CN106046358A - Technique for purifying polyetherketoneketone crude product - Google Patents
Technique for purifying polyetherketoneketone crude product Download PDFInfo
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- CN106046358A CN106046358A CN201610504967.2A CN201610504967A CN106046358A CN 106046358 A CN106046358 A CN 106046358A CN 201610504967 A CN201610504967 A CN 201610504967A CN 106046358 A CN106046358 A CN 106046358A
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- China
- Prior art keywords
- crude product
- pekk
- technique
- purification
- pekk crude
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
Abstract
The invention belongs to the technical field of high-polymer materials, and particularly relates to a technique for purifying a polyetherketoneketone crude product. The technique comprises the following steps: adding the polyetherketoneketone crude product into an ethanedioic acid ethanol solution, and heating under reflux to obtain a mixed solution; adding a sodium gluconate water solution into the mixed solution, stirring under reflux, cooling, and carrying out vacuum filtration; and washing the polyetherketoneketone subjected to vacuum filtration with ethanol at normal temperature, and carrying out vacuum filtration, and drying to obtain the polyetherketoneketone pure product. The technique has the advantages of simple operating process, high production efficiency and high product quality, and is suitable for industrial production.
Description
Technical field
The invention belongs to technical field of polymer materials, the technique being specifically related to a kind of purification PEKK crude product.
Background technology
PEKK is a kind of high-performance thermoplastic engineering plastics, its outstanding thermostability, rigidity, mechanical performance and wear-resisting
Performance, is widely used in defence and military, Aero-Space, electronic information, automobile making, petrochemical industry, health care, household electric
Device, automobile manufacturing field.
At present, the preparation of PEKK is divided into nucleophilic substitution method and electrophilic substitution reaction method two kinds.The former holds high by raw material
Expensive, complex process；Latter raw material's price is relatively low, and technique is relatively easy.In electrophilic substitution reaction method, synthesize PEKK through polycondensation
Time, general employing anhydrous Aluminum chloride is catalyst, and course of reaction need to add a large amount of catalyst, thus causes in PEKK crude product
Remain catalyst.The heat stability of resin can be brought harm greatly, during following process also by the existence of catalyst
Polymer generation side reaction can be caused.Therefore, it is possible to find a kind of effective crude product post processing purifying process, effectively remove polymerization
In thing, residual impurity is the important step of synthesized high-performance PEKK.
At present, electrophilic reaction route the post processing purifying process of the PEKK prepared is most complex loaded down with trivial details, often
All can use a large amount of solvent during secondary process, and generally require long-time cyclic washing, sometimes also need to use the pure of High Temperature High Pressure
Change method, higher to equipment requirements, washed after can produce a large amount of waste liquid, cause putting into big, efficiency is low, and effect on environment is big,
Thus limit its development and application further.
Summary of the invention
The technique that it is an object of the invention to provide a kind of purification PEKK crude product, simple to operate, cost is relatively low, it is possible to have
The content of foreign ion in the reduction PEKK crude product of effect.
The technique of purification PEKK crude product of the present invention, step is as follows:
(1) PEKK crude product is joined in the ethanol solution of ethanedioic acid, temperature rising reflux, obtain mixed liquor；
(2) in mixed liquor, add the aqueous solution of sodium gluconate, be stirred at reflux, sucking filtration after cooling；
(3) wash under the PEKK alcohol at normal temperature after sucking filtration, through sucking filtration, drying, obtain PEKK sterling.
PEKK crude product described in step (1) uses electrophilic reaction to prepare with aluminum chloride for catalyst, and particle diameter is
The powdery of 0.04-2.15mm or sheet material.
The mass concentration of the ethanol solution of the ethanedioic acid described in step (1) is 40-60%.
PEKK crude product described in step (1) is 1g:15-20ml with the proportioning of the ethanol solution of ethanedioic acid.
The mass concentration of the aqueous solution of the sodium gluconate described in step (2) is 2.5-5%.
The addition of the aqueous solution of the sodium gluconate described in step (2) is 10-15 times of PEKK crude product quality.
The time that is stirred at reflux described in step (2) is 3-5 hour.
Drying described in step (3) is first to dry 4-6 hour through normal pressure, then decompression drying 1-2 hour, reduced vacuum degree
For 0.1-0.13MPa.
Drying temperature described in step (3) is 100-120 DEG C.
The present invention compared with prior art, has the advantages that
Compared with prior art, operating procedure of the present invention is simple, production efficiency is high, good product quality, is suitable to industrialization
Produce.In the present invention, PEKK can be the most swelling, and gluconic acid radical ion can be formed with aluminium ion
Stable comple, so that it separates with PEKK, reaches to remove the purpose of metal ion, meanwhile, uses ethanol to make
Can remove other organic impurities further for detergent, improve PEKK color and luster, effect is notable.The present invention can not only be by
In PEKK, metal ion content is down to below 80ppm, raising product quality, and the consumption of the sodium gluconate used
Little, pollute substantially free of public hazards, will not be economic and environment-friendly to environmental danger.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
The PEKK crude product 30g that particle size range is 0.04-1mm is encased in tri-mouthfuls of vials of 1000ml, adds
The ethanol solution 450ml of the ethanedioic acid of 40%, and add the aqueous solution 300g of the sodium gluconate of 2.5%；Stir under reflux temperature
Mix 3 hours, sucking filtration after cooling；PEKK after Primary purification washs with under 200ml alcohol at normal temperature, and sucking filtration is dried at bipyramid
In device after 120 DEG C of dry 4h of normal pressure, then negative pressure-0.13MPa is dried 1h, and organic solvent-free residual, urges in PEKK after testing
Agent metal ion residual is 65ppm.
Embodiment 2
The PEKK crude product 23.56g that particle size range is 0.5-1.5mm is encased in tri-mouthfuls of vials of 1000ml, adds
Enter the ethanol solution 424ml of the ethanedioic acid of 48%, and add the aqueous solution 294.5g of 4% sodium gluconate；Stir under reflux temperature
Mix 4 hours, sucking filtration after cooling；PEKK after Primary purification washs with under 150ml alcohol at normal temperature, and sucking filtration is dried at bipyramid
In device after 100 DEG C of dry 6h of normal pressure, then negative pressure-0.1MPa is dried 2h, after testing organic solvent-free residual, is catalyzed in PEKK
Agent metal ion residual is 72ppm.
Embodiment 3
The PEKK crude product 20g that particle size range is 1-2.15mm is encased in tri-mouthfuls of vials of 1000ml, adds
The ethanol solution 400ml of the ethanedioic acid of 60%, and add the aqueous solution 300g of 5% sodium gluconate；Stirred under reflux temperature 5 is little
Time, sucking filtration after cooling；PEKK after Primary purification washs with under 150ml alcohol at normal temperature, sucking filtration, in double cone dryer often
After pressing 110 DEG C of dry 5h, then negative pressure-0.12MPa is dried 1.5h, after testing organic solvent-free residual, catalyst in PEKK
Metal ion residual is 48ppm.
Embodiment 4
The PEKK crude product 20g that particle size range is 0.5-1.5mm is encased in tri-mouthfuls of vials of 1000ml, adds
The ethanol solution 380ml of the ethanedioic acid of 55%, and add the aqueous solution 250g of 4% sodium gluconate；Stirred under reflux temperature 5 is little
Time, sucking filtration after cooling；PEKK after Primary purification washs with under 150ml alcohol at normal temperature, sucking filtration, in double cone dryer often
After pressing 105 DEG C of dry 5.5h, then negative pressure-0.12MPa is dried 2h, after testing organic solvent-free residual, catalyst in PEKK
Metal ion residual is 56ppm.
Comparative example 1
The PEKK crude product 30g that particle size range is 0.04-1mm is encased in tri-mouthfuls of vials of 1000ml, adds
The aqueous solution 300g of the sodium gluconate of 2.5%；Stirred under reflux temperature 4 hours, sucking filtration after cooling；Then 200ml ethanol is used
Wash 2 times under room temperature, sucking filtration, the driest, there is a small amount of organic solvent residual after testing, catalyst metal ion in PEKK
Residual is 820ppm.
Comparative example 2
The PEKK crude product 30g that particle size range is 0.04-1mm is encased in tri-mouthfuls of vials of 1000ml, adds
After 37% aqueous hydrochloric acid solution 700ml, stir 4 hours under room temperature, sucking filtration, wash for several times with under 600ml water room temperature, and centrifuge dehydration
For several times, until cleaning mixture is neutrality, at 100 DEG C, finally it is dried 5h, has a small amount of organic solvent residual after testing, in PEKK
Catalyst metal ion residual is 4520ppm.
Comparative example 3
The PEKK crude product 30g that particle size range is 0.04-1mm is encased in tri-mouthfuls of vials of 1000ml, adds
The ethanol solution 450ml of the ethanedioic acid of 40%, stirred under reflux temperature 3 hours, sucking filtration after cooling；Polyether-ketone after Primary purification
Ketone washs with under 200ml alcohol at normal temperature, sucking filtration, is dried, has a small amount of machine dissolvent residual, catalyst metals in PEKK after testing
Ion residues is 2710ppm.
Claims (9)
1. the technique of a purification PEKK crude product, it is characterised in that step is as follows:
(1) PEKK crude product is joined in the ethanol solution of ethanedioic acid, temperature rising reflux, obtain mixed liquor；
(2) in mixed liquor, add the aqueous solution of sodium gluconate, be stirred at reflux, sucking filtration after cooling；
(3) wash under the PEKK alcohol at normal temperature after sucking filtration, through sucking filtration, drying, obtain PEKK sterling.
The technique of purification PEKK crude product the most according to claim 1, it is characterised in that the polyethers described in step (1)
Ketone ketone crude product uses electrophilic reaction to prepare with aluminum chloride for catalyst, and particle diameter is powdery or the sheet material of 0.04-2.15mm.
The technique of purification PEKK crude product the most according to claim 1, it is characterised in that the second two described in step (1)
The mass concentration of the ethanol solution of acid is 40-60%.
The technique of purification PEKK crude product the most according to claim 1, it is characterised in that the polyethers described in step (1)
Ketone ketone crude product is 1g:15-20ml with the proportioning of the ethanol solution of ethanedioic acid.
The technique of purification PEKK crude product the most according to claim 1, it is characterised in that the Fructus Vitis viniferae described in step (2)
The mass concentration of the aqueous solution of sodium saccharate is 2.5-5%.
The technique of purification PEKK crude product the most according to claim 1, it is characterised in that the Fructus Vitis viniferae described in step (2)
The addition of the aqueous solution of sodium saccharate is 10-15 times of PEKK crude product quality.
The technique of purification PEKK crude product the most according to claim 1, it is characterised in that the stirring described in step (2)
Return time is 3-5 hour.
The technique of purification PEKK crude product the most according to claim 1, it is characterised in that the drying described in step (3)
It is first to dry 4-6 hour through normal pressure, then decompression drying 1-2 hour, reduced vacuum degree is 0.1-0.13MPa.
The technique of purification PEKK crude product the most according to claim 1, it is characterised in that the drying described in step (3)
Temperature is 100-120 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610504967.2A CN106046358A (en) | 2016-06-30 | 2016-06-30 | Technique for purifying polyetherketoneketone crude product |
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| CN201610504967.2A CN106046358A (en) | 2016-06-30 | 2016-06-30 | Technique for purifying polyetherketoneketone crude product |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331658A (en) * | 1998-10-23 | 2002-01-16 | 通用电气公司 | Method for reducing metal ion concentration in brain solution |
| CN101486784A (en) * | 2009-02-19 | 2009-07-22 | 吉林金正高分子材料研发有限公司 | Method for effectively reducing metal content in polyetheretherketone |
| CN102127219A (en) * | 2011-01-07 | 2011-07-20 | 金发科技股份有限公司 | Method for purifying polyether ketone/polyether sulfone polymers |
| CN102766257A (en) * | 2012-05-02 | 2012-11-07 | 浙江鹏孚隆科技有限公司 | Method for reducing metal impurities in poly(aryl ether ketone) polymer |
-
2016
- 2016-06-30 CN CN201610504967.2A patent/CN106046358A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331658A (en) * | 1998-10-23 | 2002-01-16 | 通用电气公司 | Method for reducing metal ion concentration in brain solution |
| CN101486784A (en) * | 2009-02-19 | 2009-07-22 | 吉林金正高分子材料研发有限公司 | Method for effectively reducing metal content in polyetheretherketone |
| CN102127219A (en) * | 2011-01-07 | 2011-07-20 | 金发科技股份有限公司 | Method for purifying polyether ketone/polyether sulfone polymers |
| CN102766257A (en) * | 2012-05-02 | 2012-11-07 | 浙江鹏孚隆科技有限公司 | Method for reducing metal impurities in poly(aryl ether ketone) polymer |
Non-Patent Citations (1)
| Title |
|---|
| 严莲荷: "《水处理药剂及配方手册》", 31 January 2004, 中国石化出版社 * |
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Application publication date: 20161026 |
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