CN113717377A - 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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- 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
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Abstract
本发明公开了一种适用于3D打印工艺的无定形聚芳醚酮(砜)及其制备方法，将单体、封端剂、催化剂和带水剂在溶剂中进行缩聚反应，得到无定形结构的聚合物。相比于结晶型树脂，无定形聚芳醚酮(砜)易改性且具有更高的熔体强度和更好的加工性能；氰基的引入能增强分子间作用力从而提高3D打印成型件的层间强度，解决了现有3D打印结晶型聚芳醚酮的层间粘结性不强而由于晶格的限制又难以改性的问题。通过调整单体的比例和封端，可以得到不同分子量和粘度的聚合物，从而使树脂的流动性与3D打印工艺相匹配。本发明还将无定形聚芳醚酮(砜)粉料制成丝材，通过熔融沉积成型工艺得到了3D打印样品，通过调节打印速度和底板温度，使打印件具有更高的强度和更好的性能。
The invention discloses an amorphous polyaryletherketone (sulfone) suitable for a 3D printing process and a preparation method thereof. A polycondensation reaction of a monomer, an end-capping agent, a catalyst and a water-carrying agent is carried out in a solvent to obtain an amorphous structure of polymers. Compared with crystalline resins, amorphous polyaryletherketone (sulfone) is easy to modify and has higher melt strength and better processability; the introduction of cyano groups can enhance intermolecular forces and improve 3D printing. It solves the problem that the existing 3D printing crystalline polyaryletherketone has poor interlayer adhesion and is difficult to modify due to the limitation of the crystal lattice. By adjusting the ratio of monomers and capping, polymers of different molecular weights and viscosities can be obtained to match the flowability of the resin to the 3D printing process. In the present invention, the amorphous polyaryletherketone (sulfone) powder is also made into filament, and the 3D printing sample is obtained by the fused deposition molding process. By adjusting the printing speed and the temperature of the base plate, the printed part has higher strength and better performance.
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 prints PEEK patching material secondary operation design method, adopts the nature controlled 3D printing method to make the low crystallinity PEEK raw materials that have high toughness, good plasticity, improves the crystallinity and the intensity of material through the aftertreatment. CN 108424605A discloses PEEK-MBA-PEI blend 3D printing material and a 3D printing forming method thereof, and the strength of a printed part 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 polyaryletherketones (sulfones) which are free from lattice restriction, easy to modify, high in strength, and good in plasticity and dimensional stability is very important.
In order to solve the above problems, the present application proposes an amorphous polyaryletherketone (sulfone), a preparation method and a 3D printing method.
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 printing 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, easy to obtain raw materials and low in cost.
Drawings
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 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 is 1, m is more than or equal to 0, n is more than 0, and 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 bring water generated 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 '-dihalobenzophenone (and/or the 4, 4' -dihalodiphenylsulfone) and the 2, 6-dichlorobenzonitrile to the bisphenol monomer is 100 (90-110), preferably 100 (95-105); the molar ratio of the 4,4 '-dihalobenzophenone and/or the 4, 4' -dihalodiphenylsulfone 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 2-5 h, preferably 3-4 h; the temperature of the polycondensation reaction is 150-230 ℃, and preferably 200-210 ℃; the polycondensation reaction time is 2-10 h, preferably 3-5 h.
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 24h) at 120-150 ℃ (preferably 150 ℃), then performing fused deposition forming by discharging the wire through a high-temperature 3D printer nozzle, wherein the printing speed is 30-50 mm/s (preferably 40mm/s), the printing layer thickness is 0.05-0.3 mm (preferably 0.2mm), obtaining an amorphous polyaryletherketone and/or polyarylethersulfone 3D printing product on a printing bottom plate, and completing 3D printing forming.
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 special wire for 3D printing is 1.7-1.8 mm, and the optimal diameter is 1.75 mm.
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
Phenolphthalein (having the structure shown in (1) above, the same below) (400mmol), 2, 6-dichlorobenzonitrile (280mmol), 4' -difluorobenzophenone (120mmol), 4-fluorobenzophenone (12mmol), potassium carbonate (480mmol), sulfolane (600g), and toluene (120ml) were added to a three-necked flask, heating the mixture to 150 ℃ under the protection of nitrogen while stirring for azeotropic dehydration, refluxing at constant temperature for 3h, removing toluene and water, continuing to heat to 210 ℃ for reaction for 3.5h, stopping heating, transferring the reactant into a solution with the volume ratio of ethanol to water of 1:1 for precipitation, filtering and crushing the precipitate, repeatedly boiling and washing with deionized water for 5 times to remove inorganic salt and residual solvent, drying in vacuum oven at 150 deg.C for 24 hr, the polymer powder with the structure (II) is obtained, and the structure is verified by nuclear magnetic hydrogen spectrum and infrared spectrum.
Wherein m is 0.7, n is 0.3, and the number average molecular weight is 6.0 × 104。
And 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 3D printing special wire material for 24h at 150 ℃, then discharging the wire through a nozzle of a high-temperature 3D printer to perform fused deposition molding, wherein the temperature of the nozzle is 390 ℃, 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.
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 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.
Example 2
Adding phenolphthalein (400mmol), 2, 6-dichlorobenzonitrile (280mmol), 4' -difluorobenzophenone (120mmol), 4-fluorobenzophenone (15mmol), potassium carbonate (480mmol), sulfolane (600g) and toluene (120ml) 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 205 ℃ for reaction for 3h, stopping heating, transferring the reactant into a solution with the volume ratio of ethanol to water of 1:1 for precipitation, filtering and crushing the precipitate, repeatedly boiling and washing with deionized water for 5 times to remove inorganic salt and residual solvent, drying at 150 ℃ in a vacuum oven for 24h to obtain polymer powder with a structure (II) and a small viscosity (shown in Table 1), wherein the number average molecular weight is 5.3 multiplied by 104The 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 3D printing special wire material for 24 hours at 150 ℃, then discharging the wire through a nozzle of a high-temperature 3D printer to perform 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
A three-necked flask was charged with phenolphthalein (400mmol), 2, 6-dichlorobenzonitrile (280mmol), 4' -difluorobenzophenone (120mmol), 4-fluorobenzophenone (18mmol), potassium carbonate (480mmol), sulfolane (600g), and toluene (120ml), heating the mixture to 150 ℃ under the protection of nitrogen while stirring for azeotropic dehydration, 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 1:1 for precipitation, filtering and crushing the precipitate, repeatedly boiling and washing with deionized water for 5 times to remove inorganic salts and residual solvent, drying at 150 deg.C for 24h in a vacuum oven to obtain polymer powder with structure (II) and smaller viscosity and better fluidity (see Table 1), and the number average molecular weight is 4.2 × 10.4The 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 3D printing special wire material for 24 hours at 150 ℃, then discharging the wire through a nozzle of a high-temperature 3D printer to perform 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 (400mmol), 2, 6-dichlorobenzonitrile (280mmol), 4' -difluorobenzophenone (120mmol), 4-fluorobenzophenone (10mmol), potassium carbonate (500mmol), sulfolane (650g) and toluene (150ml) 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 1:1 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 polymer powder with the structure (III), wherein the structure is also verified by nuclear magnetic hydrogen spectrum and infrared spectrum.
Wherein m is 0.7, n is 0.3, and the number average molecular weight is 5.5 × 104。
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 3D printing special wire material for 24h at 150 ℃, then discharging the wire through a nozzle of a high-temperature 3D printer to perform fused deposition molding, wherein the temperature of the nozzle is 390 ℃, 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 5
Adding phenolphthalein (400mmol), 2, 6-dichlorobenzonitrile (320mmol), 4' -difluorodiphenylsulfone (80mmol), 4-fluorobenzophenone (16mmol), potassium carbonate (550mmol), sulfolane (600g) and toluene (120ml) 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 3h, stopping heating, transferring the reactant into a solution with the volume ratio of ethanol to water of 1:1 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 (IV), wherein the structure is also verified by nuclear magnetic hydrogen spectrum and infrared spectrum.
Wherein m is 0.8, n is 0.2, and the number average molecular weight is 4.8 × 104。
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 3D printing special wire material for 24 hours at 150 ℃, then discharging the wire through a nozzle of a high-temperature 3D printer to perform 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 ℃, and obtaining an amorphous polyarylethersulfone 3D printing product on the printing base plate to finish 3D printing molding.
Example 6
Adding bisphenol fluorene (400mmol), 2, 6-dichlorobenzonitrile (320mmol), 4' -difluorodiphenylsulfone (80mmol), 4-fluorobenzophenone (15mmol), potassium carbonate (600mmol), sulfolane (680g) and toluene (150ml) 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 4h, stopping heating, transferring the reactant into a solution with the volume ratio of ethanol to water of 1:1 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 polymer powder with the structure (V), wherein the structure is also verified by nuclear magnetic hydrogen spectrum and infrared spectrum.
Wherein m is 0.8, n is 0.2, and the number average molecular weight is 4.5 × 104。
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 3D printing special wire material for 24 hours at 150 ℃, then discharging the wire through a nozzle of a high-temperature 3D printer to perform 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 the crystal polyether-ether-ketone (VI) powder in a double screw at 375 ℃ with the rotating speed of the screw being 100rpm, and obtaining the 3D printing special wire with the 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 to perform fused deposition molding, wherein the nozzle temperature is 345 ℃, the printing speed is 18mm/s, the printing layer thickness is 12mm, and obtaining an amorphous polyarylether sulfone 3D printing product on a printing bottom plate to finish 3D printing molding.
Experimental example 1
The polymer materials prepared in examples 1 to 3 were sequentially labeled as S1 to S3, samples printed with the polymers prepared in examples 1 to 3 were sequentially labeled as Y1 to Y3, and the 3D printed sample obtained in comparative example 1 was labeled as D1, and the polymer and the 3D printed sample were tested for their performance, with the results shown in table 1.
TABLE 1
It can be seen from samples S1-S3 that by adjusting the ratio of monomers and the capping, the molecular weight and viscosity of the polymer can be changed, thereby matching the resin' S flowability 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 the 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 (10)
1. An amorphous polyaryletherketone (sulfone) 3D printing polymer is characterized in that the structure of the polyaryletherketone and/or polyarylethersulfone polymer is shown as the formula (I):
in the formula (I), m + n is 1, m is more than or equal to 0, n is more than 0, wherein m and n are mole percent;
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):
2. the polymer of claim 1, wherein the polymer has a number average molecular weight of 3.0 x 104～8.0×104。
3. A method of preparing a 3D printing polymer according to claim 1 or 2, the method comprising: 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 bring water generated 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):
the molar ratio of the total amount of the 4,4 '-dihalobenzophenone (and/or the 4, 4' -dihalodiphenylsulfone) and the 2, 6-dichlorobenzonitrile to the bisphenol monomer is 100 (90-110), and preferably 100 (95-105).
4. The production method 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 (0-990), and preferably 10 (10-90).
5. The production method according to claim 3,
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).
6. The production method 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), 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.
7. The preparation method according to claim 3, wherein the temperature of the condensation reflux is 130-160 ℃, preferably 140-150 ℃; the reflux time is 2-5 h, preferably 3-4 h;
the temperature of the polycondensation reaction is 150-230 ℃, and preferably 200-210 ℃; the polycondensation reaction time is 2-10 h, preferably 3-5 h.
8. A 3D printing modeling method using the amorphous polyaryletherketone (sulfone) 3D printing polymer of claim 1 or 2, the method comprising:
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 24h) at 120-150 ℃ (preferably 150 ℃), 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 (preferably 40mm/s), the printing layer thickness is 0.05-0.3 mm (preferably 0.2mm), obtaining an amorphous polyaryletherketone and/or polyarylethersulfone 3D printing product on a printing bottom plate, and completing 3D printing molding.
9. The 3D printing and forming method according to claim 8, wherein 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);
in the first step, the diameter of the special wire for 3D printing is 1.7-1.8 mm, and preferably 1.75 mm.
10. The 3D printing forming method according to claim 8, wherein in the second step, the temperature of the 3D printing bottom plate is 240-270 ℃, preferably 250-260 ℃;
in the second step, the temperature of the 3D printing nozzle is 360-420 ℃, and preferably 380-400 ℃.
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