CN106188526A - Use the technique that PEKK crude product is purified by polyamino many ethers tetramethylene phosphonic acid - Google Patents
Use the technique that PEKK crude product is purified by polyamino many ethers tetramethylene phosphonic acid Download PDFInfo
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- CN106188526A CN106188526A CN201610498456.4A CN201610498456A CN106188526A CN 106188526 A CN106188526 A CN 106188526A CN 201610498456 A CN201610498456 A CN 201610498456A CN 106188526 A CN106188526 A CN 106188526A
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- CN
- China
- Prior art keywords
- crude product
- phosphonic acid
- tetramethylene phosphonic
- pekk
- technique
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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)
- Polyethers (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention belongs to technical field of polymer materials, be specifically related to a kind of technique using polyamino many ethers tetramethylene phosphonic acid that PEKK crude product is purified.Described technique comprises the following steps: joined by PEKK crude product in polyamino many ethers tetramethylene phosphonic acid aqueous solution, backflow, and cooling is filtered, obtained Primary purification product；Primary purification product are joined in alkaline aqueous solution, irradiates and under ul-trasonic irradiation at ultraviolet light, be passed through ozone backflow, cooling, filter, obtain secondary purification product；With the water secondary purification product of backflow washing, through filtering, being dried to obtain PEKK sterling.The present invention can be by the Al in PEKK crude product3+Content is down to below 50ppm, and polyamino many ethers tetramethylene phosphonic acid consumption is few, low cost, and energy saving technology environmental protection is effectively increased product quality, reduces production cost.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of employing polyamino many ethers tetramethylene phosphonic acid
The technique that PEKK crude product is purified.
Background technology
PEKK (PEKK) is the high-performance special engineering plastic of a kind of high temperature resistance, radiation hardness, acid and alkali-resistance, good flame resistance
Material, has important effect 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, the polyether-ketone of synthesis
Having higher aluminium ion to remain in ketone crude product, make PEKK viscosity decline, molecular weight reduces, and product structure changes, and leads
When causing the polymer by following process, produce more side reaction.Therefore, it is possible to find the purification work of a kind of PEKK crude product
Skill, effectively removing the aluminium ion of residual in polymer is the key link of synthesized high-performance PEKK.
Summary of the invention
It is an object of the invention to provide a kind of employing polyamino many ethers tetramethylene phosphonic acid PEKK crude product is carried out
The technique of purification, effectively reduces the content of metal ion in PEKK crude product.
The technique that PEKK crude product is purified by employing polyamino many ethers tetramethylene phosphonic acid of the present invention,
Comprise the following steps:
(1) PEKK crude product is joined in polyamino many ethers tetramethylene phosphonic acid aqueous solution, backflow, cooling, mistake
Filter, obtains Primary purification product；
(2) Primary purification product are joined in alkaline aqueous solution, irradiate at ultraviolet light and under ul-trasonic irradiation, be passed through ozone
Backflow, cooling, filter, obtain secondary purification product；
(3) with the water secondary purification product of backflow washing, through filtering, being dried to obtain PEKK sterling.
Wherein:
In step (1), PEKK crude product uses the electrophilic substitution reaction with aluminum trichloride (anhydrous) as catalyst to prepare, grain
Footpath is 0.1～2mm.
In step (1), the mass concentration of polyamino many ethers tetramethylene phosphonic acid aqueous solution is 1～20%.
In step (1) mass ratio of PEKK crude product and polyamino many ethers tetramethylene phosphonic acid aqueous solution be 1:10～
1:20。
In step (1), return time is 6～10 hours.
Step (2) neutral and alkali aqueous solution is with the aqueous solution that pH is 8～10 of ammonia regulation.
Step (2) neutral and alkali aqueous solution is 10:1～20:1 with the mass ratio of PEKK crude product in step (1).
Step (2) medium ultraviolet light wave a length of 280～320nm, ultrasonic power is 20KHZ.
Step (2) is irradiated and under ul-trasonic irradiation at ultraviolet light, is passed through ozone with the speed of 0.1～1L/h, backflow 3～
5 hours.
During in step (3), water consumption is step (1) 20～30 times of PEKK crude product quality.
Beneficial effects of the present invention is as follows:
The features such as the present invention has simple to operate, workable, low cost, and metal ion clearance is high, safety and environmental protection.
Polyamino many ethers tetramethylene phosphonic acid chelating agen toxicity is little, can form stable network with the many kinds of metal ions such as ferrum, aluminum chelating
Compound, effectively removes the metal ion in PEKK.Ultraviolet light irradiation, ul-trasonic irradiation and weak basic condition, strengthen smelly
The oxidisability of oxygen, utilizes the strong oxidizing property of ozone to open the unstable impurity structure in reaction, eliminates the little molecule in product.This
Invention can be by the Al in PEKK crude product3+Content is down to below 50ppm, and polyamino many ethers tetramethylene phosphonic acid is used
Amount is few, low cost, and energy saving technology environmental protection is effectively increased product quality, reduces production cost.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Take Al3+The PEKK crude product 50g of content 4300ppm, is added thereto to the polyamino polyether of mass concentration 20%
Base tetramethylene phosphonic acid aqueous solution 500g, 100 DEG C of return stirrings 6 hours, cooling is filtered, is obtained Primary purification product.
Primary purification product are joined in the 1000ml aqueous solution that pH is 8 with ammonia regulation, be the purple of 280nm at wavelength
Outer light irradiates and under 20KHZ ul-trasonic irradiation, is passed through ozone with the speed of 0.1L/h and refluxes 3 hours, and cooling is filtered, and obtains secondary
Purification product.
Secondary purification product join in 1000g water, backflow washing, through filtering, being dried, obtain white PEKK sterling.
Detect through ICP, its Al3+Content is 42ppm, meets PEKK applied at elevated temperature and processing request.
Embodiment 2
Take Al3+The PEKK crude product 50g of content 4300ppm, is added thereto to the polyamino polyether of mass concentration 10%
Base tetramethylene phosphonic acid aqueous solution 750g, 100 DEG C of return stirrings 8 hours, cooling is filtered, is obtained Primary purification product.
Primary purification product are joined in the 750ml aqueous solution that pH is 9 with ammonia regulation, be the purple of 290nm at wavelength
Outer light irradiates and under 20KHZ ul-trasonic irradiation, is passed through ozone with the speed of 0.5L/h and refluxes 4 hours, and cooling is filtered, and obtains secondary
Purification product.
Secondary purification product join in 1250g water, backflow washing, through filtering, being dried, obtain white PEKK sterling.
Detect through ICP, its Al3+Content is 28ppm, meets PEKK applied at elevated temperature and processing request.
Embodiment 3
Take Al3+The PEKK crude product 50g of content 4300ppm, is added thereto to the many ethers of polyamino of mass concentration 1%
Tetramethylene phosphonic acid aqueous solution 1000g, 100 DEG C of return stirrings 10 hours, cooling is filtered, is obtained Primary purification product.
Primary purification product are joined in the 500ml aqueous solution that pH is 10 with ammonia regulation, be the purple of 320nm at wavelength
Outer light irradiates and under 20KHZ ul-trasonic irradiation, is passed through ozone with the speed of 1L/h and refluxes 5 hours, and cooling is filtered, and obtains secondary pure
Change product.
Secondary purification product join in 1500g water, backflow washing, through filtering, being dried, obtain white PEKK sterling.
Detect through ICP, its Al3+Content is 35ppm, meets PEKK applied at elevated temperature and processing request.
Claims (10)
1. one kind uses the technique that PEKK crude product is purified by polyamino many ethers tetramethylene phosphonic acid, it is characterised in that
Comprise the following steps:
(1) PEKK crude product is joined in polyamino many ethers tetramethylene phosphonic acid aqueous solution, backflow, cooling, filter,
To Primary purification product；
(2) Primary purification product are joined in alkaline aqueous solution, irradiate at ultraviolet light and under ul-trasonic irradiation, be passed through ozone and return
Stream, cooling, filter, obtain secondary purification product；
(3) with the water secondary purification product of backflow washing, through filtering, being dried to obtain PEKK sterling.
PEKK crude product is purified by employing polyamino many ethers tetramethylene phosphonic acid the most according to claim 1
Technique, it is characterised in that: in step (1), PEKK crude product uses the electrophilic substitution reaction with aluminum trichloride (anhydrous) as catalyst
Preparing, particle diameter is 0.1～2mm.
PEKK crude product is purified by employing polyamino many ethers tetramethylene phosphonic acid the most according to claim 1
Technique, it is characterised in that: in step (1), the mass concentration of polyamino many ethers tetramethylene phosphonic acid aqueous solution is 1～20%.
PEKK crude product is purified by employing polyamino many ethers tetramethylene phosphonic acid the most according to claim 1
Technique, it is characterised in that: PEKK crude product and the mass ratio of polyamino many ethers tetramethylene phosphonic acid aqueous solution in step (1)
For 1:10～1:20.
5. according to Claims 1 to 4 arbitrary described employing polyamino many ethers tetramethylene phosphonic acid, PEKK crude product is entered
The technique of row purification, it is characterised in that: in step (1), return time is 6～10 hours.
PEKK crude product is purified by employing polyamino many ethers tetramethylene phosphonic acid the most according to claim 1
Technique, it is characterised in that: step (2) neutral and alkali aqueous solution is with the aqueous solution that pH is 8～10 of ammonia regulation.
PEKK crude product is purified by employing polyamino many ethers tetramethylene phosphonic acid the most according to claim 1
Technique, it is characterised in that: step (2) neutral and alkali aqueous solution is 10:1～20 with the mass ratio of PEKK crude product in step (1):
1。
PEKK crude product is purified by employing polyamino many ethers tetramethylene phosphonic acid the most according to claim 1
Technique, it is characterised in that: step (2) medium ultraviolet light wave a length of 280～320nm, ultrasonic power is 20KHZ.
9. according to claim 6～8 arbitrary described employing polyamino many ethers tetramethylene phosphonic acid, PEKK crude product is entered
The technique of row purification, it is characterised in that: step (2) is irradiated and under ul-trasonic irradiation at ultraviolet light, with the speed of 0.1～1L/h
It is passed through ozone, refluxes 3～5 hours.
PEKK crude product is purified by employing polyamino many ethers tetramethylene phosphonic acid the most according to claim 1
Technique, it is characterised in that: during in step (3), water consumption is step (1) 20～30 times of PEKK crude product quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610498456.4A CN106188526A (en) | 2016-06-30 | 2016-06-30 | Use the technique that PEKK crude product is purified by polyamino many ethers tetramethylene phosphonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610498456.4A CN106188526A (en) | 2016-06-30 | 2016-06-30 | Use the technique that PEKK crude product is purified by polyamino many ethers tetramethylene phosphonic acid |
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| Publication Number | Publication Date |
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| CN106188526A true CN106188526A (en) | 2016-12-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610498456.4A Pending CN106188526A (en) | 2016-06-30 | 2016-06-30 | Use the technique that PEKK crude product is purified by polyamino many ethers tetramethylene phosphonic acid |
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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 CN201610498456.4A patent/CN106188526A/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 |
|---|
| 张思梅等: "《水处理工程技术》", 30 June 2015 * |
| 王又蓉: "《工业水处理问答》", 31 January 2007 * |
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| PB01 | Publication | ||
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Application publication date: 20161207 |