CN105906802A

CN105906802A - Technique for refining polyetherketoneketone crude product by using ethylenediamine tetra(methylenephosphonic acid)

Info

Publication number: CN105906802A
Application number: CN201610505256.7A
Authority: CN
Inventors: 孙庆民; 张泰铭; 王荣海; 李光辉; 薛居强; 黄桂青; 王军; 贾远超
Original assignee: Shandong Kaisheng New Materials Co Ltd
Current assignee: Shandong Kaisheng New Materials Co Ltd
Priority date: 2016-06-30
Filing date: 2016-06-30
Publication date: 2016-08-31

Abstract

The invention relates to a refinement technique of a high-polymer material, particularly a technique for refining a polyetherketoneketone crude product by using ethylenediamine tetra(methylenephosphonic acid). The technique comprises the following steps: stirring a certain amount of the polyetherketoneketone crude product in a diphenylsulfone-containing dichloromethane solution under reflux; adding an ethylenediamine tetra(methylenephosphonic acid) water solution, stirring under reflux, cooling and filtering; and washing with water under reflux, filtering, and drying to obtain the polyetherketoneketone pure product. The diphenylsulfone is added into the dichloromethane to effectively enhance the swelling power of the dichloromethane and thoroughly push off the polyetherketoneketone molecular chain closely coated on the catalyst impurities, so that the impurity ions are dispersed into the organic phase. The efficient metal chelation capacity of the ethylenediamine tetra(methylenephosphonic acid) is utilized to continuously trap metal ions from the organic phase, thereby efficiently removing Al<3+> from the polyetherketoneketone crude product.

Description

Use the technique that PEKK crude product is refined by ethylenediamine tetramethylene phosphonic acid

Technical field

The present invention relates to the process for refining of macromolecular material, be specifically related to a kind of employing ethylenediamine tetramethylene phosphonic acid to PEKK The technique that crude product carries 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 purifying process can be found, effectively remove in polymer and remain Al³⁺It it is synthesized high-performance PEKK Key link.

Traditional handicraft 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, and organic solvent used is recovered can The process for refining of the PEKK crude product recycled.

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 ethylenediamine tetramethylene phosphonic acid pair The technique that PEKK crude product carries out refining, it is possible to effectively reduce Al in PEKK crude product³⁺Content, and organic solvent used Recovered can recycle.

The technique that PEKK crude product is refined by employing ethylenediamine tetramethylene 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 ethylenediamine tetramethylene phosphonic acid 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.

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 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 ethylenediamine tetramethylene phosphonic acid aqueous solution is 5～10%.

In step (2), the addition of ethylenediamine tetramethylene phosphonic acid 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, is circulated after distillation Utilize.

In step (3), water consumption is 20～30 times of PEKK crude product quality, and 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 will closely The PEKK strand of parcel catalyst impurities struts, and makes foreign ion diffuse in organic facies, utilizes ethylenediamine tetraacetic sub-simultaneously The efficient metal chelation abilities of methylphosphonic acid, constantly traps Al from organic facies³⁺, thus realize Al in PEKK crude product³⁺Height Effect is removed.

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 dichloromethane solution and the ethylenediamine tetramethylene phosphonic acid aqueous solution of diphenyl sulphone (DPS), and separatory obtains the two of yellow Benzene sulfone dichloromethane solution, obtains colourless dichloromethane through distilation after unified collection, is circularly used for configuring the two of diphenyl sulphone (DPS) Chloromethanes solution.

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, is conducive to fall Low production cost, improves production efficiency.The PEKK of the present invention is the most swelling in the dichloromethane solution of diphenyl sulphone (DPS), second two Amine tetramethylene phosphonic acid can with PEKK contained Al³⁺Form stable comple, reach removal Al³⁺Purpose.The present invention Can not only be by Al in PEKK³⁺Content is down to below 50ppm, improves product quality, the ethylenediamine tetramethylene phosphonic acid of use Consumption little, nuisanceless pollution, will not be to environmental danger, and the recovered reusable edible of organic solvent used, economical Environment-friendly advantage is obvious.

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； It is added thereto to the ethylenediamine tetramethylene phosphonic acid aqueous solution 400g of 10% again, 45 DEG C of return stirrings 6 hours, it is cooled to 23 DEG C of mistakes Filter, obtains PEKK primary product；Primary product washs 3 times with the backflow of 600g water respectively, then through filtering, being dried, obtains white PEKK sterling, detects through ICP, its Al³⁺Content is 35ppm, 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； It is cooled 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, It is dried, obtains lead PEKK sterling, detect through ICP, its Al³⁺Content is 2800ppm, 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 ethylenediamine tetramethylene phosphonic acid aqueous solution 300g of 5% again, 42 DEG C of return stirrings 5 hours, it is cooled to 25 DEG C Filter, obtain PEKK primary product；Primary product washs 4 times with the backflow of 500g water respectively, then through filtering, being dried, obtains white Color PEKK sterling, detects through ICP, its Al³⁺Content is 48ppm, 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 ethylenediamine tetramethylene phosphonic acid aqueous solution 200g of 8% again, 42 DEG C of return stirrings 4 hours, it is cooled to 20 DEG C of mistakes Filter, obtains PEKK primary product；Primary product washs 5 times with the backflow of 400g water respectively, then through filtering, being dried, obtains white PEKK sterling, detects through ICP, its Al³⁺Content is 38ppm, meets PEKK applied at elevated temperature and processing request.

Claims

1. one kind uses the technique that PEKK crude product is refined by ethylenediamine tetramethylene phosphonic acid, it is characterised in that include following Step:

Process for refining 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 refining the most according to claim 1, it is characterised in that: the dichloromethane solution of diphenyl sulphone (DPS) in step (1) Mass concentration be 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 be 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 be 40～ 45 DEG C, return time is 2～4 hours.

Process for refining the most according to claim 1, it is characterised in that: ethylenediamine tetramethylene phosphonic acid water in step (2) The mass concentration of solution is 5～10%.

Process for refining the most according to claim 1, it is characterised in that: ethylenediamine tetramethylene phosphonic acid water in step (2) The addition of solution 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, Return time is 4～6 hours.

9. according to the arbitrary described process for refining of claim 6～8, it is characterised in that: the filter being filtrated to get in step (2) Liquid obtains the dichloromethane solution of diphenyl sulphone (DPS) after separatory, recycles 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 20～30 times of quality, in step (3), washing times is 3～5 times.