CN105885035A - Process for removing metal ions in poly(ether-ketone-ketone) crude product - Google Patents
Process for removing metal ions in poly(ether-ketone-ketone) crude product Download PDFInfo
- Publication number
- CN105885035A CN105885035A CN201610498580.0A CN201610498580A CN105885035A CN 105885035 A CN105885035 A CN 105885035A CN 201610498580 A CN201610498580 A CN 201610498580A CN 105885035 A CN105885035 A CN 105885035A
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- China
- Prior art keywords
- crude product
- ketone
- metal ion
- technique
- pekk
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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
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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)
Abstract
The invention belongs to the technical field of polymer materials and in particular relates to a process for removing metal ions in a poly(ether-ketone-ketone) crude product. The process comprises the following steps: firstly adding the poly(ether-ketone-ketone) crude product to an organic solvent, carrying out reflux to swell the poly(ether-ketone-ketone) crude product and carrying out cooling and filtration, thus obtaining a swollen crude product; and then adding an organic polybasic phosphonic acid chelating agent water solution to the swollen crude product and carrying out reflux, cooling and filtration, thus obtaining the poly(ether-ketone-ketone) product. The process has the beneficial effects that compared with the prior art, the process has the characteristics of simplicity in operation, high aluminium ion removal rate, recycling of the solvent, no three wastes, and the like; the content of metallic aluminium ions in the poly(ether-ketone-ketone) crude product can be reduced below 50ppm; a used organic polybasic phosphonic acid chelating agent is small in usage amount and cost, is easy to store and is pollution-free; the used solvent can be recycled; and the process is energy-saving and environment-friendly and has the effect of effectively improving the product quality.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of remove the technique of metal ion in PEKK crude product.
Background technology
PEKK (PEKK) is the high-performance special engineering plastics of a kind of high temperature resistance, radiation hardness, acid and alkali-resistance, good flame resistance,
Important effect is had in fields such as Aero-Space, telecommunications, defence and military and civilian technology products.
PEKK is the product developed by DuPont, and its preparation method is divided into nucleophilic displacement of fluorine and electrophilic substitution two kinds.
Electrophilic substitution reaction method typically uses the friedel-craft with aluminum trichloride (anhydrous) as catalyst to be synthesized, in the PEKK crude product of synthesis
Having higher aluminium ion to remain, make PEKK viscosity decline, molecular weight reduces, and product structure changes, after causing using
When continuing the polymer of processing, produce more side reaction.Therefore, effectively remove the metal ion of residual in polymer, be synthesis height
The key link of performance PEKK.
Summary of the invention
It is an object of the invention to provide and a kind of remove the technique of metal ion in PEKK crude product, the most effectively reduce PEKK
The content of metal ion in crude product, and after organic solvent used reclaims, it is possible to recycle.
The technique of metal ion in removal PEKK crude product of the present invention, comprises the following steps:
(1) joining in organic solvent by PEKK crude product, backflow makes it swelling, and cooling is filtered, obtained swelling crude product；
(2) organic multicomponent phosphonic acid type chelants aqueous solution is joined in swelling crude product, backflow, cooling, filter, obtain polyethers
Ketone ketone product.
Wherein:
In step (1), PEKK crude product uses the electrophilic substitution reaction with aluminum trichloride (anhydrous) as catalyst to prepare, and particle diameter is
0.1～2mm.
In step (1), organic solvent is mass concentration 10～the malonic acid acetic acid solution of 30%.
In step (1), PEKK crude product is 1:10～1:20 with the mass ratio of organic solvent.
In step (1), return time is 1～3 hour.
The filtrate that step (1) is filtrated to get, can be with reuse after distillation.
In step (2), organic multicomponent phosphonic acid type chelants is ATMP or polyamino many ethers tetramethylene phosphonic acid.
In step (2), the mass concentration of organic multicomponent phosphonic acid type chelants aqueous solution is 1～20%.
In step (2) in organic multicomponent phosphonic acid type chelants aqueous solution and step (1) mass ratio of PEKK crude product be 10:1～
20:1。
In step (2), return time is 6～10 hours.
Beneficial effects of the present invention is as follows:
The present invention is swelling by PEKK by organic solvent, and the metal ion in PEKK is scattering in organic facies, then passes through
The chelation of chelating agen removes metal ion.Compared with prior art, the present invention has simple to operate, and aluminium ion clearance is high,
Solvent can recycle, without features such as the three wastes.Metallic aluminium ion in PEKK crude product can be down to 50ppm by the present invention
Hereinafter, the organic multicomponent phosphonic acid type chelants consumption of use is little, low cost, easily storage, nuisanceless pollution, and solvent for use can
Recycle, energy saving technology environmental protection, be effectively increased product quality.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
PEKK crude product 50g is encased in tri-mouthfuls of vials of 2000ml, adds the malonic acid acetic acid solution of mass concentration 10%
1000g, is stirred at reflux 1 hour so that it is swelling, then lowers the temperature, and filters, obtains swelling crude product.
Take ATMP 5g, be added to the water, be configured to the ATMP that 500g mass concentration is 1%
Aqueous solution.
500g ATMP aqueous solution is joined in swelling crude product, stirs evenly, under backflow, stir 6 hours, then
Cooling, filters, and is dried.Detecting through ICP, organic solvent-free remains, and in PEKK, the aluminium ion of residual is 43ppm.
Embodiment 2
PEKK crude product 50g is encased in tri-mouthfuls of vials of 2000ml, adds the malonic acid acetic acid solution of mass concentration 20%
750g, is stirred at reflux 2 hours so that it is swelling, then lowers the temperature, and filters, obtains swelling crude product.
Take ATMP 200g, be added to the water, be configured to the aminotrimethylene that 1000g mass concentration is 20%
Phosphonic acids aqueous solution.
1000g ATMP aqueous solution is joined in swelling crude product, stirs evenly, under backflow, stir 8 hours, so
Rear cooling, filters, and is dried.Detecting through ICP, organic solvent-free remains, and in PEKK, the aluminium ion of residual is 36ppm.
Embodiment 3
PEKK crude product 50g is encased in tri-mouthfuls of vials of 2000ml, adds the malonic acid acetic acid solution of mass concentration 30%
500g, is stirred at reflux 3 hours so that it is swelling, then lowers the temperature, and filters, obtains swelling crude product.
Take polyamino many ethers tetramethylene phosphonic acid 75g, be added to the water, be configured to the polyamino that 750g mass concentration is 10%
Many ethers tetramethylene phosphonic acid aqueous solution.
750g polyamino many ethers tetramethylene phosphonic acid aqueous solution is joined in swelling crude product, stirs evenly, under backflow, stir 10
Hour, then lower the temperature, filter, be dried.Detecting through ICP, organic solvent-free remains, and in PEKK, the aluminium ion of residual is
23ppm。
Claims (10)
1. remove the technique of metal ion in PEKK crude product for one kind, it is characterised in that comprise the following steps:
(1) joining in organic solvent by PEKK crude product, backflow makes it swelling, and cooling is filtered, obtained swelling crude product；
(2) organic multicomponent phosphonic acid type chelants aqueous solution is joined in swelling crude product, backflow, cooling, filter, obtain polyethers
Ketone ketone product.
The technique of metal ion in removal PEKK crude product the most according to claim 1, it is characterised in that: step (1)
Middle PEKK crude product uses the electrophilic substitution reaction with aluminum trichloride (anhydrous) as catalyst to prepare, and particle diameter is 0.1～2mm.
The technique of metal ion in removal PEKK crude product the most according to claim 1, it is characterised in that: step (1)
Middle organic solvent is mass concentration 10～the malonic acid acetic acid solution of 30%.
The technique of metal ion in removal PEKK crude product the most according to claim 1, it is characterised in that: step (1)
Middle PEKK crude product is 1:10～1:20 with the mass ratio of organic solvent.
The technique of metal ion in removal PEKK crude product the most according to claim 1, it is characterised in that: step (1)
Middle return time is 1～3 hour.
6. according to the technique of metal ion in the arbitrary described removal PEKK crude product of Claims 1 to 5, it is characterised in that:
The filtrate being filtrated to get in step (1), reuse after distillation.
The technique of metal ion in removal PEKK crude product the most according to claim 1, it is characterised in that: step (2)
Middle organic multicomponent phosphonic acid type chelants is ATMP or polyamino many ethers tetramethylene phosphonic acid.
The technique of metal ion in removal PEKK crude product the most according to claim 1, it is characterised in that: step (2)
The mass concentration of middle organic multicomponent phosphonic acid type chelants aqueous solution is 1～20%.
The technique of metal ion in removal PEKK crude product the most according to claim 1, it is characterised in that: step (2)
Middle organic multicomponent phosphonic acid type chelants aqueous solution is 10:1～20:1 with the mass ratio of PEKK crude product in step (1).
10. according to the technique of metal ion in the arbitrary described removal PEKK crude product of claim 7～9, it is characterised in that:
In step (2), return time is 6～10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610498580.0A CN105885035A (en) | 2016-06-30 | 2016-06-30 | Process for removing metal ions in poly(ether-ketone-ketone) crude product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610498580.0A CN105885035A (en) | 2016-06-30 | 2016-06-30 | Process for removing metal ions in poly(ether-ketone-ketone) crude product |
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| Publication Number | Publication Date |
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| CN105885035A true CN105885035A (en) | 2016-08-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610498580.0A Pending CN105885035A (en) | 2016-06-30 | 2016-06-30 | Process for removing metal ions in poly(ether-ketone-ketone) crude product |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640911A (en) * | 2004-12-09 | 2005-07-20 | 四川大学 | Method for purifying poly ether-ether-ketone |
| 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 |
| CN102161739A (en) * | 2011-03-08 | 2011-08-24 | 金发科技股份有限公司 | Method for purifying polymer |
| 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 |
| CN103936950A (en) * | 2013-01-17 | 2014-07-23 | 珠海市吉林大学无机合成与制备化学重点实验室 | Polyether material purifying method |
-
2016
- 2016-06-30 CN CN201610498580.0A patent/CN105885035A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640911A (en) * | 2004-12-09 | 2005-07-20 | 四川大学 | Method for purifying poly ether-ether-ketone |
| 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 |
| CN102161739A (en) * | 2011-03-08 | 2011-08-24 | 金发科技股份有限公司 | Method for purifying polymer |
| 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 |
| CN103936950A (en) * | 2013-01-17 | 2014-07-23 | 珠海市吉林大学无机合成与制备化学重点实验室 | Polyether material purifying method |
Non-Patent Citations (2)
| Title |
|---|
| 《化工百科全书》编辑委员会: "《化工百科全书 第1卷》", 31 December 1990, 化学工业出版社 * |
| 王又蓉: "《工业水处理问答》", 31 January 2007, 国防工业出版社 * |
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Application publication date: 20160824 |