CN107383293A - A kind of preparation method of polyether-ether-ketone suitable for 3D printing - Google Patents
A kind of preparation method of polyether-ether-ketone suitable for 3D printing Download PDFInfo
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- CN107383293A CN107383293A CN201710700862.9A CN201710700862A CN107383293A CN 107383293 A CN107383293 A CN 107383293A CN 201710700862 A CN201710700862 A CN 201710700862A CN 107383293 A CN107383293 A CN 107383293A
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
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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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Abstract
The invention belongs to macromolecule synthesising technology field, specifically disclose the preparation method of the polyether-ether-ketone suitable for 3D printing, this method uses sodium carbonate, potassium carbonate as reaction condensing agent, with hydroquinones and 4,4 difluoro benzophenones are raw material, using diphenyl sulphone (DPS) as solvent, by temperature reaction, then carry out decrease temperature crystalline removal of impurities and be dried to obtain；Solvent is excessive in course of reaction of the present invention, salification process stable reaction, controllable；And ultrasonication is used, reduce the problem of strand is wound, improve the homogeneity of product；So as to improve the mobility of polyether-ether-ketone product, processing characteristics is excellent；Improve the performance such as intensity, impact resistance, anticorrosive, acid and alkali-resistance, dimensionally stable, cohesive.
Description
Technical field
The invention belongs to the preparation side of macromolecule synthesising technology field, especially a kind of polyether-ether-ketone suitable for 3D printing
Method.
Background technology
3D printing (3DP) is one kind of rapid shaping technique, and it is a kind of based on mathematical model file, with powder
Shape metal or plastics etc. can jointing material, come the technology of constructed object by way of successively printing.3D printing is typically to use
Digital technology file printing machine is realized.Often it is used for modeling in fields such as Making mold, industrial designs, it is rear gradually to use
In the direct manufacture of some products, there are the parts formed using the printing of this technology.The technology is in jewelry, footwear, work
Industry design, building, engineering and construction (AEC), automobile, Aero-Space, dentistry and medical industries, education, GIS-Geographic Information System, soil
Wood engineering, gun and other field have all been applied.3D printing material is that the important substance of 3D printing technique development is basic, mesh
Preceding 3D printing material mainly includes engineering plastics, photosensitive resin, rubber type of material, metal material and ceramic material, coloured plaster
Material etc..
3D printing is compound gypsum powder using wide material, due to cheap price, the product printed
The lines that there is granular sensation to print on surface is obvious, article is had special visual effect, enjoys numerous users to praise highly.
But it quality it is crisp be easily damaged, low intensity, poor impact resistance, dimensional stability are bad, facile hydrolysis, mutability, for a long time
Efflorescence etc. is placed, is not particularly suited for printing some products being typically placed in outdoor or extreme humidity environment.
Polyether-ether-ketone (PEEK) is most typical material in PAEK (PAEK), has excellent mechanical performance, wear-resisting
Property, many-sided excellent properties such as chemical-resistant, radiation resistance, heat-resisting quantity and anti-flammability, substitute in many fields other
Product properties can be obviously improved after material.Product original powder of the polyether-ether-ketone as 3D printing, this kind of powder has very outstanding
Physics, chemical property, but during being printed, there is phenomena such as poor fluidity, percent defective are high, printing is interrupted,
Polyether-ether-ketone original powder is may adapt to so that a printer can not be designed for the structure of 3D printer at this stage and application.
Therefore, a kind of polyetheretherketonematerials materials suitable for 3D printing are developed, are the technical problems of current urgent need to resolve.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation method of the polyether-ether-ketone suitable for 3D printing, gram
Clothes in the prior art polyether-ether-ketone as the problem of 3D printing strength of materials is low, stability is poor, poor fluidity.
The technical solution adopted for the present invention to solve the technical problems is：A kind of system of polyether-ether-ketone suitable for 3D printing
Preparation Method, using sodium carbonate, potassium carbonate as condensing agent is reacted, with hydroquinones and 4,4- difluoro benzophenones are raw material, with
Diphenyl sulphone (DPS) is solvent, including following reactions steps：
(1) diphenyl sulphone (DPS) is added at ambient temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), controls solution temperature
Spend for 180~190 DEG C, then add hydroquinones, 4,4- difluoro benzophenones, and be heated to 210~220 DEG C, constant temperature stirring
25~30min is reacted, the hydroquinones, 4,4- difluoro benzophenones, the mass ratio of diphenyl sulphone (DPS) are the ﹕ 4~6 of 1 ﹕ 1；
(2) sodium carbonate, potassium carbonate are added into step (1) reaction system, is warming up to 230~235 DEG C, constant temperature stirring reaction
25~30min, 250~260 DEG C of 50~60min of constant temperature are then heated to, then be brought rapidly up to 300~320 DEG C of constant temperature and use
25~30min of ultrasonication, then 30~150min of isothermal reaction；The frequency of the ultrasonic wave is 22~38KHz, the carbonic acid
Sodium, potassium carbonate, the mass ratio of hydroquinones are the ﹕ 14~16 of 1 ﹕ 4~5；
(3) it will be extracted with organic solvent, inorganic solvent after the reacted product cooling of step (2), then dried respectively
Suitable for the polyether-ether-ketone of 3D printing.
Preferably, step (3) to product cooling use sub-sectional cooling method, be cooled to first 210~220 DEG C holdings 7~
10min, then 150~160 DEG C of 5~8min of holding are cooled to, then 100~105 DEG C of 5~8min of holding are cooled to, then cool again
To 60~70 DEG C of 10~15min of holding.
Preferably, described 150~160 DEG C be cooled to 100~105 DEG C during control crystalline rate be 1.5~2%,
It is 1~1.5% that 60~70 DEG C are cooled to from 100~105 DEG C and controls crystalline rate.
Preferably, the inorganic solvent described in step (3) is the pure water that electrical conductivity is less than or equal to 1 μ s/cm.
Preferably, the one kind of the organic solvent described in step (3) in acetone, ethanol, methanol, ethylene glycol, ether.
The beneficial effects of the invention are as follows：The present invention is polymer into chain reaction using 4,4- difluoro benzophenones and hydroquinones
Thing, using sodium carbonate, potassium carbonate as condensing agent, solvent is excessive in course of reaction, salification process stable reaction, controllable；And adopt
With ultrasonication, reduce the problem of strand is wound, improve the homogeneity of product；So as to improve polyether-ether-ketone product
Mobility, processing characteristics is excellent；Improve the performance such as intensity, impact resistance, anticorrosive, acid and alkali-resistance, dimensionally stable, cohesive；
It can be used as 3D printing material；Preparation method of the present invention is easy, easily operated, is advantageous to mass produce, and energy consumption is low, pollutant row
Put few.
Embodiment
A kind of preparation method of polyether-ether-ketone suitable for 3D printing, using sodium carbonate, potassium carbonate as reaction condensing agent,
With hydroquinones and 4,4- difluoro benzophenones are raw material, using diphenyl sulphone (DPS) as solvent, including following reactions steps：
(1) diphenyl sulphone (DPS) is added at ambient temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), controls solution temperature
Spend for 180~190 DEG C, then add hydroquinones, 4,4- difluoro benzophenones, and be heated to 210~220 DEG C, constant temperature stirring
25~30min is reacted, the hydroquinones, 4,4- difluoro benzophenones, the mass ratio of diphenyl sulphone (DPS) are the ﹕ 4~6 of 1 ﹕ 1；Diphenyl sulphone (DPS) mistake
Amount, stable reaction is controllable during the course of the reaction, improves the stability of polyether-ether-ketone；
(2) sodium carbonate, potassium carbonate are added into step (1) reaction system, is warming up to 230~235 DEG C, constant temperature stirring reaction
25~30min, 250~260 DEG C of 50~60min of constant temperature are then heated to, then be brought rapidly up to 300~320 DEG C of constant temperature and use
25~30min of ultrasonication, then 30~150min of isothermal reaction；The frequency of the ultrasonic wave is 22~38KHz, the carbonic acid
Sodium, potassium carbonate, the mass ratio of hydroquinones are the ﹕ 14~16 of 1 ﹕ 4~5；Ultrasonication effectively improves the flowing of polyether-ether-ketone
Property, make it have excellent processing characteristics；
(3) it will be extracted with organic solvent, inorganic solvent after the reacted product cooling of step (2), then dried respectively
Suitable for the polyether-ether-ketone of 3D printing.
Step (3) uses sub-sectional cooling method to product cooling, is cooled to 210~220 DEG C of 7~10min of holding first, then drop
Temperature is to 150~160 DEG C of 5~8min of holding, then is cooled to 100~105 DEG C of 5~8min of holding, is then cooled to 60~70 DEG C again
Keep 10~15min.Described 150~160 DEG C control crystalline rate during being cooled to 100~105 DEG C be 1.5~2%, from
It is 1~1.5% that 100~105 DEG C, which are cooled to 60~70 DEG C to control crystalline rate,.Sub-sectional cooling is carried out, controls crystalline rate so that
The intensity that uniform void structure improves polyether-ether-ketone is formed in cooling procedure.Crystalline rate passes through in glass transition temperature
Under, gradient cooling is carried out to realize with 10 DEG C of temperature per minute.
Inorganic solvent described in step (3) is less than or equal to 1 μ s/cm pure water for electrical conductivity, and described organic solvent is selected from
One kind in acetone, ethanol, methanol, ethylene glycol, ether.Washed first with inorganic solvent and remove the impurity such as metal ion.Then
Organic solvent extract and separate solvent diphenyl sulphone (DPS) is used again.
With reference to embodiment, the present invention is further described.
Embodiment 1：
(1) diphenyl sulphone (DPS) is added at ambient temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), controls solution temperature
Spend for 180 DEG C, then add hydroquinones, 4,4- difluoro benzophenones, and be heated to 210 DEG C, constant temperature stirring reaction 30min,
The hydroquinones, 4,4- difluoro benzophenones, the mass ratio of diphenyl sulphone (DPS) are the ﹕ 4 of 1 ﹕ 1；
(2) sodium carbonate, potassium carbonate are added into step (1) reaction system, is warming up to 230 DEG C, constant temperature stirring reaction
30min, 250 DEG C of constant temperature 60min are then heated to, then be brought rapidly up to 300 DEG C of constant temperature and use ultrasonication 30min, then
Isothermal reaction 150min；The frequency of the ultrasonic wave is 22KHz, and the sodium carbonate, potassium carbonate, the mass ratio of hydroquinones are 1 ﹕
4 ﹕ 14；
(3) sub-sectional cooling method is used to product cooling, is cooled to 210 DEG C of holding 10min first, then be cooled to 150 DEG C of guarantors
8min is held, then is cooled to 100 DEG C of holding 8min, is then cooled to 60 DEG C of holding 15min again.Described 150 DEG C are cooled to 100 DEG C
During control the crystalline rate to be 1.5%, 60 DEG C are cooled to from 100 DEG C and control crystalline rate as 1%；Then electrical conductivity is used first
The impurity such as metal ion are removed for 1 μ s/cm pure water reactant, then diphenyl sulphone (DPS) is separated with acetone extract, then dries and must fit
Polyether-ether-ketone for 3D printing.
Embodiment 2：
(1) diphenyl sulphone (DPS) is added at ambient temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), controls solution temperature
Spend for 190 DEG C, then add hydroquinones, 4,4- difluoro benzophenones, and be heated to 220 DEG C, constant temperature stirring reaction 25min,
The hydroquinones, 4,4- difluoro benzophenones, the mass ratio of diphenyl sulphone (DPS) are the ﹕ 6 of 1 ﹕ 1；
(2) sodium carbonate, potassium carbonate are added into step (1) reaction system, is warming up to 235 DEG C, constant temperature stirring reaction
25min, 260 DEG C of constant temperature 50min are then heated to, then be brought rapidly up to 320 DEG C of constant temperature and use ultrasonication 25min, then
Isothermal reaction 30min；The frequency of the ultrasonic wave is 38KHz, and the sodium carbonate, potassium carbonate, the mass ratio of hydroquinones are 1 ﹕
5 ﹕ 16；
(3) sub-sectional cooling method is used to product cooling, is cooled to 220 DEG C of holding 7min first, then be cooled to 160 DEG C of holdings
5min, then 105 DEG C of holding 5min are cooled to, 70 DEG C of holding 10min are then cooled to again.Described is cooled to 105 DEG C from 160 DEG C
During control the crystalline rate to be 2%, 70 DEG C are cooled to from 105 DEG C and control crystalline rate as 1.5%；Then electrical conductivity is used first
The impurity such as metal ion is removed for 0.8 μ s/cm pure water reactant, then with ethanol extract and separate diphenyl sulphone (DPS), then dry
Suitable for the polyether-ether-ketone of 3D printing.
Embodiment 3：
(1) diphenyl sulphone (DPS) is added at ambient temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), controls solution temperature
Spend for 185 DEG C, then add hydroquinones, 4,4- difluoro benzophenones, and be heated to 212 DEG C, constant temperature stirring reaction 30min,
The hydroquinones, 4,4- difluoro benzophenones, the mass ratio of diphenyl sulphone (DPS) are the ﹕ 5 of 1 ﹕ 1；
(2) sodium carbonate, potassium carbonate are added into step (1) reaction system, is warming up to 232 DEG C, constant temperature stirring reaction
30min, 256 DEG C of constant temperature 56min are then heated to, then be brought rapidly up to 310 DEG C of constant temperature and use ultrasonication 28min, then
Isothermal reaction 100min；The frequency of the ultrasonic wave is 30KHz, and the sodium carbonate, potassium carbonate, the mass ratio of hydroquinones are 1 ﹕
4 ﹕ 15；
(3) sub-sectional cooling method is used to product cooling, is cooled to 210 DEG C of holding 8min first, then be cooled to 156 DEG C of holdings
7min, then 100 DEG C of holding 7min are cooled to, 68 DEG C of holding 12min are then cooled to again.Described is cooled to 100 DEG C from 156 DEG C
During control the crystalline rate to be 1.6%, 68 DEG C are cooled to from 100 DEG C and control crystalline rate as 1.2%；Then conductance is used first
The pure water reactant that rate is 1 μ s/cm removes the impurity such as metal ion, then spent glycol extract and separate diphenyl sulphone (DPS), then dries
The polyether-ether-ketone of 3D printing must be applied to.
Performance test is carried out to the polyether-ether-ketone of the gained of embodiment 1~3, it is as a result as shown in the table：
| Unit | Embodiment 1 | Embodiment 3 | Embodiment 2 | Control group | |
| Tensile strength | MPa | 119 | 110 | 104 | 95 |
| Bending strength | MPa | 113 | 109 | 110 | 105 |
| Impact strength | kJ/m2 | 3.2 | 3.5 | 3.4 | 3.3 |
| Heat decomposition temperature | ℃ | 551 | 549 | 555 | 524 |
| Viscosity | Pa.S | 155 | 150 | 153 | 175 |
Wherein control group is existing polyether-ether-ketone performance, it can be seen that preparation method of the invention causes polyether-ether-ketone
Properties improve 10% or so, and intensity produced by the present invention is high, stability is high, the polyether-ether-ketone of good fluidity can be used as
3D printing material.
Claims (5)
1. the preparation method of a kind of polyether-ether-ketone suitable for 3D printing, it is characterised in that using sodium carbonate, potassium carbonate as instead
Condensing agent is answered, with hydroquinones and 4,4- difluoro benzophenones are raw material, using diphenyl sulphone (DPS) as solvent, including following reactions steps：
(1) diphenyl sulphone (DPS) is added at ambient temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), controls the solution temperature to be
180~190 DEG C, hydroquinones, 4,4- difluoro benzophenones are then added, and is heated to 210~220 DEG C, constant temperature stirring reaction
25~30min, the hydroquinones, 4,4- difluoro benzophenones, the mass ratio of diphenyl sulphone (DPS) are the ﹕ 4~6 of 1 ﹕ 1；
(2) sodium carbonate, potassium carbonate are added into step (1) reaction system, is warming up to 230~235 DEG C, constant temperature stirring reaction 25~
30min, 250~260 DEG C of 50~60min of constant temperature are then heated to, then be brought rapidly up to 300~320 DEG C of constant temperature and using ultrasound
Ripple handles 25~30min, then 30~150min of isothermal reaction；The frequency of the ultrasonic wave is 22~38KHz, the sodium carbonate,
Potassium carbonate, the mass ratio of hydroquinones are the ﹕ 14~16 of 1 ﹕ 4~5；
(3) will be extracted respectively with organic solvent, inorganic solvent after the reacted product cooling of step (2), then drying to be applicable
In the polyether-ether-ketone of 3D printing.
A kind of 2. preparation method of polyether-ether-ketone suitable for 3D printing according to claim 1, it is characterised in that step
(3) sub-sectional cooling method is used to product cooling, is cooled to 210~220 DEG C of 7~10min of holding first, then be cooled to 150~160
DEG C keep 5~8min, then be cooled to 100~105 DEG C holding 5~8min, be then cooled to again 60~70 DEG C keep 10~
15min。
3. the preparation method of a kind of polyether-ether-ketone suitable for 3D printing according to claim 2, it is characterised in that described
150~160 DEG C be cooled to 100~105 DEG C during control crystalline rate be 1.5~2%, be cooled to 60 from 100~105 DEG C
It is 1~1.5% that~70 DEG C, which control crystalline rate,.
A kind of 4. preparation method of polyether-ether-ketone suitable for 3D printing according to claim 1, it is characterised in that step
(3) inorganic solvent described in is less than or equal to 1 μ s/cm pure water for electrical conductivity.
A kind of 5. preparation method of polyether-ether-ketone suitable for 3D printing according to claim 1, it is characterised in that step
(3) one kind of organic solvent in acetone, ethanol, methanol, ethylene glycol, ether described in.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108102502A (en) * | 2017-12-05 | 2018-06-01 | 宜宾天原集团股份有限公司 | A kind of preparation method of water-soluble poly ether ether ketone coating |
| CN109438640A (en) * | 2018-10-25 | 2019-03-08 | 宜宾天原集团股份有限公司 | A kind of preparation method of high fluidity low viscosity polyether-ether-ketone |
| CN113402723A (en) * | 2021-06-03 | 2021-09-17 | 宁夏清研高分子新材料有限公司 | Super-hydrophobic polyether-ether-ketone material and preparation method thereof |
| CN113736044A (en) * | 2021-09-28 | 2021-12-03 | 吉林大学 | Special material for 3D printing-grade polyether-ether-ketone resin, preparation and application thereof, 3D printing interlayer reinforced polyether-ether-ketone alloy material and preparation thereof |
| WO2023040819A1 (en) * | 2021-09-16 | 2023-03-23 | 吉林省中研高分子材料股份有限公司 | Polyetheretherketone and preparation method therefor |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108102502A (en) * | 2017-12-05 | 2018-06-01 | 宜宾天原集团股份有限公司 | A kind of preparation method of water-soluble poly ether ether ketone coating |
| CN109438640A (en) * | 2018-10-25 | 2019-03-08 | 宜宾天原集团股份有限公司 | A kind of preparation method of high fluidity low viscosity polyether-ether-ketone |
| CN113402723A (en) * | 2021-06-03 | 2021-09-17 | 宁夏清研高分子新材料有限公司 | Super-hydrophobic polyether-ether-ketone material and preparation method thereof |
| WO2023040819A1 (en) * | 2021-09-16 | 2023-03-23 | 吉林省中研高分子材料股份有限公司 | Polyetheretherketone and preparation method therefor |
| CN113736044A (en) * | 2021-09-28 | 2021-12-03 | 吉林大学 | Special material for 3D printing-grade polyether-ether-ketone resin, preparation and application thereof, 3D printing interlayer reinforced polyether-ether-ketone alloy material and preparation thereof |
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| CN107383293B (en) | 2019-07-02 |
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Effective date of registration: 20200526 Address after: 644004, No. 61, west section of Harbour Road, Lingang Economic and Technological Development Zone, Sichuan, Yibin Co-patentee after: YIBIN TIANYI NEW MATERIAL TECHNOLOGY Co.,Ltd. Patentee after: YIBIN TIANYUAN GROUP Co.,Ltd. Address before: 644004, No. 61, west section of Harbour Road, Lingang Economic and Technological Development Zone, Sichuan, Yibin Patentee before: YIBIN TIANYUAN GROUP Co.,Ltd. |
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