CN107383293B - A kind of preparation method of the polyether-ether-ketone suitable for 3D printing - Google Patents
A kind of preparation method of the polyether-ether-ketone suitable for 3D printing Download PDFInfo
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- CN107383293B CN107383293B CN201710700862.9A CN201710700862A CN107383293B CN 107383293 B CN107383293 B CN 107383293B CN 201710700862 A CN201710700862 A CN 201710700862A CN 107383293 B CN107383293 B CN 107383293B
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- ether
- polyether
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- ketone
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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
Abstract
The invention belongs to macromolecule synthesising technology fields, 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 hydroquinone and 4,4- difluoro benzophenone is raw material, using diphenyl sulphone (DPS) as solvent, by temperature reaction, then carries out decrease temperature crystalline removal of impurities and be dried to obtain；Solvent is excessive in reaction process of the present invention, salification process stable reaction, controllable；And the problem of using ultrasonication, reducing strand winding, improve the homogeneity of product；So as to improve the mobility of polyether-ether-ketone product, processing performance is excellent；Improve the performances such as intensity, impact resistance, anticorrosive, acid and alkali-resistance, dimensionally stable, adhesiveness.
Description
Technical field
The invention belongs to macromolecule synthesising technology field, the preparation side of especially a kind of polyether-ether-ketone suitable for 3D printing
Method.
Background technique
3D printing (3DP) i.e. one kind of rapid shaping technique, it is one kind based on digital model file, with powder
The adhesive materials such as shape metal or plastics construct the technology of object by layer-by-layer printing.3D printing is usually to use
Digital technology file printing machine is realized.Often be used for modeling in fields such as mold manufacture, industrial designs, after gradually use
In the direct manufacture of some products, have using components made of the printing of this technology.The technology is in jewelry, footwear, work
Industry design, building, engineering and construction (AEC), automobile, aerospace, dentistry and medical industries, education, GIS-Geographic Information System, soil
Wood engineering, gun and other field are all applied.3D printing material is the important material base of 3D printing technique development, 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 that prints
Surface has the lines of granular sensation printing obvious, and article is made to have special visual effect, praises highly by numerous users.
But it quality it is crisp be easily damaged, intensity is low, poor impact resistance, dimensional stability are bad, facile hydrolysis, mutability, for a long time
Dusting 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 poly(aryl ether ketone) (PAEK), has excellent mechanical performance, wear-resisting
Property, many-sided excellent properties such as chemical-resistant, radiation resistance, heat-resisting quantity and anti-flammability, replace in many fields other
Product properties can be obviously improved after material.Product original powder material 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, high rejection rate, printing interruption,
It may adapt to polyether-ether-ketone original powder material so that a printer can not be designed for the structure and application of 3D printer at this stage.
Therefore, the technical issues of developing a kind of polyetheretherketonematerials materials suitable for 3D printing, being current urgent need to resolve.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparation method of polyether-ether-ketone suitable for 3D printing, gram
Take the problem of polyether-ether-ketone is low, stability is poor, poor fluidity as the 3D printing strength of materials in the prior art.
The technical solution adopted by the present invention to solve the technical problems is: a kind of system of the polyether-ether-ketone suitable for 3D printing
Preparation Method uses sodium carbonate, potassium carbonate as reaction condensing agent, and with hydroquinone and 4,4- difluoro benzophenone is raw material, with
Diphenyl sulphone (DPS) is solvent, including following reaction step:
(1) diphenyl sulphone (DPS) is added at room temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), controls solution temperature
Degree is 180~190 DEG C, hydroquinone, 4,4- difluoro benzophenone is then added, and be heated to 210~220 DEG C, constant temperature stirring
React 25~30min, the hydroquinone, 4,4- difluoro benzophenone, diphenyl sulphone (DPS) mass ratio be 1 ﹕, 1 ﹕ 4~6；
(2) sodium carbonate, potassium carbonate are added into step (1) reaction system, is warming up to 230~235 DEG C, constant temperature is stirred to react
25~30min then heats to 250~260 DEG C of 50~60min of constant temperature, then is brought rapidly up to 300~320 DEG C of constant temperature and uses
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, hydroquinone mass ratio be 1 ﹕, 4~5 ﹕ 14~16；
(3) it will be extracted with organic solvent, inorganic solvent after the product cooling after step (2) reaction, then dried respectively
Polyether-ether-ketone suitable for 3D printing.
Preferably, step (3) is cooling to product uses sub-sectional cooling method, be cooled to first 210~220 DEG C keep 7~
10min, then 150~160 DEG C of 5~8min of holding are cooled to, then be cooled to 100~105 DEG C of 5~8min of holding, then cool down again
To 60~70 DEG C of 10~15min of holding.
Preferably, it is 1.5~2% that described 150~160 DEG C, which are cooled to 100~105 DEG C to control crystalline rate in the process,
It is 1~1.5% that 60~70 DEG C of control crystalline rates are cooled to from 100~105 DEG C.
Preferably, inorganic solvent described in step (3) is the pure water that conductivity is less than or equal to 1 μ s/cm.
Preferably, organic solvent described in step (3) is selected from one of acetone, ethyl alcohol, methanol, ethylene glycol, ether.
The beneficial effects of the present invention are: the present invention is polymer into chain reaction using 4,4- difluoro benzophenone and hydroquinone
Object, using sodium carbonate, potassium carbonate as condensing agent, solvent is excessive in reaction process, salification process stable reaction, controllable；And it adopts
With ultrasonication, reduces the problem of strand is wound, improve the homogeneity of product；So as to improve polyether-ether-ketone product
Mobility, processing performance is excellent；Improve the performances such as intensity, impact resistance, anticorrosive, acid and alkali-resistance, dimensionally stable, adhesiveness；
It can be used as 3D printing material；Preparation method of the present invention is easy, easily operated, is conducive to be mass produced, and low energy consumption, pollutant row
It puts few.
Specific embodiment
A kind of preparation method of the polyether-ether-ketone suitable for 3D printing, use sodium carbonate, potassium carbonate as reaction condensing agent,
With hydroquinone and 4,4- difluoro benzophenone is raw material, using diphenyl sulphone (DPS) as solvent, including following reaction step:
(1) diphenyl sulphone (DPS) is added at room temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), controls solution temperature
Degree is 180~190 DEG C, hydroquinone, 4,4- difluoro benzophenone is then added, and be heated to 210~220 DEG C, constant temperature stirring
React 25~30min, the hydroquinone, 4,4- difluoro benzophenone, diphenyl sulphone (DPS) mass ratio be 1 ﹕, 1 ﹕ 4~6；Diphenyl sulphone (DPS) mistake
Amount, stable reaction is controllable during 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 is stirred to react
25~30min then heats to 250~260 DEG C of 50~60min of constant temperature, then is brought rapidly up to 300~320 DEG C of constant temperature and uses
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, hydroquinone mass ratio be 1 ﹕, 4~5 ﹕ 14~16；Ultrasonication effectively improves the flowing of polyether-ether-ketone
Property, make it have excellent processing performance；
(3) it will be extracted with organic solvent, inorganic solvent after the product cooling after step (2) reaction, then dried respectively
Polyether-ether-ketone suitable for 3D printing.
Step (3) is cooling to product to use sub-sectional cooling method, 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.Control crystalline rate is 1.5~2% during described 150~160 DEG C are cooled to 100~105 DEG C, from
It is 1~1.5% that 100~105 DEG C, which are cooled to 60~70 DEG C of control crystalline rates,.Sub-sectional cooling is carried out, crystalline rate is controlled, 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 with 10 DEG C of temperature per minute to realize.
Inorganic solvent described in step (3) is the pure water that conductivity is less than or equal to 1 μ s/cm, and the organic solvent is selected from
One of acetone, ethyl alcohol, methanol, ethylene glycol, ether.It is washed first with inorganic solvent and removes the impurity such as metal ion.Then
Organic solvent extraction and separation solvent diphenyl sulphone (DPS) is used again.
Below with reference to embodiment, the present invention is further described.
Embodiment 1:
(1) diphenyl sulphone (DPS) is added at room temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), controls solution temperature
Degree is 180 DEG C, hydroquinone, 4,4- difluoro benzophenone is then added, and be heated to 210 DEG C, and constant temperature is stirred to react 30min,
The hydroquinone, 4,4- difluoro benzophenone, diphenyl sulphone (DPS) mass ratio be 1 ﹕, 1 ﹕ 4；
(2) sodium carbonate, potassium carbonate are added into step (1) reaction system, is warming up to 230 DEG C, constant temperature is stirred to react
30min then heats to 250 DEG C of constant temperature 60min, then is brought rapidly up to 300 DEG C of constant temperature and uses ultrasonication 30min, then
Isothermal reaction 150min；The frequency of the ultrasonic wave be 22KHz, the sodium carbonate, potassium carbonate, hydroquinone mass ratio be 1 ﹕
4 ﹕ 14；
(3) cooling to product to use sub-sectional cooling method, it 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
Control crystalline rate is 1.5% in the process, and it is 1% that 60 DEG C of control crystalline rates are cooled to from 100 DEG C；Then conductivity is used first
The impurity such as metal ion are removed for the pure water reactant of 1 μ s/cm, then separate diphenyl sulphone (DPS) with acetone extract, then dry suitable
Polyether-ether-ketone for 3D printing.
Embodiment 2:
(1) diphenyl sulphone (DPS) is added at room temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), controls solution temperature
Degree is 190 DEG C, hydroquinone, 4,4- difluoro benzophenone is then added, and be heated to 220 DEG C, and constant temperature is stirred to react 25min,
The hydroquinone, 4,4- difluoro benzophenone, diphenyl sulphone (DPS) mass ratio be 1 ﹕, 1 ﹕ 6；
(2) sodium carbonate, potassium carbonate are added into step (1) reaction system, is warming up to 235 DEG C, constant temperature is stirred to react
25min then heats to 260 DEG C of constant temperature 50min, then is brought rapidly up to 320 DEG C of constant temperature and uses ultrasonication 25min, then
Isothermal reaction 30min；The frequency of the ultrasonic wave be 38KHz, the sodium carbonate, potassium carbonate, hydroquinone mass ratio be 1 ﹕
5 ﹕ 16；
(3) cooling to product to use sub-sectional cooling method, it 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, it is then cooled to 70 DEG C of holding 10min again.Described is cooled to 105 DEG C from 160 DEG C
Control crystalline rate is 2% in the process, and it is 1.5% that 70 DEG C of control crystalline rates are cooled to from 105 DEG C；Then conductivity is used first
The impurity such as metal ion are removed for the pure water reactant of 0.8 μ s/cm, then with ethyl alcohol extraction and separation diphenyl sulphone (DPS), then dry
Polyether-ether-ketone suitable for 3D printing.
Embodiment 3:
(1) diphenyl sulphone (DPS) is added at room temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), controls solution temperature
Degree is 185 DEG C, hydroquinone, 4,4- difluoro benzophenone is then added, and be heated to 212 DEG C, and constant temperature is stirred to react 30min,
The hydroquinone, 4,4- difluoro benzophenone, diphenyl sulphone (DPS) mass ratio be 1 ﹕, 1 ﹕ 5；
(2) sodium carbonate, potassium carbonate are added into step (1) reaction system, is warming up to 232 DEG C, constant temperature is stirred to react
30min then heats to 256 DEG C of constant temperature 56min, then is brought rapidly up to 310 DEG C of constant temperature and uses ultrasonication 28min, then
Isothermal reaction 100min；The frequency of the ultrasonic wave be 30KHz, the sodium carbonate, potassium carbonate, hydroquinone mass ratio be 1 ﹕
4 ﹕ 15；
(3) cooling to product to use sub-sectional cooling method, it 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, it is then cooled to 68 DEG C of holding 12min again.Described is cooled to 100 DEG C from 156 DEG C
Control crystalline rate is 1.6% in the process, and it is 1.2% that 68 DEG C of control crystalline rates are cooled to from 100 DEG C；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 extraction and separation diphenyl sulphone (DPS), then dries
Obtain the polyether-ether-ketone suitable for 3D printing.
The resulting polyether-ether-ketone of Examples 1 to 3 is tested for the property, 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 |
| Thermal 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 makes polyether-ether-ketone
Properties improve 10% or so, and intensity produced by the present invention is high, stability is high, good fluidity polyether-ether-ketone can be used as
3D printing material.
Claims (5)
1. a kind of preparation method of the polyether-ether-ketone suitable for 3D printing, which is characterized in that use sodium carbonate, potassium carbonate as anti-
Condensing agent is answered, with hydroquinone and 4,4- difluoro benzophenone is raw material, using diphenyl sulphone (DPS) as solvent, including following reaction step:
(1) diphenyl sulphone (DPS) is added at room temperature, leads to argon gas protection, while heating melts diphenyl sulphone (DPS), control solution temperature is
180~190 DEG C, hydroquinone, 4,4- difluoro benzophenone is then added, and be heated to 210~220 DEG C, constant temperature is stirred to react
25~30min, the hydroquinone, 4,4- difluoro benzophenone, diphenyl sulphone (DPS) mass ratio be 1 ﹕, 1 ﹕ 4~6；
(2) sodium carbonate, potassium carbonate are added into step (1) reaction system, is warming up to 230~235 DEG C, constant temperature is stirred to react 25~
30min then heats to 250~260 DEG C of 50~60min of constant temperature, then is brought rapidly up to 300~320 DEG C of constant temperature and using ultrasound
Wave handles 25~30min, then 30~150min of isothermal reaction；The frequency of the ultrasonic wave be 22~38KHz, the sodium carbonate,
Potassium carbonate, hydroquinone mass ratio be 1 ﹕, 4~5 ﹕ 14~16；
(3) it will be extracted respectively with organic solvent, inorganic solvent after the product cooling after step (2) reaction, then dry applicable
In the polyether-ether-ketone of 3D printing.
2. a kind of preparation method of polyether-ether-ketone suitable for 3D printing according to claim 1, which is characterized in that step
(3) cooling to product to use sub-sectional cooling method, it 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 of 5~8min of holdings, be then cooled to again 60~70 DEG C of holdings 10~
15min。
3. a kind of preparation method of polyether-ether-ketone suitable for 3D printing according to claim 2, which is characterized in that described
150~160 DEG C to be cooled to control crystalline rate during 100~105 DEG C be 1.5~2%, be cooled to 60 from 100~105 DEG C
~70 DEG C of control crystalline rates are 1~1.5%.
4. a kind of preparation method of polyether-ether-ketone suitable for 3D printing according to claim 1, which is characterized in that step
(3) inorganic solvent described in is the pure water that conductivity is less than or equal to 1 μ s/cm.
5. a kind of preparation method of polyether-ether-ketone suitable for 3D printing according to claim 1, which is characterized in that step
(3) organic solvent described in is selected from one of acetone, ethyl alcohol, methanol, ethylene glycol, ether.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108102502B (en) * | 2017-12-05 | 2020-06-05 | 宜宾天原集团股份有限公司 | Preparation method of water-soluble polyether-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 |
| CN113912799B (en) * | 2021-09-16 | 2022-05-10 | 吉林省中研高分子材料股份有限公司 | Polyether-ether-ketone and preparation method thereof |
| CN113736044B (en) * | 2021-09-28 | 2022-11-15 | 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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