to 9 phr and is chosen from a mixture comprising two (meth)acrylic functional compounds.

[0131] In a third more preferred embodiment, the (meth)acrylic monomer (M2) is present in the (meth)acrylic composition MCI at 0.01 to 9 phr and is chosen from a mixture comprising at least two (meth)acrylic functional compounds.

[0132] In a fourth more preferred embodiment, the (meth)acrylic monomer (M2) is present in the (meth)acrylic composition MCI at 0.01 to 9 phr and is selected from a mixture of compounds comprising at least two (meth)acrylic functional groups. At least one compound in the mixture comprises only two (meth)acrylic functional groups and constitutes at least 50% by weight, preferably at least 60% by weight of the mixture of (meth)acrylic monomers (M2). Another compound in the mixture comprises more than two (meth)acrylic functional groups.

[0133] According to another embodiment of the wetting step, the thermoplastic composition may be a thermoplastic resin precursor.

[0134] The precursor or initiator (Ini) is capable of continuing the polymerization or starting the polymerization of the (meth)acrylic monomers (M1) and (M2) and is selected from free radical initiators.

[0135] Preferably, the initiator (Ini) is activated thermally.

[0136] The free radical initiator (Ini) may be selected from compounds containing a peroxy group or compounds containing an azo group, and is preferably selected from compounds containing a peroxy group.

[0137] Preferably, the compound comprising a peroxide group comprises from 2 to 30 carbon atoms.

[0138] Preferably, the compound comprising a peroxy group is selected from a diacyl peroxide, a peroxy ester, a peroxy dicarbonate, a dialkyl peroxide, a peroxy acetal, a hydroperoxide or a peroxy ketale; or a mixture.

[0139] The initiator (Ini) is selected from diisobutyryl peroxide, isopropyl peroxyneodecanoate, di(3-methoxybutyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, isopropyl 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 peroxyneodecanoate, di-n-butyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate Peroxypivalic acid 1,1,3,3-tetramethylbutyl ester, peroxyneoheptanoic acid tert-butyl ester, peroxypivalic acid tert-amyl ester, peroxypivalic acid tert-butyl ester, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, peroxy-2-ethylhexanoic acid 1,1,3,3-tetramethylbutyl ester, peroxy-2-ethylhexanoic acid tert-amyl ester, dibenzoyl peroxide, peroxy-2-ethylhexanoic acid tert-butyl ester, peroxydiethyl acetate tert-butyl peroxyisobutyrate, 1,1-di(tert-butylperoxy )-3,3,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, tert-amylperoxy-2-ethylhexylcarbonate, tert-amylperoxyacetate, tert-butylperoxy-3,5,5-trimethylhexanoate, 2,2-di(tert-butylperoxy)butane, tert-butylperoxyisopropylcarbonate, tert-butylperoxy-2-ethylhexylcarbonate, tert-amylperoxybenzoate, tert-butylperoxyacetate, butyl4,4-di(tert-butylperoxy)valerate, tert-butylperoxybenzoate, di-tert-amylperoxide, diisopropylbenzene peroxide, di-(2-tert-butylperoxy)butane or mixtures thereof.

[0140] Preferably, the initiator (Ini) is selected from the group consisting of isopropyl peroxyneodecanoate, di(3-methoxybutyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, isopropyl peroxyneodecanoate, 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 peroxyneodecanoate, 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-tetramethylbutyl peroxy-2-ethylhexanoate; or a mixture thereof.

[0141] The thermoplastic composition may comprise between 0.1 and 5 phr of an initiator (Ini) to start the polymerization of the (meth)acrylic monomers (M1) and (M2).

[0142] The method 100 according to the invention may comprise a heating step 130. Preferably, the heating step is implemented by a heating device 15. The heating step allows triggering and initiating polymerization 131 of the thermoplastic composition 14 with impregnated fibers 12 to form a heated thermoplastic composite material 16 with a first section S1.

[0143] Heating also allows the space between molecules to be increased, thereby allowing the flexibility of the heated thermoplastic composite material to be increased in order to facilitate the molding in the next step. As described above, the thermoplastic composite material has the characteristic of being generally solid at room temperature, softening during temperature increase, especially after exceeding its glass transition temperature (Tg) or melting temperature (Tf), and becoming solid again when the temperature is reduced to the melting point and below its glass transition temperature. Due to the heating step, polymerization occurs, thereby increasing the partial pressure and ensuring greater fluidity and flexibility; therefore, the heated thermoplastic composite material will be more easily deformed.

[0144] The heating step may include heating by convection, by conduction, by IR (infrared) including NIR and MIR (near and mid infrared), by microwaves, by UV (ultraviolet) and / or by induction.

[0145] According to one embodiment of the heating step 130, the polymerization may be carried out at a temperature generally below 140°C, preferably below 130°C, and even more preferably below 125°C.

[0146] According to one embodiment of the heating step, the polymerization may be carried out at a temperature of at least 40°C, preferably at least 50°C, and more preferably at least 60°C.

[0147] Preferably, the polymerization may be carried out at a temperature between 40°C and 140°C, preferably between 50°C and 130°C, even more preferably between 60°C and 125°C.

[0148] Advantageously, the heating step may be performed continuously or discontinuously.

[0149] The heating step and the polymerization reaction allow the conversion from a thermoplastic composition having impregnated fibers (thermoplastic resin or thermoplastic resin precursor) and being liquid to a heated thermoplastic composite material 16 .

[0150] The heating step allows obtaining a heated thermoplastic composite material 16 having a first section S1 .

[0151] The first section may comprise a predetermined thickness or width, and / or diameter (inner or outer), or volume or area or circumference.

[0152] The thermoplastic composite material, preferably the heated thermoplastic composite material, can have different geometric shapes. The geometric shape can be tubular, conical, elliptical, pyramidal, cubic or cuboid. Preferably, the thermoplastic composite material is not limited by its geometric shape. In addition, the thermoplastic composite material, preferably the heated thermoplastic composite material, can have different sizes, such as thickness, diameter, length, width, height, area, volume, perimeter.

[0153] Preferably, the heated thermoplastic composite is not limited in its dimensions, such as its length.

[0154] The thermoplastic composite material, and preferably the first section of the heated thermoplastic composite material, can have different geometric shapes depending on the geometric shape of the heated thermoplastic composite material. For example, the section can be circular, triangular, square, rectangular, parallelepiped, trapezoidal. Preferably, the section is not limited by its geometric shape. The thermoplastic composite material, and preferably the first section of the heated thermoplastic composite material, can have different sizes depending on the size of the heated thermoplastic composite material. Preferably, the section is not limited by its size.

[0155] For example, if the heated thermoplastic composite material is conical, the first section may be circular, elliptical, parabolic or hyperbolic. Preferably, the section is determined according to the horizontal axis. According to another example, the heated thermoplastic composite material may be pyramidal, in which case the first section may be triangular, or the heated thermoplastic composite material may be tubular and the first section may be parallelepiped, rectangular, square, trapezoidal. The geometry may affect the polymerization. Therefore, according to the geometry of the thermoplastic composite material, more monomers may be converted into polymers and the impregnation may be improved.

[0156] During the heating step, the resin polymerizes from liquid resin to solid state with a high volume shrinkage, usually between 5% and 20% (18% for neat resin). This shrinkage causes pressure loss in the pultrusion process. This pressure loss leads to relatively high porosity, which results in reduced mechanical properties of the thermoplastic composite, increased residual monomers, increased water absorption, changes in electrical conductivity and chemical resistance.

[0157] The method according to the present invention may include a step 140 of shaping the heated thermoplastic composite material 16. Preferably, this step is implemented by pulling the heated thermoplastic composite material 16 through a shaping device 17. The shaping device 17 has a second section S2, and the second section S2 is smaller than the first section S1. The shaping step 140 allows providing a heated thermoplastic composite material 18 having a second section S2.

[0158] Advantageously, during the forming step 140, the heated thermoplastic composite material 16 passes through the forming device 17, wherein, due to the smaller sections of the forming device 17, pressure is applied to the heated thermoplastic composite material 16. Preferably, the heated thermoplastic composite material 16 is further heated and thus deformable. Heating the heated thermoplastic composite material 16 allows the forming step 140 to be facilitated.

[0159] Preferably, the temperature of the heated thermoplastic composite material at the inlet of the molding device may be between 100°C and 160°C, and is preferably higher than Tg.

[0160] Advantageously, the time of the forming step can be predetermined according to the thermoplastic composition, the ratio of the fiber content and / or the first section of the heated thermoplastic composite material. For example, the time of the forming step can be between 10 seconds and 3 minutes, depending on the stretching rate and the length of the forming device.

[0161] As mentioned above, the shaping step involves the application of pressure (due to the smaller sections of the shaping device), which surprisingly leads to a reduction in porosity. Figure 3As shown, the porosity content has been reduced from 5% to 1%, as determined by porosity measurements of microanalysis (optical) and calcination tests (ISO1172). In addition, due to the reduced porosity, there is less "air" and volatile compounds present in the thermoplastic composite, and therefore less empty spaces in the thermoplastic composite, which leads to lower water absorption and, therefore, lower conductivity and better chemical resistance. In fact, with less porosity and empty spaces, less water penetrates into the thermoplastic composite, and therefore less water penetration and less water absorption (by weighing). In addition, due to the heating step before the molding step, fewer volatile compounds are trapped in the fibers, which also allows the porosity to be reduced. In addition, the less porous the thermoplastic composite, the better its conductivity. In addition, the surface appearance is better, such as smoother and glossier. A better surface appearance is very important for the optional steps of coating, painting or packaging. In addition, the molding step can offset the effects of shrinkage.

[0162] According to one embodiment, the molding step can reduce the volume of the heated thermoplastic composite material by 1% to 15%. Preferably, the molding step can reduce the volume of the heated thermoplastic composite material by 2% to 12%, and more preferably, the molding step can reduce the volume of the heated thermoplastic composite material by 3% to 10%.

[0163] According to another embodiment, the shaping step can reduce the diameter of the heated thermoplastic composite material by 1% to 15%. Preferably, the shaping step can reduce the diameter of the heated thermoplastic composite material by 2% to 12%, and more preferably by 3% to 10%.

[0164] According to another embodiment, the molding step can reduce the surface or area of ​​the heated thermoplastic composite material by 1% to 15%. Preferably, the molding step can reduce the surface or area of ​​the heated thermoplastic composite material by 2% to 12%, and more preferably, reduce the surface or area of ​​the heated thermoplastic composite material by 3% to 10%.

[0165] According to another embodiment, the shaping step can reduce the circumference of the heated thermoplastic composite material by 1% to 15%. Preferably, the shaping step can reduce the circumference of the heated thermoplastic composite material by 2% to 12%, and more preferably by 3% to 10%.

[0166] For example, the molding apparatus may be configured such that the heated thermoplastic may have a first section, such as about 13 mm in diameter, and a second section, such as about 12.6 mm in diameter.

[0167] According to another example, the molding apparatus can be configured such that the heated thermoplastic composite material can have a first segment (e.g., a thickness of approximately 10 mm) and a second segment (e.g., a thickness of approximately 9.7 mm) in one dimension, while the thickness (width) in the perpendicular dimension remains unchanged or also decreases for the two segments.

[0168] The invention is not limited to exact values ​​but is very advantageously applicable to any type of segment value.

[0169] The second section of the heated thermoplastic composite material having the second section may have the same geometry as the first section of the heated thermoplastic composite material having the first section.

[0170] For example, a first section of a heated thermoplastic composite material may be circular, and a second section of the same heated thermoplastic composite material having a second section may also be circular after passing through a forming device, but may have different dimensions, for example, the second section may be smaller than the first section in terms of, for example, diameter and / or area and / or circumference.

[0171] Alternatively, after passing through the forming device, the second section of the heated thermoplastic composite material having the second section may have a different geometry than the first section of the heated thermoplastic composite material having the first section.

[0172] For example, a first section of a heated thermoplastic composite material may be circular or tubular, while a second section of the same heated thermoplastic composite material may be square after passing through a forming device, but having different dimensions, such as the second section being smaller than the first section in terms of, for example, area and / or circumference.

[0173] According to another example, the first section of the heated thermoplastic composite material can be a parallelepiped, and the second section of the uniform heated thermoplastic composite material can be a rectangle, a square or even a trapezoid after passing through the molding device, but with different dimensions, for example, the second section is smaller than the first section in aspects such as area and / or perimeter.

[0174] The second section is smaller than the first section in at least one dimension.

[0175] In order to further improve the porosity and properties of the heated thermoplastic composite material, the method according to the present invention may include a vacuuming step 135. Preferably, the vacuuming step includes vacuuming air, volatile compounds, monomers, reagents, other fluids and / or gaseous compounds. Advantageously, the vacuuming step may be performed before the molding step. The vacuuming step may be performed by removing the air space (in the Figure 2The pultrusion process can be performed by applying a vacuum between the pultrusion die and the forming device. The evacuation step allows for exhaust before the forming step.

[0176] The method according to the present invention may include a cooling step 150. In a specific embodiment, the cooling step may be achieved by a cooling device 19. In addition, the cooling step may be achieved at a given cooling temperature and / or within a given cooling time.

[0177] According to one embodiment, the cooling temperature and / or cooling time can be selected according to the glass transition temperature (Tg) and / or the melting temperature of the heated thermoplastic composite material. Preferably, the cooling step is carried out at a cooling temperature below the glass transition temperature of the heated thermoplastic composite material having the second section. For example, Tg can be below 130°C, preferably below 120°C, and more preferably below 110°C. The glass transition temperature (Tg) of the polymer can be measured using a device capable of thermomechanical analysis (DMA). The RDAII "Rheometrics Dynamic Analyzer" proposed by Rheometrics has been used. Thermomechanical analysis accurately measures the viscoelastic changes of the sample as a function of temperature, strain or applied deformation. During the controlled temperature change program, the device continuously records the sample deformation, keeping the strain fixed. The results are obtained by plotting the elastic modulus (G'), loss modulus (G") and tanδ as a function of temperature. When the derivative of tanδ is equal to zero, Tg is the highest temperature value read in the tanδ curve.

[0178] According to another embodiment, the cooling temperature and / or the cooling time can be selected depending on the size of the heated thermoplastic composite, on the heating temperature, on the heating time, on the type of heating, on the section of the thermoplastic composite, on the geometry of the thermoplastic composite, on the pulling rate, on the length of the cooling device and / or on the thermoplastic composition.

[0179] For example, the cooling temperature may be less than or equal to 150° C., preferably less than or equal to 130° C., more preferably less than or equal to 110° C., and even more preferably less than or equal to 100° C. The cooling temperature may be greater than or equal to 50° C., preferably greater than or equal to 60° C., more preferably greater than or equal to 70° C., and even more preferably greater than or equal to 80° C. The cooling temperature may be between 50° C. and 150° C., preferably between 60° C. and 130° C., more preferably between 70° C. and 130° C., and even more preferably between 80° C. and 110° C.

[0180] The cooling step 150 allows producing a shaped thermoplastic composite material 10, preferably a shaped thermoplastic composite material having a second section. More preferably, the cooling step allows stabilizing the geometry and in particular the sections.

[0181] According to a preferred embodiment, the cooling step can be performed simultaneously with the shaping step. According to another embodiment, the cooling step can be performed after the shaping step.

[0182] The method of the present invention may include other optional steps 160, such as coating, bending, heating, cooling, cutting, welding, bonding and / or laminating. The optional steps may be implemented according to the shaped thermoplastic composite material to be produced. The optional steps may also improve the quality and / or properties of the shaped thermoplastic composite material.

[0183] According to another embodiment, the present invention relates to a shaped thermoplastic composite material 10 obtainable, preferably obtainable, by the method according to the invention.

[0184] As mentioned above, the shaped thermoplastic composite material according to the present invention comprises a polymer matrix and fibers.

[0185] According to one embodiment, the shaped thermoplastic composite may comprise at least 50 volume % fibers, preferably at least 60 volume % fibers, and more preferably at least 70 volume % fibers.

[0186] The shaped thermoplastic composite is preferably obtained from a thermoplastic composite comprising 35% or less by volume of a polymer matrix (including a (meth) acrylic polymer) and at least 65% by volume of fibers. The shaped thermoplastic composite can also be obtained from a thermoplastic composite comprising 20% ​​to 30% by volume of a polymer matrix (including a (meth) acrylic polymer) and 70% to 80% by volume of fibers.

[0187] According to one embodiment, the shaped thermoplastic composite may comprise 20 to 30 volume % of the polymer matrix and 60 to 80 volume % of the fibers.

[0188] Preferably, the polymer matrix may comprise at least 20% by weight of (meth)acrylic polymer and at least 60% by volume of fibers.

[0189] Furthermore, the (meth)acrylic polymer may be cross-linked.

[0190] The shaped thermoplastic composite material may have different segments, such as circular, elliptical, parabolic or hyperbolic triangle, oval, parallelepiped. Preferably, the segments may be defined by an axis perpendicular to the longitudinal axis of the shaped thermoplastic composite material. The shaped thermoplastic composite material is not limited by the segment geometry.

[0191] The molded thermoplastic composites can have different dimensions (thickness, diameter, length, width, height).

[0192] The shaped thermoplastic composite material is preferably used to produce a reinforcing element for reinforcing a structure. The reinforcing element may be, for example, a plate, a rod, a bar, a rebar or a sheet. According to one embodiment, the shaped thermoplastic composite material may include a plurality of sheets.

[0193] Advantageously, the shaped thermoplastic composite material according to the present invention meets all the requirements of the standard Specification for Solid Round Glass Fiber Reinforced Polymer Bars for Concrete Reinforcement.

[0194] Advantageously, the porosity of the shaped thermoplastic composite material according to the invention may be less than or equal to 10%, preferably less than or equal to 8%, more preferably less than or equal to 5%, and even more preferably less than or equal to 1%. The porosity may be measured by optical microscopy analysis and / or calcination tests. Due to its low porosity, the shaped thermoplastic composite material according to the invention has better mechanical and thermal properties, better chemical properties and chemical resistance, better electrical conductivity and less water absorption.

[0195] For example, the water absorption of the shaped thermoplastic composite according to the present invention may be between 5 and 15% by weight of the shaped thermoplastic composite, while the water absorption of the same thermoplastic composite not shaped according to the present invention is between 20 and 40%. The water absorption can be measured by weighing (adjusted according to ASTM D570). The water absorption of the shaped thermoplastic composite according to the present invention is divided by 2 compared to the same thermoplastic composite not shaped according to the present invention. The water absorption of the shaped thermoplastic composite according to the present invention is improved by 10% to 50%.

[0196] Advantageously, the shaped thermoplastic composite material according to the present invention may include a roughness that is less than that of the same thermoplastic composite material that is not shaped. For example, the outer surface of the shaped thermoplastic composite material according to the present invention may be smoother or more shiny. In the case where the surface of the thermoplastic composite material is treated (e.g., using a coating), the appearance of the surface may be important. In fact, it will be easier to treat using the shaped thermoplastic composite material of the present invention, for example, more permeable and more durable. The appearance can be measured by any method currently used in the art, such as by visual measurement.

[0197] According to another aspect of the invention, the invention relates to the use of the shaped thermoplastic composite material according to the invention in automotive, transport, marine, railway, sports, aviation, aerospace, photovoltaic, computing, building and construction, telecommunications and / or wind energy applications.

[0198] According to another aspect, the present invention relates to a forming device 17. The forming device is configured to reduce a first section of a thermoplastic composite material, preferably a thermoplastic composite material according to the present invention and even more preferably a heated thermoplastic composite material according to the present invention, to a second section to form a formed thermoplastic composite material preferably according to the present invention having a second section that is smaller than the first section. The second section is smaller than the first section in at least one dimension, such as diameter and / or perimeter and / or area. In this case, the formed thermoplastic composite material has at least one dimension that is smaller than the heated thermoplastic composite material, which dimension may be, for example, volume, perimeter and / or diameter.

[0199] Advantageously, the forming device according to the invention comprises at least one inlet and at least one outlet. The at least one inlet is preferably facing the pultrusion die. The at least one outlet is preferably facing the cooling die. In addition, the outlet is smaller than the inlet in at least one dimension, preferably the outlet has a smaller section than the inlet.

[0200] According to one embodiment of the invention, the molding device may include a heating device and / or a cooling device. In fact, the molding device may be configured to heat and / or cool the molded thermoplastic composite material to bend or manipulate the molded thermoplastic composite material, depending on the section of the thermoplastic composite material or depending on the final form of the molded thermoplastic composite material.

[0201] The forming device may include a mold, a forming channel and / or a thermally adjustable mold.

[0202] The forming device according to the invention is not limited to a specific form or a specific geometry or size.The forming device may have an adaptable form or geometry or size, depending on the reduction of the thermoplastic composite material section.

[0203] For example, the shaping device may be in the shape of a cone, a pyramid, or a frustum.

[0204] Furthermore, the molding device according to the present invention is not limited in size. For example, the molding device can have different lengths, thicknesses, diameters, widths, slopes. Preferably, this enables the molding device to be adapted to the first section thermoplastic composite material to obtain the second section thermoplastic composite material.

[0205] Advantageously, parts of the forming device may also be adjustable and / or adaptable.

[0206] According to a preferred embodiment, the molding device according to the present invention can be configured to adapt to the size of the thermoplastic composite material. Preferably, the molding device according to the present invention can be configured to adapt to the heated thermoplastic composite material. More preferably, the molding device according to the present invention can be configured to adapt to the shrinkage of the resin in the heated thermoplastic composite material. The shrinkage rate can be between 3% and 15%.

[0207] Advantageously, the inlet of the forming device corresponds perfectly in size to the last device of the pultrusion die. For example, if the last pultrusion device in the pultrusion die is a heating device, the inlet of the forming device has the same dimensional characteristics as the heating device.

[0208] Preferably, the molding device is detachable. The molding device can be fixed to the pultrusion die in a non-fixed manner, and preferably fixed to the die before the inlet of the molding device, so that the heated thermoplastic composite material with the first section enters the inlet molding device. A detachable fixture corresponds to being able to be easily detached, removed or dismantled without destroying the fastening device, because there is no fastening device or because the fastening device is easily and quickly detachable (for example, notch, screw, tab, lug, clamp). For example, by detachable it should be understood that the object is not fixed by welding or any other means that are not intended to allow the object to be detachable. This also makes it possible to change the segment and is suitable for any type of segment of the thermoplastic composite material.

[0209] For example, the shaping device can be mechanically fixed by being screwed onto the preceding die of the shaping device inlet in the pultrusion die.

[0210] Alternatively, the shaping device may be non-detachably fixed to the pultrusion die, for example by welding the inlet of the shaping device to the preceding die of the pultrusion die.

[0211] According to another alternative, the forming device can be placed at a distance from the pultrusion die so as to leave a gap between the pultrusion die and the shrinking die (i.e., the forming device). The gap can be configured to create an empty space and / or vacuum and / or air space before the forming device to allow exhaust.

[0212] The forming device allows for the reduction of sections of the thermoplastic composite material, and more preferably the reduction of sections of the heated thermoplastic composite material.

[0213] The forming device may correspond to the contraction zone.

[0214] Due to its sections being adapted to each type of thermoplastic composite material, the shaping device can in a particularly advantageous manner exert pressure on the thermoplastic composite material in order to reduce the porosity of the thermoplastic composite material.

[0215] Advantageously, the forming device can be digitally / automatically controlled and / or mobile or manually controlled.

[0216] According to another aspect, the present invention is directed to a system 200 for producing a formed thermoplastic composite material. Figure 2 An example of this system is shown.

[0217] The system 200 for producing the molded thermoplastic composite material 10 may include:

[0218] a fiber feeding device 11 configured to provide fibers 12 in the direction of the pultrusion path A,

[0219] an impregnation device 13 configured to wet the fibers 12 with a thermoplastic composition 14 which is a thermoplastic resin or a thermoplastic resin precursor and comprises at least 50% by weight of monomers,

[0220] a heating device 15 configured to polymerize the thermoplastic composition 14 to form a heated thermoplastic composite material 16 having a first section S1 ,

[0221] - a molding device 17, which is configured to mold the heated thermoplastic composite material 16 according to the second section S2, the molding device 17 has a second section, and the second section is smaller than the first section to provide a heated thermoplastic composite material 18 having a second section, the molding device 17 is adapted to the previous device, and the molding device is preferably a facing device,

[0222] A cooling device 19 configured to produce a shaped thermoplastic composite material 10 at a cooling temperature below the glass transition temperature of the heated thermoplastic composite material with the second section 18 .

[0223] Preferably, all devices of the system operate continuously.

[0224] The system 200 according to the invention may comprise a fiber feeding device 11. The fiber feeding device is configured to provide fibers 12 in the direction of a pultrusion path A.

[0225] The fiber feeding device may include at least one bobbin, reel, roller on which the fibers are wound. These fibers may be unwound from the bobbin, reel, roller by one or more redirecting and guiding devices that guide and connect the unwound fibers to gather the fibers into bundles.

[0226] The fiber bundle is pulled toward the impregnation device 13 by traction.

[0227] The system 200 according to the present invention may include a pulling device that pulls the fiber in a forward direction and preferably on a pultrusion path A. For example, the pulling device may include one or more preferably opposing clamps or gripping surfaces and be actuated to drive the fiber, thermoplastic composite, heated thermoplastic composite in direction A. The speed of the device may be configurable.

[0228] The system 200 may include an impregnation device 13 configured to wet the fibers 12 with a thermoplastic composition 14, which is a thermoplastic resin or a thermoplastic resin precursor and contains at least 50% by weight of monomers. Preferably, the thermoplastic composition is a thermoplastic composition disclosed above.

[0229] For example, the pulling device can be configured to guide the fiber through one or more baths, one or more injection chambers, one or more soaking tanks, or one or more impregnation chambers.

[0230] The impregnation apparatus is configured to receive the fibers and wet the fibers by capillary absorption or injection to ensure complete impregnation of the fibers with the thermoplastic composition, preferably in liquid form.

[0231] According to one embodiment, the impregnation device may include a comb, a scraper brush, a series of rings of decreasing diameter, a tubular channel to eliminate excess thermoplastic composition.

[0232] The system according to the present invention may include a heating device 15 configured to cause polymerization of the thermoplastic composition 14 to form a heated thermoplastic composite material 16 having a first section S1 .

[0233] The heating means may be selected from conduction, convection, radiation and / or volumetric heating means.

[0234] The heating device may comprise a mould, a housing, a microwave source, an IR source (NIR / MIR), a blower, an oven and / or an induction source. Preferably, the heating device comprises an infrared heating device or a microwave heating device. This ensures sufficiently uniform heating and ensures polymerization of the thermoplastic composition.

[0235] The polymerization makes it possible to obtain a thermoplastic composite material having a first section, preferably a solid heated thermoplastic composite material having a first section.

[0236] Advantageously, the heating device may comprise one or more heating sensors of the IR or thermometer type to control different heating temperatures, and / or a timer to control the heating time.

[0237] The system according to the invention may comprise a forming device 17. Preferably, the forming device is as described above.

[0238] The molding device 17 is configured to mold the heated thermoplastic composite material 16 according to the second section S2. The molding device 17 may have an inlet and an outlet, and preferably the inlet has a first section and the outlet has a second section, and more preferably the second section is smaller than the first section, to provide a heated thermoplastic composite material 18 having a second section. The molding device is configured to apply pressure on the heated thermoplastic composite material having a first section to reduce the first section to a second section. Preferably, the pressure is applied by a portion of the molding device, and preferably by the second section, which is smaller than the heated thermoplastic composite material having the first section.

[0239] Advantageously, the shaping device 17 is adjusted to the preceding device or the preceding die of the pultrusion die. Preferably, the pultrusion die includes all the devices preceding the shaping device. The shaping device can perfectly adapt and fit the dimensional features of the preceding die or device. Preferably, the inlet of the shaping device is adapted to the dimensional features of the preceding die or device. Preferably, the outlet of the shaping device faces the cooling device.

[0240] According to one embodiment, the forming device is at a distance from the previous mold or device to allow venting and / or application of a vacuum. In this case, the system may include an air space, a vacuum or an empty space. Preferably, an air space, a vacuum or an empty space is arranged between the heating device and the forming device.

[0241] The system according to the present invention may include a cooling device 19. The cooling device may be configured to cool to a temperature below the glass transition temperature of the heated thermoplastic composite material having the second section 18 to produce a molded thermoplastic composite material 10.

[0242] The cooling device of the system of the present invention may be configured to solidify the heated thermoplastic composite material having the second section to form a shaped thermoplastic composite material.

[0243] Preferably, the cooling device is capable of cooling the heated thermoplastic composite material sufficiently so that the heated thermoplastic composite material becomes solid and can be removed from the system without deformation.

[0244] Advantageously, the cooling device may be configured to cool the heated thermoplastic composite material directly or indirectly (ie by direct contact or indirect contact).

[0245] The cooling device can cool the heated thermoplastic composite material to a cooling temperature that causes the heated thermoplastic composite material to become solid and thermally shrink. The thermal shrinkage rate can be between 0 and 5%, preferably between 1 and 5%.

[0246] Preferably, the cooling temperature is lower than the glass transition temperature of the thermoplastic composite material, and preferably lower than the glass transition temperature of the heated thermoplastic composite material, for example, lower than or equal to 120°C, preferably lower than or equal to 110°C.

[0247] Furthermore, the cooling device is adapted to achieve rapid cooling of the heated thermoplastic composite material. It may depend on the length and the pulling speed. Advantageously, only the shape of the heated thermoplastic composite material is cooled.

[0248] Advantageously, it may be an instantaneous cooling or alternatively a slow cooling.

[0249] To this end, the molding device can be equipped with a cooling device to actively cool the heated thermoplastic composite material. This can include compressed air.

[0250] Alternatively, the cooling device may be adapted to induce passive cooling or automatic cooling. It may be a mold, a nozzle, a refrigerant circuit, a cooling fluid flow and / or a fan.

[0251] Preferably, the system comprises a specific arrangement of different devices. For example, it is preferred that the feeding device appears before the impregnation device in the direction A of the pultrusion path. It is also preferred that the impregnation device appears before the heating device, the heating device appears before the forming device, and the forming device appears before the cooling device.

[0252] Advantageously, a vacuum or an empty space or an air space is arranged between the heating device and the forming device. This arrangement is particularly advantageous for reducing the porosity, volatile compounds of the formed thermoplastic composite material and for improving the mechanical and chemical properties.

[0253] The system according to the invention may comprise other devices, such as bending devices, twisting devices, cutting devices, vacuum devices, surface texturing devices.

[0254] The present invention may be the subject of many variations and applications other than those described above. Unless otherwise indicated, the different structural and functional features of the various embodiments described above should not be considered to be combined with each other and / or closely and / or inseparably linked together, but rather to be considered as simple juxtapositions. In addition, the structural and / or functional features of the different embodiments described above may be the subject of any different juxtapositions or any different combinations in whole or in part. [Example]

[0255] Table 1 : Examples of rod-shaped thermoplastic composite materials obtained by the molding process of the invention and without the need for molding, and comprising 60% of fibers and at least 20% of a thermoplastic composition with a (meth)acrylic resin.

[0256] A liquid composition was prepared by dissolving 25 wt. % of PMMA (BS520, MMA copolymer containing ethyl acrylate as comonomer) as (P1) in 75 wt. % of methyl methacrylate as (M1), which was stabilized with HQME (hydroquinone monomethyl ether) as the (meth)acrylic composition MCI. 2 phr of dilauroyl peroxide (LP- LP from Arkema) was added to the liquid composition.

[0257] The liquid composition is used in a pultrusion process in a method and apparatus according to the present invention, which method and apparatus include a forming step and a forming apparatus, and a comparative method and apparatus that do not include the forming step and the forming apparatus.

[0258] The temperature of the heating device during the heating step was 120°C.

[0259] The individual rods obtained were evaluated by measuring, inter alia, the respective diameter, porosity and water absorption.

[0260] The results are summarized in Table 1.

[0261] Table 1

[0262]

[0263] As shown in Table 1, the shaped thermoplastic composite material according to the present invention shows improved chemical and mechanical properties, and in particular low porosity.

Claims

1. A method (100) for producing a shaped thermoplastic composite material (10), the method comprising a pultrusion process and comprising: - a feeding step (110) by means of a fiber feeding device (11), said feeding step providing the fibers (12) in the direction A of the pultrusion path, - a step (120) of wetting the fibers (12) by means of an impregnation device (13), which comprises passing the fibers through a thermoplastic composition (14), said thermoplastic composition (14) being a thermoplastic resin or a thermoplastic resin precursor and comprising at least 50% by weight of monomers, a heating step (130) by means of a heating device (15), which comprises polymerizing (131) the thermoplastic composition (14) with which the fibers have been impregnated, to form a heated thermoplastic composite material (16) having a first section (S1), - a step (140) of shaping the heated thermoplastic composite material (16) by pulling the heated thermoplastic composite material (16) through a shaping device (17), the shaping device (17) having a second section (S2), and the second section (S2) being smaller than the first section (S1), to provide a heated thermoplastic composite material (18) having the second section (S2), and - A step (150) of cooling by a cooling device (19) at a cooling temperature below the glass transition temperature of the heated thermoplastic composite material (18) having the second section (S2) to produce a molded thermoplastic composite material (10).

2. The method (100) for producing a shaped thermoplastic composite material (10) according to claim 1, characterized in that The pultrusion process is a reactive pultrusion process.

3. The method (100) for producing a molded thermoplastic composite material (10) according to claim 1 or 2, characterized in that: The feeding step (110) and the wetting step (120) are performed such that the shaped thermoplastic composite material comprises at least 60 volume percent fibers.

4. The method (100) for producing a shaped thermoplastic composite material (10) according to any one of the preceding claims, characterized in that The cooling step (150) is performed simultaneously with the forming step (140).

5. The method (100) for producing a shaped thermoplastic composite material (10) according to any one of the preceding claims, characterized in that The method (100) includes a vacuuming step (135) prior to the forming step (140).

6. The method (100) for producing a shaped thermoplastic composite material (10) according to any one of claims 1 to 5, characterized in that: The thermoplastic composition (14) is a (meth)acrylic composition MCI comprising a (meth)acrylic monomer (M1) and a (meth)acrylic polymer (PI).

7. The method (100) for producing a shaped thermoplastic composite material (10) according to any one of claims 1 to 5, characterized in that: The thermoplastic composition (14) comprises 10 to 50 wt% of a (meth)acrylic polymer (PI) and 50 to 90 wt% of a (meth)acrylic monomer (M1).

8. The method (100) for producing a shaped thermoplastic composite material (10) according to any one of claims 6 or 7, characterized in that: The thermoplastic composition 14 or the (meth)acrylic composition MCI may additionally contain a (meth)acrylic monomer (M2).

9. The method (100) for producing a shaped thermoplastic composite material (10) according to claim 8, characterized in that The (meth)acrylic monomer (M2) is selected from compounds comprising at least two (meth)acrylic functional groups.

10. The method (100) for producing a shaped thermoplastic composite material (10) according to claim 8, characterized in that The (meth)acrylic monomer (M2) is selected from 1,3-butylene glycol dimethacrylate; 1,4-butylene glycol dimethacrylate; 1,6-hexanediol diacrylate; 1,6-hexanediol dimethacrylate; diethylene glycol dimethacrylate; dipropylene glycol diacrylate; ethoxylated (10) bisphenol A diacrylate; ethoxylated (2) bisphenol A dimethacrylate; ethoxylated (3) bisphenol A diacrylate; ethoxylated (3) bisphenol A dimethacrylate; ethoxylated (4 ) bisphenol A diacrylate; ethoxylated (4) bisphenol A dimethacrylate; ethoxylated bisphenol A dimethacrylate; ethoxylated (10) bisphenol dimethacrylate; ethylene glycol dimethacrylate; polyethylene glycol (200) diacrylate; polyethylene glycol (400) diacrylate; polyethylene glycol (400) dimethacrylate; polyethylene glycol (400) dimethacrylate; polyethylene glycol (600) diacrylate; polyethylene glycol (600) dimethacrylate; Polyethylene glycol 400 diacrylate; propoxylated (2) neopentyl glycol diacrylate; tetraethylene glycol diacrylate; tetraethylene glycol dimethacrylate; tricyclodecane dimethanol diacrylate; tricyclodecane dimethanol dimethacrylate; triethylene glycol diacrylate; triethylene glycol dimethacrylate; tripropylene glycol diacrylate; ethoxylated (15) trimethylolpropane triacrylate; ethoxylated (3) trimethylolpropane triacrylate; ethoxylated (6) trimethylolpropane triacrylate; ethoxylated (9) trimethylolpropane triacrylate; ethoxylated 5-pentaerythritol triacrylate; ethoxylated 20) trimethylolpropane triacrylate; propoxylated (3) glycerol triacrylate; trimethylolpropane triacrylate; propoxylated (5.5) glycerol triacrylate; pentaerythritol triacrylate; propoxylated (3) glycerol triacrylate; propoxylated (3) trimethylolpropane triacrylate; trimethylolpropane triacrylate; trimethylolpropane trimethacrylate; tris(2-hydroxyethyl)isocyanurate triacrylate; di-trimethylolpropane tetraacrylate; dipentaerythritol pentaacrylate; ethoxylated (4) pentaerythritol tetraacrylate; pentaerythritol tetraacrylate; dipentaerythritol Tetraol hexaacrylate; 1,10-decanediol diacrylate; 1,3-butylene glycol diacrylate; 1,4-butylene glycol diacrylate; 1,9-nonanediol diacrylate; 2-(2-vinyloxyethoxy)ethyl acrylate; 2-butyl-2-ethyl-1,3-propanediol diacrylate; 2-methyl-1,3-propanediol diacrylate; 2-methyl-1,3-propanediol ethoxy acrylate; 3-methyl-1,5-pentanediol diacrylate; alkoxylated cyclohexanedimethanol diacrylate; alkoxylated hexanediol diacrylate; cyclohexanedimethanol diacrylate; ethoxylated cyclohexanedimethanol diacrylate; diethylene glycol diacrylate; dioxanediol diacrylate; ethoxylated dipentaerythritol hexaacrylate; ethoxylated glycerol triacrylate; ethoxylated neopentyl glycol diacrylate; hydroxy neopentyl hydroxyl neopentyl acrylate diacrylate; neopentyl glycol diacrylate; poly(tetramethylene glycol) diacrylate; polypropylene glycol 400 diacrylate; polypropylene glycol 700 diacrylate; propoxylated (6) ethoxylated bisphenol A diacrylate; propoxylated ethylene glycol diacrylate; propoxylated (5) pentaerythritol tetraacrylate; and propoxylated trimethylolpropane triacrylate or mixtures thereof.

11. The method (100) for producing a shaped thermoplastic composite material (10) according to claim 8, characterized in that The (meth)acrylic monomer (M2) in the thermoplastic composition 14 or the (meth)acrylic composition MCI is present in an amount of 0.01 to 10 phr by weight, preferably 0.1 to 9.5 phr.

12. A shaped thermoplastic composite material (10) obtained by the method (100) according to any one of claims 1 to 11.

13. The shaped thermoplastic composite material (10) according to any one of the preceding claims, characterized in that It comprises a porosity less than or equal to 10% based on the total volume of the shaped thermoplastic composite material (10).

14. Use of the shaped thermoplastic composite material (10) according to the preceding claim in automotive, transport, marine, railway, sports, aviation, aerospace, photovoltaic, computing, building and construction, telecommunications and / or wind energy applications.

15. A molding device (17) configured to reduce a first section (S1) of a heated thermoplastic composite material to a second section (S2) to form a molded thermoplastic composite material (10) having a second section (S2), wherein the second section (S2) is smaller than the first section (S1), and the molded thermoplastic composite material (10) contains at least 60% by volume of fibers.

16. The forming device (17) according to claim 15, characterized in that The forming device includes at least one inlet and at least one outlet, and the outlet is smaller than the inlet.

17. A system (200) for producing a molded thermoplastic composite material (10), comprising - a fiber feeding device (11) configured to provide fibers (12) in the direction of the pultrusion path A, - an impregnation device (13) configured to wet the fibers (12) with a thermoplastic composition (14) which is a thermoplastic resin or a thermoplastic resin precursor and comprises at least 50% by weight of monomers, a heating device (15) configured to polymerize the thermoplastic composition (14) impregnated with the fibers to form a heated thermoplastic composite material (16) having a first section (S1), - a molding device (17) configured to mold the heated thermoplastic composite material (16) according to the second section (S2), the molding device (17) having the second section (S2), and the second section (S2) being smaller than the first section (S1) to provide a heated thermoplastic composite material (18) having the second section (S2), the molding device (17) facing the previous device, - A cooling device (19) configured to produce a shaped thermoplastic composite material (10) at a cooling temperature below the glass transition temperature of the heated thermoplastic composite material (18) having the second section (S2).

18. The system (200) for producing a molded thermoplastic composite material (10) according to claim 17, characterized in that: It includes empty space, a vacuum or air space.

19. The system (200) for producing a molded thermoplastic composite material (10) according to claim 18, characterized in that: An empty space, vacuum or air space is arranged between the heating device (15) and the forming device (17).

20. The system (200) for producing a shaped thermoplastic composite material (10) according to any one of claims 17 to 19, characterized in that: The forming device (17) comprises at least one inlet and at least one outlet, the outlet facing the cooling device (19).

21. The system (200) for producing a molded thermoplastic composite material (10) according to claim 17, characterized in that: The molding device (17) is configured to reduce the heated first section (S1) of the thermoplastic composite material to a second section (S2) to form a molded thermoplastic composite material (10) having the second section (S2), wherein the second section (S2) is smaller than the first section (S1) and the molded thermoplastic composite material (10) contains at least 60 volume % of fibers.

22. The system (200) for producing a molded thermoplastic composite material (10) according to claim 17, characterized in that: The forming device includes at least one inlet and at least one outlet, and the outlet is smaller than the inlet.

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