CN113717377B - Amorphous polyaryletherketone (sulfone) 3D printing polymer and preparation and printing methods thereof - Google Patents
Amorphous polyaryletherketone (sulfone) 3D printing polymer and preparation and printing methods thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
- C08G65/405—(I) or (II) containing oxygen other than as phenol or carbonyl group in ring structure, e.g. phenolphtalein
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4031—(I) or (II) containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
Abstract
The invention discloses amorphous polyaryletherketone (sulfone) suitable for a 3D printing process and a preparation method thereof. Compared with crystalline resin, amorphous polyaryletherketone (sulfone) is easy to modify and has higher melt strength and better processability; the introduction of the cyano group can enhance intermolecular force so as to improve the interlayer strength of a 3D printing formed part, and solve the problems that the interlayer cohesiveness of the existing 3D printing crystalline polyaryletherketone is not strong and the modification is difficult due to the limitation of crystal lattices. By adjusting the proportion of the monomers and the end capping, polymers with different molecular weights and viscosities can be obtained, so that the fluidity of the resin is matched with the 3D printing process. The invention also prepares amorphous polyaryletherketone (sulfone) powder into a wire material, obtains a 3D printing sample through a fused deposition molding process, and enables the printed product to have higher strength and better performance by adjusting the printing speed and the bottom plate temperature.
Description
Technical Field
The invention discloses amorphous polyaryletherketone (sulfone), a preparation method and a 3D printing method, and belongs to the technical field of 3D printing materials.
Background
By virtue of the advantages of high forming speed, low cost, high precision and the like, the 3D printing technology is widely applied to the fields of aerospace, electronics and electrics, buildings, medical treatment and the like. The Fused Deposition Modeling (FDM) melts the thermoplastic wire through the high-temperature nozzle, and the thermoplastic wire is modeled layer by layer on the bottom plate, so that the Fused Deposition Modeling (FDM) is simple to operate, low in cost, high in raw material utilization rate and wide in source range, and becomes one of the most widely applied 3D printing processes. However, the maturity of usable 3D printing materials cannot keep pace with the development speed of the 3D printing market, and 3D printing materials are important factors that restrict the development of 3D printing technology, so that the development of novel and high-performance 3D printing materials becomes an important research direction.
The polyaryletherketone (sulfone) as a special engineering plastic has excellent mechanical and electrical properties, heat resistance, chemical corrosion resistance and good flame retardant property, and has wide application in the fields of aerospace, electronic information, national defense and military industry and the like. The cyano group has strong polarity, and the intermolecular force can be enhanced, so that the interlayer strength of the 3D printing formed part is improved. Polyether ether ketone (PEEK) is polyaryletherketone which is most widely applied in the field of 3D printing at present, is used as a semi-crystalline polymer, has excellent strength and better thermal stability and chemical stability, and is widely applied to the fields of medical treatment, automobiles and the like. However, the crystalline polyetheretherketone has low plasticity and poor toughness and dimensional stability.
CN 107756783A discloses a 3D printing PEEK repairing material secondary processing and shaping method, and adopts a controlled 3D printing method to manufacture a low-crystallinity PEEK raw material with high toughness and good plasticity, and improves the crystallinity and the strength of the material through post-treatment. CN 108424605A discloses a PEEK-MBA-PEI blend 3D printing material and a 3D printing forming method thereof, and the strength of a printed piece is enhanced to a certain extent by blending amorphous PEI. However, the interlayer adhesiveness of polyetheretherketone molded by fused deposition is difficult to satisfy the strength of a 3D printed molded article, and thus modification of polyetheretherketone is required to enhance the interlayer strength. However, in the process of modifying the crystal form of polyether-ether-ketone, the orderly arranged sequence structure of the polyether-ether-ketone is likely to be damaged, and the resin performance is influenced. Therefore, the development of amorphous poly (aryl ether ketone) (sulfone) which has no lattice restriction, is easy to modify, has high strength, and has good plasticity and dimensional stability is very important.
In order to solve the above problems, an amorphous poly (aryl ether ketone) (sulfone), a preparation method and a 3D printing method are proposed in the present application.
Disclosure of Invention
By adjusting the proportion of monomers and adding a blocking agent, the invention provides an amorphous polyaryletherketone (sulfone), a preparation method and a 3D printing method.
The invention provides amorphous polyaryletherketone (sulfone) 3D printing resin which is easy to modify and has higher melt strength and better processability compared with crystalline resin; the introduction of the cyano group can enhance intermolecular force so as to improve the interlayer strength of the 3D printing formed part. The molecular weight and viscosity of the polymer can be changed by adjusting the proportion and the end capping of the monomers in the synthesis process, so that the fluidity of the resin is matched with the 3D printing process. Based on the high-temperature fused deposition molding of special engineering plastics, the printed piece can have higher strength and better performance by adjusting the printing speed and the temperature of the bottom plate. The method is simple, easy to operate, available in raw materials and low in cost.
Drawings
FIG. 1 is a nuclear magnetic spectrum of amorphous polyaryletherketone prepared in example 1 of the present invention;
FIG. 2 is an IR spectrum of amorphous polyaryletherketone prepared in example 1 of the present invention;
FIG. 3 is an XRD diffraction pattern of amorphous polyaryletherketone prepared according to example 1 of the present invention, no diffraction signal is observed in the range of 5-40 deg., demonstrating that the polymer is amorphous structure.
Detailed Description
The invention provides an amorphous polyaryletherketone (sulfone) 3D printing polymer, wherein the structure of the polyaryletherketone and/or polyarylethersulfone polymer is shown as the formula (I):
wherein m + n =1, and m is more than or equal to 0, n ≧ 0, where m and n are mole percentages;
ar is selected from one or more than two of the following structures (a) to (d):
the X is selected from one or more than two of the following structures (A) or (B):
the invention also provides a preparation method of the amorphous polyaryletherketone (sulfone) 3D printing polymer, which comprises the following steps: heating bisphenol monomer, 2, 6-dichlorobenzonitrile (when the molar weight is 0, namely the monomer is not added), 4 '-dihalobenzophenone and/or 4,4' -dihalodiphenylsulfone, a capping agent, a catalyst and a water carrying agent in a solvent for reaction, firstly carrying out condensation reflux by using a condensing device with a water segregator, carrying out condensation reaction by using the water carrying agent to carry out water produced in the reaction process out of the reaction device, then heating and carrying out condensation polymerization reaction to obtain amorphous polyaryletherketone and/or amorphous polyarylethersulfone suitable for a 3D printing process;
the bisphenol monomer is selected from one or more than two of the following structures (1) to (4):
according to the invention, the 4,4' -dihalobenzophenone is 4,4' -difluorobenzophenone and/or 4,4' -dichlorobenzophenone; the 4,4' -dihalo diphenyl sulfone is 4,4' -difluoro diphenyl sulfone and/or 4,4' -dichloro diphenyl sulfone; the molar ratio of the total amount of the 4,4 '-dihalo benzophenone (and/or the 4,4' -dihalo diphenyl sulfone) and the 2, 6-dichlorobenzonitrile to the bisphenol monomer is 100 (90-110), preferably 100 (95-105); the molar ratio of the 4,4 '-dihalo diphenyl ketone and/or the 4,4' -dihalo diphenyl sulfone to the 2, 6-dichlorobenzonitrile is 10 (0-990), and preferably 10 (10-90).
According to the invention, the end-capping reagent is one or more than two of 4-fluorobenzophenone, 4-chlorobenzophenone, 4- (p-fluorobenzoyl) biphenyl, 4- (p-chlorobenzoyl) biphenyl, 4- (p-fluorobenzoyl) diphenyl ether and 4- (p-chlorobenzoyl) diphenyl ether; the molar ratio of the bisphenol monomer to the end-capping reagent is 100 (1-10), preferably 100 (2-5); the catalyst is anhydrous potassium carbonate and/or anhydrous sodium carbonate; the molar ratio of the bisphenol monomer to the catalyst is 10 (10-20), preferably 10 (12-15).
According to the invention, the solvent is sulfolane and/or dimethyl sulfoxide; the mass ratio of the monomer raw material to the solvent is 1 (1-20), preferably 1 (2-5); the water-carrying agent is toluene and/or xylene; the ratio of the mass of the solvent to the amount of the water-carrying agent is 10g (1-10) ml, preferably 10g (2-5) ml.
According to the invention, the temperature of the condensation reflux is 130-160 ℃, preferably 140-150 ℃; the reflux time is 2 to 5 hours, preferably 3 to 4 hours; the temperature of the polycondensation reaction is 150-230 ℃, preferably 200-210 ℃; the polycondensation reaction time is 2 to 10 hours, preferably 3 to 5 hours.
The invention also provides a 3D printing and forming method for 3D printing of the polymer by adopting the amorphous polyaryletherketone (sulfone), which is characterized by comprising the following steps:
the method comprises the following steps: melting and extruding the amorphous polyaryletherketone and/or polyarylethersulfone powder obtained by polymerization in a double screw, and obtaining a 3D printing special wire under the action of a traction device;
step two: drying the special 3D printing wire material in the step one for 12-24 h (preferably 24 h) at 120-150 ℃ (preferably 150 ℃), then performing fused deposition molding by discharging the wire through a high-temperature 3D printer nozzle, wherein the printing speed is 30-50 mm/s (preferably 40 mm/s), the printing layer thickness is 0.05-0.3 mm (preferably 0.2 mm), obtaining an amorphous polyaryletherketone and/or polyarylethersulfone 3D printing product on a printing bottom plate, and completing 3D printing molding.
According to the invention, in the first step, the melt extrusion temperature is 320-360 ℃ (preferably 330-350 ℃), and the screw rotation speed is 60-110 rpm (preferably 80-100 rpm); the diameter of the 3D printing special wire is 1.7-1.8 mm, and preferably 1.75mm.
In the second step, the temperature of the 3D printing bottom plate is 240-270 ℃, and preferably 250-260 ℃; the temperature of the 3D printing nozzle is 360-420 ℃, and is preferably 380-400 ℃.
The invention is described in further detail below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention, which can be embodied in many different forms and should be construed as being limited only by the claims set forth below.
Example 1
Adding phenolphthalein (the structure is shown in the above (1), the same below) (400 mmol), 2, 6-dichlorobenzonitrile (280 mmol), 4' -difluorobenzophenone (120 mmol), 4-fluorobenzophenone (12 mmol), potassium carbonate (480 mmol), sulfolane (600 g) and toluene (120 ml) into a three-neck flask, heating the mixture to 150 ℃ under nitrogen protection while stirring for azeotropic dehydration, refluxing at constant temperature for 3h to remove toluene and water, continuing heating to 210 ℃ for reaction for 3.5h, stopping heating, transferring reactants into a solution with the volume ratio of ethanol to water of 1 for precipitation, filtering and crushing the precipitate, repeatedly boiling with deionized water for 5 times to remove inorganic salts and residual solvents, and drying in a vacuum oven at 150 ℃ for 24h to obtain polymer powder with the structure of (II), wherein the structure is verified by nuclear magnetic spectrum and infrared spectrum.
Wherein m =0.7, n =0.3, and the number average molecular weight is 6.0 × 10 4 。
And (3) melting and extruding the powder obtained by polymerization in a double screw at 350 ℃, wherein the rotating speed of the screw is 100rpm, and obtaining the 3D printing special wire with the diameter of 1.75mm and uniform thickness under the action of a traction device. Drying the special wire material for 3D printing at 150 ℃ for 24h, then discharging the wire through a nozzle of a high-temperature 3D printer, carrying out fused deposition molding, wherein the nozzle temperature is 390 ℃, the printing speed is 40mm/s, the printing layer thickness is 0.2mm, the printing bottom plate temperature is 260 ℃, and obtaining an amorphous polyaryletherketone 3D printing product on the printing bottom plate to finish 3D printing molding.
FIG. 1 shows the NMR spectra of amorphous polyaryletherketones prepared according to example 1 of the present invention; FIG. 2 is an IR spectrum of amorphous polyaryletherketone prepared according to example 1 of the present invention; FIG. 3 is an XRD diffraction pattern of amorphous polyaryletherketone prepared according to example 1 of the present invention, no diffraction signal is observed in the range of 5-40 deg., demonstrating that the polymer is amorphous structure.
Example 2
Adding phenolphthalein (400 mmol), 2, 6-dichlorobenzonitrile (280 mmol), 4' -difluorobenzophenone (120 mmol), 4-fluorobenzophenone (15 mmol), potassium carbonate (480 mmol), sulfolane (600 g) and toluene (120 ml) into a three-neck flask, heating the mixture to 150 ℃ under the protection of nitrogen to remove water by azeotropic distillation while stirring, refluxing at constant temperature for 3h, removing toluene and water, continuing to heat to 205 ℃ for reaction for 3h, stopping heating, transferring the reaction product into a solution with a volume ratio of ethanol to water of 1 for precipitation, filtering and crushing the precipitate, repeatedly washing with deionized water for 5 times to remove inorganic salts and residual solvent, and drying at 150 ℃ for 24h in a vacuum oven to obtain a polymer powder with a structure (II) and a small viscosity (see table 1), wherein the number average molecular weight is 5.3 × 10 4 The structure is verified by nuclear magnetic hydrogen spectrum and infrared spectrum.
And (3) melting and extruding the powder obtained by polymerization in a double screw at 340 ℃, wherein the rotating speed of the screw is 100rpm, and obtaining the 3D printing special wire with the diameter of 1.75mm and uniform thickness under the action of a traction device. Drying the special wire material for 3D printing at 150 ℃ for 24h, then discharging the wire through a nozzle of a high-temperature 3D printer, carrying out fused deposition molding, wherein the temperature of the nozzle is 380 ℃, the printing speed is 40mm/s, the thickness of a printing layer is 0.2mm, the temperature of a printing bottom plate is 260 ℃, and obtaining an amorphous polyaryletherketone 3D printing product on the printing bottom plate to finish 3D printing molding.
Example 3
Phenolphthalein (400 mmol) was added to a three-necked flaskHeating the mixture to 150 ℃ under the protection of nitrogen, azeotropically removing water, refluxing at constant temperature for 3h, removing toluene and water, continuously heating to 200 ℃ for reaction for 3.5h, stopping heating, transferring the reactant into a solution with the volume ratio of ethanol to water being 1, precipitating, filtering and crushing the precipitate, repeatedly boiling and washing with deionized water for 5 times to remove inorganic salts and residual solvents, and drying at 150 ℃ in a vacuum oven for 24h to obtain polymer powder with the structure (II) and lower viscosity and better fluidity (see Table 1), wherein the number average molecular weight is 4.2 multiplied by 10, and the polymer powder has the structure (II) 4 The structure is verified by nuclear magnetic hydrogen spectrum and infrared spectrum.
And melting and extruding the powder obtained by polymerization in a double screw at 330 ℃ with the rotating speed of the screw being 100rpm, and obtaining the 3D printing special wire with the diameter of 1.75mm and uniform thickness under the action of a traction device. Drying the special wire material for 3D printing at 150 ℃ for 24h, then discharging the wire through a nozzle of a high-temperature 3D printer, carrying out fused deposition molding, wherein the temperature of the nozzle is 380 ℃, the printing speed is 40mm/s, the thickness of a printing layer is 0.2mm, the temperature of a printing bottom plate is 260 ℃, and obtaining an amorphous polyaryletherketone 3D printing product on the printing bottom plate to finish 3D printing molding.
Example 4
Adding bisphenol fluorene (400 mmol), 2, 6-dichlorobenzonitrile (280 mmol), 4' -difluorobenzophenone (120 mmol), 4-fluorobenzophenone (10 mmol), potassium carbonate (500 mmol), sulfolane (650 g) and toluene (150 ml) into a three-neck flask, heating the mixture to 150 ℃ under the protection of nitrogen for azeotropic dehydration while stirring, refluxing at constant temperature for 3h, removing toluene and water, continuously heating to 210 ℃ for reaction for 3.5h, stopping heating, transferring the reactant into a solution with the volume ratio of ethanol to water of 1 for precipitation, filtering and crushing the precipitate, repeatedly boiling and washing with deionized water for 5 times to remove inorganic salt and residual solvent, and drying in a vacuum oven at 150 ℃ for 24h to obtain the polymer powder with the structure of (III), wherein the structure is also verified by nuclear magnetic hydrogen spectrum and infrared spectrum.
Wherein m =0.7, n =0.3, and the number average molecular weight is 5.5 × 10 4 。
And (3) melting and extruding the powder obtained by polymerization in a double screw at 340 ℃, wherein the rotating speed of the screw is 100rpm, and obtaining the 3D printing special wire with the diameter of 1.75mm and uniform thickness under the action of a traction device. Drying the special wire material for 3D printing at 150 ℃ for 24h, then discharging the wire through a nozzle of a high-temperature 3D printer, carrying out fused deposition molding, wherein the nozzle temperature is 390 ℃, the printing speed is 40mm/s, the printing layer thickness is 0.2mm, the printing bottom plate temperature is 260 ℃, and obtaining an amorphous polyaryletherketone 3D printing product on the printing bottom plate to finish 3D printing molding.
Example 5
Adding phenolphthalein (400 mmol), 2, 6-dichlorobenzonitrile (320 mmol), 4' -difluorodiphenylsulfone (80 mmol), 4-fluorobenzophenone (16 mmol), potassium carbonate (550 mmol), sulfolane (600 g) and toluene (120 ml) into a three-neck flask, heating the mixture to 150 ℃ under the protection of nitrogen to remove water by azeotropic distillation while stirring, refluxing at constant temperature for 3h, removing toluene and water, continuing to heat to 210 ℃ for reaction for 3h, stopping heating, transferring the reactant into a solution with the volume ratio of ethanol to water being 1 for precipitation, filtering and crushing the precipitate, repeatedly boiling and washing the precipitate with deionized water for 5 times to remove inorganic salt and residual solvent, and drying in a vacuum oven at 150 ℃ for 24h to obtain the polymer powder with the structure (IV), wherein the structure is also verified by nuclear magnetic hydrogen spectrum and infrared spectrum.
Wherein m =0.8, n =0.2, and the number average molecular weight is 4.8 × 10 4 。
And (3) performing melt extrusion on the powder obtained by polymerization in a double screw at 340 ℃, wherein the rotation speed of the screw is 100rpm, and obtaining the 3D printing special wire with the diameter of 1.75mm and uniform thickness under the action of a traction device. Drying the 3D printing special wire material at 150 ℃ for 24 hours, then discharging the wire through a nozzle of a high-temperature 3D printer, carrying out fused deposition molding, wherein the temperature of the nozzle is 380 ℃, the printing speed is 40mm/s, the thickness of a printing layer is 0.2mm, the temperature of a printing base plate is 260 ℃, obtaining an amorphous polyarylethersulfone 3D printing product on the printing base plate, and completing 3D printing molding.
Example 6
Adding bisphenol fluorene (400 mmol), 2, 6-dichlorobenzonitrile (320 mmol), 4' -difluorodiphenyl sulfone (80 mmol), 4-fluorobenzophenone (15 mmol), potassium carbonate (600 mmol), sulfolane (680 g) and toluene (150 ml) into a three-neck flask, heating the mixture to 150 ℃ under the protection of nitrogen for azeotropic dehydration while stirring, refluxing at constant temperature for 3h, removing toluene and water, continuing to heat to 210 ℃ for reaction for 4h, stopping heating, transferring the reactant into a solution with the volume ratio of ethanol to water of 1 for precipitation, filtering and crushing the precipitate, repeatedly boiling and washing the precipitate with deionized water for 5 times to remove inorganic salt and residual solvent, and drying in a vacuum oven at 150 ℃ for 24h to obtain the polymer powder with the structure of (V), wherein the structure is also verified by nuclear magnetic hydrogen spectrum and infrared spectrum.
Wherein m =0.8, n =0.2, and the number average molecular weight is 4.5 × 10 4 。
And (3) melting and extruding the powder obtained by polymerization in a double screw at 340 ℃, wherein the rotating speed of the screw is 100rpm, and obtaining the 3D printing special wire with the diameter of 1.75mm and uniform thickness under the action of a traction device. Drying the special wire for 3D printing at 150 ℃ for 24h, then discharging the wire through a nozzle of a high-temperature 3D printer, carrying out fused deposition molding, wherein the temperature of the nozzle is 380 ℃, the printing speed is 40mm/s, the thickness of a printing layer is 0.2mm, the temperature of a printing base plate is 250 ℃, and obtaining an amorphous polyarylethersulfone 3D printing product on the printing base plate to finish 3D printing molding.
Comparative example 1
And (2) melting and extruding crystal polyether-ether-ketone (VI) powder in a double screw at 375 ℃ at a rotating speed of 100rpm, and obtaining the 3D printing special wire with a wire diameter of 1.5mm and uniform thickness under the action of a traction device. Drying the special 3D printing wire material at 125 ℃ for 3h, then discharging the wire through a nozzle of a high-temperature 3D printer for fused deposition molding, wherein the nozzle temperature is 345 ℃, the printing speed is 18mm/s, the printing layer thickness is 12mm, obtaining an amorphous polyarylethersulfone 3D printing product on a printing bottom plate, and completing 3D printing molding.
Experimental example 1
The polymer materials prepared in examples 1 to 3 were sequentially labeled as S1 to S3, samples printed using the polymers prepared in examples 1 to 3 were sequentially labeled as Y1 to Y3, and 3D printed samples obtained in comparative example 1 were labeled as D1, and the polymer and the 3D printed samples thereof were tested for their properties, with the results shown in table 1.
TABLE 1
It can be seen from samples S1-S3 that by adjusting the monomer ratio and end capping, the molecular weight and viscosity of the polymer can be changed, thereby matching the resin fluidity with the 3D printing process; as can be seen from the performances of the printing samples of Y1-Y3 and D1, the mechanical strength of 3D printed amorphous polyaryletherketone is higher, and the performances are more excellent. In summary, the amorphous polyaryletherketone (sulfone) of the present invention is a new material that can be applied in the field of 3D printing.
Claims (15)
1. The application of amorphous polyaryletherketone and/or polyarylethersulfone polymer in 3D printing is characterized in that the structure of the polyaryletherketone and/or polyarylethersulfone polymer is shown as the formula (I):
the end-capping reagent is one or more than two of 4-fluorobenzophenone, 4-chlorobenzophenone, 4- (p-fluorobenzoyl) biphenyl, 4- (p-chlorobenzoyl) biphenyl, 4- (p-fluorobenzoyl) diphenyl ether and 4- (p-chlorobenzoyl) diphenyl ether.
2. Use according to claim 1, wherein the polymer has a number average molecular weight of 3.0 x 10 4 ～8.0×10 4 。
3. The use according to claim 1,
the bisphenol monomer is selected from one or more than two of the following structures (1) to (4):
4. The use according to claim 3, wherein the molar ratio of the total amount of 4,4 '-dihalobenzophenone and/or 4,4' -dihalodiphenylsulfone and 2, 6-dichlorobenzonitrile to bisphenol monomer is 100 (95-105).
5. Use according to claim 3,
the 4,4' -dihalobenzophenone is 4,4' -difluorobenzophenone and/or 4,4' -dichlorobenzophenone; the 4,4' -dihalo diphenyl sulfone is 4,4' -difluoro diphenyl sulfone and/or 4,4' -dichloro diphenyl sulfone;
the molar ratio of the 4,4 '-dihalobenzophenone and/or the 4,4' -dihalodiphenylsulfone to the 2, 6-dichlorobenzonitrile is 10 (10-90).
6. Use according to claim 3,
the molar ratio of the bisphenol monomer to the end-capping reagent is 100 (1-10);
the catalyst is anhydrous potassium carbonate and/or anhydrous sodium carbonate;
the molar ratio of the bisphenol monomer to the catalyst is 10 (10-20).
7. Use according to claim 3,
the solvent is sulfolane and/or dimethyl sulfoxide;
the mass ratio of the monomer raw material to the solvent is 1 (1-20);
the water-carrying agent is toluene and/or xylene;
the ratio of the mass of the solvent to the dosage of the water-carrying agent is 10g (1-10) ml.
8. The use according to claim 3, wherein the temperature of the condensing reflux is 130-160 ℃; the reflux time is 2-5 h;
the temperature of the polycondensation reaction is 150-230 ℃; the polycondensation reaction time is 2-10 h.
9. The use according to any one of claims 3 or 6 to 8,
the molar ratio of the bisphenol monomer to the end-capping reagent is 100 (2-5); the molar ratio of the bisphenol monomer to the catalyst is 10 (12-15); the mass ratio of the monomer raw material to the solvent is 1 (2-5); the ratio of the mass of the solvent to the amount of the water-carrying agent is 10g (2-5) ml;
the temperature of the condensation reflux is 140-150 ℃; the reflux time is 3-4 h;
the temperature of the polycondensation reaction is 200-210 ℃; the polycondensation reaction time is 3-5 h.
10. Use according to claim 1 or 2, characterized in that a process for 3D printing shaping of amorphous polyaryletherketone and/or polyarylethersulfone polymers, comprises:
the method comprises the following steps: melting and extruding the amorphous polyaryletherketone and/or polyarylethersulfone powder obtained by polymerization in a double screw, and obtaining a 3D printing special wire under the action of a traction device;
step two: drying the special 3D printing wire material in the step one at 120-150 ℃ for 12-24 h, then performing fused deposition molding by discharging the wire through a nozzle of a high-temperature 3D printer, wherein the printing speed is 30-50 mm/s, the printing layer thickness is 0.05-0.3 mm, and obtaining an amorphous polyaryletherketone and/or polyarylethersulfone 3D printing product on a printing bottom plate to finish 3D printing molding.
11. The use of claim 10, wherein in step one, the melt extrusion temperature is 320-360 ℃ and the screw rotation speed is 60-110 rpm;
in the first step, the diameter of the special wire for 3D printing is 1.7-1.8 mm.
12. Use according to claim 10, characterized in that in step two: drying the special 3D printing wire material in the step one at 150 ℃ for 24h, then discharging the wire through a nozzle of a high-temperature 3D printer to perform fused deposition molding, wherein the printing speed is 40mm/s, the printing layer thickness is 0.2mm, and obtaining an amorphous polyaryletherketone and/or polyarylethersulfone 3D printing product on a printing base plate to complete 3D printing molding.
13. The use according to claim 11, wherein in step one, the melt extrusion temperature is 330-350 ℃, the screw rotation speed is 80-100 rpm;
in the first step, the diameter of the special 3D printing wire is 1.75mm.
14. The use according to claim 10, wherein in the second step, the 3D printing backplane temperature is 240 to 270 ℃;
in the second step, the temperature of the 3D printing nozzle is 360-420 ℃.
15. The use according to claim 14, wherein in the second step, the 3D printing substrate temperature is 250-260 ℃;
in the second step, the temperature of the 3D printing nozzle is 380-400 ℃.
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