Three-dimensional printing method of fiber composite material

Abstract

The invention describes a three-dimensional printing method of a composite material, comprising the following steps: feeding at least one continuous filament element (4) to a feeding head (7); said continuous filamentary element (4) comprising at least one dispersed phase (3) and at least one continuous phase (2) reacted by a leading edge polymerization reaction; -depositing said continuous filamentary element (4) on a support surface (9); -providing an amount of energy (5) to said continuous filamentary element (4) to bring said at least one continuous phase (2) to an initiation temperature to initiate a front polymerization reaction front in said at least one continuous phase (2); -during the deposition step, providing said amount of energy (5) to said continuous filamentary element (4) in a repeating manner and at different locations in the direction of extension thereof, thereby producing the initiation of the leading edges of different leading edge polymerization reactions.

Description

Technical Field

[0001] The present invention relates to the field of three-dimensional printing of composite materials.

[0002] In particular, the present invention relates to a three-dimensional printing apparatus and method for fiber composite materials with a thermoplastic matrix or a thermosetting matrix. Background Art

[0003] As is known, the term "composite material" generally refers to a material obtained by combining two or more components so that the final product has properties different from those of the individual components. In order to better define the meaning of the term "composite material" in the technical field, the category of composite materials is usually limited to reinforced materials in which at least one component (usually in the form of fibers) has much higher mechanical properties than the other components.

[0004] In general, two or more components that are different in shape and chemical composition, immiscible and separated by an interface, combined by adhesion or cohesion, can be defined as a “composite material” or simply “composite”.

[0005] Composite materials usually consist of a continuous phase, called the matrix, and a dispersed phase, often in the form of reinforcing elements. The mechanical properties of the material (strength and stiffness) are mainly dependent on the dispersed phase, while the task of transferring external loads to the dispersed phase is undertaken by the continuous phase. This transfer is achieved through shear stresses at the interface between the dispersed phase and the continuous phase. In addition to stabilizing the composite material by compression, the matrix also has the function of fixing the fibers together and protecting the fibers as well as the molded parts.

[0006] Ultimately, a composite material is an artificially manufactured multiphase material that is different from its constituent parts: performance is optimized by carefully designing the combination of two or more different materials based on the principle of combined action.

[0007] Depending on the matrix material that constitutes the continuous phase, composites are divided into metal-based composites, ceramic-based composites and polymer-based composites.

[0008] Polymer-based composites are typically composed of synthetic fibers (e.g., carbon fibers, nylon fibers, aramid fibers, or glass fibers) embedded in a polymer matrix that surrounds, protects, and secures the fibers. Typically, the fibers account for about 50% to 60% of the volume of the polymer-based composite.

[0009] Accordingly, within the category of polymer-based composites, there are two subcategories that make up polymer-based composites: thermoplastic polymers and thermosetting polymers.

[0010] Thermoplastic polymers are a class of plastic materials that acquire plasticity under the influence of temperature. Under the influence of temperature, thermoplastic polymers can be molded or formed into a finished product and return to a rigid structure after cooling. In fact, the viscosity decreases not only with increasing temperature, but also with increasing shear rate and shear stress. In theory, this heating / cooling cycle can be repeated many times, depending on the characteristics of the different plastic materials; in practice, the number of cycles is limited, because too many heating cycles degrade the polymer.

[0011] Thermosetting polymer materials have a cross-linked molecular structure formed by covalent bonds. Thermosetting polymers cross-link by a process called "curing", during which the resin undergoes a series of chemical transformations from a gel or rubber state to a glassy state while in a fluid state. Some thermosetting resins cross-link by heating or by a combination of heat and pressure. In other cases, the chemical reaction can occur at room temperature (cold thermoset), by light radiation, by evaporation of the substance, by activation by humidity, and by forced mixing of two elements (usually a resin and a catalyst).

[0012] Although thermosetting resin products can soften due to heating (Tg, glass transition temperature), the covalent bonds in the lattice prevent them from returning to the fluid state before cross-linking; if heated above the degradation temperature, they will carbonize and decompose. Therefore, thermosetting materials cannot be reheated and melted like thermoplastic materials.

[0013] Three-dimensional printing processes for composite materials are described, for example, in US 9987798, US 10011073 and US 9126367.

[0014] The Applicant notes that the known processes for three-dimensional printing of fiber composite materials have limitations in terms of the types of materials and / or processes that can be used. For example, the Applicant points out that in the case of thermosetting monomers that can be photopolymerized by electromagnetic radiation, the choices are generally limited, for example, it is not possible to use opaque reinforcing fibers (e.g. carbon fibers, basalt fibers, aramid fibers, etc.). Another limitation in this case is the thickness that can be used, which cannot be too high.

[0015] The above two limitations lead to defects in the uniformity and quality of the obtained products.

[0016] Furthermore, the applicant has noted that, with regard to epoxy resins, they generally have pronounced kinetic limitations, in other words, the reaction that produces the polymer is very slow, and therefore these materials are less suitable for use in three-dimensional printing processes. Summary of the invention

[0017] Therefore, a first aspect of the present invention relates to a method for three-dimensional printing of a composite material, comprising the following steps:

[0018] - feeding at least one continuous filamentary element to a feed head; said continuous filamentary element comprising at least one dispersed phase (preferably comprising a thermally conductive material) and at least one continuous phase reacting by frontal polymerization;

[0019] - depositing said continuous filamentary element on a supporting surface;

[0020] - providing energy to said continuous filamentary element so as to bring said at least one continuous phase to an initiation temperature, thereby initiating a frontal polymerization reaction front in said at least one continuous phase;

[0021] - during the deposition step, providing said energy to said continuous filamentary element in a repeated manner and at different positions along the extension direction of said continuous filamentary element, so as to induce different polymerisation fronts.

[0022] For the purposes of the present invention, the following definitions apply:

[0023] "Frontal polymerization and / or frontal polymerization" refers to polymerization reactions in which polymerization (i.e., the chemical reaction of forming polymer chains from simple molecules called monomers) occurs in a directed manner and proceeds by propagation from local reaction sites [JA Pojman, "Frontal Polymerization," in Polymer Science: A Comprehensive Reference, Elsevier, 2012, pp. 957–980.]. This reaction occurs due to initiation by local stimulation and, once initiated, propagates through the material under the action of the reaction enthalpy without the need for additional energy stimulation. In the frontal photopolymerization process, the heat generated by the reaction itself during the polymer chain propagation step becomes the driving force for the propagation of the reaction itself due to the activation of thermal initiator species when the initiation temperature is reached [F. Petko, A. and J.Ortyl, “Photoinitiating systems and kinetics of frontal photopolymerization processes–the prospects for efficient preparation of composites and thick 3D structures,” Polym.Chem., vol.12, no.32, pp.4593–4612, 2021, doi:10.1039 / D1PY00596K]. In particular, the activation of thermal initiator species (defined as those chemical species capable of generating reactive species through the action of temperature) is achieved by reaching the initiation temperature, which is characteristic of the specific thermal initiator species considered. In addition, it is clear that monomer species capable of leading to frontal polymerization reactions exhibit strongly exothermic reactions and are therefore able to promote the propagation of the reaction front.

[0024] "Preliminary polymerization" refers to polymerization of at least a portion of the filamentary elements at a time before the filamentary elements are fed to the feed head and / or at a location before the feed head.

[0025] "Initiation temperature" refers to the temperature at which, in the case of frontal polymerization, thermal initiator species are activated, ie, the temperature that facilitates rapid decomposition of the initiator into reactive chemical species, thereby enabling the polymerization reaction to be initiated.

[0026] "Photosensitive material and / or photosensitizer for short" means: a chemical substance which, when subjected to electromagnetic radiation, is able to absorb electromagnetic radiation and put itself into an excited state. In this state, the photosensitive substance is able to transfer energy to the photoinitiator, for example, through an electron transfer or charge transfer mechanism, so that it is activated and thus produces reactive chemical species. The use of a photosensitizer may be necessary in cases where the photoinitiator is unable to absorb radiation and therefore cannot be activated independently, especially within the electromagnetic spectrum provided by the electromagnetic radiation source used. The use of a photosensitizer may be convenient in cases where the photoinitiator has a low efficiency in the radiation absorption process in the electromagnetic spectrum provided by the electromagnetic radiation source used (instead of the energy stimulus source).

[0027] "Photoinitiator" refers to a chemical species capable of generating different reactive chemical species by absorption of electromagnetic radiation, usually in the ultraviolet or visible electromagnetic spectrum. In systems capable of photopolymerization by electromagnetic radiation, involving a collection or mixture of monomeric substances, photoinitiators and possible synergistic compounds, there are two main industrially relevant chemical processes: free radical processes and cationic processes. In the former case, the absorption of radiation by the initiator leads to the generation of reactive free radicals. In the second case, the absorption of radiation by the initiator leads to the generation of Bronsted or Lewis acids, which are able to initiate a ring-opening polymerization process, i.e. a type of chain polymerization reaction in which the reactive end of the polymer chain undergoing the propagation step chemically attacks the ring-terminal monomer to form a longer polymer chain.

[0028] "Cationic initiator" refers to a chemical species that is capable of generating various reactive chemical species (e.g., Bronsted or Lewis acids) by photochemical or chemical stimulation. Specifically, the term cationic initiator refers to a chemical species that is capable of initiating a cationic chain polymerization process by charge transfer between the initiator itself and the precursor monomers of the polymer being formed, thereby making it reactive toward other monomers. The generation of reactive species can be due to direct absorption of radiation (usually in the ultraviolet electromagnetic spectrum) by the cationic initiator species, or due to oxidation reactions in the presence and participation of other reactive species (e.g., free radical species).

[0029] "Synergistic compounds" are elements conveniently added to a photopolymerizable mixture that increase the photoactivity of the mixture itself compared to the component materials of the mixture used alone. Synergistic effects are reflected in improved system efficiency in the radiation absorption step, the polymerization step, or both. For example, the use of a combination of different photoinitiators in a mixture enables the use of different energy sources. The addition of elements such as amines or thiols can mitigate the reaction inhibition effect caused by the presence of atmospheric oxygen, which is a known cause of inefficiency in free radical photopolymerization reactions.

[0030] In the above aspects, the present invention may have at least one preferred feature described below.

[0031] Preferably, an amount of energy is applied directly to the continuous phase.

[0032] Conveniently, an amount of energy is applied to the dispersed phase to bring the at least one continuous phase to an initiation temperature.

[0033] Advantageously, the method comprises:

[0034] - spreading at least one end of the continuous filamentary element on a respective support surface;

[0035] - applying energy to said end of said filamentary element so as to bring said at least one continuous phase to an initiation temperature, thereby initiating a frontal polymerization reaction front in said at least one continuous phase;

[0036] - moving the feeding head relative to a fixed point according to a predetermined path defining the object to be printed.

[0037] Energy may be provided to heat the continuous phase directly or to heat the dispersed phase.

[0038] The energy may be provided by a source of electromagnetic radiation.

[0039] Conveniently, said electromagnetic radiation is selected from the infrared spectrum.

[0040] Conveniently, the feeding and depositing steps are achieved by applying a tensile force to the continuous filamentary element by relative movement between respective feeding heads and a support surface or by extrusion.

[0041] Advantageously, the at least one dispersed phase comprises a fiber material selected from the group consisting of carbon fibers, glass fibers, poly(p-phenylene terephthalamide) fibers, ultra-high molecular weight polyethylene (UHMWPE) fibers, poly(aryletherketone) (PAEK) fibers, poly(p-phenylene-2,6-benzobisoxazole) fibers, polyethersulfone (PES) fibers, beryllium fibers, tungsten fibers, carbon nanofibers, silicon carbide (SiC) fibers, boron fibers, polyimide (PI) fibers, polybenzimidazole fibers, polyoxymethylene (POM) fibers, polyetherimide (PEI) fibers, metal alloy fibers, basalt fibers, natural fibers, combinations thereof, and similar materials.

[0042] The at least one dispersed phase may comprise the material in powdered form or in nanostructured form.

[0043] Preferably, the powdery material is selected from carbon black, silicon dioxide, graphite, titanium oxide, boron nitride, zirconium oxide, calcium carbonate, calcium phosphate, molybdenum disulfide, lignin, combinations thereof, and the like.

[0044] Preferably, the material in nanostructure form is selected from graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes, fullerenes, clay nanosheets, combinations thereof, and the like.

[0045] Conveniently, the continuous phase comprises at least one first compound comprising:

[0046] - a thermal initiator in an amount greater than or equal to about 0.001 mol % and less than or equal to about 10 mol %;

[0047] - a first monomer in an amount greater than or equal to about 20 mol % and less than or equal to about 99.9 mol %;

[0048] - a cationic initiator in an amount greater than or equal to about 0.001 mol % and less than or equal to about 10 mol %; and

[0049] - A first diluent in an amount greater than or equal to about 0 mol % and less than or equal to about 70 mol %.

[0050] Advantageously:

[0051] - the thermal initiator is selected from: 1,1,2,2-tetraphenyl-1,2-ethylene glycol (TPED), benzopinacol bistrimethylsilyl ether (TPED-Si), dimethylsulfonyl peroxide (DMSP), tert-butyl peroxide (TBPO), tert-butyl cyclohexyl peroxydicarbonate (TBC-PDC), benzoyl peroxide (BPO), azobis(isobutyronitrile) (AIBN) and combinations thereof;

[0052] - The first monomer is selected from the group consisting of bisphenol A diglycidyl ether (DGEBA), bisphenol F diglycidyl ether (DGEBF), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (CE), 4-vinyl-1-cyclohexane-1,2-epoxide, vinyl cyclohexene dioxide, 4,5-epoxytetrahydrophthalic acid diglycidyl ester, glycidyl methacrylate, pentaerythritol glycidyl ether, trimethylolpropane triglycidyl ether, 2-(3,4- Epoxycyclohexyl)ethyl trimethoxysilane, poly(ethylene glycol) diglycidyl ether, epoxidized soybean oil, N,N-diglycidyl-4-glycidyloxyaniline, bis-3,4-epoxycyclohexyl methyl adipate, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, allyl glycidyl ether, phenyl glycidyl ether, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4,4"-methylenebis[N,N-bis(2,3-epoxypropyl)aniline], tris(2, 3-epoxypropyl) isocyanurate, m-(2,3-epoxypropyloxy)-N,N-bis(2,3-epoxypropyl)aniline, p-(2,3-epoxypropyloxy)-N,N-bis(2,3-epoxypropyl)aniline, triethoxy(3-glycidyloxypropyl)silane, 1,2-epoxycyclohexane, tris(4-hydroxyphenyl)methane triglycidyl ether, epoxy novolac resins (including those derived from novolac resins), 9-[2-(2-methoxyethyl)-

[0063] -9- [3- (oxiranylmethoxy) propyl] -2,5,8,10,13,16-hexaoxa-9-sila-heptadecane, glycidyl stearate, resorcinol diglycidyl ether, 1,4-butanediol diglycidyl ether (BDGE), vinyl ether, epoxy phenolic resin (including those derived from dicyclopentadiene), carboxyl-terminated nitrile rubber (CTBN), epoxy-terminated nitrile rubber (ETBN), and combinations thereof;

[0053] The cationic initiator is selected from: [4-(4-diphenylsulfoniumphenyl)sulfonylphenyl]-diphenylsulfonium tris hexafluorophosphate, (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate, (9-oxofluoren-2-yl)-phenyliodonium hexafluoroantimonate, [4-(4-diphenylsulfoniumphenyl)sulfonylphenyl]-diphenylsulfonium hexafluoroantimonate, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 10-(4-phenylphenyl)-2- Propan-2-ylthioxanthen-10-ium-9-one hexafluorophosphate, bis(4-dodecylphenyl)iodonium hexafluoroantimonate, bis-(4-tert-butylphenyl)iodonium hexafluorophosphate, bis[4-(tert-butyl)phenyl]iodonium tetrakis(nonafluoro-tert-butyloxy)aluminate, diphenyl(4-phenylthio)phenylsulfonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, bis(4-methylphenyl)iodonium hexafluorophosphate, (4-methylphenyl)[4-(propan-2-yl)phenyl]iodonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate, and combinations thereof;

[0054] -The first diluent is selected from: multifunctional glycidyl ether, monofunctional aliphatic glycidyl ether, monofunctional aromatic glycidyl ether, 3-ethyl-3-oxetanemethanol (EOM), 3-methyl-3-oxetanemethanol, 1,4-bis(glycidyloxy)benzene (CHDGE), 1,6-hexanediol diglycidyl ether (HDDGE), neopentyl glycol diglycidyl ether (NPDGE), 1,4-butanediol diglycidyl ether (BDGE) and combinations thereof.

[0055] Preferably, the first compound may include a photosensitive material.

[0056] Advantageously, the photosensitive material is present in an amount greater than or equal to about 0.001 mol % and less than or equal to about 5 mol %.

[0057] Preferably, the photosensitive material is selected from anthracene, perylene, benzophenone, 9,10-diethoxyanthracene, 2,2-dimethoxy-2-phenylacetophenone, 2-isopropylthioxanthone (ITX), thioxan-9-one, vinylcarbazole and combinations thereof.

[0058] Alternatively, the amount of energy is provided by electromagnetic radiation selected from the ultraviolet spectrum.

[0059] Alternatively, the energy is provided by a convectionally operated energy source.

[0060] According to an alternative embodiment, the continuous phase may comprise at least one second compound comprising:

[0061] - a photoinitiator in an amount greater than or equal to about 0.01 mol % and less than or equal to about 10 mol %;

[0062] - a second monomer in an amount greater than or equal to about 20 mol % and less than or equal to about 99.9 mol %;

[0063] Advantageously, the second compound further comprises:

[0064] - a synergistic compound in an amount greater than or equal to 0 mol % and less than or equal to about 50 mol %;

[0065] - A second diluent in an amount greater than 0 mol % and less than or equal to about 70 mol %.

[0066] Preferably, the second compound is present in an amount greater than or equal to 0.1 mol% and less than or equal to 20 mol%. Conveniently, the second compound undergoes a preliminary polymerization step upstream of the feed head. Preferably, the second diluent is selected from the group consisting of neopentyl acrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, and combinations thereof. Preferably, the synergistic compound is selected from: molecules with amine groups (including triethylamine, tri-N-butylamine, 2-dimethylaminoethanol, N-methyldiethanolamine, triethanolamine, 2-(dimethylamino)ethylbenzoate, ethyl 4-(dimethylamino)benzoate, 2-ethylhexyl-4-dimethylaminobenzoate, isopentyl-4-(dimethylamino)benzoate, 2-butoxyethyl-4-(dimethylamino)benzoate, N-phenylglycine, 4,4',4"-tris(dimethylamino)-triphenylmethane and combinations and analogs thereof, etc.) or molecules with thiol groups (including butyl 3-mercaptopropionate, trihydroxymethyl

[0063] The photoinitiator is selected from the group consisting of 2-hydroxy-2-methyl-propiophenone, 2,2-dimethyl-2-hydroxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropiophenone, 2-hydroxy-2-methyl-2-thio ... Methyl-4'-tert-butyl-propiophenone, 2-hydroxy-2-methyl-1-(4-tert-butylphenyl)-propiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methyl-propiophenone, 2-hydroxy-[4'-(2-hydroxypropoxy)]-2-methyl-propiophenone, 2-hydroxy-[4'-(2-hydroxypropoxy)phenyl]-2-methylpropiophenone, oligomeric 2-hydroxy-2-methyl-1-[4-(1-methyl-vinyl)phenyl]propiophenone, 2-hydroxy-1-[4[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl]-2-methyl-1- ketone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-benzyl-2-(dimethylamino)-4-morpholinobutyrophenone, 2-(4-methylbenzyl)-2-(dimethylamino)-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-1-phenylacetophenone, 2-isopropoxy-2-phenylacetophenone, 2-n-butoxy-2-phenylacetophenone, 2-isobutoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)-(2,4-bispentyloxyphenyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphite, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, phenyl-bis-(2,4,6-trimethylbenzoyl)phosphine oxide, 4'-(tert-butyl)-2,2,2-trichloroacetophenone, 4'-(phenoxy)-2,2-dichloroacetophenone, 2-(4-methoxyphenyl)-4,6-bis-(trichloromethyl)-s-triazine, 2,4-bis-( trichloromethyl)-6-(p-methoxyphenyl)-s-triazine, 2,4-bis-(trichloromethyl)-6-(3,4-dimethoxy)-phenyl-s-triazine, 2,4-bis-(trichloromethyl)-6-(3,4-dimethoxy)-phenyl-s-triazine, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]-octane-1,2-dione- 2-(o-benzoyl oxime), benzophenone, 4-methylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone-2-carboxy-(tetraethoxy)acrylate, 4-phenylbenzophenone, 2-benzoylbenzoic acid methyl ester, 1-{-4-[benzoylphenylsulfonyl]phenyl}-2-methyl-2-(4-methylphenylsulfonyl)-propan-1-one, 2-isopropylthioxanthone, 4-isopropyl 1-chloro-4-propoxy-thioxanthone, 2,4-diisopropyl-thioxanthone, methyl phenylglyoxylate, 2-ethylanthraquinone, 2-ethyl-9,10-anthracenedione, polyethylene glycol-bis-[(4-acetylphenyl)-piperazine propionate], 3-benzoyl-7-methoxy-2H-chromene-2-one and combinations thereof. Preferably, the second monomer is selected from: monomers having a (meth)acrylate group (including: tricyclodecane dimethanol diacrylate, 3-[2,2-dimethyl-1-oxo-3-[(1-oxo-2-propenyl)oxy]propoxy]-2,2-dimethylpropyl acrylate, dihydrodicyclopentadienyl acrylate, pentaerythritol triacrylate, pentaerythritol tetramethacrylate, dipropylene glycol diacrylate, ditrimethylolpropane tetraacrylate, isobornyl acrylate, dipentaerythritol hexaacrylate, tert-butyl acrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, bisphenol A diacrylate n- Ethoxylate (1<n≤10), bisphenol A diacrylate, 3,3,5-trimethylcyclohexyl acrylate, (5-ethyl-1,3-dioxane-5-yl) methacrylate, trimethylolpropane triacrylate n-ethoxylate (1<n≤10), neopentyl glycol diacrylate, triethylene glycol diacrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobutyl acrylate, dodecyl acrylate, butyl acrylate, isodecyl acrylate, dodecafluoroheptyl acrylate, hexahydro-4,7-methylene-1H-indenyl acrylate, acrylic acid), or selected from acrylamide monomers (including N,N-dimethylacrylamide, isobutylhydroxymethylacrylamide acrylate, 4-acryloylmorpholine, N-isopropylacrylamide, N,N-dimethylaminopropylacrylamide, N-hydroxyethylacrylamide, N,N-diethylacrylamide, tris[2-(acryloyloxy)ethyl]isocyanurate).

[0067] In addition, the second monomer is selected from monomers containing urethane groups and monomers having (meth)acrylate functional groups. Further features and advantages of the present invention will become more apparent from the detailed description of some preferred but non-exclusive embodiments of the method for three-dimensional printing of fiber composite materials according to the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] The following description will be made in conjunction with the accompanying drawings, which are provided by way of example only and not as a limitation, in which:

[0069] - Figure 1a-1c Three consecutive moments of a step of depositing a continuous filamentary element in a method for three-dimensional printing of a composite material according to the present invention are shown, wherein an energy source directly transmits energy to the continuous phase until the initiation temperature of the front polymerization reaction is reached;

[0070] - Figure 2a-2c Three consecutive moments of a step of depositing a continuous filamentary element in a method for three-dimensional printing of a composite material according to the present invention are shown, wherein an energy source transmits energy to a dispersed phase, which is then heated by transferring heat to a continuous phase until the initiation temperature of a front polymerization reaction is reached;

[0071] - Figure 3a-3c Three consecutive moments of a step of depositing a continuous filamentary element in a method for three-dimensional printing of a composite material according to the invention are shown, wherein an energy source transmits energy to a dispersed phase, in particular in the case where the dispersed phase contains some discontinuous or powdered material;

[0072] - Figure 4 A three-dimensional printing device for composite materials according to the method of the present invention is shown; and

[0073] - Figure 5 A table showing some possible continuous phase formulations. DETAILED DESCRIPTION

[0074] With reference to the figures, a three-dimensional printing device for fiber composite materials is indicated as a whole by reference numeral 100. Specifically, the device 100 is suitable for printing composite materials from continuous filamentary elements 4 composed of at least one continuous phase 2 and at least one dispersed phase 3.

[0075] Generally speaking, the at least one dispersed phase 3 comprises a fiber material, and the fiber material is selected from: carbon fiber, glass fiber, poly(p-phenylene terephthalamide) fiber, ultra-high molecular weight polyethylene (UHMWPE) fiber, polyaryletherketone (PAEK) fiber, poly(p-phenylene-2,6-benzobisoxazole) fiber, polyethersulfone (PES) fiber, beryllium fiber, tungsten fiber, carbon nanofiber, silicon carbide (SiC) fiber, boron fiber, polyimide (PI) fiber, polybenzimidazole fiber, polyoxymethylene (POM) fiber, polyetherimide (PEI) fiber, metal alloy fiber, basalt fiber, natural fiber and combinations thereof.

[0076] Generally speaking, the fibers contained in the dispersed phase 3 may be one or more continuous fibers or long fibers connected together to form a continuous unit, or may be short fibers (not connected together).

[0077] The dispersed phase 3 may also contain powdered materials or materials in nanostructured form, such as Figure 3a-3c As shown, these materials are configured for specific tasks, such as receiving energy from a suitable energy source 8 (preferably via electromagnetic radiation) to increase the temperature of the dispersed phase 3 and / or the continuous phase 2 to initiate a front polymerization reaction.

[0078] The powdered material is selected from carbon black, silicon dioxide, graphite, titanium oxide, boron nitride, zirconium oxide, calcium carbonate, calcium phosphate, molybdenum disulfide, lignin and combinations thereof.

[0079] The material in nanostructured form is selected from the group consisting of graphene, single-walled carbon nanofibers, multi-walled carbon nanofibers, fullerenes, clay nanosheets, and combinations thereof.

[0080] Preferably, the continuous phase comprises at least one first compound comprising:

[0081] - a thermal initiator in an amount greater than or equal to about 0.001 mol % and less than or equal to about 10 mol %;

[0082] - a first monomer in an amount greater than or equal to about 20 mol % and less than or equal to about 99.9 mol %;

[0083] - a cationic initiator in an amount greater than or equal to about 0.001 mol % and less than or equal to about 10 mol %; and

[0084] - A first diluent in an amount greater than or equal to about 0 mol % and less than or equal to about 70 mol %.

[0085] Preferably, the thermal initiator is selected from: 1,1,2,2-tetraphenyl-1,2-ethylene glycol (TPED), benzopinacol bistrimethylsilyl ether (TPED-Si), dimethylsulfonyl peroxide (DMSP), tert-butyl peroxide (TBPO), tert-butyl cyclohexyl peroxydicarbonate (TBC-PDC), benzoyl peroxide (BPO), azobis(isobutyronitrile) (AIBN) and combinations thereof. Preferably, the first monomer is selected from: bisphenol A diglycidyl ether (DGEBA), bisphenol F diglycidyl ether (DGEBF), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (CE), 4-vinyl-1-cyclohexane-1,2-epoxide, vinyl cyclohexene dioxide, 4,5-epoxytetrahydrophthalic acid diglycidyl ester, glycidyl methacrylate, pentaerythritol glycidyl ether, trimethylolpropane triglycidyl ether, 2-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, polyethylene glycol diglycidyl ether, epoxidized soybean oil, N,N-diglycidyl-4-glycidyloxyaniline, bis-3,4-epoxycyclohexyl methyl adipate, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, allyl glycidyl ether, phenyl glycidyl ether, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4,4"-methylenebis[N,N-bis(2,3-epoxypropyl)aniline], tris(2 ,3-epoxypropyl) isocyanurate, m-(2,3-epoxypropyloxy)-N,N-bis(2,3-epoxypropyl)aniline, p-(2,3-epoxypropyloxy)-N,N-bis(2,3-epoxypropyl)aniline, triethoxy(3-glycidyloxypropyl)silane, 1,2-epoxycyclohexane, tris(4-hydroxyphenyl)methane triglycidyl ether, epoxy novolac resins (including those derived from novolac resins), 9-[2-(2-methoxy)- ethoxy)ethoxy]-9-[3-(oxiranylmethoxy)propyl]-2,5,8,10,13,16-hexaoxa-9-silaheptadecane, glycidyl stearate, resorcinol diglycidyl ether, 1,4-butanediol diglycidyl ether (BDGE), vinyl ethers, epoxy phenolic resins (including those derived from dicyclopentadiene), carboxyl-terminated nitrile rubber (CTBN), epoxy-terminated nitrile rubber (ETBN), and combinations thereof;Preferably, the cationic initiator is selected from: [4-(4-diphenylsulfoniumphenyl)sulfonylphenyl]-diphenylsulfonium tris hexafluorophosphate, (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate, (9-oxofluoren-2-yl)-phenyliodonium hexafluoroantimonate, [4-(4-diphenylsulfoniumphenyl)sulfonylphenyl]-diphenylsulfonium hexafluoroantimonate, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 10-(4-phenylphenyl)- 2-propan-2-ylthioxanthen-10-ium-9-one hexafluorophosphate, bis(4-dodecylphenyl)iodonium hexafluoroantimonate, bis-(4-tert-butylphenyl)iodonium hexafluorophosphate, bis[4-(tert-butyl)phenyl]iodonium tetrakis(nonafluorotert-butyloxy)aluminate, diphenyl(4-phenylthio)phenylsulfonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, bis(4-methylphenyl)iodonium hexafluorophosphate, (4-methylphenyl)[4-(propan-2-yl)phenyl]iodonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate, and combinations thereof. ;

[0086] Preferably, the first diluent is selected from: multifunctional glycidyl ether, monofunctional aliphatic glycidyl ether, monofunctional aromatic glycidyl ether, 3-ethyl-3-oxetanemethanol (EOM), 3-methyl-3-oxetanemethanol, 1,4-bis(glycidyloxy)benzene (CHDGE), 1,6-hexanediol diglycidyl ether (HDDGE), neopentyl glycol diglycidyl ether (NPDGE), 1,4-butanediol diglycidyl ether (BDGE) and combinations thereof.

[0087] Furthermore, other additives and reinforcing materials may also be present in the continuous filamentary element 4 .

[0088] According to another embodiment, the continuous filamentary element 4 and in particular its continuous phase 2 may contain a photosensitive material, which is configured to receive energy provided by electromagnetic radiation 5 in the ultraviolet or visible spectrum through a suitable energy source 8, thereby chemically activating the photosensitizer and, in turn, activating the cationic initiator to produce an exothermic reaction suitable for raising the temperature of the continuous phase to the initiation temperature of the front polymerization reaction.

[0089] Preferably, the photosensitive material is present in an amount greater than or equal to about 0.001 mol % and less than or equal to about 5 mol %.

[0090] The photosensitive material is selected from the group consisting of anthracene, perylene, benzophenone, 9,10-diethoxyanthracene, 2,2-dimethoxy-2-phenylacetophenone, 2-isopropylthioxanthone (ITX), thioxanthen-9-one, vinylcarbazole and combinations thereof.

[0091] The device 100 includes a feed head 7 for a continuous filamentary element 4, a support surface 9 (the continuous filamentary element 4 is deposited on the support surface 9 to produce a three-dimensional object 20 preferably to be printed), a relative movement component between the feed head 7 and the support surface 9 (to apply tension to the continuous filamentary element 4), and an energy source 8 (configured to provide a predetermined amount of energy to the continuous filamentary element 4).

[0092] Specifically, the energy source 8 is configured to provide a predetermined amount of energy to the continuous filamentary element 4 so that the continuous phase thereof reaches an initiation temperature, thereby initiating a frontal polymerization reaction in the continuous phase itself.

[0093] Frontal polymerization may be a RICFP (radical induced cationic frontal polymerization) type of reaction. The rapid formation of a molecular network with high conversion (monomer-polymer conversion) produced by frontal polymerization makes this type of reaction an effective alternative to conventional processes used to produce polymer matrix composites. Furthermore, frontal polymerization utilizes the heat generated by the reaction itself to produce a self-propagating reaction front, making it more energy efficient and resulting in a more uniform reaction product.

[0094] The feed head 7 is advantageously supported by a movement assembly for producing a relative movement between the feed head 7 itself and the object 20 to be printed.

[0095] During the feeding of the continuous filamentary element 4, the moving assembly exerts a tensile force on the continuous filamentary element 4 and thus also on the continuous fibers contained therein.

[0096] Therefore, this tensile force is also transmitted to the fibers.

[0097] Note that this pulling force causes the same continuous filamentary element 4 to be fed into the feed head 7 .

[0098] Therefore, the higher the relative speed, the faster the continuous filamentary element 4 is fed.

[0099] According to another embodiment, the feeding of the continuous thread-like element 4 is achieved by extruding the continuous thread-like element from a feeding head 7 .

[0100] Advantageously, in the case where the dispersed phase 3 comprises discontinuous powdered fibers or nanostructures, the feeding of the continuous filamentary elements 4 is achieved by extruding the continuous filamentary elements.

[0101] In more detail, the mobile device comprises at least one device with numerically controlled movement in at least three axes.

[0102] According to a first embodiment not shown in the figures, the numerically controlled device comprises a motorized arm 23 to support the above-mentioned feed head 7 at respective ends.

[0103] The motorized arm 23 , which is not described or illustrated in detail because it is of a known type, is suitable for moving the feed head in at least three spatial axes and for orienting the feed head according to any position relative to the object 20 .

[0104] Note that the support surface 9 (arranged below the feed head 7) can be moved accordingly closer to / away from the feed head 7. The support surface 9 can be constituted by the continuous filamentary element 4 deposited in advance during the process of manufacturing the three-dimensional object 20.

[0105] according to Figure 1a-1c In the first embodiment shown, the energy source 8 may consist of a thermal emission source provided for heating the continuous filamentary element 4 .

[0106] This type of energy source 8 is usually based on providing a hot air flow 5 .

[0107] Alternatively, the energy source 8 may be an electromagnetic radiation source ( Figure 2a-2c , 3a-3c). In this case, the energy source 8 may for example consist of at least one source of electromagnetic radiation in the infrared field or in the ultraviolet field, depending on the type of material from which the continuous filamentary element 4 is made.

[0108] The energy source 8 is located downstream of the feed head and is configured to provide energy to the continuous filamentary element 4 at the support surface 9 .

[0109] Regardless, the energy source 8 is basically configured to transmit energy to the continuous filamentary element 4 or at least one phase of the continuous filamentary element throughout the deposition process and at different locations of the deposition element itself.

[0110] In other words, the energy source 8 is configured to repeatedly apply a predetermined amount of energy to the continuous filamentary element 4 during deposition of the continuous filamentary element.

[0111] According to an alternative embodiment, the energy source 8 is configured to continuously apply a predetermined amount of energy to the continuous filamentary element 4 during the deposition of the continuous filamentary element 4; for example Figure 1a-3c As shown. Note that the certain amount of energy can be varied during the deposition step. Conveniently, the certain amount of energy can be adjusted according to the speed of the relative movement.

[0112] Thus, following the precise path of the continuous filamentary element 4, energy transfer to the continuous filamentary element 4 during its deposition onto the support surface 9 occurs at different sites of the continuous filamentary element 4 itself, thereby supporting leading-edge polymerization reactions.

[0113] In the embodiment shown in the figures, preferably upstream of the energy source 8 , there is a cutting tool, not shown in the figures, which may be represented by at least one movable blade for cutting the continuous filamentary element 4 by moving closer / away.

[0114] According to this embodiment, the cutting tool acts on the continuous thread-like element 4 after a portion of the continuous thread-like element has been applied to the supporting surface 9 .

[0115] The present invention relates to a method for three-dimensional printing of a composite material having at least one dispersed phase (the dispersed phase comprising at least one preferably thermally conductive material) and at least one continuous phase reacting by frontal polymerization, the method comprising the following steps:

[0116] - feeding at least one continuous filamentary element 4 to a feeding head 7; and;

[0117] - depositing said continuous filamentary element 4 on a supporting surface 9;

[0118] - Applying a certain amount of energy to the continuous filamentary element 4 so that the at least one continuous phase reaches an initiation temperature, thereby initiating a front of a front polymerization reaction in the at least one continuous phase; the polymerization reaction can be a RICFP (radical induced cationic front polymerization) type reaction. The rapid formation of a molecular network with a high conversion rate (monomer-polymer conversion) produced by the front polymerization RICFP reaction makes this type of reaction considered as an effective alternative to traditional processes used in the production of polymer-based composite materials. In addition, the front polymerization RICFP reaction uses the heat generated by the reaction itself to form a self-propagating reaction front, making it more energy-efficient and making the reaction product more uniform.

[0119] - During the deposition process, supplying said amount of energy to said continuous filamentary element 4 in a repeated manner and at different positions along the extension direction of the continuous filamentary element, thereby initiating a plurality of frontal polymerization fronts.

[0120] The feeding and deposition steps are achieved by applying a traction force to the continuous filamentary element 4 , which is generated by a relative movement between the feeding head 7 and the three-dimensional object 20 to be printed or between the feeding head 7 and the supporting surface 9 .

[0121] In other words, by moving the feed head 7 through the action of the numerical control device, the continuous filamentary element 4 is gradually deposited on the support surface 9 or on a prefabricated part of the three-dimensional object 20, which is produced by the feeding of the continuous filamentary element 4.

[0122] In some cases, the feeding of the continuous filamentary element 4 is achieved by extruding the continuous filamentary element from a feeding head 7 .

[0123] In more detail, in order to carry out the printing process, the continuous filiform element 4 coming out of the nozzle of the feed head 7 is first spread out on a corresponding support surface 9 .

[0124] At this time, the continuous filamentary element 4 (especially the end of the continuous filamentary element located on the support surface 9) is subjected to a predetermined amount of energy, thereby inducing a frontal polymerization front and forming a fixed point between the continuous filamentary element 4 and the support surface 9.

[0125] The deposition of the continuous filamentary element 4 may then be performed according to a predefined path and trajectory to form the three-dimensional object 20 to be printed.

[0126] The fixed site thus formed allows the continuous filamentary element 4 to be arranged on the support surface 9 according to a precise path and to draw the object 20 to be printed as the numerical control device moves.

[0127] Thus, the feed head 7 is moved by means of a numerical control device according to a predetermined path defining the object 20 to be printed.

[0128] The path is determined by appropriate management software, which is not described in this specification because it is beyond the scope of the present invention.

[0129] At the end of the printing process or when the continuous feeding of the continuous thread-like element 4 must be interrupted in any case, the thread-like element or its derivatives are severed by a cutting mechanism.

[0130] The transition of the continuous filamentary element 4 to the composite material is initially near the fixed point between the support surface 9 and the continuous filamentary element 4 ( Figure 1a , 2a , 3a) started.

[0131] In all cases, the transition is achieved by supplying a predetermined amount of energy to the continuous filamentary element 4, which serves to raise the temperature of the continuous phase until a temperature is reached that initiates polymerization at the front.

[0132] Specifically, if the continuous filamentary element 4 does not have a dispersed phase capable of effectively increasing its temperature when subjected to electromagnetic radiation energy, such as glass fibers, silicon oxide, zirconium oxide, it is advantageous to provide energy to the continuous filamentary element 4 by using an energy source operating by convection or conduction.

[0133] In this case, the heat supplied results in a direct increase in the temperature of the continuous phase, thereby bringing the temperature of the continuous phase above the initiation temperature of the frontal polymerisation reaction. Preferably, the polymerisation reaction is a RICFP (radical induced cationic frontal polymerisation) type reaction.

[0134] When the temperature of the continuous phase 2 is equal to or greater than the initiation temperature, a front polymerization reaction capable of propagating inside the continuous filamentary element 4 will be initiated.

[0135] Deposition of the continuous filamentary element 4 according to a predetermined trajectory subsequently shifts the site of energy application in the form of heat, thereby causing the initiation of subsequent frontal polymerization reactions ( Figure 1b ), thereby forming an overall front polymerization reaction that propagates and is maintained therefrom at a rate comparable to the deposition rate of the continuous filamentary element 4.

[0136] The application of energy to the continuous filamentary element 4 can be performed at very close time intervals or continuously, for example Figure 1a-3c shown.

[0137] Preferably, energy is applied to the filiform element in the form of heat throughout the duration of the step of deposition of the continuous filiform element 4 .

[0138] In addition, if the continuous filamentary element 4 has a dispersed phase that can effectively increase its temperature when subjected to electromagnetic radiation energy, such as carbon fibers, basalt fibers, carbon black, graphene, carbon nanotubes, carbon nanofibers, metal alloys, it is advantageous that the energy acting on the continuous filamentary element 4 is provided by electromagnetic radiation preferably emitted by an electromagnetic radiation source in the infrared or visible spectrum.

[0139] In this case, if Figure 2a-3c As shown in the example in FIG. 1 , the energy 5 provided by the energy source 8 raises the temperature of the dispersed phase 3, which preferably raises the temperature of the continuous phase by conduction to a temperature above the initiation temperature of the leading polymerization reaction.

[0140] When the temperature of the continuous phase 2 is equal to or greater than the initiation temperature, a front polymerization reaction capable of propagating inside the continuous filamentary element 4 will be initiated.

[0141] Deposition of the continuous filamentary element 4 according to a preset trajectory subsequently shifts the site of energy application, leading to the initiation of subsequent front polymerization reactions, thereby forming an overall front polymerization reaction that propagates and is sustained at a rate comparable to the deposition rate of the continuous filamentary element 4 .

[0142] The application of energy to the continuous filamentary element 4 may be performed at very close time intervals or continuously.

[0143] Preferably, energy is applied to the continuous filamentary element 4 in the form of heat throughout the deposition step of the continuous filamentary element 4 .

[0144] Alternatively, if the continuous filamentary element 4 has a continuous phase comprising a sensitizer (e.g., 2-isopropylthioxanthone, thioxan-9-one, vinylcarbazole), the energy acting on the continuous filamentary element 4 is applied by electromagnetic radiation, which is preferably emitted by an electromagnetic radiation source and selected in the ultraviolet or visible spectrum.

[0145] In this case, the energy provided chemically activates the sensitizer, which in turn activates the cationic initiator to produce an exothermic reaction suitable for raising the temperature of the continuous phase to the initiation temperature of the leading edge polymerization reaction.

[0146] Figure 5 A table with some continuous phase formulations is shown in as an example; in the above table, for each component, its type and percentage mole fraction (if any) are listed.

[0147] It can be clearly seen from the above description that the present invention can overcome the limitations of the known three-dimensional printing process of fiber composite materials in terms of available materials and / or processes.

[0148] Furthermore, the present invention successfully overcomes the limitations on process speeds inherent in these types of chemical reactions once alternative polymerization mechanisms (e.g., front polymerization) are understood that are conveniently used to produce highly homogeneous composite materials. Thus, the present invention is proposed as a solution to enable the efficient use of these types of monomers and chemical reactions in three-dimensional printing processes for fiber composites.

[0149] Several changes may be made to the embodiments described in detail, but all are nevertheless within the scope of protection of the invention as defined by the following claims.

Claims

1. A three-dimensional printing method for a fiber composite material, comprising the following steps: - feeding at least one continuous filamentary element (4) to a feeding head (7); said continuous filamentary element (4) comprising at least one dispersed phase and at least one continuous phase reacting by frontal polymerization; - depositing said continuous filamentary element (4) on a supporting surface (9); - applying energy (5) to said continuous filamentary element (4) so ​​as to bring said at least one continuous phase (2) to an initiation temperature, thereby initiating a frontal polymerization reaction front in said at least one continuous phase; - during the deposition step, providing said energy to said continuous filamentary element (4) in a repeated manner and at different positions along the extension direction of said continuous filamentary element (4), so as to induce different polymerisation fronts.

2. The three-dimensional printing method of fiber composite material according to claim 1, characterized in that: The energy (5) is applied directly to the continuous phase (2).

3. The three-dimensional printing method of fiber composite material according to claim 1, characterized in that: The energy (5) is applied to the dispersed phase (3) so as to bring the at least one continuous phase (2) to the initiation temperature.

4. The three-dimensional printing method of a fiber composite material according to any one of claims 1 to 3, characterized in that: The method comprises: - spreading at least one end of the continuous filamentary element (4) on a corresponding supporting surface (9); - applying said energy (5) to said end of said continuous filamentary element (4) so ​​as to bring said at least one continuous phase (2) to an initiation temperature, thereby initiating a front of a frontal polymerization reaction in said at least one continuous phase (2); - moving the feeding head (7) relative to a fixed point according to a predetermined path defining the object (20) to be printed.

5. The three-dimensional printing method of a fiber composite material according to any one of the preceding claims 1 to 4, characterized in that: The feeding and depositing steps are achieved by applying a tensile force to the continuous filamentary element (4) through relative movement between the corresponding feeding head (7) and the supporting surface (9) or through extrusion of the continuous filamentary element (4).

6. The three-dimensional printing method of a fiber composite material according to any one of the preceding claims 1 to 5, characterized in that: The at least one dispersed phase (3) comprises a fiber material, and the fiber material is selected from the group consisting of carbon fiber, glass fiber, poly(p-phenylene terephthalamide) fiber, ultra-high molecular weight polyethylene (UHMWPE) fiber, polyaryletherketone (PAEK) fiber, poly(p-phenylene-2,6-benzobisoxazole) fiber, polyethersulfone (PES) fiber, beryllium fiber, tungsten fiber, carbon nanofiber, silicon carbide (SiC) fiber, boron fiber, polyimide (PI) fiber, polybenzimidazole fiber, polyoxymethylene (POM) fiber, polyetherimide (PEI) fiber, metal alloy fiber, basalt fiber, natural fiber and combinations thereof.

7. The three-dimensional printing method of a fiber composite material according to any one of claims 1 to 6, characterized in that: The at least one dispersed phase (3) comprises a powdered material or a material in nanostructured form; the powdered material is selected from carbon black, silica, graphite, titanium oxide, boron nitride, zirconium oxide, calcium carbonate, calcium phosphate, molybdenum disulfide, lignin and a combination thereof; the material in nanostructured form is selected from graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes, fullerenes, clay nanosheets and a combination thereof.

8. The three-dimensional printing method of a fiber composite material according to any one of the preceding claims 1 to 7, characterized in that: The continuous phase (2) comprises at least one first compound, wherein the first compound comprises: - a thermal initiator in an amount greater than or equal to about 0.001 mol % and less than or equal to about 10 mol %; - a first monomer in an amount greater than or equal to about 20 mol % and less than or equal to about 99.9 mol %; - a cationic initiator in an amount greater than or equal to about 0.001 mol % and less than or equal to about 10 mol %; and - A first diluent in an amount greater than or equal to about 0 mol % and less than or equal to about 70 mol %.

9. The three-dimensional printing method of fiber composite material according to claim 8, characterized in that: - the thermal initiator is selected from: 1,1,2,2-tetraphenyl-1,2-ethylene glycol (TPED), benzopinacol bistrimethylsilyl ether (TPED-Si), dimethylsulfonyl peroxide (DMSP), tert-butyl peroxide (TBPO), tert-butyl cyclohexyl peroxydicarbonate (TBC-PDC), benzoyl peroxide (BPO), azobis(isobutyronitrile) (AIBN) and combinations thereof; - The monomer is selected from: bisphenol A diglycidyl ether (DGEBA), bisphenol F diglycidyl ether (DGEBF), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (CE), 4-vinyl-1-cyclohexane-1,2-epoxide, vinyl cyclohexene dioxide, 4,5-epoxytetrahydrophthalic acid diglycidyl ester, glycidyl methacrylate, pentaerythritol glycidyl ether, trimethylolpropane triglycidyl ether, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, poly(ethylene glycol) diglycidyl ether, epoxidized soybean oil, N,N-diglycidyl-4-glycidyloxyaniline, diglycidyl ether, bis ... -3,4-Epoxycyclohexyl methyl adipate, 1,2-cyclohexane dicarboxylic acid diglycidyl ester, allyl glycidyl ether, phenyl glycidyl ether, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4,4"-methylenebis[N,N-bis(2,3-epoxypropyl)aniline], tris(2,3-epoxypropyl)isocyanurate, m-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline, p-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline, triethoxy(3-glycidyloxypropyl)silane, 1,2-epoxycyclohexane, tris(4-hydroxy phenyl)methane triglycidyl ether, epoxy phenolic resins (including those derived from novolac phenolics), 9-[2-(2-methoxyethoxy)ethoxy]-9-[3-(oxiranylmethoxy)propyl]-2,5,8,10,13,16-hexaoxa-9-silaheptadecane, glycidyl stearate, resorcinol diglycidyl ether, 1,4-butanediol diglycidyl ether (BDGE), vinyl ethers, epoxy phenolic resins (including those derived from dicyclopentadiene), carboxyl-terminated nitrile rubber (CTBN), epoxy-terminated nitrile rubber (ETBN), and combinations thereof, The cationic initiator is selected from: [4-(4-diphenylsulfoniumphenyl)sulfonylphenyl]-diphenylsulfonium tris hexafluorophosphate, (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate, (9-oxofluoren-2-yl)-phenyliodonium hexafluoroantimonate, [4-(4-diphenylsulfoniumphenyl)sulfonylphenyl]-diphenylsulfonium hexafluoroantimonate, [4-[(2-hydroxytetradecyl)oxy]phenyl]phenyliodonium hexafluoroantimonate, 4-octyloxydiphenyliodonium hexafluoroantimonate, 10-(4-phenylphenyl)-2- Propan-2-ylthioxanthen-10-ium-9-one hexafluorophosphate, bis(4-dodecylphenyl)iodonium hexafluoroantimonate, bis-(4-tert-butylphenyl)iodonium hexafluorophosphate, bis[4-(tert-butyl)phenyl]iodonium tetrakis(nonafluoro-tert-butyloxy)aluminate, diphenyl(4-phenylthio)phenylsulfonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, bis(4-methylphenyl)iodonium hexafluorophosphate, (4-methylphenyl)[4-(propan-2-yl)phenyl]iodonium tetrakis(2,3,4,5,6-pentafluorophenyl)borate, and combinations thereof; - The diluent is selected from: multifunctional glycidyl ether, monofunctional aliphatic glycidyl ether, monofunctional aromatic glycidyl ether, 3-ethyl-3-oxetanemethanol (EOM), 3-methyl-3-oxetanemethanol, 1,4-bis(glycidyloxy)benzene (CHDGE), 1,6-hexanediol diglycidyl ether (HDDGE), neopentyl glycol diglycidyl ether (NPDGE), 1,4-butanediol diglycidyl ether (BDGE) and combinations thereof.

10. The three-dimensional printing method of a fiber composite material according to any one of the preceding claims 1 to 9, characterized in that: The continuous phase (2) comprises at least one photosensitive material.

11. The three-dimensional printing method of fiber composite material according to claim 10, characterized in that: The photosensitive material is present in an amount of greater than or equal to about 0.001 mol % and less than or equal to about 5 mol %.

12. The three-dimensional printing method of fiber composite material according to claim 10 or 11, characterized in that: The photosensitive material is selected from the group consisting of anthracene, perylene, benzophenone, 9,10-diethoxyanthracene, 2,2-dimethoxy-2-phenylacetophenone, 2-isopropylthioxanthone (ITX), thioxan-9-one, vinylcarbazole and combinations thereof.

13. The three-dimensional printing method of a fiber composite material according to any one of the preceding claims 1 to 12, characterized in that: The energy (5) is provided by a source of electromagnetic radiation (8).

14. The three-dimensional printing method of a fiber composite material according to any one of claims 1 to 12, characterized in that: The energy (5) is provided by a convection-operated energy source (8).

15. The three-dimensional printing method of a fiber composite material according to any one of claims 1 to 13, characterized in that: The energy (5) is provided by electromagnetic radiation in the infrared spectrum.

16. The three-dimensional printing method of a fiber composite material according to any one of claims 1 to 13, characterized in that: The energy (5) is provided by electromagnetic radiation in the ultraviolet spectrum.

17. The three-dimensional printing method of a fiber composite material according to any one of claims 1 to 16, characterized in that: The continuous phase (2) comprises at least one second compound, wherein the second compound comprises: - a photoinitiator in an amount greater than or equal to about 0.001 mol % and less than or equal to about 10 mol %; - A second monomer in an amount greater than or equal to about 20 mol % and less than or equal to about 99.9 mol %.

18. The three-dimensional printing method of fiber composite material according to claim 17, characterized in that: The second compound further comprises: - a synergistic compound in an amount greater than 0 mol % and less than or equal to about 50 mol %; - A second diluent in an amount greater than 0 mol % and less than or equal to about 70 mol %.

19. The three-dimensional printing method of fiber composite material according to claim 17 or 18, characterized in that: The second compound is present in an amount greater than or equal to about 0.1 mol % and less than or equal to 20 mol %.

20. The three-dimensional printing method of a fiber composite material according to any one of claims 17 to 19, characterized in that: The second compound undergoes a preliminary polymerization step upstream of the feed block (7).

21. The three-dimensional printing method of a fiber composite material according to any one of claims 17 to 20, characterized in that: The second diluent is selected from the group consisting of neopentyl acrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, and combinations thereof.

22. The three-dimensional printing method of a fiber composite material according to any one of claims 17 to 21, characterized in that: The synergistic compound is selected from molecules having an amine group or a thiol group. The molecule having an amine group includes triethylamine, tri-N-butylamine, 2-dimethylaminoethanol, N-methyldiethanolamine, triethanolamine, 2-(dimethylamino)ethylbenzoate, 4-(dimethylamino)ethylbenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, isopentyl-4-(dimethylamino)benzoate, 2-butoxyethyl-4-(dimethylamino)benzoate, N-phenylglycine, 4,4',4"-tris(dimethylamino)-triphenylmethane and combinations thereof, The molecules having a thiol group include butyl 3-mercaptopropionate, trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(2-mercaptopropionate), 2-benzothiazole thiol, 2-benzimidazolol, 1,6-hexane bis(3-mercaptopropionate), di[trimethylolpropane tris(3-mercaptopropionate)], pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-butanediyl bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate) and combinations thereof.

23. The three-dimensional printing method of a fiber composite material according to any one of claims 17 to 22, characterized in that: The photoinitiator is selected from: 2-Hydroxy-2-methyl-propiophenone, 2,2-dimethyl-2-hydroxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropiophenone, 2-hydroxy-2-methyl-4'-tert-butyl-propiophenone, 2-hydroxy-2-methyl-1-(4-tert-butylphenyl)-propiophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methyl-propiophenone, 2-hydroxy-[4'-(2-hydroxypropoxy)]-2-methyl-propiophenone, 2-hydroxy-[4'-(2-hydroxypropoxy)phenyl]-2-methylpropiophenone, oligomeric 2-hydroxy-2-methyl-1-[4-(1-methyl-vinyl)phenyl]propiophenone, 2-hydroxy-1-[4[4-(2-hydroxy-2-methyl-propionyl)phenyl]propiophenone )-benzyl]-phenyl]-2-methyl-propan-1-one, 2-methyl-4'-(methylthio)-2-morpholino-propiophenone, 2-benzyl-2-(dimethylamino)-4-morpholinobutyrophenone, 2-(4-methylbenzyl)-2-(dimethylamino)-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenyl-acetophenone, 2,2-diethoxy-2-phenyl-acetophenone, 2,2-diethoxy-1-phenylacetophenonediethoxyacetophenone, 2-isopropoxy-2-phenylacetophenone, 2-n-butoxy-2-phenylacetophenone, 2-isobutoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)-(2,4-bispentyloxyphenyl)phosphine oxide, ethyl(2,4,6-trimethylbenzoyl)- acyl) phenylphosphite, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, phenyl-bis-(2,4,6-trimethylbenzoyl)phosphine oxide, 4'-(tert-butyl)-2,2,2-trichloroacetophenone, 4'-(phenoxy)-2,2-dichloroacetophenone, 2-(4-methoxyphenyl)-4,6-bis-(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-dimethoxy)-phenyl-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-dimethoxy)-phenyl-s-triazine, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl) oxime, 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(o-benzoyloxime), benzophenone, 4-methylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, benzophenone-2-carboxy-(tetraethoxy)acrylate, 4-phenylbenzophenone, 2-benzoylbenzoic acid methyl ester, 1-{-4-[benzoylphenylsulfonyl]phenyl}-2-methyl-2-(4-methylphenylsulfonyl)-propan-1-one, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,4-diisopropylthioxanthone, methyl phenylglyoxylate, 2-ethylanthraquinone, 2-ethyl-9,10-Anthracene dione, polyethylene glycol-bis-[(4-acetylphenyl)-piperazine propionate], 3-benzoyl-7-methoxy-2H-chromene-2-one and combinations thereof.

24. The three-dimensional printing method of a fiber composite material according to any one of claims 17 to 23, characterized in that: The second monomer is selected from monomers having a (meth)acrylate group or acrylamide monomers, The monomers having a (meth)acrylate group include tricyclodecane dimethanol diacrylate, 3-[2,2-dimethyl-1-oxo-3-[(1-oxo-2-propenyl)oxy]propoxy]-2,2-dimethylpropyl acrylate, dihydrodicyclopentadienyl acrylate, pentaerythritol triacrylate, pentaerythritol tetramethacrylate, dipropylene glycol diacrylate, ditrimethylolpropane tetraacrylate, isobornyl acrylate, dipentaerythritol hexaacrylate, tert-butyl acrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, bisphenol A diacrylate. -ethoxylates (where 1<n≤10), bisphenol A diacrylate, 3,3,5-trimethylcyclohexyl acrylate, (5-ethyl-1,3-dioxane-5-yl) methacrylate, trimethylolpropane triacrylate n-ethoxylate (1<n≤10), neopentyl glycol diacrylate, triethylene glycol diacrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobutyl acrylate, dodecyl acrylate, butyl acrylate, isodecyl acrylate, dodecafluoroheptyl acrylate, hexahydro-4,7-methylene-1H-indenyl acrylate, acrylic acid, The acrylamide monomers include N,N-dimethylacrylamide, isobutylhydroxymethylacrylamide acrylate, 4-acryloylmorpholine, N-isopropylacrylamide, N,N-dimethylaminopropylacrylamide, N-hydroxyethylacrylamide, N,N-diethylacrylamide, tris[2-(acryloyloxy)ethyl]isocyanurate and combinations thereof.

25. The three-dimensional printing method of a fiber composite material according to any one of claims 17 to 24, characterized in that: The second monomer is selected from monomers containing a urethane group and having a (meth)acrylate functional group.

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