CN105884989A - Method for refining poly(ether-ketone-ketone) crude product by using hydrochloric acid water solution of oxalic acid - Google Patents
Method for refining poly(ether-ketone-ketone) crude product by using hydrochloric acid water solution of oxalic acid Download PDFInfo
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- CN105884989A CN105884989A CN201610498067.1A CN201610498067A CN105884989A CN 105884989 A CN105884989 A CN 105884989A CN 201610498067 A CN201610498067 A CN 201610498067A CN 105884989 A CN105884989 A CN 105884989A
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- Prior art keywords
- ketone
- acid
- crude product
- pekk
- 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
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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
- C08G65/38—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)
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to refining methods of polymer materials and in particular relates to a method for refining a poly(ether-ketone-ketone) crude product by using a hydrochloric acid water solution of oxalic acid. The refining method comprises the following steps: firstly carrying out reflux stirring on a certain amount of poly(ether-ketone-ketone) crude product in a water solution containing dimethyl sulfoxide; and then adding the hydrochloric acid water solution of oxalic acid, carrying out reflux stirring and carrying out filtration after cooling; then carrying out reflux washing with a mixed water solution of glycolic acid and formic acid and carrying out filtration and drying, thus obtaining the poly(ether-ketone-ketone) pure product. Poly(ether-ketone-ketone) molecular chains tightly wrapping catalyst impurities can be unfurled by utilizing the poly(ether-ketone-ketone) swelling characteristic of the water solution containing dimethyl sulfoxide, so that impurity ions are exposed and diffused into media, and meanwhile, metal ions are continuously trapped by utilizing the metal ion chelating characteristic of oxalic acid under acidic conditions, thus achieving efficient removal of Al<3+> in the poly(ether-ketone-ketone) crude product.
Description
Technical field
The present invention relates to the process for purification of macromolecular material, be specifically related to the aqueous hydrochloric acid solution of a kind of oxalic acid to PEKK crude product
The method carrying out refining.
Background technology
PEKK (PEKK) is a kind of high-performance semicrystalline thermoplastic polymer, belongs to speciality polymer material PAEK
A member in family, has mechanical performance, heat stability, chemical resistance, radioprotective and the anti-flammability of excellence, in national defence
The fields such as 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, the most residual in polymer
Leave 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, the Al in product3+
Content will directly affect its resistance characteristic, Al in PEKK3+Residual quantity becomes one of key index weighing product quality.Therefore
A kind of effective crude product refining purification process can be found, effectively remove in polymer and remain Al3+It it is synthesized high-performance PEKK
Key link.And, in the course of the polymerization process owing to there is the most branched unstable structure, it is easily generated in hot procedure
Benzene radical, thus cause intermolecular cross-linking and degraded, affect it and apply further.
Traditional method typically uses hydrochloric acid, alkyl chloride, alcohols equal solvent, removes remaining metal ions impurity, mistake through cyclic washing
Journey 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 scale
Produce, and production cost remains high, and has a strong impact on large-scale application and the popularization of PEKK.CN200410081436 uses
The method that organic solvent and surfactant are 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
The method of acid solution 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 heat stability, and nothing
The process for purification of the PEKK crude product that organic solvent participates in.
Summary of the invention
It is an object of the invention to provide the aqueous hydrochloric acid solution of a kind of simple to operate, with low cost, safe and reliable use oxalic acid to polyethers
The method that ketone ketone crude product carries out refining, it is possible to effectively reduce Al in PEKK crude product3+Content.
The method that PEKK crude product is refined by the aqueous hydrochloric acid solution of oxalic acid of the present invention, comprises the following steps:
(1) by the aqueous solution of PEKK crude product Yu dimethyl sulfoxide, temperature rising reflux；
(2) in above-mentioned system, add the aqueous hydrochloric acid solution of oxalic acid, 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.
Wherein:
In step (1), PEKK crude product is lamellar or powdery, with AlCl3The polymerization of electrophilic substitution reaction route is used for catalyst
Obtaining, size range is 0.1～2mm.
In step (1), the mass concentration of the aqueous solution of dimethyl sulfoxide is 1～5%.
In step (1), PEKK crude product is 1:10～1:20 with the mass ratio of the aqueous solution of dimethyl sulfoxide.
In step (1), return time is 2～4 hours.
The compound method of the aqueous hydrochloric acid solution of step (2) mesoxalic acid is that oxalic acid joins the hydrochloric acid water that mass concentration is 5～10%
In solution, obtaining the aqueous hydrochloric acid solution of oxalic acid, the mass concentration of solution mesoxalic acid is 5～10%.
The addition of the aqueous hydrochloric acid solution of step (2) mesoxalic acid is 10～20 times of PEKK crude product quality.
In step (2), return time is 4～6 hours.
In step (3) 20～30 times that mixed aqueous solution consumption is PEKK crude product quality of hydroxyacetic acid and formic acid, hydroxyl
Acetic acid is with the mixed aqueous solution of formic acid, and the mass concentration of hydroxyacetic acid is 2～4%, and the mass concentration of formic acid is 1～5%.
In step (3), washing times is 3～5 times.
The present invention is by adding dimethyl sulfoxide in aqueous, it is possible to effective swelling PEKK, by miscellaneous for tight catalyst
The PEKK strand of matter struts, and makes foreign ion expose and diffuses in medium, utilizing oxalic acid the most right simultaneously
The chelating properties of metal ion, constantly traps Al3+, thus realize Al in PEKK crude product3+Efficient removal.Hydroxyacetic acid with
Formic acid with the use of, kish impurity in PEKK can be removed further, and be effectively improved its heat stability, beneficially postorder heat
Machine-shaping.
PEKK crude product is due to containing AlCl3Deng impurity, color is yellow, after step (1), (2) operation, big in crude product
Partial impurities is transferred in the aqueous hydrochloric acid solution of dimethyl sulfoxide and oxalic acid, and after filtration, mother solution color is relatively deep, after through hydroxyacetic acid
White PEKK sterling is obtained with the mixed aqueous solution of formic acid after repeatedly washing.
Beneficial effects of the present invention is as follows:
Compared with prior art, the present invention has the advantages that method is simple, purification efficiency is high, workable, is conducive to fall
Low production cost, improves production efficiency.The PEKK of the present invention is the most swelling in the aqueous solution of dimethyl sulfoxide, oxalic acid energy
Reach and contained Al in PEKK3+Form stable comple, using the mixed aqueous solution of hydroxyacetic acid and formic acid as cleaning mixture, reach
Arrive 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 aqueous hydrochloric acid solution of oxalic acid is little, and whole process organic solvent-free participates in, processing cost
Lower, safety is higher, will not be economic and environment-friendly with the obvious advantage to environmental danger.
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, the rear aqueous solution 400g adding the dimethyl sulfoxide that mass concentration is 5%, rise high-temperature and be stirred at reflux 2 hours；Again to it
The aqueous hydrochloric acid solution 400g of the oxalic acid of middle addition 10%, return stirring 6 hours, it is cooled to 23 DEG C of filtrations, obtains at the beginning of PEKK
Level product；Primary product washs 3 times with the mixed aqueous solution backflow of 600g hydroxyacetic acid with formic acid respectively, then through filtering, being dried,
To white PEKK sterling, detect through ICP, its Al3+Content is 35ppm, and at 380 DEG C, 5kg melt index is 126g/10min,
Meet PEKK applied at elevated temperature and processing request.
The compound method of the aqueous hydrochloric acid solution of oxalic acid is to be joined by oxalic acid in the aqueous hydrochloric acid solution that mass concentration is 5%, obtains oxalic acid
Aqueous hydrochloric acid solution, the mass concentration of solution mesoxalic acid is 10%.
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 5%.
Comparative example 1
Take 20g PEKK crude product (Al3+Content 4200ppm), particle size range is 1～2mm, adds 1000ml reaction vessel
In, the rear aqueous solution 400g adding the dimethyl sulfoxide that mass concentration is 5%, rise high-temperature and be stirred at reflux 2 hours；Again to it
The aqueous hydrochloric acid solution 400g of the oxalic acid of middle addition 10%, return stirring 6 hours, it is cooled to 23 DEG C of filtrations, obtains at the beginning of PEKK
Level product；Primary product washs 3 times with the backflow of 600g water respectively, then through filtering, being dried, obtains PEKK sterling, examines through ICP
Survey, its Al3+Content is 112ppm, and at 380 DEG C, 5kg melt index is that 63g/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, the rear aqueous solution 300g adding the dimethyl sulfoxide that mass concentration is 2%, rise high-temperature and be stirred at reflux 3 hours；Again
It is added thereto to the aqueous hydrochloric acid solution 300g of the oxalic acid of 5%, return stirring 5 hours, is cooled to 25 DEG C of filtrations, obtains polyether-ketone
Ketone primary product；Primary product washs 4 times with the mixed aqueous solution backflow of 500g hydroxyacetic acid with formic acid respectively, then through filtering, being dried,
Obtain white PEKK sterling, detect through ICP, its Al3+Content is 44ppm, and at 380 DEG C, 5kg melt index is
113g/10min, meets PEKK applied at elevated temperature and processing request.
The compound method of the aqueous hydrochloric acid solution of oxalic acid is to be joined by oxalic acid in the aqueous hydrochloric acid solution that mass concentration is 8%, obtains oxalic acid
Aqueous hydrochloric acid solution, the mass concentration of solution mesoxalic acid is 5%.
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, the rear aqueous solution 200g adding the dimethyl sulfoxide that mass concentration is 1%, rise high-temperature and be stirred at reflux 4 hours；Again to
Wherein add the aqueous hydrochloric acid solution 200g of the oxalic acid of 8%, return stirring 4 hours, be 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 through filtering, being dried,
Obtain white PEKK sterling, detect through ICP, its Al3+Content is 39ppm, and at 380 DEG C, 5kg melt index is
106g/10min, meets PEKK applied at elevated temperature and processing request.
The compound method of the aqueous hydrochloric acid solution of oxalic acid is to be joined by oxalic acid in the aqueous hydrochloric acid solution that mass concentration is 10%, obtains grass
The aqueous hydrochloric acid solution of acid, the mass concentration of solution mesoxalic acid is 8%.
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 1%.
Claims (10)
1. method PEKK crude product refined with the aqueous hydrochloric acid solution of oxalic acid, it is characterised in that comprise the following steps:
(1) by the aqueous solution of PEKK crude product Yu dimethyl sulfoxide, temperature rising reflux；
(2) in above-mentioned system, add the aqueous hydrochloric acid solution of oxalic acid, 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 purification the most according to claim 1, it is characterised in that: in step (1) PEKK crude product be lamellar or
Powdery, with AlCl3Using the polymerization of electrophilic substitution reaction route to obtain for catalyst, size range is 0.1～2mm.
Process for purification the most according to claim 1, it is characterised in that: the aqueous solution of dimethyl sulfoxide in step (1)
Mass concentration is 1～5%.
Process for purification the most according to claim 1, it is characterised in that: PEKK crude product and dimethyl in step (1)
The mass ratio of the aqueous solution of sulfoxide is 1:10～1:20.
5. according to the arbitrary described process for purification of Claims 1 to 4, it is characterised in that: in step (1) return time be 2～
4 hours.
Process for purification the most according to claim 1, it is characterised in that: joining of the aqueous hydrochloric acid solution of step (2) mesoxalic acid
Method processed be oxalic acid is joined mass concentration be 5～10% aqueous hydrochloric acid solution in, obtain the aqueous hydrochloric acid solution of oxalic acid, in solution
The mass concentration of oxalic acid is 5～10%.
Process for purification the most according to claim 1, it is characterised in that: adding of the aqueous hydrochloric acid solution of step (2) mesoxalic acid
Enter that amount is PEKK crude product quality 10～20 times.
8. according to the process for purification described in claim 6 or 7, it is characterised in that: in step (2), return time is 4～6 little
Time.
Process for purification the most according to claim 1, it is characterised in that: hydroxyacetic acid and the mixing of formic acid in step (3)
Amount of aqueous solution used 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%.
Process for purification the most according to claim 9, it is characterised in that: in step (3), washing times is 3～5 times.
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| CN201610498067.1A CN105884989A (en) | 2016-06-30 | 2016-06-30 | Method for refining poly(ether-ketone-ketone) crude product by using hydrochloric acid water solution of oxalic acid |
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| CN201610498067.1A CN105884989A (en) | 2016-06-30 | 2016-06-30 | Method for refining poly(ether-ketone-ketone) crude product by using hydrochloric acid water solution of oxalic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115806650A (en) * | 2022-12-29 | 2023-03-17 | 山东君昊高性能聚合物有限公司 | Method for purifying and preparing implant-grade polyether-ether-ketone by subcritical technology |
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| 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 |
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2016
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| CN1640911A (en) * | 2004-12-09 | 2005-07-20 | 四川大学 | Method for purifying poly ether-ether-ketone |
| CN101842411A (en) * | 2007-08-28 | 2010-09-22 | 沙伯基础创新塑料知识产权有限公司 | Poly(arylene ether) preparation method |
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Cited By (1)
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|---|---|---|---|---|
| CN115806650A (en) * | 2022-12-29 | 2023-03-17 | 山东君昊高性能聚合物有限公司 | Method for purifying and preparing implant-grade polyether-ether-ketone by subcritical technology |
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Application publication date: 20160824 |