CN106146825A - Technique PEKK crude product refined with sodium gluconate - Google Patents
Technique PEKK crude product refined with sodium gluconate Download PDFInfo
- Publication number
- CN106146825A CN106146825A CN201610498817.5A CN201610498817A CN106146825A CN 106146825 A CN106146825 A CN 106146825A CN 201610498817 A CN201610498817 A CN 201610498817A CN 106146825 A CN106146825 A CN 106146825A
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- CN
- China
- Prior art keywords
- pekk
- crude product
- refining
- sodium gluconate
- aqueous solution
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
Abstract
The present invention relates to the process for refining of macromolecular material, be specifically related to the technique that PEKK crude product is refined by a kind of sodium gluconate.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 sodium gluconate aqueous solution return stirring, 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 the efficient metal chelation abilities of sodium gluconate simultaneously, 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 sodium gluconate to PEKK crude product
The technique carrying 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 a kind of simple to operate, with low cost, safe and reliable with sodium gluconate to polyethers
The technique that ketone ketone crude product carries out refining, it is possible to effectively reduce Al in PEKK crude product3+Content, and organic solvent used is through returning
Receipts can recycle.
The technique that PEKK crude product is refined by sodium gluconate of the present invention, comprises the following steps:
(1) PEKK crude product is mixed with the dichloromethane solution of diphenyl sulphone (DPS), temperature rising reflux；
(2) in above-mentioned system, add sodium gluconate aqueous solution, continue to be heated to reflux, filter after cooling, obtain polyethers
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, 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 sodium gluconate aqueous solution is 5～10%.
In step (2), the addition of sodium gluconate 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 Portugal simultaneously
The efficient metal chelation abilities of grape sodium saccharate, constantly traps Al from organic facies3+, thus realize Al in PEKK crude product3+'s
Efficiently remove.Hydroxyacetic acid and formic acid with the use of, kish impurity in PEKK can be removed further, and be effectively improved 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 sodium gluconate aqueous solution of diphenyl sulphone (DPS), and separatory obtains the diphenyl sulphone (DPS) of yellow
Dichloromethane solution, obtains colourless dichloromethane through distilation after unified collection, is circularly used for configuring the dichloro of diphenyl sulphone (DPS)
Dichloromethane.
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),
Glucose acid group can with PEKK contained Al3+Form stable comple, with the mixed aqueous solution of hydroxyacetic acid Yu formic acid
As cleaning mixture, reach removal Al3+Purpose.The present invention can not only be by Al in PEKK3+Content be down to 50ppm with
Under, PEKK high temperatures significantly improves, and the consumption of the sodium gluconate of use is little, nuisanceless, will not produce environment
Raw harm, and the recovered reusable edible of organic solvent used, economic and environment-friendly with the obvious advantage.
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 sodium gluconate aqueous solution 400g of 10%, 45 DEG C of return stirrings 6 hours, it is cooled to 23 DEG C of filtrations, is gathered
Ether ketone ketone primary product；Primary product washs 3 times with the mixed aqueous solution backflow of 600g hydroxyacetic acid with formic acid respectively, then through filtering,
It is dried, obtains white PEKK sterling, detect through ICP, its Al3+Content is 32ppm, and at 380 DEG C, 5kg melt index is
105g/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 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 sodium gluconate aqueous solution 400g of 10%, 45 DEG C of return stirrings 6 hours, it is cooled to 23 DEG C of filtrations, is gathered
Ether ketone ketone primary product；Primary product washs 3 times with the backflow of 600g water respectively, then through filtering, being dried, obtains PEKK sterling, warp
ICP detects, its Al3+Content is 121ppm, and at 380 DEG C, 5kg melt index is that 62g/10min, PEKK exist a small amount of crosslinking.
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 sodium gluconate aqueous solution 300g of 5% again, 42 DEG C of return stirrings 5 hours, it is cooled to 25 DEG C of filtrations,
To PEKK primary product；Primary product washs 4 times with the mixed aqueous solution backflow of 500g hydroxyacetic acid with formic acid respectively, then passes through
Filter, be dried, obtain white PEKK sterling, detect through ICP, its Al3+Content is 49ppm, and at 380 DEG C, 5kg melt index is
118g/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 sodium gluconate aqueous solution 200g of 8% again, 42 DEG C of return stirrings 4 hours, it is cooled to 20 DEG C of filtrations, is gathered
Ether ketone ketone primary product；Primary product washs 5 times with the mixed aqueous solution backflow of 400g hydroxyacetic acid with formic acid respectively, then through filtering,
It is dried, obtains white PEKK sterling, detect through ICP, its Al3+Content is 41ppm, and at 380 DEG C, 5kg melt index is
122g/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 3%, and the mass concentration of formic acid is
5%.
Claims (10)
1. technique PEKK crude product refined with sodium gluconate, it is characterised in that comprise the following steps:
(1) PEKK crude product is mixed with the dichloromethane solution of diphenyl sulphone (DPS), temperature rising reflux；
(2) in above-mentioned system, add sodium gluconate aqueous solution, continue to be heated to reflux, filter after cooling, obtain 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, 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: the quality of sodium gluconate aqueous solution in step (2)
Concentration is 5～10%.
Process for refining the most according to claim 1, it is characterised in that: the addition of sodium gluconate aqueous solution in step (2)
Amount is 10～20 times of 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.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610498817.5A CN106146825A (en) | 2016-06-30 | 2016-06-30 | Technique PEKK crude product refined with sodium gluconate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610498817.5A CN106146825A (en) | 2016-06-30 | 2016-06-30 | Technique PEKK crude product refined with sodium gluconate |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113698A (en) * | 1976-02-10 | 1978-09-12 | Imperial Chemical Industries Limited | Aromatic polymer production |
| CN1513013A (en) * | 2001-05-30 | 2004-07-14 | Process for purifying polyetherketones with water | |
| CN100513013C (en) * | 1999-08-27 | 2009-07-15 | 杰富意钢铁株式会社 | Heating method of ladle |
| CN101778886A (en) * | 2007-06-22 | 2010-07-14 | 沙伯基础创新塑料知识产权有限公司 | Method of purifying a polymer |
| 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 |
-
2016
- 2016-06-30 CN CN201610498817.5A patent/CN106146825A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113698A (en) * | 1976-02-10 | 1978-09-12 | Imperial Chemical Industries Limited | Aromatic polymer production |
| CN100513013C (en) * | 1999-08-27 | 2009-07-15 | 杰富意钢铁株式会社 | Heating method of ladle |
| CN1513013A (en) * | 2001-05-30 | 2004-07-14 | Process for purifying polyetherketones with water | |
| CN101778886A (en) * | 2007-06-22 | 2010-07-14 | 沙伯基础创新塑料知识产权有限公司 | Method of purifying a polymer |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 严莲荷: "《水处理药剂及配方手册》", 31 January 2004, 中国石化出版社 * |
| 李本高等: "《现代工业水处理技术与应用》", 30 June 2004, 中国石化出版社 * |
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Application publication date: 20161123 |