CN113321800A - Application of selective laser sintering by using polyether-ether-ketone prepared from tetramethylguanidine tetrafluoroborate as raw material - Google Patents
Application of selective laser sintering by using polyether-ether-ketone prepared from tetramethylguanidine tetrafluoroborate as raw material Download PDFInfo
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Abstract
The invention discloses application of selective laser sintering by taking polyether-ether-ketone prepared from tetramethylguanidine tetrafluoroborate as a raw material, belonging to the field of heat-resistant high polymer materials. Use of a polyetheretherketone prepared using tetramethylguanidium tetrafluoroborate as a starting material for selective laser sintering, the use comprising: synthesizing polyether ether ketone by using tetramethylguanidine tetrafluoroborate as a solvent. When the synthesized polyetheretherketone is used as a raw material of a selective laser sintering technology, a pure product of powdered polyetheretherketone with the particle size distribution of 30-70 mu m can be obtained, and the polyetheretherketone has a smooth surface, is spherical-like and has high powder fluidity, so that the polyetheretherketone meets the requirements of the selective laser sintering technology.
Description
The invention relates to a divisional application with application number 201711191777.0, and the invention name of the application number 201711191777.0 is a method for selective laser sintering by taking polyether-ether-ketone as a raw material, and the application date is 11 months and 24 days in 2017.
Technical Field
The invention relates to the field of heat-resistant polymer materials, in particular to application of selective laser sintering by taking polyether-ether-ketone prepared from tetramethylguanidine tetrafluoroborate as a raw material.
Background
The Selective Laser Sintering (SLS) technique can print out the substituted skeleton which is completely consistent with the requirement of the physical characteristics of the patient, and the size precision and the shape matching degree of the substituted skeleton are far more than those of the prior alloy skeleton, so the selective Laser Sintering technique is valued and popularized by the medical field. According to the Frenkel sintering neck length equation, factors that affect the quality of sintering include the apparent density of the powder raw material and the particle size of the powder raw material. In order to ensure the quality of the selective laser sintering technology, the particle size of the raw material used as the selective laser sintering technology is required to be concentrated between 30 and 70 mu m, the particle appearance is close to spherical, and the apparent density is 0.3 to 0.5g/cm3If these requirements are not satisfied, the powder is unevenly spread during the sintering process, the surface of the sintered product is rough, and the shrinkage of each phase of the material is poor.
Polyether Ether Ketone (PEEK) is a special engineering plastic containing benzene rings, Ether bonds and carbonyl groups in a molecular main chain. Due to the excellent biocompatibility of the polyether-ether-ketone, the polyether-ether-ketone shows attractive application prospects in the fields of human bones and the like, and can be used as a selective laser sintering technical material for customizing a substitute bone consistent with the requirements of the physical characteristics of patients. The existing method for preparing polyether-ether-ketone adopts 4,4' -difluorobenzophenone and 1, 4-benzenediol as raw materials, anhydrous potassium carbonate and anhydrous sodium carbonate as catalysts, diphenyl sulfone (the melting point is 334 ℃) as a solvent, and starts to synthesize a product through nucleophilic substitution reaction at the initial temperature of 140-150 ℃, and the reaction is completed when the temperature is raised to 320 ℃. And (3) cooling the obtained product to room temperature, grinding, washing to obtain relatively pure polyetheretherketone, mechanically mixing the obtained polyetheretherketone with micron-sized hydroxyapatite together, and performing selective laser sintering forming to obtain the composite material with high porosity.
In the process of implementing the invention, the inventor finds that the prior art has at least the following problems:
when the polyether-ether-ketone is prepared, the obtained product needs to be ground, so that the polyether-ether-ketone prepared by the prior art has poor shape stability, less spherical particles, rough surface and wider particle size distribution, the prepared molded composite material has low size precision and poor quality, the mechanical property of the composite material prepared by the polyether-ether-ketone prepared by the prior art as a raw material through a selective laser sintering technology is much lower than that of the composite material prepared by the traditional injection molding or hot press molding method, and the application range of the composite material prepared by the prior art is very small.
Disclosure of Invention
In order to solve the problems of less spheroidal particles, rough surface and wide particle size distribution of the composite material in the prior art, the embodiment of the invention provides the application of selective laser sintering by taking polyether-ether-ketone prepared from tetramethylguanidine tetrafluoroborate as a raw material. The technical scheme is as follows:
the embodiment of the invention provides an application of selective laser sintering by taking polyether-ether-ketone prepared by adopting tetramethylguanidine tetrafluoroborate as a raw material, which comprises the following steps: synthesizing polyether ether ketone by using tetramethylguanidine tetrafluoroborate as a solvent.
Specifically, the application comprises the following steps:
(1) under the inert gas, adding a difluoro monomer into the solvent, and fully dissolving the difluoro monomer into the solvent to obtain a difluoro solution;
(2) under inert gas, uniformly mixing a diphenol monomer, anhydrous potassium carbonate and anhydrous sodium carbonate, adding the mixture into the difluoro solution, fully dissolving the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate in the difluoro solution to obtain a mixed solution, heating the mixed solution to 140-200 ℃, reacting until no carbon dioxide gas is generated, finishing the reaction to obtain a reaction product, and purifying the reaction product to obtain the polyether-ether-ketone with the particle size distribution of 30-70 mu m.
Specifically, the specific method of step (1) is as follows: 1) and under the inert gas, adding a difluoro monomer into the solvent, and continuously stirring at 25-60 ℃ to fully dissolve the difluoro monomer into the solvent to obtain a difluoro solution.
Specifically, in the step (2), the specific method for adding the diphenol monomer, anhydrous potassium carbonate and anhydrous sodium carbonate into the difluoro solution after uniformly mixing the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate comprises the following steps: uniformly mixing diphenol monomer, anhydrous potassium carbonate and anhydrous sodium carbonate, adding the mixture into the difluoro solution for 3-5 times respectively, wherein the interval time between two adjacent times of adding is 20-40 min, and continuously stirring after each time of adding.
Specifically, in the step (2), the specific method for obtaining the mixed solution is as follows: uniformly mixing the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate, adding the mixture into the difluoro solution, heating to 120-140 ℃, and preserving heat for 1-3 hours to fully dissolve the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate in the difluoro solution to obtain a mixed solution.
Further, the specific method of step (2) comprises: uniformly mixing the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate, adding the mixture into the difluoro solution, heating the mixture from room temperature to 120-140 ℃ at the speed of 5-20 ℃/min, preserving the heat for 1-3 hours, fully dissolving the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate in the difluoro solution to obtain a mixed solution, and heating the mixed solution to 140-200 ℃ at the speed of 2-10 ℃/min.
Further, the difluoro monomer is 4,4 '-difluorobenzophenone, 3' -difluorobenzophenone, 2, 3-difluorobenzophenone, 2, 5-difluorobenzaldehyde, 2, 6-difluorobenzaldehyde, bis (4-fluorophenyl) ether, 4 '-difluorodiphenylmethane, 2, 5-difluoroanisole, 2, 5-difluorobenzophenone, 3, 5-difluorobenzonitrile, 2, 5-difluorobenzoic acid methyl ester, 2, 4-difluorobenzoic acid ethyl ester or 4,4' -difluorobenzylpiperazine.
Preferably, the difluoro monomer is 4,4 '-difluorobenzophenone, 3' -difluorobenzophenone, and bis (4-fluorophenyl) ether.
Further, the diphenol monomer is 1, 4-benzenediol, bisphenol A, 1, 5-naphthalenediol, 2, 6-naphthalenediol, tert-butylhydroquinone, 2-methoxyhydroquinone, trimethylhydroquinone, tetramethylhydroquinone, 2, 5-di-tert-octylhydroquinone, 2, 5-diisooctylhydroquinone, 2, 5-diphenylhydroquinone or 2, 5-di-tert-amylhydroquinone.
Preferably, the diphenol monomers are 1, 4-benzenediol, bisphenol a and 2, 5-diphenylhydroquinone.
Specifically, the purification comprises: filtration and washing, the filtration and washing comprising: adding ethanol into the reaction product, carrying out primary filtration to obtain primary filtered filter residue, washing the primary filtered filter residue with ethanol and acetone respectively for 1-2 times, then carrying out secondary filtration to obtain secondary filtered filter residue, and washing the secondary filtered filter residue with deionized water twice.
Further, the purifying further comprises: drying, the method of drying comprising: and (3) drying the washed product at 120 ℃ in vacuum to obtain the powdered polyether-ether-ketone.
The technical scheme provided by the embodiment of the invention has the following beneficial effects: the embodiment of the invention provides an application of selective laser sintering by taking polyether-ether-ketone prepared by adopting tetramethylguanidine tetrafluoroborate as a raw material. In the preparation process of the polyetheretherketone, the selected solvent is in a stable liquid state at room temperature or a high temperature close to room temperature to 300 ℃, so that the reaction temperature for synthesizing the polyetheretherketone can be reduced, the polyetheretherketone can be prepared at a relatively low temperature, the reaction is ensured to be always carried out in a liquid phase, meanwhile, the reaction system is still kept in the liquid phase state after the reaction is finished and the temperature is reduced to the room temperature, the subsequent treatment process of the polyetheretherketone is greatly facilitated, the problem that the polymer and the solvent are solidified into a group after the diphenyl sulfone is cooled in the synthesis process of the polyetheretherketone in the prior art is completely avoided, the synthesized polyetheretherketone can be directly used as a raw material of a selective laser sintering technology, the particle size of the prepared pure polyetheretherketone powder is distributed at 30-70 mu m through the detection of a dry-wet-cold-laser particle size analyzer, the surface of the prepared polyetheretherketone powder is smooth through the observation of a scanning electron microscope, and the polyether-ether-ketone is spherical-like and has high powder fluidity, so that the polyether-ether-ketone meets the requirements of a selective laser sintering technology.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below.
The tetramethylguanidine tetrafluoroborate used in this example is from Sigma-Aldrich, with CP as its specification, and has a purity of 98% or higher.
The difluoro monomers 4,4 '-difluorobenzophenone, 3' -difluorobenzophenone, 2, 3-difluorobenzophenone, 2, 5-difluorobenzaldehyde, 2, 6-difluorobenzaldehyde and bis (4-fluorophenyl) ether selected in the embodiment are all from Shanghai-sourced leaf Biotech limited company, the specification of which is AR, and the purity is more than or equal to 99.5%; 4,4 '-difluorodiphenylmethane, 2, 5-difluoroanisole, 2, 5-difluorobenzophenone, 3, 5-difluorobenzonitrile, 2, 5-difluorobenzoic acid methyl ester, 2, 4-difluorobenzoic acid ethyl ester and 4,4' -difluorobenzylpiperazine are all from the national pharmacy group, the specification of the compound is AR, and the purity is more than or equal to 99.5%.
The diphenol monomers selected in the embodiment are 1, 4-benzenediol, bisphenol A, 1, 5-naphthalenediol and 2, 6-naphthalenediol, the specification of which is AR from the national medicine group, and the purity of the diphenol monomers is more than or equal to 99.5 percent; tert-butylhydroquinone, 2-methoxyhydroquinone, trimethylhydroquinone, tetramethylhydroquinone, 2, 5-di-tert-octylhydroquinone, 2, 5-di-iso-octylhydroquinone, 2, 5-diphenylhydroquinone and 2, 5-di-tert-amylhydroquinone were all from Fuji film company, with specification AR and purity of not less than 99.5%.
Other reagents such as sodium carbonate and potassium carbonate were purchased from Shilang chemical with specification AR and purity > 99%.
Example one
10.90g of 4,4 '-difluorobenzophenone was added to 163.00g of a solvent of tetramethylguanidium tetrafluoroborate under argon to give a 4,4' -difluorobenzophenone solution, wherein the tetramethylguanidium tetrafluoroborate has the structure shown as:
heating the 4,4' -difluorobenzophenone solution to 60 ℃, stirring the 4,4' -difluorobenzophenone solution to fully dissolve the 4,4' -difluorobenzophenone, and cooling to normal temperature for later use; under the protection of argon, uniformly mixing 12.82g of bisphenol A, 0.69g of anhydrous potassium carbonate and 4.77g of anhydrous sodium carbonate, dividing into three parts with equal mass, respectively adding the three parts into a 4,4' -difluorobenzophenone solution, continuously stirring at a high speed (the stirring speed can be 100-500 r/min), keeping the stirring speed for 1h, fully dissolving the 4,4' -difluorobenzophenone, the anhydrous potassium carbonate and the anhydrous sodium carbonate in the 4,4' -difluorobenzophenone solution at an interval of 40min, heating from normal temperature to 130 ℃, the heating rate is 20 ℃/min, keeping the temperature for 1h, heating to 200 ℃, the heating rate is 5 ℃/min, after continuously reacting for 12h, naturally cooling the reaction system to room temperature under the condition of keeping stirring to obtain a reaction product, adding 100ml of ethanol into the reaction product, and carrying out primary filtration by using a Buchner funnel, and (3) obtaining primary filtered filter residue, washing the primary filtered filter residue for 1-2 times respectively by using ethanol and acetone, filtering again, washing the secondary filtered filter residue for two times by using 100ml of deionized water, and carrying out vacuum drying treatment at 120 ℃ after filtering to obtain 18.98g of polyether-ether-ketone powder with the yield of 85%.
The polyetheretherketone obtained in this example was subjected to a particle size distribution test using a dry-wet cold-laser particle size analyzer, specifically using an instrument: dry wet cold shockOptical particle size analyzer, manufacturer: zhuhai Oumek, type: LS-CIII, the particle size distribution test method is as follows: 0.1g of the polyether-ether-ketone obtained in the fifth embodiment is dissolved in 5g of ethanol, and the solution is subjected to ultrasonic dispersion to prepare a suspension for testing, so that the particle size of the polyether-ether-ketone is normally distributed, the average particle size is mainly distributed in the range of 30-70 μm, and the polyether-ether-ketone has better particle size distribution and uniformity. Meanwhile, apparent density detection is carried out on the polyether-ether-ketone powder, and a testing instrument: particle apparent density instrument, manufacturer: zhejiang ruike, type: FT-105C, method: selecting 50g of polyether-ether-ketone powder, placing the powder into an upper funnel, quickly drawing away a baffle plate of the funnel, freely stacking the powder into a measuring cup, measuring the volume of the powder in the measuring cup, and finally measuring that the apparent density of the polyether-ether-ketone powder is 0.40g/cm3The polyether-ether-ketone powder has good fluidity (the fluidity is determined by the shape and the roughness of the powder together and is comprehensively judged mainly by the shape, the particle size distribution, the apparent density and the powder laying efficiency of the powder), so that the ball bearing effect is generated in the powder laying process of the polyether-ether-ketone powder, and the quality of a selective laser sintering technical product is favorably improved.
The polyetheretherketone obtained in the first example is used as a raw material for a selective laser sintering technique, which specifically comprises the following steps: sieving the obtained polyetheretherketone powder with a 200-mesh sieve, taking 5kg of the sieved polyetheretherketone powder, performing on a selective laser sintering rapid forming machine, setting a scanning interval of 0.1mm, a single-layer thickness of 0.15mm, a scanning speed of 1500mm/s, a preheating temperature of 120-140 ℃, and a laser power of 16W, preparing a complete polyetheretherketone tensile sample strip (the sample strip has a middle length of 60mm, a full length of 85mm and a thickness of 2mm) and an impact sample strip (the sample strip has a length multiplied by the width multiplied by the thickness of 125mm multiplied by 12mm multiplied by 5mm), respectively measuring the tensile sample strip and the impact sample strip, and measuring the measured density of 0.723g/cm3Tensile strength of 80MPa and impact strength of 20KJ/m2Young modulus is 3GPa, the mechanical property of a sintered part is close to that of a polyether-ether-ketone molded part, wherein the polyether-ether-ketone molded part adopts the following equipment: TYU-2500 linkage mode-locking vertical injection molding machine; the manufacturer: giant Yu machine; the molding process comprises the following steps: adopting a double-screw extruder, wherein the temperature of a screw section is 350 ℃, the temperature of a nozzle is 380 ℃, the rotating speed of the screw is 100 r/min, and the injection pressure is 130MPa for injection molding.
The embodiment of the invention provides an application of selective laser sintering by taking polyether-ether-ketone prepared by adopting tetramethylguanidine tetrafluoroborate as a raw material. In the preparation process of the polyetheretherketone, the selected solvent is in a stable liquid state at room temperature or a high temperature close to room temperature to 300 ℃, so that the reaction temperature for synthesizing the polyetheretherketone can be reduced, the polyetheretherketone can be prepared at a relatively low temperature, the reaction is ensured to be always carried out in a liquid phase, meanwhile, the reaction system is still kept in the liquid phase state after the reaction is finished and the temperature is reduced to the room temperature, the subsequent treatment process of the polyetheretherketone is greatly facilitated, the problem that a polymer and the solvent are solidified into a group after the diphenyl sulfone is cooled in the synthesis process of the polyetheretherketone in the prior art is completely avoided, the particle size distribution of a product of the powdered polyetheretherketone is detected to be 30-70 mu m by a dry-wet-cold-laser particle size analyzer when the synthesized polyetheretherketone can be directly used as a raw material of a selective laser sintering technology, and the surface of the polyetheretherketone is smooth by observation of a scanning electron microscope, and is spheroidal with an apparent density of 0.40g/cm3And the polyether-ether-ketone has high powder fluidity, so that the polyether-ether-ketone meets the requirements of selective laser sintering technology.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. Use of a polyetheretherketone prepared using tetramethylguanidium tetrafluoroborate as starting material for selective laser sintering, characterized in that it comprises the following steps:
(1) under inert gas, adding a difluoro monomer into a solvent, continuously stirring at 25-60 ℃ to fully dissolve the difluoro monomer into the solvent to obtain a difluoro solution, and synthesizing polyether-ether-ketone by using tetramethylguanidine tetrafluoroborate as the solvent;
(2) under inert gas, uniformly mixing a diphenol monomer, anhydrous potassium carbonate and anhydrous sodium carbonate, adding the mixture into the difluoro solution, fully dissolving the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate in the difluoro solution to obtain a mixed solution, heating the mixed solution to 140-200 ℃, reacting until no carbon dioxide gas is generated, finishing the reaction to obtain a reaction product, and purifying the reaction product to obtain the polyether-ether-ketone with the particle size distribution of 30-70 mu m.
2. The use of claim 1, wherein in the step (2), the specific method for adding the diphenol monomer, anhydrous potassium carbonate and anhydrous sodium carbonate into the difluoro solution after uniformly mixing comprises the following steps: uniformly mixing diphenol monomer, anhydrous potassium carbonate and anhydrous sodium carbonate, adding the mixture into the difluoro solution for 3-5 times respectively, wherein the interval time between two adjacent times of adding is 20-40 min, and continuously stirring after each time of adding.
3. The use of claim 1, wherein in the step (2), the specific method for obtaining the mixed solution is as follows: uniformly mixing the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate, adding the mixture into the difluoro solution, heating to 120-140 ℃, and preserving heat for 1-3 hours to fully dissolve the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate in the difluoro solution to obtain a mixed solution.
4. The use of claim 3, wherein the specific method of step (2) comprises: uniformly mixing the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate, adding the mixture into the difluoro solution, heating the mixture from room temperature to 120-140 ℃ at the speed of 5-20 ℃/min, preserving the heat for 1-3 hours, fully dissolving the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate in the difluoro solution to obtain a mixed solution, and heating the mixed solution to 140-200 ℃ at the speed of 2-10 ℃/min.
5. The use according to claim 1, wherein said difluoro monomer is 4,4 '-difluorobenzophenone, 3' -difluorobenzophenone, 2, 3-difluorobenzophenone, 2, 5-difluorobenzaldehyde, 2, 6-difluorobenzaldehyde, bis (4-fluorophenyl) ether, 4 '-difluorodiphenylmethane, 2, 5-difluoroanisole, 2, 5-difluorobenzophenone, 3, 5-difluorobenzonitrile, methyl 2, 5-difluorobenzoate, ethyl 2, 4-difluorobenzoate or 4,4' -difluorobenzylpiperazine.
6. Use according to claim 1, wherein the diphenol monomer is 1, 4-benzenediol, bisphenol a, 1, 5-naphthalenediol, 2, 6-naphthalenediol, tert-butylhydroquinone, 2-methoxyhydroquinone, trimethylhydroquinone, tetramethylhydroquinone, 2, 5-di-tert-octylhydroquinone, 2, 5-di-iso-octylhydroquinone, 2, 5-diphenylhydroquinone or 2, 5-di-tert-amylhydroquinone.
7. Use according to claim 1, wherein the purification comprises: filtration and washing, the filtration and washing comprising: adding ethanol into the reaction product, carrying out primary filtration to obtain primary filtered filter residue, washing the primary filtered filter residue with ethanol and acetone respectively for 1-2 times, then carrying out secondary filtration to obtain secondary filtered filter residue, and washing the secondary filtered filter residue with deionized water twice.
8. The use of claim 7, wherein the purifying further comprises: drying, the method of drying comprising: and (3) drying the washed product at 120 ℃ in vacuum to obtain the powdered polyether-ether-ketone.
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| CN202110662441.8A CN113321800B (en) | 2017-11-24 | 2017-11-24 | Application of selective laser sintering by taking polyether-ether-ketone prepared from tetramethyl guanidine tetrafluoroborate as raw material |
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| CN201711191777.0A CN108034047B (en) | 2017-11-24 | 2017-11-24 | Application of selective laser sintering by taking polyether-ether-ketone as raw material |
| CN202110662441.8A CN113321800B (en) | 2017-11-24 | 2017-11-24 | Application of selective laser sintering by taking polyether-ether-ketone prepared from tetramethyl guanidine tetrafluoroborate as raw material |
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| CN202110662443.7A Active CN113429532B (en) | 2017-11-24 | 2017-11-24 | Application of polyether-ether-ketone prepared from 1-butyl-3-methylimidazole bromide in selective laser sintering |
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| CN115322315A (en) * | 2022-08-22 | 2022-11-11 | 北京理工大学 | Polymerization-precipitation method for preparing spherical polyaryletherketone micro powder |
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| CN110157148B (en) * | 2019-04-11 | 2020-12-08 | 华中科技大学 | PEEK powder with high processability and preparation method and application thereof |
| CN110655666B (en) * | 2019-10-30 | 2023-01-20 | 中山大学 | Polyaryletherketone powder and preparation method thereof |
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| US20110218315A1 (en) * | 2008-01-11 | 2011-09-08 | Jilin Jinzheng Macromolecule Materials R&D Co., Ltd | Process for preparing a polyether ether ketone |
| CN103665283A (en) * | 2012-09-12 | 2014-03-26 | 北京师范大学 | Method of preparing polyaryletherketone |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110218315A1 (en) * | 2008-01-11 | 2011-09-08 | Jilin Jinzheng Macromolecule Materials R&D Co., Ltd | Process for preparing a polyether ether ketone |
| CN103665283A (en) * | 2012-09-12 | 2014-03-26 | 北京师范大学 | Method of preparing polyaryletherketone |
Non-Patent Citations (1)
| Title |
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| H.Q.NIMAL GUNARATNE ET AL: "Production of polyetheretherketone in ionic liquid media" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115322315A (en) * | 2022-08-22 | 2022-11-11 | 北京理工大学 | Polymerization-precipitation method for preparing spherical polyaryletherketone micro powder |
| CN115322315B (en) * | 2022-08-22 | 2023-12-01 | 北京理工大学 | Polymerization-precipitation method for preparing spherical polyaryletherketone micropowder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113429532B (en) | 2023-05-23 |
| CN113429532A (en) | 2021-09-24 |
| CN113429562B (en) | 2023-05-23 |
| CN113321800B (en) | 2023-05-23 |
| CN108034047A (en) | 2018-05-15 |
| CN113429563B (en) | 2023-05-23 |
| CN113429562A (en) | 2021-09-24 |
| CN108034047B (en) | 2021-06-22 |
| CN113429563A (en) | 2021-09-24 |
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