CN113429563B - Application of selective laser sintering by taking polyether-ether-ketone prepared by solvent as raw material - Google Patents
Application of selective laser sintering by taking polyether-ether-ketone prepared by solvent as raw material Download PDFInfo
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Abstract
The invention discloses an application of selective laser sintering by taking polyether-ether-ketone prepared by a solvent as a raw material, belonging to the field of heat-resistant high polymer materials. Use of selective laser sintering of polyetheretherketone prepared using a solvent as a starting material, the use comprising: the polyether-ether-ketone is synthesized by taking chlorinated 1, 3-bis (2-methoxy-2-oxyethyl) imidazole as a solvent. When the synthesized polyether-ether-ketone is used as a raw material of the selective laser sintering technology, the powdery polyether-ether-ketone with the particle size distribution of 30-70 mu m can be obtained to obtain a pure product, and the polyether-ether-ketone has smooth surface, is sphere-like and has high powder flowability, so that the polyether-ether-ketone meets the requirements of the selective laser sintering technology.
Description
The invention discloses a method for selectively sintering polyether-ether-ketone serving as a raw material by laser, which is a divisional application with application number 201711191777.0, wherein the application number 201711191777.0 is 2017, 11 and 24.
Technical Field
The invention relates to the field of heat-resistant high polymer materials, in particular to an application of selective laser sintering by taking polyether-ether-ketone prepared by a solvent as a raw material.
Background
The selective laser sintering technology (Selected Laser Sintering; SLS) can print out the substituted bones which are completely consistent with the physical characteristic requirements of patients, and the size precision and the shape matching degree are far superior to those of the prior alloy bones, so that the selective laser sintering technology is valued and popularized by the medical community. According toThe Frenkel sintering neck length equation, factors affecting the sintering quality include the apparent density of the powder feedstock, the particle size of the powder feedstock, and the like. 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 morphology is approximate to a sphere, and the apparent density is between 0.3 and 0.5g/cm 3 If these requirements are not met, uneven powder spreading during sintering can be caused, the surface of the sintered product is rough, and the shrinkage rate of each phase of the material is poor.
Polyether Ether Ketone (Poly-Ether-Ether-Ketone; PEEK) is a special engineering plastic containing benzene ring, ether bond and carbonyl in its molecular main chain. Because of the excellent biocompatibility of the polyether-ether-ketone, the polyether-ether-ketone has attractive application prospect in the fields of human bones and the like, and can be used as a selective laser sintering technology material for customizing the substituted bones consistent with the physical characteristic requirements of patients. The existing method for preparing polyether-ether-ketone adopts 4,4' -difluorobenzophenone and 1, 4-dihydroxybenzene as raw materials, anhydrous potassium carbonate and anhydrous sodium carbonate as catalysts, diphenyl sulfone (melting point is 334 ℃) as solvent, and the synthesis of the product is started through nucleophilic substitution reaction at the initial temperature of 140-150 ℃, and the reaction is completed when the temperature is raised to 320 ℃. The obtained product is cooled to room temperature, then is ground and washed with water to obtain relatively pure polyether-ether-ketone, and then the obtained polyether-ether-ketone and the micron-sized hydroxyapatite are mechanically mixed together, and the mixture is subjected to selective laser sintering forming to obtain the composite material with relatively high porosity.
In carrying out the invention, the inventors have found 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 relatively poor shape stability, relatively few spheroidal particles and relatively wide particle size distribution, the prepared molded composite material has low dimensional accuracy and poor quality, and the mechanical property of the composite material obtained by taking the polyether-ether-ketone prepared by the prior art as a raw material through a selective laser sintering technology is measured to be much lower than that of the composite material obtained by a traditional injection molding or hot press molding method, so that 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 fewer spheroidal particles, rough surface and wider particle size distribution of the composite material in the prior art, the embodiment of the invention provides an application of selective laser sintering by taking polyether-ether-ketone prepared by a solvent 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 a solvent as a raw material, which comprises the following steps: the polyether-ether-ketone is synthesized by taking chlorinated 1, 3-bis (2-methoxy-2-oxyethyl) imidazole as a solvent.
Specifically, the application of the polyether-ether-ketone comprises the following steps:
(1) Under inert gas, adding a difluoro monomer into the solvent to enable the difluoro monomer to be fully dissolved in the solvent, so as to obtain a difluoro solution;
(2) Under inert gas, evenly mixing 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 into the difluoro solution to obtain mixed solution, heating the mixed solution to 140-200 ℃, ending the reaction when no carbon dioxide gas is generated, obtaining 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 the step (1) is as follows: 1) And adding a difluoro monomer into the solvent under inert gas, and continuously stirring at 25-60 ℃ to enable the difluoro monomer to be fully dissolved in the solvent, so as to obtain a difluoro solution.
Specifically, in the step (2), after the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate are uniformly mixed, the specific method for adding the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate into the difluoro solution is as follows: evenly mixing diphenol monomer, anhydrous potassium carbonate and anhydrous sodium carbonate, then adding the mixture into the difluoro solution for 3 to 5 times respectively, wherein the interval time between two adjacent times is 20 to 40 minutes, and stirring is continuously carried out after each time of adding.
Specifically, in the step (2), the specific method for obtaining the mixed solution is as follows: and after 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 enable the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate to be fully dissolved in the difluoro solution, so as to obtain a mixed solution.
Further, the specific method of the step (2) comprises the following steps: uniformly mixing the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate, adding the mixture into the difluoro solution, heating the mixture to 120-140 ℃ from room temperature at a 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 into the difluoro solution to obtain a mixed solution, and heating the mixed solution to 140-200 ℃ at a 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, methyl 2, 5-difluorobenzoate, ethyl 2, 4-difluorobenzoate or 4,4' -difluorobenzopiperazine.
Preferably, the difluoro monomers are 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-tert-octylbenzenediol, 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 includes: filtering and washing, said filtering and washing comprising: adding ethanol into the reaction product, performing primary filtration to obtain primary filtration residues, respectively washing the primary filtration residues with ethanol and acetone for 1-2 times, performing secondary filtration to obtain secondary filtration residues, and washing the secondary filtration residues with deionized water for two times.
Further, the purifying further comprises: drying, the method of drying comprising: and (3) vacuum drying the washed product at 120 ℃ to obtain the powdery polyether-ether-ketone.
The technical scheme provided by the embodiment of the invention has the beneficial effects that: the embodiment of the invention provides an application of selective laser sintering by taking polyether-ether-ketone prepared by a solvent as a raw material, wherein the application is to synthesize polyether-ether-ketone by taking chlorinated 1, 3-bis (2-methoxy-2-oxyethyl) imidazole as the solvent and take the synthesized polyether-ether-ketone as the raw material of a selective laser sintering technology. In the preparation process of the polyether-ether-ketone, the selected solvent is in a stable liquid state at room temperature or a high temperature of approximately room temperature to 300 ℃, so that the reaction temperature for synthesizing the polyether-ether-ketone can be reduced, the polyether-ether-ketone can be prepared at a relatively low temperature, the reaction is always carried out in a liquid phase, meanwhile, a reaction system still keeps in the liquid phase state after the reaction is cooled to normal temperature, the subsequent treatment process of the polyether-ether-ketone is greatly facilitated, the condition that a polymer and the solvent solidify into a group after diphenyl sulfone is cooled in the synthesis of the conventional polyether-ether-ketone is completely avoided, the synthesized polyether-ether-ketone can be directly used as a raw material of a selective laser sintering technology, the particle size of the prepared pure polyether-ether-ketone powder is detected to be distributed at 30-70 mu m by a dry-wet-cold-laser particle size analyzer, the surface of the polyether-ether-ketone prepared by observation of a scanning electron microscope is smooth, and has high powder fluidity, and the polyether-ether-ketone meets the requirement 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 chlorinated 1, 3-bis (2-methoxy-2-oxyethyl) imidazole selected in this example was obtained from the open source scientific and technological laboratory of Sanmen county, zhejiang province, and had a CP specification and a purity of 98%.
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 example are all from Shanghai source leaf biotechnology Co., ltd, and have the specification of AR and the purity of not less than 99.5%;4,4 '-difluorodiphenylmethane, 2, 5-difluoroanisole, 2, 5-difluorobenzophenone, 3, 5-difluorobenzonitrile, 2, 5-difluorobenzoacid methyl ester, 2, 4-difluorobenzoacid ethyl ester and 4,4' -difluorobenzopiperazine are all from the national pharmaceutical group, and the specification is AR, and the purity is more than or equal to 99.5 percent.
The diphenol monomers 1, 4-benzenediol, bisphenol A, 1, 5-naphthalenediol and 2, 6-naphthalenediol selected in the embodiment are from the national drug group, wherein the specification is AR, and the purity is more than or equal to 99.5%; the tert-butyl hydroquinone, the 2-methoxy hydroquinone, the trimethyl hydroquinone, the tetramethyl hydroquinone, the 2, 5-di-tert-octyl hydroquinone, the 2-tert-octyl benzene diphenol, the 2, 5-di-isooctyl hydroquinone, the 2, 5-diphenyl hydroquinone and the 2, 5-di-tert-amyl hydroquinone are all obtained from Fuji film company, and have the specification of AR and the purity of more than or equal to 99.5 percent.
Other reagents such as sodium carbonate and potassium carbonate were purchased from the chemical industry of the ridge, AR, with a purity of > 99%.
Example 1
21.80g of 3,3 '-difluorobenzophenone was added to 218.00g of 1, 3-bis (2-methoxy-2-oxyethyl) imidazole chloride solvent under argon protection to give a 4,4' -difluorobenzophenone solution, wherein the structure of 1, 3-bis (2-methoxy-2-oxyethyl) imidazole chloride was schematically shown as:
heating the 4,4' -difluorobenzophenone solution to 25 ℃, stirring the 4,4' -difluorobenzophenone solution to fully dissolve the 4,4' -difluorobenzophenone, and cooling to normal temperature for standby; under the protection of argon, 22.83g bisphenol A, 1.38g anhydrous potassium carbonate and 9.64g anhydrous sodium carbonate are uniformly mixed and divided into four parts with equal mass, and are respectively added into 3,3' -difluorobenzophenone solution, and continuously stirred at high speed (the stirring speed can be high)100-500 rpm), the interval time between two adjacent additions is 20min, the temperature is raised to 120 ℃ from normal temperature, the temperature raising rate is 10 ℃/min, the heat is preserved for 1h, 4 '-difluorobenzophenone, anhydrous potassium carbonate and anhydrous sodium carbonate are fully dissolved in 3,3' -difluorobenzophenone solution, the temperature is raised to 200 ℃, the temperature raising rate is 10 ℃/min, the reaction system is naturally cooled to room temperature under the condition of keeping stirring after the reaction is continuously carried out for 2h, a reaction product is obtained, 100ml of ethanol is added into the reaction product, a buchner funnel is adopted for primary filtration, primary filtration residues are obtained, the primary filtration residues are respectively washed for 1-2 times by ethanol and acetone, the secondary filtration residues are washed for two times by 100ml of deionized water, and the filtration residues are subjected to vacuum drying treatment at 120 ℃ to obtain 38.83g of polyetheretherketone powder, and the yield is 88%.
The reaction is schematically shown below:
the polyether-ether-ketone obtained in this example was subjected to particle size distribution testing using a dry-wet-cold-laser particle size analyzer, specifically using an instrument: dry-wet cold-laser particle size analyzer, manufacturer: zhuhai European and American grams, model: LS-CIII particle size distribution testing method comprises the following steps: and (3) dissolving 0.1g of the polyether-ether-ketone obtained in the second embodiment into 5g of ethanol, performing ultrasonic dispersion to prepare a suspension for testing, and measuring that the particle size of the polyether-ether-ketone is in normal distribution, and the average particle size is mainly distributed at 30-70 mu m, so that the polyether-ether-ketone has better particle size distribution and uniformity. Meanwhile, the apparent density of the polyether-ether-ketone powder is detected, and a testing instrument is used for: particle apparent density instrument, manufacturer: zhejiang Ruicaceae, model: FT-105C, method: 50g of PEEK powder is selected and put into an upper funnel, a baffle plate of the funnel is rapidly pulled away, the powder is freely piled up in a measuring cup, the volume of the powder in the measuring cup is measured, and finally the apparent density of the PEEK powder is measured to be 0.38g/cm 3 Has good fluidity (fluidity is determined by the shape and roughness of the powder, and is mainly determined comprehensively by the shape, particle size distribution, apparent density and powder spreading efficiency of the powder), which can lead toThe polyether-ether-ketone powder can produce ball bearing effect during powder spreading, and is favorable to raising the quality of selective laser sintering product.
The polyether-ether-ketone obtained in the first embodiment is used as a raw material for a selective laser sintering technology, and specifically comprises the following steps: sieving the obtained polyether-ether-ketone powder with 200 meshes, taking 5kg of the sieved polyether-ether-ketone powder, carrying out on a selective laser sintering rapid forming machine, setting the scanning interval to be 0.1mm, the single-layer thickness to be 0.15mm, the scanning speed to be 1500mm/s, preheating the polyether-ether-ketone powder at the temperature of between 120 and 140 ℃ and the laser power to be 16W to prepare a complete polyether-ether-ketone stretching spline (60 mm in length, 85mm in length and 2mm in thickness) and an impact spline (125 mm x width x thickness: 12mm x 5 mm), and measuring the stretching spline and the impact spline respectively to obtain the density of 0.723g/cm 3 Tensile strength of 80MPa and impact strength of 20KJ/m 2 The Young's modulus is 3GPa, and the mechanical property of the sintered part is similar to that of a polyether-ether-ketone molding part, wherein the polyether-ether-ketone molding part adopts equipment: TYU-2500 linked mode-locking vertical injection molding machine; the manufacturer: a Dayu machine; the forming process comprises the following steps: and 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 revolutions per minute, 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 a solvent as a raw material, wherein the application is to synthesize polyether-ether-ketone by taking chlorinated 1, 3-bis (2-methoxy-2-oxyethyl) imidazole as the solvent and take the synthesized polyether-ether-ketone as the raw material of a selective laser sintering technology. In the preparation process of the polyether-ether-ketone, the selected solvent is in a stable liquid state at room temperature or a high temperature of between approximately room temperature and 300 ℃, so that the reaction temperature for synthesizing the polyether-ether-ketone can be reduced, the polyether-ether-ketone 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 cooled to the room temperature, the subsequent treatment process of the polyether-ether-ketone is greatly facilitated, and the condition that the polymer and the solvent solidify into a group after diphenyl sulfone is cooled in the synthesis of the polyether-ether-ketone is completely avoided, so that the synthesized polyether-ether-ketone can be directly used as a raw material of a selective laser sintering technologyThe particle size distribution of the pure product of the powdery polyetheretherketone is detected to be 30-70 mu m by a dry-wet-cold-laser particle size analyzer, and the polyetheretherketone is observed by a scanning electron microscope to obtain the polyetheretherketone which has smooth surface, is similar to a sphere and has the apparent density of 0.38g/cm 3 The polyether-ether-ketone meets the requirements of selective laser sintering technology due to high powder flowability.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. Use of selective laser sintering of polyetheretherketone prepared with a solvent as a raw material, characterized in that it comprises the following steps:
(1) Adding difluoro monomer into solvent under inert gas, continuously stirring at 25-60 ℃ to make the difluoro monomer fully dissolved in the solvent to obtain difluoro solution, and synthesizing polyether ether ketone by using chlorinated 1, 3-bis (2-methoxy-2-oxyethyl) imidazole as solvent;
(2) Under inert gas, evenly mixing 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 into the difluoro solution to obtain mixed solution, heating the mixed solution to 140-200 ℃, ending the reaction when no carbon dioxide gas is generated, obtaining 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 according to claim 1, wherein in step (2), after the diphenol monomer, anhydrous potassium carbonate and anhydrous sodium carbonate are uniformly mixed, the specific method of adding the diphenol monomer to the difluoro solution is as follows: evenly mixing diphenol monomer, anhydrous potassium carbonate and anhydrous sodium carbonate, then adding the mixture into the difluoro solution for 3 to 5 times respectively, wherein the interval time between two adjacent times is 20 to 40 minutes, and stirring is continuously carried out after each time of adding.
3. The use according to claim 1, wherein in step (2), the specific method for obtaining the mixed solution is: and after 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 enable the diphenol monomer, the anhydrous potassium carbonate and the anhydrous sodium carbonate to be fully dissolved in the difluoro solution, so as to obtain a mixed solution.
4. The use according to 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 to 120-140 ℃ from room temperature at a 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 into the difluoro solution to obtain a mixed solution, and heating the mixed solution to 140-200 ℃ at a speed of 2-10 ℃/min.
5. Use according to claim 1, characterized in that 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, methyl 2, 5-difluorobenzoate, ethyl 2, 4-difluorobenzoate or 4,4' -difluorobenzopiperazine.
6. Use according to claim 1, characterized in that 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.
7. The use according to claim 1, wherein the purification comprises: filtering and washing, said filtering and washing comprising: adding ethanol into the reaction product, performing primary filtration to obtain primary filtration residues, respectively washing the primary filtration residues with ethanol and acetone for 1-2 times, performing secondary filtration to obtain secondary filtration residues, and washing the secondary filtration residues with deionized water for two times.
8. The use of claim 7, wherein the purifying further comprises: drying, the method of drying comprising: and (3) vacuum drying the washed product at 120 ℃ to obtain the powdery polyether-ether-ketone.
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| CN100582133C (en) * | 2008-01-11 | 2010-01-20 | 吉林金正高分子材料研发有限公司 | Preparation method for polyetheretherketone |
| CN104530418A (en) * | 2014-12-17 | 2015-04-22 | 江门市优巨新材料有限公司 | Industrial synthesis method of high-thermal-stability terminated polyaryletherketone resin |
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| CN103665283A (en) * | 2012-09-12 | 2014-03-26 | 北京师范大学 | Method of preparing polyaryletherketone |
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| H.Q.Nimal Gunaratne et al.Production of polyetheretherketone in ionic liquid media.《Green Chemistry》.2013,第1166-1172页. * |
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| Publication number | Publication date |
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| CN113321800A (en) | 2021-08-31 |
| CN113429532B (en) | 2023-05-23 |
| CN113429562A (en) | 2021-09-24 |
| CN113429562B (en) | 2023-05-23 |
| CN113429532A (en) | 2021-09-24 |
| CN108034047A (en) | 2018-05-15 |
| CN108034047B (en) | 2021-06-22 |
| CN113429563A (en) | 2021-09-24 |
| CN113321800B (en) | 2023-05-23 |
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