CN106188528A - Use the technique that PEKK crude product is refined by sodium gluconate - Google Patents

Use the technique that PEKK crude product is refined by sodium gluconate Download PDF

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Publication number
CN106188528A
CN106188528A CN201610505225.1A CN201610505225A CN106188528A CN 106188528 A CN106188528 A CN 106188528A CN 201610505225 A CN201610505225 A CN 201610505225A CN 106188528 A CN106188528 A CN 106188528A
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CN
China
Prior art keywords
pekk
crude product
refining
sodium gluconate
dps
Prior art date
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.)
Pending
Application number
CN201610505225.1A
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Chinese (zh)
Inventor
孙庆民
张泰铭
王荣海
李光辉
薛居强
黄桂青
王军
贾远超
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Shandong Kaisheng New Materials Co Ltd
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Shandong Kaisheng New Materials Co Ltd
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Priority to CN201610505225.1A priority Critical patent/CN106188528A/en
Publication of CN106188528A publication Critical patent/CN106188528A/en
Pending legal-status Critical Current

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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 technique using sodium gluconate that PEKK crude product is refined.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 water backflow washing, 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

Use the technique that PEKK crude product is refined by sodium gluconate
Technical field
The present invention relates to the process for refining of macromolecular material, be specifically related to a kind of employing sodium gluconate thick to PEKK The technique that product carry 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.
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, and organic solvent warp used Reclaim the process for refining of the PEKK crude product of 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 employing sodium gluconate to poly- The technique that ether ketone ketone crude product carries out refining, it is possible to effectively reduce Al in PEKK crude product3+Content, and organic solvent warp used Recovery can recycle.
The technique that PEKK crude product is refined by employing 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 water, through filtering, being dried, obtains 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), water consumption is 20～30 times of PEKK crude product quality, and in step (3), washing times is 3～5 Secondary.
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.
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, reach removal Al3+Purpose.The present invention is not It is only capable of Al in PEKK3+Content is down to below 50ppm, improves product quality, and the consumption of the sodium gluconate of use is little, Nuisanceless pollution, 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 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 white PEKK pure Product, detect through ICP, its Al3+Content is 33ppm, meets PEKK applied at elevated temperature and processing request.
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 8 hours to 41 DEG C；Fall Temperature, to 20 DEG C of filtrations, obtains PEKK primary product；Primary product washs 3 times with the backflow of 600g water respectively, then through filtering, being dried, Obtain lead PEKK sterling, detect through ICP, its Al3+Content is 2850ppm, it is impossible to meet PEKK applied at elevated temperature And processing request.
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 backflow of 500g water respectively, then through filtering, being dried, obtains white PEKK Sterling, detects through ICP, its Al3+Content is 45ppm, meets PEKK applied at elevated temperature and processing request.
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 backflow of 400g water respectively, then through filtering, being dried, obtains white PEKK pure Product, detect through ICP, its Al3+Content is 38ppm, meets PEKK applied at elevated temperature and processing request.

Claims (10)

1. one kind uses the technique that PEKK crude product is refined by 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 water, through filtering, being dried, obtains 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: in step (3), water consumption is PEKK crude product matter 20～30 times of amount, in step (3), washing times is 3～5 times.
CN201610505225.1A 2016-06-30 2016-06-30 Use the technique that PEKK crude product is refined by sodium gluconate Pending CN106188528A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1331658A (en) * 1998-10-23 2002-01-16 通用电气公司 Method for reducing metal ion concentration in brain solution
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
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
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1331658A (en) * 1998-10-23 2002-01-16 通用电气公司 Method for reducing metal ion concentration in brain solution
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
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
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 (1)

* Cited by examiner, † Cited by third party
Title
严莲荷: "《水处理药剂及配方手册》", 31 January 2004 *

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Application publication date: 20161207