Interlayer reinforced composite material, preparation method thereof and application of interlayer reinforced composite material as 3D printing material

Abstract

The invention belongs to the technical field of 3D printing materials, and particularly relates to an interlayer reinforced composite material, a preparation method thereof and application of the interlayer reinforced composite material as a 3D printing material. A copolymerization group is introduced into polyaryletherketone, so that polyaryletherketone has a unique molecular structure and can compete with folding of an ether ketone chain segment in the crystallization process, in this way, in-situ copolymerization polyaryletherketone has a lower crystallization rate compared with polyether-ether-ketone or a polyether ketone system, the healing time of adjacent fused filaments of a 3D printing product is prolonged, and the 3D printing quality is improved. Compared with a conventional 3D printing material, the 3D printing material has the advantages that the interlayer strength is effectively improved and the interlayer reinforcing effect is achieved due to the long healing time, the interlayer performance of a 3D printing product obtained by using the 3D printing material is good, the tensile strength is 120-130 MPa, the interlayer tensile strength is 20-30 MPa, and the application range is wider. The interlayer reinforced composite material provided by the invention has the advantages of lower melting point, favorable processability, favorable mechanical properties, favorable high-temperature resistance and excellent comprehensive properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of 3D printing materials, and in particular relates to an interlayer reinforced composite material and a preparation method thereof and an application thereof as a 3D printing material. Background Art

[0002] As an important semi-crystalline special engineering plastic, polyetheretherketone (PEEK) has become one of the high-performance thermoplastic resins that attracts attention in the field of fused deposition modeling (FDM) 3D printing due to its excellent high temperature resistance, corrosion resistance, aging resistance and mechanical properties. With the continuous development of FDM 3D printing technology, the performance of FDM 3D printed carbon fiber / polyetheretherketone composite materials in specific directions has approached that of injection molding products.

[0003] However, existing carbon fiber / polyetheretherketone composites have disadvantages such as too fast crystallization rate, which leads to short healing time between adjacent molten filaments and weak interlayer bonding strength when FDM 3D printing Z-direction samples, seriously limiting the application of carbon fiber / polyetheretherketone composites in structural parts. Summary of the invention

[0004] The object of the present invention is to provide an interlayer reinforced composite material and a preparation method thereof and application as a 3D printing material. The interlayer reinforced composite material provided by the present invention has a slow crystallization rate and high interlayer strength.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides an interlayer reinforced composite material, which is prepared by including the following raw materials in parts by weight:

[0007] In-situ copolymerization modified polyaryletherketone 60-99.9 parts; fiber reinforced filler 0.1-40 parts;

[0008] The structural unit of the in-situ copolymerized modified polyaryletherketone comprises a first structural unit and a second structural unit; the first structural unit accounts for 50% to 99.5%; the structure of the first structural unit is shown in Formula I, and the structure of the second structural unit is shown in Formula II:

[0009]

[0010] In Formula I, Ar 1 The structure is shown in Formula 1-1 or Formula 1-2; in Formula II, Ar 2 The structure is shown in Formula 2-1, Formula 2-2, Formula 2-3, Formula 2-4, Formula 2-5 or Formula 2-6:

[0011]

[0012]

[0013] Preferably, the melt index of the in-situ copolymerized modified polyaryletherketone is 10 to 150 g / 10 min.

[0014] Preferably, the fiber-reinforced filler includes one or more of carbon fiber and glass fiber; the fiber-reinforced filler has a length of more than 6 mm and a diameter of 7 μm.

[0015] The present invention also provides a method for preparing the interlayer reinforced composite material described in the above scheme, comprising the following steps:

[0016] The in-situ copolymerized modified polyaryletherketone and the fiber-reinforced filler are melt-extruded to obtain the interlayer reinforced composite material.

[0017] Preferably, the preparation method of the in-situ copolymerization modified polyaryletherketone comprises the following steps: mixing 4,4'-difluorobenzophenone, a first monomer, a second monomer, a catalyst, a water-carrying agent and an organic solvent to carry out azeotropic water-carrying, removing the water-carrying agent and polymerization reaction; the first monomer comprises one or more of 4,4'-dihydroxybenzophenone and hydroquinone; and the second monomer is a polyphenyl ring bisphenol monomer.

[0018] Preferably, the melt extrusion includes sequentially performing first heating, second heating, third heating and extrusion; the temperature of the first heating is 290-330°C; the temperature of the second heating is 330-380°C; the temperature of the third heating is 330-380°C.

[0019] Preferably, the melt extrusion further comprises heat treatment of the extrudate obtained; the heat treatment temperature is 100 to 200° C., and the heat preservation time is 4 to 12 hours.

[0020] The present invention also provides the use of the interlayer reinforced composite material described in the above scheme or the interlayer reinforced composite material obtained by the preparation method described in the above scheme as a 3D printing material.

[0021] In the present invention, the application method comprises the following steps: sequentially melting, extruding, cooling, drawing and 3D printing the interlayer reinforced composite material to obtain a 3D printed molded part.

[0022] Preferably, the 3D printing further includes annealing the obtained product.

[0023] The present invention provides an interlayer reinforced composite material. The present invention introduces a copolymerization group into polyaryletherketone so that the polyaryletherketone has a unique molecular structure, which can compete with the folding of the etherketone chain segment during the crystallization process, so that the in-situ copolymerized polyaryletherketone has a slower crystallization rate than polyetheretherketone or polyetherketone system, and improves the healing time of adjacent molten filaments of 3D printed products. The longer healing time effectively improves the interlayer strength and achieves the interlayer reinforcement effect. The 3D printed products obtained as 3D printing materials have good interlayer performance, tensile strength of 120-130MPa, interlayer tensile strength of 20-30MPa, and a wider range of applications. At the same time, the addition of copolymerization groups in polyaryletherketone can form π-π interactions with fiber-reinforced fillers, effectively improve the interfacial compatibility of polyaryletherketone matrix resin, and then give full play to the reinforcing effect of fiber-reinforced fillers, which plays an effect of efficiently improving the mechanical properties of interlayer reinforced composite materials. The interlayer reinforced composite material provided by the present invention has a lower melting point, reduces the processing temperature, has good processing performance and mechanical properties, and has good high temperature resistance, is basically not decomposed at 500°C, and has excellent comprehensive performance.

[0024] The present invention also provides a method for preparing the interlayer reinforced composite material described in the above scheme. The preparation method provided by the present invention has simple steps, is easy to operate, and is easy to realize industrialized mass production.

[0025] The present invention also provides the use of the interlayer reinforced composite material described in the above scheme or the interlayer reinforced composite material obtained by the preparation method described in the above scheme as a 3D printing material. The interlayer reinforced composite material provided by the present invention has good interlayer performance, a tensile strength of 120 to 130 MPa along the printing direction, an interlayer tensile strength of 20 to 30 MPa, good processing performance and high temperature resistance, and basically does not decompose at 500°C, and can be used as a 3D printing material in the fields of FDM 3D printing and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0027] Figure 1 This is the infrared test spectrum of the interlayer reinforced composite material of Example 1;

[0028] Figure 2 The DSC curves of the interlayer reinforced composite materials of Example 1 and the comparative example;

[0029] Figure 3The tensile performance curves of the 3D printed molded parts of Example 1 and the control example along the printing direction (X-axis direction);

[0030] Figure 4 The tensile performance curve (interlayer performance) of the 3D printed molded parts of Example 1 and the control example in the vertical printing direction (Z-axis direction);

[0031] Figure 5 This is a thermogravimetric curve of the interlaminar reinforced composite material of Example 1. DETAILED DESCRIPTION

[0032] The present invention provides an interlayer reinforced composite material, which is prepared by including the following raw materials in parts by weight:

[0033] In-situ copolymerization modified polyaryletherketone 60-99.9 parts; fiber reinforced filler 0.1-40 parts;

[0034] The structural unit of the in-situ copolymerized modified polyaryletherketone comprises a first structural unit and a second structural unit; the first structural unit accounts for 50% to 99.5%; the structure of the first structural unit is shown in Formula I, and the structure of the second structural unit is shown in Formula II:

[0035]

[0036] In Formula I, Ar 1 The structure is shown in Formula 1-1 or Formula 1-2; in Formula II, Ar 2 The structure is shown in Formula 2-1, Formula 2-2, Formula 2-3, Formula 2-4, Formula 2-5 or Formula 2-6:

[0037]

[0038] In parts by mass, the interlaminar reinforced composite material provided by the present invention includes 60 to 99.9 parts of in-situ copolymerized modified polyaryletherketone, specifically 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 97 parts, 99 parts, 99.2 parts, 99.5 parts, 99.7 parts or 99.9 parts.

[0039] In the present invention, the melt index of the in-situ copolymerized modified polyaryletherketone can be 10 to 150 g / 10 min, specifically 10 g / 10 min, 20 g / 10 min, 40 g / 10 min, 60 g / 10 min, 80 g / 10 min, 100 g / 10 min, 120 g / 10 min or 150 g / 10 min; the melt index of the in-situ copolymerized modified polyaryletherketone is measured according to standard GB / T 3682.1-2018, the measuring temperature is 400 ° C, and the nominal load is 5 kg.

[0040] In the present invention, the proportion of the first structural unit is 50% to 99.5%, specifically 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.3% or 99.5%.

[0041] Based on the mass fraction of the in-situ copolymerized modified polyaryletherketone, the interlaminar reinforced composite material provided by the present invention includes 0.1 to 40 parts of fiber-reinforced filler, specifically 0.1 parts, 0.5 parts, 1 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts.

[0042] In the present invention, the fiber-reinforced filler may include one or more of carbon fiber and glass fiber; the length of the fiber-reinforced filler may be greater than 6 mm, specifically 6 mm, 10 mm, 50 mm or continuous fiber, and the diameter may be 7 μm.

[0043] The present invention also provides a method for preparing the interlayer reinforced composite material described in the above scheme, comprising the following steps:

[0044] The in-situ copolymerized modified polyaryletherketone and the fiber-reinforced filler are melt-extruded to obtain the interlayer reinforced composite material.

[0045] In the present invention, the preparation method of the in-situ copolymerization modified polyaryletherketone may include the following steps: mixing 4,4'-difluorobenzophenone, a first monomer, a second monomer, a catalyst, a water-carrying agent and an organic solvent to carry out azeotropic water-carrying, removing the water-carrying agent and polymerizing.

[0046] In the present invention, the first monomer may include one or more of 4,4'-dihydroxybenzophenone and hydroquinone.

[0047] In the present invention, the molar ratio of the 4,4'-difluorobenzophenone to the first monomer may be 0.8-1.2:0.500-0.995, specifically 0.8:0.5, 0.9:0.5, 1:0.5, 1.1:0.5, 1.2:0.5, 0.8:0.6, 0.9:0.6, 1:0.6, 1.1:0.6, 1.2:0.6, 0.8:0.7, 0.9:0.7, 1:0.7, 1.1:0.7, 1.2:0.7, 0.8:0.8, 0.9:0.8, 1:0.8, 1.1:0.8, 1.2:0.8, 0.8:0.9, 1:0.9, 1.1:0.9, 1.2:0.9, 0.8:0.95, 0.9:0.95, 1:0.95, 1.1:0.95, 1.2:0.95, 0.8:0.99, 0.9:0.99, 1:0.99, 1.1:0.99, 1.2:0.99, 0.8:0.995, 0.9:0.995, 1:0.995, 1.1:0.995, or 1.2:0.995.

[0048] In the present invention, the second monomer may be a polybenzene ring bisphenol monomer; the polybenzene ring bisphenol monomer may include one or more of bisphenol fluorene, resorcinol, biphenol, phenolphthalein, 2,6-naphthalene diol and bisphenol A.

[0049] In the present invention, the molar ratio of the 4,4'-difluorobenzophenone to the second monomer may be 0.8-1.2:0.005-0.500, specifically 0.8:0.005, 0.9:0.005, 1:0.005, 1.1:0.005, 1.2:0.005, 0.8:0.01, 0.9:0.01, 1:0.01, 1.1:0.01, 1.2:0.01, 0.8:0.05, 0.9:0.05, 1:0.05, 1.1:0.05, 1.2:0.05, 0.8:0.1, 0.9:0.1, 1:0.1, 1.1:0.1, 1.2:0.1, 0.8:0.2, 0.9:0.2, 1:0.2, 1.1:0.2, 1.2:0.2, 0.8:0.3, 0.9:0.3, 1:0.3, 1.1:0.3, 1.2:0.3, 0.8:0.4, 0.9:0.4, 1:0.4, 1.1:0.4, 1.2:0.4, 0.8:0.5, 0.9:0.5, 1:0.5, 1.1:0.5, or 1.2:0.5.

[0050] In the present invention, the catalyst may be an alkali metal salt; the alkali metal salt may be an alkali metal carbonate; the alkali metal carbonate may include one or both of potassium carbonate and sodium carbonate; when the catalyst is potassium carbonate and sodium carbonate, the molar ratio of potassium carbonate to sodium carbonate may be no greater than 0.01:1, specifically 0.01:1, 0.01:1.1, 0.01:1.2, 0.01:1.5, 0.01:2, 0.01:5, 0.01:10, 0.01:20, 0.01:30, 0.01:50, 0.01:80, 0.01:120 or 0.01:200. The present invention preferably uses potassium carbonate and sodium carbonate as catalysts, which can provide better catalytic effect.

[0051] In the present invention, the molar ratio of the catalyst to 4,4'-difluorobenzophenone can be 0.01-1.3:1-1.1, specifically 0.01:1, 0.03:1, 0.05:1, 0.07:1, 0.1:1, 0.5:1, 0.8:1, 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 0.01:1.05, 0.03:1.05, 0.05:1.05, 0.07:1.05, 0.1:1.05, 0.5:1 .05, 0.8:1.05, 1:1.05, 1.05:1.05, 1.1:1.05, 1.15:1.05, 1.2:1.05, 1.25:1.05, 1.3:1.05, 0.01:1.1, 0.03:1.1, 0.05:1.1, 0.07:1.1, 0.1:1.1, 0.5:1.1, 0.8:1.1, 1:1.1, 1.05:1.1, 1.1:1.1, 1.15:1.1, 1.2:1.1, 1.25:1.1 or 1.3:1.1. The present invention controls the catalyst within the above range, which is conducive to more fully catalyzing the reaction, and then is conducive to preparing the in-situ copolymerized modified polyaryletherketone.

[0052] In the present invention, the water-carrying agent may be a homologue of benzene; the homologue of benzene may include one or more of xylene and toluene.

[0053] In the present invention, the organic solvent may be a sulfone solvent; the sulfone solvent may include one or more of diphenyl sulfone and cyclopentane.

[0054] In the present invention, the mass ratio of the water-carrying agent to the organic solvent may be 6 to 16:100, specifically 6:100, 8:100, 10:100, 12:100, 14:100 or 16:100.

[0055] In the present invention, the ratio of the total mass of the 4,4'-difluorobenzophenone, the first monomer, the second monomer and the catalyst to the volume of the organic solvent may be (50-442) g:100 mL, specifically 50 g:100 mL, 60 g:100 mL, 70 g:100 mL, 80 g:100 mL, 90 g:100 mL, 100 g:100 mL, 120 g:100 mL, 150 g:100 mL, 180 g:100 mL, 221 g:100 mL, 260 g:100 mL, 320 g:100 mL, 380 g:100 mL or 442 g:100 mL.

[0056] In the present invention, the temperature of the azeotropic water can be 140-230°C, specifically 140°C, 170°C, 200°C or 230°C, and the time of the azeotropic water can be 0.5-8h, specifically 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h; the azeotropic water can be carried out in a protective atmosphere; the protective atmosphere can be argon or nitrogen. The present invention removes moisture from the system by azeotropic water, avoids affecting the subsequent polymerization reaction, promotes the forward reaction, and maintains a constant temperature of the system.

[0057] In the present invention, the temperature for removing the water-carrying agent can be 230-250°C, specifically 230°C, 235°C, 240°C, 245°C or 250°C, and the time for removing the water-carrying agent can be 1-2h, specifically 1h, 1.5h or 2h; the removal of the water-carrying agent can be carried out in a protective atmosphere; the protective atmosphere can be argon or nitrogen.

[0058] In the present invention, the polymerization reaction may be carried out in a protective atmosphere; the protective atmosphere may be argon or nitrogen; the polymerization reaction may include a first stage polymerization reaction and a second stage polymerization reaction carried out sequentially.

[0059] In the present invention, the temperature of the first stage polymerization reaction can be 230-280°C, specifically 230°C, 250°C, 270°C or 280°C, and the insulation time can be 2-3h, specifically 2h, 2.5h or 3h.

[0060] In the present invention, the temperature of the second stage polymerization reaction can be 280-310°C, specifically 280°C, 290°C, 300°C or 310°C, and the holding time can be 0.2-4h, specifically 0.2h, 0.5h, 1h, 2h, 3h or 4h. Dividing the polymerization reaction into two steps is conducive to the reaction of the reaction raw materials.

[0061] In the present invention, after the polymerization reaction, the obtained reaction product may be precipitated in water and then crushed, washed and dried in sequence; the water may be deionized water; and the crushing equipment may be a high-speed stirrer.

[0062] In the present invention, the washing may include alternately washing with water and washing with alcohol; the water used for the water washing may be deionized water; the number of the water washing may be more than one time, specifically 5 times or 8 times; the alcohol used for the alcohol washing may be ethanol; the number of the alcohol washing may be more than one time, specifically 5 times or 8 times. The present invention fully removes impurities such as solvents and catalysts in the product by washing in the above manner.

[0063] In the present invention, the in-situ copolymerization modified polyaryletherketone and the fiber-reinforced filler may be dried before the melt extrusion; the drying may be oven drying; the oven drying temperature may be 100 to 200°C, specifically 100°C, 120°C, 140°C, 160°C, 180°C or 200°C, and the heat preservation time may be 5 to 20h, specifically 5h, 7h, 9h, 12h, 15h, 18h or 20h.

[0064] In the present invention, the melt extrusion may include sequentially performing first heating, second heating, third heating and extrusion.

[0065] In the present invention, the first heating temperature may be 290-330°C, specifically 290°C, 300°C, 310°C, 320°C or 300°C.

[0066] In the present invention, the second heating temperature may be 330-380°C, specifically 330°C, 340°C, 350°C, 360°C, 370°C or 380°C.

[0067] In the present invention, the third heating temperature may be 330-380°C, specifically 330°C, 340°C, 350°C, 360°C, 370°C or 350°C.

[0068] In the present invention, the extrusion speed can be 15-45 rpm, specifically 15 rpm, 20 rpm, 25 rpm, 30 rpm, 35 rpm, 40 rpm or 45 rpm. The residence time of the in-situ copolymerized modified polyaryletherketone and the fiber-reinforced filler in each zone is subject to the extrusion speed of the melt extrusion.

[0069] In the present invention, the melt extrusion device can be a twin-screw extruder. When adding materials, the raw materials are fed into the twin-screw extruder through the feeding port.

[0070] In the present invention, the melt extrusion may further include heat treatment of the extrudate; the heat treatment temperature may be 100-250°C, specifically 100°C, 125°C, 150°C, 175°C, 200°C, 225°C or 250°C, the heat preservation time may be 4-12h, specifically 4h, 6h, 8h, 10h or 12h; the heat treatment equipment may be a vacuum oven. The present invention discharges moisture from the material through heat treatment.

[0071] In the present invention, the melt extrusion may further include granulation.

[0072] The present invention also provides the use of the interlayer reinforced composite material described in the above scheme or the interlayer reinforced composite material obtained by the preparation method described in the above scheme as a 3D printing material.

[0073] In the present invention, the application method may include the following steps: sequentially melting, extruding, cooling, drawing and 3D printing the interlayer reinforced composite material to obtain a 3D printed molded part.

[0074] In the present invention, the interlayer reinforced composite material may be dried before use. The interlayer reinforced composite material will absorb water during storage, so it is preferably fully dried before use.

[0075] In the present invention, the melting device may be a screw extruder; the screw extruder may be a single screw extruder; the melting may include heating A, heating B and heating C in sequence.

[0076] In the present invention, the heating temperature of A may be 290-330°C, specifically 290°C, 300°C, 310°C, 320°C or 330°C.

[0077] In the present invention, the temperature of the heating B may be 330-380°C, specifically 330°C, 340°C, 350°C, 360°C, 370°C or 380°C.

[0078] In the present invention, the temperature of the heating C may be 330-380° C., specifically 330° C., 340° C., 350° C., 360° C., 370° C. or 380° C. The residence time of the interlayer reinforced composite material in each zone is subject to the extrusion rotation speed.

[0079] In the present invention, the extrusion equipment may be a screw extruder; the screw extruder may be a single screw extruder; the extrusion speed may be 5 to 30 rpm, specifically 5 rpm, 10 rpm, 15 rpm, 20 rpm, 25 rpm or 30 rpm.

[0080] In the present invention, the wire drawing obtains the interlayer reinforced composite material wire; the wire drawing may further include winding the interlayer reinforced composite material wire; the diameter of the interlayer reinforced composite material wire may be 1.7-1.8 mm.

[0081] In the present invention, the working parameters of the 3D printing are: the nozzle temperature can be 300-460°C, specifically 300°C, 320°C, 350°C, 370°C, 400°C, 420°C, 440°C or 460°C; the printing layer height can be 0.1-0.4mm, specifically 0.1mm, 0.15mm, 0.2mm, 0.25mm, 0.3mm, 0.35mm or 0.4mm; the printing speed can be 15-60mm / s, specifically 15mm / s, 20mm / s, 25mm / s, 30mm / s, 35mm / s, 40mm / s, 45mm / s, 50mm / s, 55mm / s or 60mm / s.

[0082] In the present invention, the 3D printing may further include annealing the obtained product; the annealing temperature may be 200-280°C, specifically 200°C, 215°C, 230°C, 245°C, 260°C or 280°C, the holding time may be 2-10h, specifically 2h, 3h, 4h, 6h, 8h or 10h; the annealing may be performed under vacuum conditions. The present invention can improve the crystallinity of the material through annealing, thereby increasing the modulus of the material.

[0083] In order to further illustrate the present invention, the scheme of the present invention is described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be understood as limiting the protection scope of the present invention.

[0084] Example 1

[0085] (1) 99.1 g (0.9 mol) of hydroquinone, 35.0 g (0.1 mol) of bisphenol fluorene, 221.5 g (1.015 mol) of 4,4'-difluorobenzophenone, 1 kg (798.7 mL) of diphenyl sulfone, 128 g (1.207 mol) of sodium carbonate and 2 g (0.014 mol) of potassium carbonate were mixed and added into a three-necked flask equipped with an argon inlet, a mechanical stirrer and a water collector. The mixture was mechanically stirred for degassing for 1 h, and then the temperature was raised to 230°C. The water generated by the reaction was removed from the reaction system by using xylene. The temperature was maintained for 1 h, and the temperature was further raised to 280°C for polymerization reaction for 1 h. The temperature was then raised to 310°C, and then 2.2 g of 4,4'-difluorobenzophenone was added for end-capping. The end-capping time was 0.5 h.

[0086] (2) The end-capping product solution is continuously stirred in deionized water to precipitate the product into filaments, and the precipitates are crushed, washed and dried in sequence; the washing is performed by washing in deionized water for 8 times and in ethanol for 8 times, and the drying is performed by drying in a vacuum oven at 140° C. for 12 hours to obtain an in-situ copolymerized modified polyaryletherketone having a melt index of 45 g / 10 min.

[0087] (3) 180 g of in-situ copolymerized modified polyaryletherketone and 20 g of carbon fiber (length greater than 6 mm, diameter 7 μm) were melt-extruded in a twin-screw extruder, including three heating zones, zone 1, zone 2 and zone 3, wherein the temperature of zone 1 was 320° C., the temperature of zone 2 was 360° C., the temperature of zone 3 was 360° C., and the extrusion speed was 30 rpm. The extruded product was granulated to obtain a granular interlaminar reinforced composite material.

[0088] (4) After drying the interlayer reinforced composite material, it is melt-extruded, cooled and drawn in sequence, wherein the melt extrusion is carried out in a single-screw extruder, and the single-screw extruder includes three heating zones, namely zone one, zone two and zone three, wherein the temperature of zone one is 320°C, the temperature of zone two is 360°C, the temperature of zone three is 360°C, and the extrusion rotation speed is 10 rpm to obtain an interlayer reinforced composite wire.

[0089] (5) The interlayer reinforced composite material wire is 3D printed, wherein the 3D printing nozzle temperature is 420° C., the printing layer height is 0.2 mm, and the printing speed is 30 mm / s to obtain a 3D printed molded part.

[0090] Example 2

[0091] (1) 99.1 g (0.9 mol) of hydroquinone, 17.5 g (0.05 mol) of bisphenol fluorene, 11.4 g (0.05 mol) of bisphenol A, 221.8 g (1.016 mol) of 4,4'-difluorobenzophenone, 1 kg (798.7 mL) of diphenyl sulfone and 130 g (1.227 mol) of sodium carbonate were mixed and added into a three-necked flask equipped with an argon inlet, a mechanical stirrer and a water collector. The mixture was mechanically stirred for degassing for 1 h, and then the temperature was raised to 230°C. The water generated by the reaction was removed from the reaction system by using xylene. The temperature was maintained for 1 h, and the temperature was further raised to 280°C for polymerization for 1 h. The temperature was then raised to 310°C, and then 2.2 g of 4,4'-difluorobenzophenone was added for end-capping. The end-capping time was 0.5 h.

[0092] (2) The end-capping product solution is continuously stirred in deionized water to precipitate the product into filaments, and the precipitates are crushed, washed and dried in sequence; the washing is performed by washing in deionized water for 8 times and in ethanol for 8 times, and the drying is performed by drying in a vacuum oven at 140° C. for 12 hours to obtain an in-situ copolymerized modified polyaryletherketone having a melt index of 53 g / 10 min.

[0093] (3) 180 g of in-situ copolymerized modified polyaryletherketone and 20 g of carbon fiber (length greater than 6 mm, diameter 7 μm) were melt-extruded in a twin-screw extruder, including three heating zones, zone 1, zone 2 and zone 3, wherein the temperature of zone 1 was 320° C., the temperature of zone 2 was 360° C., the temperature of zone 3 was 360° C., and the extrusion speed was 30 rpm. The extruded product was granulated to obtain a granular interlayer reinforced composite material.

[0094] (4) After drying the interlayer reinforced composite material, it is melt-extruded, cooled and drawn in sequence, wherein the melt extrusion is carried out in a single-screw extruder, and the single-screw extruder includes three heating zones, namely zone one, zone two and zone three, wherein the temperature of zone one is 320°C, the temperature of zone two is 360°C, the temperature of zone three is 360°C, and the extrusion rotation speed is 10 rpm to obtain an interlayer reinforced composite wire.

[0095] (5) The interlayer reinforced composite material wire is 3D printed, wherein the 3D printing nozzle temperature is 420° C., the printing layer height is 0.2 mm, and the printing speed is 30 mm / s to obtain a 3D printed molded part.

[0096] Example 3

[0097] (1) 99.1 g (0.9 mol) of hydroquinone, 22.8 g (0.1 mol) of bisphenol A, 221.8 g (1.016 mol) of 4,4'-difluorobenzophenone, 1 kg (798.7 mL) of diphenyl sulfone, 110 g (1.038 mol) of sodium carbonate and 20 g (0.14 mol) of potassium carbonate were mixed and added into a three-necked flask equipped with an argon inlet, a mechanical stirrer and a water conveyor. The mixture was mechanically stirred for degassing for 1 h, and then the temperature was raised to 230°C. The water generated by the reaction was removed from the reaction system by using xylene. The temperature was maintained for 1 h, and the temperature was further raised to 280°C for polymerization for 1 h. The temperature was then raised to 310°C, and then 2.2 g of 4,4'-difluorobenzophenone was added for end-capping. The end-capping time was 0.5 h.

[0098] (2) The end-capping product solution is continuously stirred in deionized water to precipitate the product into filaments, and the precipitates are crushed, washed and dried in sequence; the washing is performed by washing in deionized water for 8 times and in ethanol for 8 times, and the drying is performed by drying in a vacuum oven at 140° C. for 12 hours to obtain an in-situ copolymerized modified polyaryletherketone having a melt index of 90 g / 10 min.

[0099] (3) 170 g of in-situ copolymerized modified polyaryletherketone and 30 g of carbon fiber (length greater than 6 mm, diameter 7 μm) were melt-extruded in a twin-screw extruder, including three heating zones, zone 1, zone 2 and zone 3, wherein the temperature of zone 1 was 320°C, the temperature of zone 2 was 360°C, the temperature of zone 3 was 360°C, and the extrusion speed was 30 rpm. The extruded product was granulated to obtain a granular interlaminar reinforced composite material.

[0100] (4) After drying the interlayer reinforced composite material, it is melt-extruded, cooled and drawn in sequence, wherein the melt extrusion is carried out in a single-screw extruder, and the single-screw extruder includes three heating zones, namely zone one, zone two and zone three, wherein the temperature of zone one is 320°C, the temperature of zone two is 360°C, the temperature of zone three is 360°C, and the extrusion rotation speed is 10 rpm to obtain an interlayer reinforced composite wire.

[0101] (5) The interlayer reinforced composite material wire is 3D printed, wherein the 3D printing nozzle temperature is 420° C., the printing layer height is 0.2 mm, and the printing speed is 30 mm / s to obtain a 3D printed molded part.

[0102] Example 4

[0103] (1) 171.4 g (0.8 mol) of 4,4'-dihydroxybenzophenone, 35.0 g (0.1 mol) of bisphenol fluorene, 22.8 g (0.1 mol) of bisphenol A, 221.8 g (1.016 mol) of 4,4'-difluorobenzophenone, 1 kg (798.7 mL) of diphenyl sulfone and 130 g (1.227 mol) of sodium carbonate were mixed and added into a three-necked flask equipped with an argon inlet, a mechanical stirrer and a water conveyor. The mixture was mechanically stirred for degassing for 1 h, and then the temperature was raised to 230°C. The water generated by the reaction was removed from the reaction system by using xylene. The temperature was maintained for 1 h, and the temperature was further raised to 280°C for polymerization for 1 h. The temperature was then raised to 310°C, and then 2.2 g of 4,4'-difluorobenzophenone was added for end-capping. The end-capping time was 0.5 h.

[0104] (2) The end-capping product solution is continuously stirred in deionized water to precipitate the product into filaments, and the precipitates are crushed, washed and dried in sequence; the washing is performed by washing in deionized water for 8 times and in ethanol for 8 times, and the drying is performed by drying in a vacuum oven at 140° C. for 12 hours to obtain an in-situ copolymerized modified polyaryletherketone having a melt index of 70 g / 10 min.

[0105] (3) 160 g of in-situ copolymerized modified polyaryletherketone and 40 g of carbon fiber (length greater than 6 mm, diameter 7 μm) were melt-extruded in a twin-screw extruder, including three heating zones, zone 1, zone 2 and zone 3, wherein the temperature of zone 1 was 320°C, the temperature of zone 2 was 360°C, the temperature of zone 3 was 360°C, and the extrusion speed was 30 rpm. The extruded product was granulated to obtain a granular interlayer reinforced composite material.

[0106] (4) After drying the interlayer reinforced composite material, it is melt-extruded, cooled and drawn in sequence, wherein the melt extrusion is carried out in a single-screw extruder, and the single-screw extruder includes three heating zones, namely zone one, zone two and zone three, wherein the temperature of zone one is 320°C, the temperature of zone two is 360°C, the temperature of zone three is 360°C, and the extrusion rotation speed is 10 rpm to obtain an interlayer reinforced composite wire.

[0107] (5) The interlayer reinforced composite material wire is 3D printed, wherein the 3D printing nozzle temperature is 420° C., the printing layer height is 0.2 mm, and the printing speed is 30 mm / s to obtain a 3D printed molded part.

[0108] Example 5

[0109] (1) 71.6 g (0.65 mol) of hydroquinone, 35.0 g (0.1 mol) of bisphenol fluorene, 46.6 g (0.25 mol) of biphenyl diphenol, 221.8 g (1.016 mol) of 4,4'-difluorobenzophenone, 1 kg (798.7 mL) of diphenyl sulfone and 130 g (1.227 mol) of sodium carbonate were mixed and added into a three-necked flask equipped with an argon inlet, a mechanical stirrer and a water conveyor. The mixture was mechanically stirred for degassing for 1 h, and then the temperature was raised to 230°C. The water generated by the reaction was removed from the reaction system by using xylene. The temperature was maintained for 1 h, and the temperature was further raised to 280°C for polymerization for 1 h. The temperature was then raised to 310°C, and then 2.2 g of 4,4'-difluorobenzophenone was added for end-capping. The end-capping time was 0.5 h.

[0110] (2) The end-capping product solution is continuously stirred in deionized water to precipitate the product into filaments, and the precipitates are crushed, washed and dried in sequence; the washing is performed by washing in deionized water for 8 times and in ethanol for 8 times, and the drying is performed by drying in a vacuum oven at 140° C. for 12 hours to obtain an in-situ copolymerized modified polyaryletherketone having a melt index of 57 g / 10 min.

[0111] (3) 160 g of in-situ copolymerized modified polyaryletherketone and 40 g of carbon fiber (length greater than 6 mm, diameter 7 μm) were melt-extruded in a twin-screw extruder, including three heating zones, zone 1, zone 2 and zone 3, wherein the temperature of zone 1 was 320°C, the temperature of zone 2 was 360°C, the temperature of zone 3 was 360°C, and the extrusion speed was 30 rpm. The extruded product was granulated to obtain a granular interlayer reinforced composite material.

[0112] (4) After drying the interlayer reinforced composite material, it is melt-extruded, cooled and drawn in sequence, wherein the melt extrusion is carried out in a single-screw extruder, and the single-screw extruder includes three heating zones, namely zone one, zone two and zone three, wherein the temperature of zone one is 320°C, the temperature of zone two is 360°C, the temperature of zone three is 360°C, and the extrusion rotation speed is 10 rpm to obtain an interlayer reinforced composite wire.

[0113] (5) The interlayer reinforced composite material wire is 3D printed, wherein the 3D printing nozzle temperature is 420° C., the printing layer height is 0.2 mm, and the printing speed is 30 mm / s to obtain a 3D printed molded part.

[0114] Example 6

[0115] (1) 82.6 g (0.75 mol) of hydroquinone, 46.6 g (0.25 mol) of biphenyl diphenol, 221.8 g (1.016 mol) of 4,4'-difluorobenzophenone, 1 kg (798.7 mL) of diphenyl sulfone and 130 g (1.227 mol) of sodium carbonate were mixed and added into a three-necked flask equipped with an argon inlet, a mechanical stirrer and a water collector. The mixture was mechanically stirred for degassing for 1 h, and then the temperature was raised to 230°C. The water generated by the reaction was removed from the reaction system by using xylene. The temperature was maintained for 1 h. The temperature was further raised to 280°C for polymerization for 1 h. The temperature was then raised to 310°C, and 2.2 g of 4,4'-difluorobenzophenone was added for end-capping. The end-capping time was 0.5 h.

[0116] (2) The end-capping product solution is continuously stirred in deionized water to precipitate the product into filaments, and the precipitates are crushed, washed and dried in sequence; the washing is performed by washing in deionized water for 8 times and in ethanol for 8 times, and the drying is performed by drying in a vacuum oven at 140° C. for 12 hours to obtain an in-situ copolymerized modified polyaryletherketone having a melt index of 62 g / 10 min.

[0117] (3) 180 g of in-situ copolymerized modified polyaryletherketone and 20 g of carbon fiber (length greater than 6 mm, diameter 7 μm) were melt-extruded in a twin-screw extruder, including three heating zones, zone 1, zone 2 and zone 3, wherein the temperature of zone 1 was 320° C., the temperature of zone 2 was 360° C., the temperature of zone 3 was 360° C., and the extrusion speed was 30 rpm. The extruded product was granulated to obtain a granular interlayer reinforced composite material.

[0118] (4) After drying the interlayer reinforced composite material, it is melt-extruded, cooled and drawn in sequence, wherein the melt extrusion is carried out in a single-screw extruder, and the single-screw extruder includes three heating zones, namely zone one, zone two and zone three, wherein the temperature of zone one is 320°C, the temperature of zone two is 360°C, the temperature of zone three is 360°C, and the extrusion rotation speed is 10 rpm to obtain an interlayer reinforced composite wire.

[0119] (5) The interlayer reinforced composite material wire is 3D printed, wherein the 3D printing nozzle temperature is 420° C., the printing layer height is 0.2 mm, and the printing speed is 30 mm / s to obtain a 3D printed molded part.

[0120] Example 7

[0121] The preparation method of this embodiment is the same as that of embodiment 6, except that the amount of hydroquinone is adjusted to 0.95 mol and the amount of biphenol is adjusted to 0.05 mol.

[0122] Example 8

[0123] The preparation method of this embodiment is the same as that of embodiment 6, except that the amount of hydroquinone is adjusted to 0.995 mol and the amount of biphenol is adjusted to 0.005 mol.

[0124] Example 9

[0125] The preparation method of this embodiment is the same as that of embodiment 6, except that the amount of hydroquinone is adjusted to 0.5 mol and the amount of biphenol is adjusted to 0.5 mol.

[0126] Example 10

[0127] The preparation method of this embodiment is the same as that of Example 6, except that the amount of in-situ copolymerized modified polyaryletherketone is adjusted to 120 g, and the amount of carbon fiber is adjusted to 80 g.

[0128] Embodiment 11

[0129] The preparation method of this embodiment is the same as that of Example 6, except that the amount of in-situ copolymerized modified polyaryletherketone is adjusted to 140 g, and the amount of carbon fiber is adjusted to 60 g.

[0130] Example 12

[0131] The preparation method of this embodiment is the same as that of Example 6, except that the amount of in-situ copolymerized modified polyaryletherketone is adjusted to 198 g, and the amount of carbon fiber is adjusted to 2 g.

[0132] Comparison example

[0133] Commercially available carbon fiber polyetheretherketone composite wire (Dongguan Yuanzhu Intelligent Technology Co., Ltd., product model PEEK-CF, melt index of 20g / 10min, carbon fiber content of 10wt%) was used for 3D printing, and the printing method and parameters were the same as those in Example 1.

[0134] Test Example 1

[0135] The interlayer reinforced composite materials prepared in Example 1 and the comparative example were subjected to infrared testing. The results are as follows: Figure 1 As shown. Figure 1 It can be seen that the interlayer reinforced composite material prepared by the present invention has the same infrared absorption peak as polyetheretherketone.

[0136] Test Example 2

[0137] The interlayer reinforced composite material prepared in Example 1 was tested by differential scanning calorimetry (DSC), and the obtained DSC curve is as follows: Figure 2 As shown. Figure 2 It can be seen that the melting point of the composite material of Example 1 is 321° C., and the melting point of the composite material of the control example is 342° C. The interlayer reinforced composite material of Example 1 has a lower melting point and is easy to process.

[0138] Test Example 3

[0139] The tensile properties of the 3D printed parts of Example 1 and the control example were tested along the printing direction (X-axis direction) according to the test method: GB / T 1040.2-2006. The results are as follows: Figure 3 As shown. Figure 3 It can be seen that the tensile strength of the 3D printed molded part prepared in Example 1 in the X-axis direction is 133 MPa, while the tensile strength of the 3D printed molded part of the control example in the X-axis direction is only 90 MPa.

[0140] Test Example 4

[0141] The 3D printed parts prepared in Example 1 and the control example were subjected to a tensile property test (interlayer performance) in the vertical printing direction (Z-axis direction) according to the test method: GB / T 1040.2-2006. The results are as follows: Figure 4 As shown. Figure 4It can be seen that the tensile strength of the 3D printed molded part prepared in Example 1 in the Z-axis direction is 20 MPa, while the tensile strength of the 3D printed molded part in the control example in the Z-axis direction is only 6.8 MPa. Example 1 has higher interlayer strength, which is increased by nearly 300% compared with the control example.

[0142] Test Example 5

[0143] The extrusion and 3D printing of raw materials are both carried out under high temperature conditions, requiring the material to have good thermal stability. The interlayer reinforced composite material prepared in Example 1 was subjected to thermogravimetric analysis. The test method was: the temperature range was 100-800°C, the heating rate was 10°C / min, and the test was carried out in an air atmosphere. The results are as follows: Figure 5 As shown. Figure 5 It can be seen that the interlayer reinforced composite material prepared by the present invention has a polymer decomposition of 1.2% below 500° C., which proves that it has good thermal stability in an air atmosphere and can meet the high temperature resistance requirements of wire extrusion and 3D printing.

[0144] The test results of the interlaminar reinforced composite materials prepared in Examples 2 to 12 are similar to those in Example 1.

[0145] It can be seen from the above embodiments that the interlayer reinforced composite material provided by the present invention has a lower melting point, reduces the processing temperature, has good processing performance and mechanical properties, and has good high temperature resistance. It basically does not decompose at 500°C, has excellent comprehensive performance, and can be used as a 3D printing material in FDM 3D printing and other fields.

[0146] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. An interlayer reinforced composite material, characterized in that: The preparation is obtained by including the following raw materials in parts by weight: 60-99.9 parts of in-situ copolymerized modified polyaryletherketone; Fiber reinforced filler 0.1 to 40 parts; The structural unit of the in-situ copolymerized modified polyaryletherketone comprises a first structural unit and a second structural unit; the first structural unit accounts for 50% to 99.5%; the structure of the first structural unit is shown in Formula I, and the structure of the second structural unit is shown in Formula II: In Formula I, the structure of Ar1 is as shown in Formula 1-1 or Formula 1-2; in Formula II, the structure of Ar2 is as shown in Formula 2-1, Formula 2-2, Formula 2-3, Formula 2-4, Formula 2-5 or Formula 2-6:

2. The interlayer reinforced composite material according to claim 1, characterized in that: The melt index of the in-situ copolymerized modified polyaryletherketone is 10 to 150 g / 10 min.

3. The interlayer reinforced composite material according to claim 1 or 2, characterized in that: The fiber-reinforced filler includes one or more of carbon fiber and glass fiber; the fiber-reinforced filler has a length of more than 6 mm and a diameter of 7 μm.

4. The method for preparing the interlayer reinforced composite material according to any one of claims 1 to 3, characterized in that: The following steps are involved: The in-situ copolymerized modified polyaryletherketone and the fiber-reinforced filler are melt-extruded to obtain the interlayer reinforced composite material.

5. The preparation method according to claim 4, characterized in that: The preparation method of the in-situ copolymerization modified polyaryletherketone comprises the following steps: mixing 4,4'-difluorobenzophenone, a first monomer, a second monomer, a catalyst, a water-carrying agent and an organic solvent to carry out azeotropic water-carrying, removing the water-carrying agent and polymerization reaction; the first monomer comprises one or more of 4,4'-dihydroxybenzophenone and hydroquinone; and the second monomer is a polyphenyl ring bisphenol monomer.

6. The preparation method according to claim 4, characterized in that: The melt extrusion includes sequentially performing first heating, second heating, third heating and extrusion; the temperature of the first heating is 290-330°C; the temperature of the second heating is 330-380°C; the temperature of the third heating is 330-380°C.

7. The preparation method according to claim 4 or 6, characterized in that: After the melt extrusion, the method further comprises heat treating the extrudate obtained; the heat treatment temperature is 100 to 200° C., and the heat preservation time is 4 to 12 hours.

8. Use of the interlayer reinforced composite material according to any one of claims 1 to 3 or the interlayer reinforced composite material obtained by the preparation method according to any one of claims 4 to 7 as a 3D printing material.

9. The use according to claim 8, characterized in that: The application method comprises the following steps: sequentially melting, extruding, cooling, drawing and 3D printing the interlayer reinforced composite material to obtain a 3D printed molded part.

10. The use according to claim 9, characterized in that: The 3D printing process also includes annealing the obtained product.

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