3D photocuring printing ink, preparation method and application thereof, polyether-ether-ketone composite material and application thereof

Abstract

The invention belongs to the technical field of lubricating materials, and particularly relates to 3D photocuring printing ink, a preparation method and application thereof, a polyether-ether-ketone composite material and application thereof. The 3D photocuring printing ink provided by the invention is prepared from the following components in parts by mass: 40 to 80 parts of photosensitive polyether-ether-ketone oligomer, 30 to 40 parts of reactive diluent, 10 to 20 parts of active cross-linking agent, 5 to 10 parts of solid lubricating additive, 5 to 10 parts of liquid lubricating additive, 1 to 2 parts of photoinitiator, 2 to 5 parts of wetting agent and 0.5 to 3 parts of organic solvent, the photosensitive polyether-ether-ketone oligomer has a structure as shown in a formula 1. The number-average molecular weight of the photosensitive polyether-ether-ketone oligomer is 200 to 20000 g / mol. The composite material with good mechanical strength and low friction coefficient can be obtained through printing under the combined action of all the components.

Description

Technical Field

[0001] This invention belongs to the field of lubricating materials technology, specifically relating to a 3D photocurable printing ink and its preparation method and application, and a polyether ether ketone composite material and its application. Background Technology

[0002] Friction and wear are ubiquitous phenomena. Mechanical parts and equipment can suffer serious accidents due to lubrication failure or excessive wear, and friction and wear also cause economic losses. Currently, the main methods to reduce friction and wear are adding lubricants to materials or forming a lubricating layer on the material surface.

[0003] Photopolymer 3D printing is an additive manufacturing technology based on the selective curing of liquid photosensitive resins under ultraviolet light. It achieves the molding of complex three-dimensional structures through layer-by-layer curing and has advantages such as rapid curing, low energy consumption, and high-precision molding. However, existing methods for reducing friction and wear are difficult to directly apply to photopolymer 3D printing materials; existing photopolymer 3D printing materials generally suffer from poor tribological properties (friction coefficient > 0.6 under 10N load). Summary of the Invention

[0004] In view of this, the present invention provides a 3D photocurable printing ink and its preparation method and application, a polyetheretherketone composite material and its application. The polyetheretherketone composite material printed using the 3D photocurable printing ink provided by the present invention has good mechanical properties and a low coefficient of friction.

[0005] To address the aforementioned technical problems, this invention provides a 3D photopolymerizable printing ink, comprising the following components in parts by weight:

[0006]

[0007] The photosensitive polyetheretherketone oligomer has the structure shown in Formula 1:

[0008]

[0009] Formula 1; the number average molecular weight of the photosensitive polyether ether ketone oligomer is 200-20000 g / mol.

[0010] Preferably, the solid lubricant additive includes one or more of polytetrafluoroethylene, silicon dioxide, titanium dioxide, carbon nanotubes, carbon fibers, and fluorinated graphite.

[0011] Preferably, the liquid lubricant additive includes one or more of polyalphaolefin lubricating oil, ultra-high molecular weight polyethylene, perfluoropolyether lubricating oil, dimethyl silicone oil, and supramolecular gel;

[0012] The viscosity of the liquid lubricant additive is 100–3000 cps.

[0013] Preferably, the reactive diluent includes one or more of N-vinylpyrrolidone, N,N-dimethylacrylamide, and polyethylene glycol diacrylate;

[0014] The active crosslinking agent includes ethoxylated trimethylolpropane triacrylate and / or triacrylate phosphate;

[0015] The photoinitiator includes one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and 2-isopropylthioxanthrone.

[0016] The organic solvent includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide;

[0017] The wetting agent includes oily wetting agents from the BYK series; the oily wetting agents from the BYK series include BYK-306, BYK-307, BYK-1160, BYK-1165 or BYK-W909.

[0018] This invention also provides a method for preparing the 3D photopolymer printing ink described in the above technical solution, comprising the following steps:

[0019] The photosensitive polyether ether ketone oligomer, reactive diluent, reactive crosslinking agent and organic solvent are first mixed to obtain a first mixture;

[0020] A second mixture is obtained by adding a solid lubricating additive to the first mixture.

[0021] A third mixture is obtained by adding a liquid lubricant additive to the second mixture.

[0022] A fourth mixture is prepared by sequentially adding an initiator and a wetting agent to the third mixture to obtain the 3D photocurable printing ink.

[0023] The present invention also provides the application of the 3D photopolymerization printing ink described in the above technical solution in the preparation of polyetheretherketone composite materials.

[0024] The present invention also provides a polyetheretherketone composite material, which is prepared by the following method:

[0025] A blank is obtained by 3D photopolymerization printing using 3D photopolymerization printing ink; the 3D photopolymerization printing ink is the 3D photopolymerization printing ink described in the above technical solution.

[0026] The preform is heat-treated to obtain the polyetheretherketone composite material.

[0027] Preferably, the conditions for 3D photopolymerization printing include: the light source is ultraviolet light, and the light source power is 2000–7000 mW / cm². 2 The thickness of a single slice is 0.01–0.06 mm, and the exposure time for a single slice is 10–20 s.

[0028] The heat treatment is a stepped heating and holding process. The initial temperature of the stepped heating and holding process is 20-80℃, the final temperature of the stepped heating and holding process is 200-300℃, the temperature difference between two adjacent holding processes is 10-50℃, the holding time of each holding process is 0.5-5h, and the heating rate of the stepped heating and holding process is 1-5℃ / min.

[0029] Preferably, the coefficient of friction is 0.03 to 0.05.

[0030] This invention also provides the application of the polyetheretherketone composite material described above in the fields of aerospace, high-end equipment manufacturing, and microelectronics.

[0031] This invention provides a 3D photocurable printing ink, comprising the following components in parts by weight: 40-80 parts of photosensitive polyether ether ketone oligomer, 30-40 parts of reactive diluent, 10-20 parts of reactive crosslinking agent, 5-10 parts of solid lubricant additive, 5-10 parts of liquid lubricant additive, 1-2 parts of photoinitiator, 2-5 parts of wetting agent, and 0.5-3 parts of organic solvent; wherein the photosensitive polyether ether ketone oligomer has the structure shown in Formula 1:

[0032] Formula 1; the number-average molecular weight of the photosensitive polyether ether ketone oligomer is 200–20000 g / mol. This invention uses the compound with the structure shown in Formula 1 as the main component. This invention simultaneously adds solid and liquid lubricant additives to the 3D photocurable printing ink. The solid lubricant additive fixes the liquid lubricant additive, allowing it to be uniformly dispersed without phase separation. Simultaneously, the lubricant improves the dispersibility of the solid lubricant additive in the photosensitive polyether ether ketone oligomer, preventing sedimentation. Using the 3D photocurable printing ink provided by this invention to print composite materials improves the friction resistance of the printed material. Through the combined action of the components, this invention can print composite materials with good mechanical strength and a low coefficient of friction.

[0033] The coefficient of friction of the composite material formed by printing with the 3D photopolymerization printing ink provided by this invention is 0.032 to 0.05. Attached Figure Description

[0034] Figure 1 The image shows the actual product of the polyetheretherketone composite material (lubricated joint) prepared in Example 3.

[0035] Figure 2 A photograph of the polyetheretherketone composite material (lubricated gear) prepared in Example 4;

[0036] Figure 3 The friction coefficient curves of the polyetheretherketone composite materials of Examples 1-4 and Comparative Example 1 are shown.

[0037] Figure 4 This is a thermal decomposition curve of the polyetheretherketone composite material in Example 2;

[0038] Figure 5 The graph shows the thermal decomposition curve of the polyetheretherketone composite material in Example 4. Detailed Implementation

[0039] This invention provides a 3D photopolymerizable printing ink, comprising the following components in parts by weight:

[0040]

[0041] The photosensitive polyetheretherketone oligomer has the structure shown in Formula 1:

[0042]

[0043] Formula 1; the number average molecular weight of the photosensitive polyether ether ketone oligomer is 200-20000 g / mol.

[0044] The 3D photopolymer printing ink provided by this invention comprises 40-80 parts of photosensitive polyether ether ketone oligomer, specifically 45, 50, 55, 60, 65, 70, 75, or 80 parts by weight. In this invention, the number average molecular weight of the photosensitive polyether ether ketone oligomer is 200-20000 g / mol, specifically 500-10000 g / mol, or 2000-8000 g / mol, specifically 1000 g / mol, 2000 g / mol, 3000 g / mol, 5000 g / mol, 6000 g / mol, or 8000 g / mol. In this invention, the photosensitive polyether ether ketone oligomer has good solubility in reactive diluents and reactive crosslinking agents, and the reactive double bonds contained in the molecular structure of the photosensitive polyether ether ketone oligomer serve as photosensitive groups that can be rapidly photocured; moreover, the photosensitive polyether ether ketone oligomer has excellent solubility in reactive diluents, reactive crosslinking agents, and organic solvents.

[0045] Based on the mass fraction of photosensitive polyetheretherketone oligomer, the 3D photocurable printing ink provided by this invention comprises 30-40 parts of reactive diluent, specifically 30, 35, or 40 parts. In one specific embodiment of this invention, the reactive diluent may include one or more of N-vinylpyrrolidone, N,N-dimethylacrylamide, and polyethylene glycol diacrylate, specifically N-vinylpyrrolidone, N,N-dimethylacrylamide, or polyethylene glycol diacrylate. In embodiments of this invention, the reactive diluent may be a mixture of 25 parts N-vinylpyrrolidone and 5 parts polyethylene glycol diacrylate, a mixture of 20 parts N-vinylpyrrolidone and 10 parts polyethylene glycol diacrylate, or N-vinylpyrrolidone. In another specific embodiment of this invention, the weight-average molecular weight of the polyethylene glycol diacrylate may be 500-700 g / mol, specifically 600 g / mol. The present invention adds an active diluent to 3D photopolymer printing ink to improve the moldability of 3D photopolymer printing ink and the flexibility of polyetheretherketone composite material.

[0046] Based on the mass fraction of photosensitive polyetheretherketone oligomer, the 3D photocurable printing ink provided by this invention includes 10-20 parts of an active crosslinking agent, specifically 10 parts, 15 parts, or 20 parts. As a specific embodiment of this invention, the active crosslinking agent may include ethoxylated trimethylolpropane triacrylate and / or triacrylate phosphate, specifically ethoxylated trimethylolpropane triacrylate or triacrylate phosphate. This invention, by introducing an active crosslinking agent, enables the printing material to possess excellent photosensitivity, increases the crosslinking density of the formed component during printing, thereby increasing the mechanical properties and heat resistance of the formed component. For polyetheretherketone composite materials, the introduction of the active crosslinking agent enhances the dispersibility of solid lubricant additives in the 3D photocurable printing ink; simultaneously, the crosslinked network formed by the active crosslinking agent after printing can lock the solid lubricant additives, ensuring their uniform dispersion, while guaranteeing excellent tribological behavior of the polyetheretherketone composite material.

[0047] Based on the mass fraction of photosensitive polyether ether ketone oligomer, the 3D photocurable printing ink provided by this invention includes 5 to 10 parts of solid lubricant additive, specifically 5, 8, or 10 parts. As a specific embodiment of this invention, the solid lubricant additive may include one or more of polytetrafluoroethylene, silica, titanium dioxide, carbon nanotubes, carbon fibers, and fluorinated graphite, specifically polytetrafluoroethylene, silica, titanium dioxide, carbon nanotubes, carbon fibers, or fluorinated graphite. In one specific embodiment of the present invention, the average particle size of the polytetrafluoroethylene can be 500 nm to 500 μm, or 1 to 400 μm, specifically 1 μm, 5 μm, 50 μm, or 100 μm; the average particle size of the silicon dioxide can be 20 to 500 nm, specifically 20 nm, 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, or 500 nm; the average particle size of the titanium dioxide can be 20 to 500 nm, specifically 20 nm, 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, or 500 nm. The average length of the carbon nanotubes can be 50-500 nm, specifically 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, or 500 nm; the average length of the carbon fibers can be 100-300 μm, specifically 100 μm, 150 μm, 200 μm, 250 μm, or 300 μm; the average particle size of the fluorinated graphite can be 100 nm-1 μm, or 200-800 nm, specifically 200 nm, 300 nm, 500 nm, 600 nm, or 700 nm. In this invention, the solid lubricant additive has good compatibility and dispersibility with the photosensitive polyether ether ketone oligomer. Furthermore, by selecting solid lubricant additives with specific shapes and sizes, this invention can improve the dispersibility of the solid lubricant additive in the system and simultaneously improve the wear resistance of the printed polyether ether ketone composite material.

[0048] Based on the mass fraction of photosensitive polyether ether ketone oligomer, the 3D photocurable printing ink provided by this invention includes 5 to 10 parts of liquid lubricant additive, specifically 5, 6, 8, or 10 parts. As a specific embodiment of this invention, the liquid lubricant additive may include one or more of polyalphaolefin lubricating oil, ultra-high molecular weight polyethylene, perfluoropolyether lubricating oil, dimethyl silicone oil, and supramolecular gel, specifically polyalphaolefin lubricating oil, ultra-high molecular weight polyethylene, perfluoropolyether lubricating oil, dimethyl silicone oil, or supramolecular gel; the polyalphaolefin lubricating oil may be ISO VG20; the viscosity of the liquid lubricant additive may be 100–3000 cps, or 500–2000 cps. Traditional oil-containing self-lubricating composite materials and devices are mainly formed into porous composite materials and devices through molding during sintering, and finally, liquid lubricant additives are impregnated in the porous structure through vacuum impregnation, thereby forming oil-containing lubricating materials and devices with liquid lubricant composites, thus reducing their friction and wear; however, the formation of continuous pores greatly reduces the mechanical properties of the composite materials and devices. This invention combines the advantages of additive manufacturing technology with photocuring 3D polyetheretherketone composite materials. It directly introduces liquid lubricating additives into a liquid photosensitive system, thereby preparing self-lubricating solid / liquid lubricating composite materials and oil-lubricated devices with high oil content. Without reducing its mechanical properties, it greatly reduces the friction coefficient and wear rate of photosensitive polyetheretherketone self-lubricating composite materials, and realizes the integrated rapid manufacturing of complex, irregular and customized oil-lubricated composite materials.

[0049] Based on the mass fraction of the photosensitive polyether ether ketone oligomer, the 3D photocurable printing ink provided by this invention includes 1 to 2 parts of photoinitiator, specifically 1 part, 1.5 parts, or 2 parts. As a specific embodiment of this invention, the photoinitiator may include one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphine acid, and 2-isopropylthioxanthraphenone, specifically phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphine acid, or 2-isopropylthioxanthraphenone.

[0050] Based on the mass fraction of photosensitive polyether ether ketone oligomer, the 3D photocurable printing ink provided by this invention comprises 2 to 5 parts of wetting agent, specifically 2, 3, 4, or 5 parts. As a specific embodiment of this invention, the wetting agent may include oil-based wetting agents from the BYK series; the oil-based wetting agents from the BYK series may include BYK-306, BYK-307, BYK-1160, BYK-1165, or BYK-W909.

[0051] Based on the mass fraction of photosensitive polyetheretherketone oligomer, the 3D photocurable printing ink provided by this invention comprises 0.5 to 3 parts of organic solvent, specifically 1 part, 2 parts, or 3 parts. As a specific embodiment of this invention, the organic solvent may include one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide, specifically N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, or dimethyl sulfoxide.

[0052] This invention also provides a method for preparing the 3D photopolymer printing ink described in the above technical solution, comprising the following steps:

[0053] The photosensitive polyether ether ketone oligomer, reactive diluent, reactive crosslinking agent and organic solvent are first mixed to obtain a first mixture;

[0054] A second mixture is obtained by adding a solid lubricating additive to the first mixture.

[0055] A third mixture is obtained by adding a liquid lubricant additive to the second mixture.

[0056] A fourth mixture is prepared by sequentially adding an initiator and a wetting agent to the third mixture to obtain the 3D photocurable printing ink.

[0057] This invention involves first mixing a photosensitive polyether ether ketone oligomer, an reactive diluent, an reactive crosslinking agent, and an organic solvent to obtain a first mixture. As a specific embodiment of this invention, the first mixing method may include ball milling, ultrasonic dispersion, or mechanical stirring; this invention does not impose special limitations on the conditions for the first mixing, as long as uniform mixing is achieved. In one specific embodiment of the present invention, the rotational speed of the ball mill can be 100–5000 r / min, or 1000–3000 r / min, specifically 2000 r / min or 3000 r / min; the ball milling time can be 1–60 min, or 3–30 min, specifically 10 min, 15 min, 20 min, 25 min or 30 min; the ultrasonic dispersion power can be 10–1000 W, or 100–500 W; the ultrasonic dispersion time can be 30–60 min, or 35–50 min; the mechanical stirring rotational speed can be 1000–3000 r / min, or 1500–2000 r / min; the mechanical stirring time can be 10 min–10 h, or 3–5 h.

[0058] After obtaining the first mixture, the present invention adds a solid lubricating additive to the first mixture to obtain a second mixture. The present invention does not require any special treatment for the second mixture, as long as it can be mixed evenly.

[0059] After obtaining the second mixture, the present invention adds a liquid lubricant additive as a third mixture to the second mixture to obtain the third mixture. The present invention does not require any special third mixture, as long as it can be mixed evenly.

[0060] After obtaining the third mixture, the present invention sequentially adds an initiator and a wetting agent to the third mixture as a fourth mixture to obtain the 3D photocurable printing ink. The present invention does not require any special fourth mixture, as long as it can be mixed evenly.

[0061] As a specific embodiment of the present invention, the fourth mixing may further include: degassing the fourth mixed system; the degassing may be vacuum degassing, the temperature of the vacuum degassing may be 30-100℃, or 50-80℃; the time of the vacuum degassing may be 5-60 min, or 10-30 min; the present invention has no special requirements on the vacuum degree of the vacuum degassing, as long as the vacuum conditions are met.

[0062] The present invention also provides the application of the 3D photopolymerization printing ink described in the above technical solution in the preparation of polyetheretherketone composite materials.

[0063] The present invention also provides a polyetheretherketone composite material, which is prepared by the following method:

[0064] A blank is obtained by 3D photopolymerization printing using 3D photopolymerization printing ink; the 3D photopolymerization printing ink is the 3D photopolymerization printing ink described in the above technical solution.

[0065] The preform is heat-treated to obtain the polyetheretherketone composite material.

[0066] This invention utilizes 3D photopolymer printing ink for 3D photopolymer printing to obtain a blank. As a specific embodiment of this invention, the conditions for 3D photopolymer printing may include: the light source is ultraviolet light with a wavelength of 400–410 nm, and the power of the light source is 2000–7000 mW / cm². 2 The thickness of a single-layer slice is 0.01–0.06 mm, and the exposure time for a single layer is 10–20 s; alternatively, the ultraviolet light wavelength is 405 nm, and the power of the light source is 3000–5000 mW / cm². 2The thickness of a single-layer slice is 0.03–0.05 mm, and the exposure time for a single layer is 15–20 s. As a specific embodiment of the present invention, the photopolymerization 3D printing method may include stereolithography (SLA), digital light processing (DLP), liquid crystal display (LCD), or direct writing printing (DIW).

[0067] In one specific embodiment of the present invention, the 3D photopolymerization printing process may further include cleaning the structure after 3D photopolymerization printing. In another specific embodiment of the present invention, the cleaning may be ultrasonic cleaning or solvent cleaning; the present invention does not specifically limit the operation of ultrasonic cleaning and solvent cleaning, as long as ultrasonic cleaning and solvent cleaning well known to those skilled in the art can completely remove residual ink from the surface of the printed part.

[0068] After obtaining the preform, the present invention heat-treats the preform to obtain the polyetheretherketone composite material. In one specific embodiment of the present invention, the heat treatment can be a stepped heating and holding process. The initial temperature of the stepped heating and holding process can be 20–80°C, specifically 20°C, 50°C, 60°C, or 80°C; the ending temperature of the stepped heating and holding process is 200–300°C, specifically 200°C, 250°C, or 300°C; the temperature difference between two adjacent holding processes is 10–50°C, specifically 20°C, 25°C, 30°C, or 40°C; the holding time for each holding process is 0.5–5 hours, specifically 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours; the heating rate of the stepped heating and holding process is 1–5°C / min, specifically 1°C / min, 1.5°C / min, 2°C / min, or 5°C / min. This invention enhances the overall performance of polyetheretherketone (PEEK) composite materials through heat treatment and allows liquid lubricant additives to grow on the structural surface, thereby reducing the coefficient of friction of PEEK composite materials and improving their friction resistance.

[0069] In one specific embodiment of the present invention, the heat treatment may further include: sequentially cooling and post-treatment the heat-treated product; the temperature after cooling can be room temperature, which can be 20–35°C, or 25–30°C; the cooling method can be natural cooling; the post-treatment may include one or more of polishing, ultrasonic cleaning, and ethanol cleaning. The present invention does not specifically limit the polishing or ultrasonic cleaning operation, as long as it can make the surface of the heat-treated product flat, smooth, and clean.

[0070] This invention introduces solid and liquid lubricating additives into photosensitive 3D printed polyether ether ketone composite materials. By employing preparation processes and the selection and synergistic combination of additives, it solves technical problems such as the dispersibility of solid lubricating additives, the formability of composite materials, and post-processing. After molding and post-processing using photopolymerization 3D printing technology, the resulting composite components possess excellent lubricity, high temperature resistance, mechanical strength, and molding accuracy.

[0071] This invention utilizes the synergistic effect of solid and liquid lubricating additives to significantly reduce the friction coefficient and wear rate of composite materials without compromising the overall performance of the base material. It achieves integrated rapid prototyping of photopolymer 3D printed polyetheretherketone composite parts with high forming accuracy, lubricity, high temperature resistance, mechanical strength, and dimensional stability. While ensuring high tensile strength (>80MPa) and thermal decomposition temperature (>400℃), the friction coefficient is reduced to below 0.05.

[0072] As a specific embodiment of the present invention, the coefficient of friction of the polyetheretherketone composite material can be 0.03 to 0.05, specifically 0.042, 0.043, 0.046 or 0.048.

[0073] This invention also provides applications of the polyetheretherketone (PEEK) composite materials described above in aerospace, high-end equipment, precision machinery, and microelectronics. The 3D printing method provided by this invention is suitable for manufacturing customized, miniature, precision, irregularly shaped, thin-walled, and self-lubricating PEEK composite components, which can be widely used in aerospace, high-end equipment, precision machinery, microelectronics, nuclear energy, and deep space exploration.

[0074] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0075] Example 1

[0076] Sixty parts of photosensitive polyether ether ketone oligomer with the structure shown in Formula 1 (number average molecular weight of about 3000 g / mol), reactive diluent (25 parts of N-vinylpyrrolidone, 5 parts of polyethylene glycol diacrylate with a weight average molecular weight of about 600 g / mol), 10 parts of reactive crosslinking agent ethoxylated trimethylolpropane triacrylate and 3 parts of organic solvent N,N-dimethylformamide were added to a ball mill jar and ball milled for 10 min at a speed of 3000 r / min to obtain the first mixture.

[0077] Add 5 parts of solid lubricant polytetrafluoroethylene (average particle size of about 5 μm) to the first mixture and ball mill at a speed of 3000 r / min for 10 min to obtain the second mixture;

[0078] Add 5 parts of liquid lubricant dimethyl silicone oil to the second mixture, and ball mill at a speed of 3000 r / min for 10 min to obtain the third mixture;

[0079] Two parts of photoinitiator phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and three parts of wetting agent BYK-306 were added to the third mixture. The mixture was ball-milled at a speed of 3000 r / min for 10 min and then degassed in a vacuum oven at 50℃ for 30 min to obtain 3D photocurable printing ink.

[0080] DLP printing was performed using 3D photopolymer ink with the following parameters: light source wavelength of 405nm, light source intensity of 3000mW / cm2, single-layer exposure time of 15s, and single-layer slice thickness of 0.05mm. After printing, the printed part was removed and ultrasonically cleaned to remove residual 3D photopolymer ink from the surface. Then, it underwent heat treatment. The heat treatment process was as follows: heating to 80℃ and holding for 5 hours, then heating to 100℃ and holding for 2 hours, then heating to 125℃ and holding for 2 hours, then heating to 150℃ and holding for 2 hours, then heating to 175℃ and holding for 2 hours, and then heating to 200℃ and holding for 4 hours, with a heating rate of 2℃ / min. After natural cooling to room temperature (25℃), the surface was polished and cleaned with ethanol. After drying, a polyetheretherketone composite material was obtained.

[0081] Example 2

[0082] 50 parts of photosensitive polyether ether ketone oligomer with the structure shown in Formula 1 (number average molecular weight of about 8000 g / mol), 30 parts of reactive diluent N-vinylpyrrolidone, 10 parts of reactive crosslinking agent triacrylate phosphate and 3 parts of organic solvent N,N-dimethylformamide were added to a ball mill jar and ball milled for 20 min at a speed of 3000 r / min to obtain the first mixture.

[0083] Five parts of solid lubricant carbon nanotubes (average length 200 nm) were added to the first mixture and ball-milled at a speed of 3000 r / min for 20 min to obtain the second mixture.

[0084] Add 5 parts of liquid lubricant additive polyalphaolefin lubricating oil (ISO VG20) to the second mixture, and ball mill at a speed of 3000 r / min for 20 min to obtain the third mixture;

[0085] Add 1.5 parts of photoinitiator phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 5 parts of wetting agent BYK-1160 to the third mixture, ball mill at 3000 r / min for 20 min, and degas in a vacuum oven at 50℃ for 30 min to obtain 3D photocurable printing ink.

[0086] DLP printing was performed using 3D photopolymer ink with the following parameters: light source wavelength of 405nm, light source intensity of 2500mW / cm2, single-layer exposure time of 20s, and single-layer slice thickness of 0.03mm. After printing, the printed part was removed and ultrasonically cleaned to remove residual 3D photopolymer ink from the surface. Then, it underwent heat treatment. The heat treatment process was as follows: heating to 80℃ and holding for 5 hours, then heating to 100℃ and holding for 3 hours, then heating to 125℃ and holding for 3 hours, then heating to 150℃ and holding for 1 hour, then heating to 175℃ and holding for 2 hours, and then heating to 200℃ and holding for 5 hours, with a heating rate of 1℃ / min. After natural cooling to room temperature (25℃), the surface was polished and cleaned with ethanol. After drying, a polyetheretherketone composite material was obtained.

[0087] Example 3

[0088] 55 parts of photosensitive polyether ether ketone oligomer with the structure shown in Formula 1 (number average molecular weight of about 5000 g / mol), 30 parts of reactive diluent N-vinylpyrrolidone, 10 parts of reactive crosslinking agent ethoxylated trimethylolpropane triacrylate and 2 parts of organic solvent N,N-dimethylformamide were added to a ball mill jar and ball milled for 30 min at a speed of 3000 r / min to obtain the first mixture.

[0089] Add 5 parts of solid lubricant silica (average particle size 20nm) to the first mixture and ball mill at a speed of 3000r / min for 30min to obtain the second mixture;

[0090] Ten parts of liquid lubricant additive supramolecular gel lubricant were added to the second mixture, and the mixture was ball-milled at a speed of 3000 r / min for 310 min to obtain the third mixture.

[0091] Two parts of photoinitiator phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and three parts of wetting agent BYK-1160 were added to the third mixture. The mixture was ball-milled at a speed of 3000 r / min for 30 min and then degassed in a vacuum oven at 50℃ for 30 min to obtain 3D photocurable printing ink.

[0092] DLP printing was performed using 3D photopolymer ink with the following parameters: light source wavelength of 405nm, light source intensity of 5000mW / cm2, single-layer exposure time of 20s, and single-layer slice thickness of 0.05mm. After printing, the printed part was removed and ultrasonically cleaned to remove residual 3D photopolymer ink from the surface. Then, it underwent heat treatment. The heat treatment process was as follows: heating to 80℃ and holding for 3h, then heating to 100℃ and holding for 3h, then heating to 125℃ and holding for 3h, then heating to 150℃ and holding for 3h, then heating to 175℃ and holding for 2h, and then heating to 200℃ and holding for 4h, with a heating rate of 1.5℃ / min. After natural cooling to room temperature (25℃), the surface was polished and cleaned with ethanol. After drying, a polyetheretherketone composite material was obtained.

[0093] Example 4

[0094] 50 parts of photosensitive polyether ether ketone oligomer with the structure shown in Formula 1 (number average molecular weight of about 6000 g / mol), reactive diluent (20 parts of N-vinylpyrrolidone, 10 parts of polyethylene glycol diacrylate with a weight average molecular weight of about 600 g / mol), 10 parts of reactive crosslinking agent triacrylate phosphate and 3 parts of organic solvent N,N-dimethylformamide were added to a ball mill jar and ball milled at a speed of 3000 r / min for 30 min to obtain the first mixture;

[0095] Add 10 parts of solid lubricant titanium dioxide (average particle size of 100 nm) to the first mixture and ball mill at a speed of 3000 r / min for 30 min to obtain the second mixture;

[0096] Add 10 parts of liquid lubricant additive polyalphaolefin lubricating oil (ISO VG20) to the second mixture, and ball mill at a speed of 3000 r / min for 30 min to obtain the third mixture;

[0097] Two parts of photoinitiator phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and five parts of wetting agent BYK-307 were added to the third mixture. The mixture was ball-milled at a speed of 3000 r / min for 30 min and then degassed in a vacuum oven at 50℃ for 30 min to obtain 3D photocurable printing ink.

[0098] DLP printing was performed using 3D photopolymer ink with the following parameters: light source wavelength of 405nm, light source intensity of 3000mW / cm2, single-layer exposure time of 20s, and single-layer slice thickness of 0.03mm. After printing, the printed part was removed and ultrasonically cleaned to remove residual 3D photopolymer ink from the surface. Then, it underwent heat treatment. The heat treatment process was as follows: heating to 80℃ and holding for 3h, then heating to 100℃ and holding for 4h, then heating to 125℃ and holding for 3h, then heating to 150℃ and holding for 4h, then heating to 175℃ and holding for 4h, and then heating to 200℃ and holding for 6h, with a heating rate of 1℃ / min. After natural cooling to room temperature (25℃), the surface was polished and cleaned with ethanol. After drying, a polyetheretherketone composite material was obtained.

[0099] Comparative Example 1

[0100] Sixty parts of photosensitive polyether ether ketone oligomer with the structure shown in Formula 1 (number average molecular weight of about 8000 g / mol), reactive diluent (30 parts of N-vinylpyrrolidone, 10 parts of polyethylene glycol diacrylate with a weight average molecular weight of about 600 g / mol), 2 parts of photoinitiator phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 20 parts of organic solvent N,N-dimethylformamide were added to a ball mill jar and ball milled for 30 min at a speed of 3000 r / min to obtain 3D photocurable printing ink.

[0101] DLP printing was performed using 3D photopolymer ink with the following parameters: light source wavelength of 405nm, light source intensity of 2000mW / cm2, single-layer exposure time of 8s, and single-layer slice thickness of 0.075mm. After printing, the printed part was removed and ultrasonically cleaned to remove residual 3D photopolymer ink from the surface. Then, it underwent heat treatment. The heat treatment process was as follows: heating to 80℃ and holding for 5 hours, then heating to 100℃ and holding for 2 hours, then heating to 125℃ and holding for 2 hours, then heating to 150℃ and holding for 2 hours, then heating to 175℃ and holding for 4 hours, and then heating to 200℃ and holding for 4 hours, with a heating rate of 2℃ / min. After natural cooling to room temperature (25℃), the surface was polished and cleaned with ethanol. After drying, a polyetheretherketone composite material was obtained.

[0102] Figure 1 This is a photograph of the polyetheretherketone composite material (lubricated joint) prepared in Example 3. Figure 2 This is a physical image of the polyetheretherketone composite material (lubricated gear) prepared in Example 4.

[0103] The performance of the polyetheretherketone composite materials printed in Examples 1-4 and Comparative Example 1 was tested according to the following methods, and the results are listed in Table 1: thermal decomposition temperature GB / T 27761-2011; glass transition temperature GB / T 19466.1-2004; tensile strength and elastic modulus GB / T1040-1992; printing accuracy was mainly tested by the printing layer thickness; friction test was carried out using a reciprocating friction testing machine, and the test conditions were: load of 10N, frequency of 1Hz, time of 1800s, and friction pair of GCr15 steel ball with a diameter of 6mm.

[0104] Based on the friction test results, plot the friction coefficient curve, such as... Figure 3 As shown.

[0105] Plot the thermal decomposition curve based on the results of the thermal decomposition experiment, such as... Figures 4-5 As shown; Figure 4 This is a thermal decomposition curve of the polyetheretherketone composite material in Example 2. Figure 5 The graph shows the thermal decomposition curve of the polyetheretherketone composite material in Example 4.

[0106] Table 1 Performance parameters of photopolymer 3D printed parts from Examples 1-4 and Comparative Example 1

[0107]

[0108] Combining Table 1 and Figures 3-4 It is known that the polyetheretherketone composite material provided by the present invention has good mechanical properties, heat resistance (can be used for a long time at a temperature of 200℃), low coefficient of friction, good molding accuracy (optical accuracy less than 50μm), and excellent dimensional stability (dimensional shrinkage rate <1%).

[0109] Table 1 shows that Comparative Example 1, without the addition of solid or liquid lubricating additives, exhibits high mechanical properties and a high thermal decomposition temperature. In Examples 1-4, the introduction of liquid lubricating additives into the polyetheretherketone (PEEK) composites resulted in a slight decrease in mechanical properties and thermal decomposition temperature, but the reduction was within an acceptable range, and the achieved mechanical properties and heat resistance met the requirements for engineering applications. Importantly, the introduction of liquid lubricating additives significantly reduced the coefficient of friction of the composite lubricating materials and devices, providing a feasible solution for their friction requirements in harsh environments. This invention, through the combined action of its components, maintains good mechanical properties while achieving a low coefficient of friction in the PEEK composite material.

[0110] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A 3D photopolymer printing ink, characterized in that, The components include the following parts by weight: The photosensitive polyetheretherketone oligomer has the structure shown in Formula 1: Formula 1; the number average molecular weight of the photosensitive polyether ether ketone oligomer is 200-20000 g / mol.

2. The 3D photopolymer printing ink according to claim 1, characterized in that, The solid lubricant additive includes one or more of polytetrafluoroethylene, silicon dioxide, titanium dioxide, carbon nanotubes, carbon fibers, and fluorinated graphite.

3. The 3D photopolymer printing ink according to claim 1, characterized in that, The liquid lubricant additive includes one or more of polyalphaolefin lubricating oil, ultra-high molecular weight polyethylene, perfluoropolyether lubricating oil, dimethyl silicone oil, and supramolecular gel. The viscosity of the liquid lubricant additive is 100–3000 cps.

4. The 3D photopolymer printing ink according to claim 1, characterized in that, The reactive diluent includes one or more of N-vinylpyrrolidone, N,N-dimethylacrylamide and polyethylene glycol diacrylate; The active crosslinking agent includes ethoxylated trimethylolpropane triacrylate and / or triacrylate phosphate; The photoinitiator includes one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and 2-isopropylthioxanthrone. The organic solvent includes one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide; The wetting agent includes oily wetting agents from the BYK series; the oily wetting agents from the BYK series include BYK-306, BYK-307, BYK-1160, BYK-1165 or BYK-W909.

5. The method for preparing the 3D photopolymer printing ink according to any one of claims 1 to 4, characterized in that, Includes the following steps: The photosensitive polyether ether ketone oligomer, reactive diluent, reactive crosslinking agent and organic solvent are first mixed to obtain a first mixture; A second mixture is obtained by adding a solid lubricating additive to the first mixture. A third mixture is obtained by adding a liquid lubricant additive to the second mixture. A fourth mixture is prepared by sequentially adding an initiator and a wetting agent to the third mixture to obtain the 3D photocurable printing ink.

6. The use of the 3D photopolymerization printing ink according to any one of claims 1 to 4 in the preparation of polyetheretherketone composite materials.

7. A polyetheretherketone composite material, characterized in that, It was prepared according to the following method: A blank is obtained by 3D photocurable printing using 3D photocurable printing ink; wherein the 3D photocurable printing ink is the 3D photocurable printing ink according to any one of claims 1 to 4. The preform is heat-treated to obtain the polyetheretherketone composite material.

8. The polyetheretherketone composite material according to claim 7, characterized in that, The conditions for the 3D photopolymerization printing include: the light source is ultraviolet light, and the light source power is 2000–7000 mW / cm². 2 The thickness of a single slice is 0.01–0.06 mm, and the exposure time for a single slice is 10–20 s. The heat treatment is a stepped heating and holding process. The initial temperature of the stepped heating and holding process is 20-80℃, the final temperature of the stepped heating and holding process is 200-300℃, the temperature difference between two adjacent holding processes is 10-50℃, the holding time of each holding process is 0.5-5h, and the heating rate of the stepped heating and holding process is 1-5℃ / min.

9. The polyetheretherketone composite material according to claim 7 or 8, characterized in that, The coefficient of friction is 0.03 to 0.

05.

10. The application of the polyetheretherketone composite material according to any one of claims 7 to 9 in the fields of aerospace, high-end equipment manufacturing and microelectronics.

Images