CN106117544A - Technique PEKK crude product refined with 2,3 dyhydrobutanedioic acids - Google Patents
Technique PEKK crude product refined with 2,3 dyhydrobutanedioic acids Download PDFInfo
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- CN106117544A CN106117544A CN201610498025.8A CN201610498025A CN106117544A CN 106117544 A CN106117544 A CN 106117544A CN 201610498025 A CN201610498025 A CN 201610498025A CN 106117544 A CN106117544 A CN 106117544A
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- Prior art keywords
- pekk
- crude product
- refining
- acid
- aqueous solution
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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
- 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
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the process for refining of macromolecular material, be specifically related to a kind of with 2, the technique that PEKK crude product is refined by 3 dyhydrobutanedioic acids.Described process for refining is first by a certain amount of PEKK crude product return stirring in the dichloromethane solution containing diphenyl sulphone (DPS)；Then add 2,3 dyhydrobutanedioic acid aqueous solution return stirrings, filter after cooling；Again with the mixed aqueous solution backflow washing of hydroxyacetic acid with formic acid, obtain PEKK sterling through filtering, drying.The present invention is by adding diphenyl sulphone (DPS) in dichloromethane, it is effectively improved the Swelling Capacity of dichloromethane, thoroughly the PEKK strand of tight catalyst impurities is strutted, foreign ion is made to diffuse in organic facies, utilize 2 simultaneously, the 3 efficient metal chelation abilities of dyhydrobutanedioic acid, constantly capture metal ions from organic facies, thus realize Al in PEKK crude product3+Efficient removal.
Description
Technical field
The present invention relates to the process for refining of macromolecular material, be specifically related to one 2,3 dihydroxybutanedioic acid to polyether-ketone
The technique that ketone crude product carries out refining.
Background technology
PEKK (PEKK) is a kind of high-performance semicrystalline thermoplastic polymer, belongs to the poly-virtue of speciality polymer material
A member in Mi Tong family, has mechanical performance, heat stability, chemical resistance, radioprotective and the anti-flammability of excellence, in state
The fields such as anti-military project, Aero-Space, electronic information, automobile making, petrochemical industry, health care, household electrical appliance have wide
Application prospect.
Electrophilic substitution reaction route synthesis PEKK generally uses friedel-craft catalysts AlCl3Synthesis, course of reaction needs
A large amount of catalyst, due to the winding of macromolecular chain, partial catalyst is wrapped in polymer securely, can not keep away in polymer
Exempt to remain catalyst, higher Al3+Residual quantity will cause the secondary catalytic effect during applied at elevated temperature and machine-shaping, make
Product variable color or infinitesimal solution, make the heat stability of polymer be deteriorated.And for the application in electronic applications, in product
Al3+Content will directly affect its resistance characteristic, Al in PEKK3+Residual quantity becomes one of key index weighing product quality.Cause
This can find a kind of effective crude product refining purifying process, effectively removes in polymer and remains Al3+It it is synthesized high-performance polyethers
The key link of ketone ketone.And, in the course of the polymerization process owing to there is the most branched unstable structure, in hot procedure easily
Produce benzene radical, thus cause cross-linking further and degrading, affect it and apply further.
Traditional handicraft typically uses hydrochloric acid, alkyl chloride, alcohols equal solvent, removes remaining metal ions through cyclic washing miscellaneous
Matter, process is loaded down with trivial details, treatment effeciency is low, toxicity is big, security risk is high, environmental pollution is serious, is unfavorable for constant product quality and rule
Modelling produces, and production cost remains high, and has a strong impact on large-scale application and the popularization of PEKK.CN200410081436
The method using organic solvent and surfactant to be purified, adds the consumption of organic solvent, increases production cost；
US20050004340 uses the purification process of High Temperature High Pressure, improves the use requirement of equipment；CN200910009128 uses acid
The method of liquid purification, the biochemical treatment that substantial amounts of acid solution produces waste water to the later stage brings difficulty.
Need exploitation one at present badly and can effectively reduce Al in PEKK crude product3+Content, improves PEKK stability, and institute
Process for refining with the PEKK crude product of organic solvent reusable edible.
Summary of the invention
It is an object of the invention to provide and a kind of simple to operate, with low cost, safe and reliable use 2,3 dihydroxybutanedioic acid
The technique that PEKK crude product is refined, it is possible to effectively reduce Al in PEKK crude product3+Content, and used organic molten
Agent is recovered can be recycled.
The technique that PEKK crude product is refined by 2,3 dihydroxybutanedioic acid of the present invention, including following step
Rapid:
(1) PEKK crude product is mixed with the dichloromethane solution of diphenyl sulphone (DPS), temperature rising reflux；
(2) in above-mentioned system, add 2,3 dihydroxybutanedioic acid aqueous solution, continue to be heated to reflux, filter after cooling,
To PEKK primary product；
(3) it is heated to reflux washing PEKK primary product with the mixed aqueous solution of hydroxyacetic acid Yu formic acid, through filtering, doing
Dry, obtain PEKK sterling.
Wherein:
In step (1), PEKK crude product is lamellar or powdery, with AlCl3Electrophilic substitution reaction route is used for catalyst
Polymerization obtains, and size range is 0.1～2mm.
In step (1), the mass concentration of the dichloromethane solution of diphenyl sulphone (DPS) is 1～5%.
In step (1), PEKK crude product is 1:10～1:20 with the mass ratio of the dichloromethane solution of diphenyl sulphone (DPS).
In step (1), reflux temperature is 40～45 DEG C, and return time is 2～4 hours.
In step (2), the mass concentration of 2,3 dihydroxybutanedioic acid aqueous solution is 5～10%.
In step (2), the addition of 2,3 dihydroxybutanedioic acid aqueous solution is 10～20 times of PEKK crude product quality.
In step (2), reflux temperature is 40～45 DEG C, and return time is 4～6 hours.
The filtrate being filtrated to get in step (2) obtains the dichloromethane solution of diphenyl sulphone (DPS) after separatory, laggard through distillation
Row recycles.
In step (3) 20～30 times that mixed aqueous solution consumption is PEKK crude product quality of hydroxyacetic acid and formic acid,
In the mixed aqueous solution of hydroxyacetic acid and formic acid, the mass concentration of hydroxyacetic acid is 2～4%, the mass concentration of formic acid be 1～
5%；In step (3), washing times is 3～5 times.
The present invention is by adding diphenyl sulphone (DPS) in dichloromethane, it is possible to effectively promote the Swelling Capacity of dichloromethane, thoroughly
The PEKK strand of tight catalyst impurities is strutted, makes foreign ion diffuse in organic facies, utilize 2 simultaneously,
The efficient metal chelation abilities of 3-dyhydrobutanedioic acid, constantly traps Al from organic facies3+, thus realize in PEKK crude product
Al3+Efficient removal.Hydroxyacetic acid and formic acid with the use of, kish impurity in PEKK can be removed further, and effectively carry
High its heat stability, beneficially postorder thermo forming.
PEKK crude product is due to containing AlCl3Deng impurity, color is yellow, after step (1), (2) operation, in crude product
Major part impurity is transferred in dichloromethane solution and the 2,3 dihydroxybutanedioic acid aqueous solution of diphenyl sulphone (DPS), and separatory obtains yellow
Diphenyl sulphone (DPS) dichloromethane solution, obtains colourless dichloromethane through distilation after unified collection, is circularly used for configuring diphenyl sulphone (DPS)
Dichloromethane solution.
Beneficial effects of the present invention is as follows:
Compared with prior art, the present invention has the advantages that technique is simple, purification efficiency is high, workable, favorably
In reducing production cost, improve production efficiency.The PEKK of the present invention is the most swelling in the dichloromethane solution of diphenyl sulphone (DPS),
2,3 dihydroxybutanedioic acid can with PEKK contained Al3+Form stable comple, with the mixing of hydroxyacetic acid Yu formic acid
Aqueous solution, as cleaning mixture, has reached removal Al3+Purpose.The present invention can not only be by Al in PEKK3+Content is down to
Below 50ppm, and PEKK high temperatures significantly improves, and the consumption of the 2,3 dihydroxybutanedioic acid of use is little, nothing
Public hazards are polluted, will not be to environmental danger, and the recovered reusable edible of organic solvent used, economic and environment-friendly advantage is bright
Aobvious.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Take 20g PEKK crude product (Al3+Content 4200ppm), particle size range is 1～2mm, adds 1000ml reaction vessel
In, rear addition mass concentration is the diphenyl sulphone (DPS) dichloromethane solution 400g of 5%, rises high-temperature and is stirred at reflux 2 hours to 45 DEG C；Again
It is added thereto to the 2,3 dihydroxybutanedioic acid aqueous solution 400g of 10%, 45 DEG C of return stirrings 6 hours, it is cooled to 23 DEG C of filtrations,
Obtain PEKK primary product；Primary product washs 3 times with the mixed aqueous solution backflow of 600g hydroxyacetic acid with formic acid respectively, then warp
Filter, be dried, obtain white PEKK sterling, detect through ICP, its Al3+Content is 31ppm, 5kg melt index at 380 DEG C
For 103g/10min, meet PEKK applied at elevated temperature and processing request.
Hydroxyacetic acid is with the mixed aqueous solution of formic acid, and the mass concentration of hydroxyacetic acid is 4%, and the mass concentration of formic acid is
1%.
Comparative example 1
Take 20g PEKK crude product (Al3+Content 4200ppm), particle size range is 1～2mm, adds 1000ml reaction vessel
In, rear addition mass concentration is the diphenyl sulphone (DPS) dichloromethane solution 400g of 5%, rises high-temperature and is stirred at reflux 2 hours to 41 DEG C；Again
It is added thereto to the 2,3 dihydroxybutanedioic acid aqueous solution 400g of 10%, 45 DEG C of return stirrings 6 hours, it is cooled to 23 DEG C of filtrations,
Obtain PEKK primary product；Primary product washs 3 times with the backflow of 600g water respectively, then through filtering, being dried, obtains PEKK pure
Product, detect through ICP, its Al3+Content is 115ppm, and at 380 DEG C, 5kg melt index is that 66g/10min, PEKK exist a small amount of friendship
Connection.
Embodiment 2
Take 20g PEKK crude product (Al3+Content 4200ppm), particle size range is 0.5～1.5mm, adds 1000ml reaction
In container, rear addition mass concentration is the diphenyl sulphone (DPS) dichloromethane solution 300g of 2%, and it is little that liter high-temperature is stirred at reflux 3 to 42 DEG C
Time；It is added thereto to the 2,3 dihydroxybutanedioic acid aqueous solution 300g of 5% again, 42 DEG C of return stirrings 5 hours, it is cooled to 25 DEG C of mistakes
Filter, obtains PEKK primary product；Primary product washs 4 times with the mixed aqueous solution backflow of 500g hydroxyacetic acid with formic acid respectively,
Again through filtering, being dried, obtain white PEKK sterling, detect through ICP, its Al3+Content is 47ppm, and at 380 DEG C, 5kg melts
Index is 112g/10min, meets PEKK applied at elevated temperature and processing request.
Hydroxyacetic acid is with the mixed aqueous solution of formic acid, and the mass concentration of hydroxyacetic acid is 2%, and the mass concentration of formic acid is
2%.
Embodiment 3
Take 20g PEKK crude product (Al3+Content 4200ppm), particle size range is 0.1～1mm, adds 1000ml reaction and holds
In device, rear addition mass concentration is the diphenyl sulphone (DPS) dichloromethane solution 200g of 1%, rises high-temperature and is stirred at reflux 4 hours to 41 DEG C；
It is added thereto to the 2,3 dihydroxybutanedioic acid aqueous solution 200g of 8% again, 42 DEG C of return stirrings 4 hours, it is cooled to 20 DEG C of filtrations,
Obtain PEKK primary product；Primary product washs 5 times with the mixed aqueous solution backflow of 400g hydroxyacetic acid with formic acid respectively, then warp
Filter, be dried, obtain white PEKK sterling, detect through ICP, its Al3+Content is 40ppm, 5kg melt index at 380 DEG C
For 118g/10min, meet PEKK applied at elevated temperature and processing request.
Hydroxyacetic acid is with the mixed aqueous solution of formic acid, and the mass concentration of hydroxyacetic acid is 3%, and the mass concentration of formic acid is
5%.
Claims (10)
1. technique PEKK crude product refined with 2,3 dihydroxybutanedioic acid, it is characterised in that include following step
Rapid:
(1) PEKK crude product is mixed with the dichloromethane solution of diphenyl sulphone (DPS), temperature rising reflux；
(2) in above-mentioned system, add 2,3 dihydroxybutanedioic acid aqueous solution, continue to be heated to reflux, filter after cooling, gathered
Ether ketone ketone primary product；
(3) it is heated to reflux washing PEKK primary product with the mixed aqueous solution of hydroxyacetic acid Yu formic acid, through filtering, being dried,
To PEKK sterling.
Process for refining the most according to claim 1, it is characterised in that: in step (1), PEKK crude product is lamellar or powder
Shape, with AlCl3Using the polymerization of electrophilic substitution reaction route to obtain for catalyst, size range is 0.1～2mm.
Process for refining the most according to claim 1, it is characterised in that: the dichloromethane solution of diphenyl sulphone (DPS) in step (1)
Mass concentration is 1～5%.
Process for refining the most according to claim 1, it is characterised in that: PEKK crude product and diphenyl sulphone (DPS) in step (1)
The mass ratio of dichloromethane solution is 1:10～1:20.
5. according to the arbitrary described process for refining of Claims 1 to 4, it is characterised in that: in step (1), reflux temperature is 40～45
DEG C, return time is 2～4 hours.
Process for refining the most according to claim 1, it is characterised in that: 2,3 dihydroxybutanedioic acid aqueous solution in step (2)
Mass concentration be 5～10%.
Process for refining the most according to claim 1, it is characterised in that: 2,3 dihydroxybutanedioic acid aqueous solution in step (2)
10～20 times that addition is PEKK crude product quality.
Process for refining the most according to claim 1, it is characterised in that: in step (2), reflux temperature is 40～45 DEG C, backflow
Time is 4～6 hours.
9. according to the arbitrary described process for refining of claim 6～8, it is characterised in that: the filtrate warp being filtrated to get in step (2)
Obtain the dichloromethane solution of diphenyl sulphone (DPS) after separatory, recycle after distillation.
Process for refining the most according to claim 1, it is characterised in that: hydroxyacetic acid and the mixing water of formic acid in step (3)
Solution usage is 20～30 times of PEKK crude product quality, in the mixed aqueous solution of hydroxyacetic acid and formic acid, hydroxyacetic acid
Mass concentration is 2～4%, and the mass concentration of formic acid is 1～5%；In step (3), washing times is 3～5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610498025.8A CN106117544A (en) | 2016-06-30 | 2016-06-30 | Technique PEKK crude product refined with 2,3 dyhydrobutanedioic acids |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610498025.8A CN106117544A (en) | 2016-06-30 | 2016-06-30 | Technique PEKK crude product refined with 2,3 dyhydrobutanedioic acids |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3088647A1 (en) | 2018-11-15 | 2020-05-22 | Arkema France | REUSABLE POLY (ETHER-CETONE-CETONE) POWDER FOR SINTERING PROCESS |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602853A (en) * | 2009-07-16 | 2009-12-16 | 扬州奥巴玛科技发展有限公司 | A kind of purification process of crude product of poly (aryl ether ketone) s |
| 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 CN201610498025.8A patent/CN106117544A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602853A (en) * | 2009-07-16 | 2009-12-16 | 扬州奥巴玛科技发展有限公司 | A kind of purification process of crude product of poly (aryl ether ketone) s |
| 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 (3)
| Title |
|---|
| 张光华: "《水处理化学品制备与应用指南》", 31 October 2003, 中国石化出版社 * |
| 梁治齐: "《实用清洗技术手册》", 31 January 2000, 化学工业出版社 * |
| 魏文德: "《有机化工原料大全 中卷》", 31 January 1999, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3088647A1 (en) | 2018-11-15 | 2020-05-22 | Arkema France | REUSABLE POLY (ETHER-CETONE-CETONE) POWDER FOR SINTERING PROCESS |
| WO2020099803A1 (en) | 2018-11-15 | 2020-05-22 | Arkema France | Reusable poly(ether-ketone-ketone) powder for sintering method |
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Application publication date: 20161116 |