CN105885034A

CN105885034A - Method for refining poly(ether-ketone-ketone) crude product by adopting 2,3-dihydroxybutanedioic acid

Info

Publication number: CN105885034A
Application number: CN201610498551.4A
Authority: CN
Inventors: 李光辉; 贾远超; 张泰铭; 孙庆民; 王荣海; 薛居强; 黄桂青; 李云龙
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: 2016-08-24

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 adopting 2,3-dihydroxybutanedioic 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; then adding a 2,3-dihydrobutanedioic acid water solution, carrying out reflux stirring and carrying out filtration after cooling; and then carrying out reflux washing with water 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 efficient metal chelating capacity of 2,3-dihydrobutanedioic acid, thus achieving efficient removal of Al<3+> in the poly(ether-ketone-ketone) crude product.

Description

Use the method that PEKK crude product is refined by 2,3 dihydroxybutanedioic acid

Technical field

The present invention relates to the process for purification of macromolecular material, be specifically related to a kind of employing 2,3 dihydroxybutanedioic acid thick to PEKK The method that product carry 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.

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, and the PEKK of organic solvent-free The process for purification of crude product.

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 2,3 dihydroxybutanedioic acid to poly- The method that ether 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 employing 2,3 dihydroxybutanedioic 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 2,3 dihydroxybutanedioic acid aqueous solution, continue to be heated to reflux, filter after cooling, gathered Ether 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 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.

In step (2), the mass concentration of 2,3 dihydroxybutanedioic acid aqueous solution is 5～10%.

In step (2), the addition of 2,3 dihydroxybutanedioic acid aqueous solution is 10～20 times of PEKK crude product quality.

In step (2), return time is 4～6 hours.

In step (3), water consumption is 20～30 times of PEKK crude product quality.

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 2,3 dihydroxybutanedioic acid efficient simultaneously Metal chelation abilities, constantly trap Al³⁺, thus realize Al in PEKK crude product³⁺Efficient removal.

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 dimethyl sulfoxide and 2,3 dihydroxybutanedioic acid aqueous solution, and after filtration, mother solution color is relatively deep, after through repeatedly Available white PEKK sterling after 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, 2,3-dihydroxies Base succinic acid can with PEKK contained Al³⁺Form stable comple, reach removal Al³⁺Purpose.The present invention can not only Enough by Al in PEKK³⁺Content is down to below 50ppm, raising product quality, and the use of the 2,3 dihydroxybutanedioic acid used Measure little, nuisanceless pollution, 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 2,3 dihydroxybutanedioic acid aqueous solution 400g of middle addition 10%, return stirring 6 hours, it is cooled to 23 DEG C of filtrations, obtains polyethers Ketone ketone primary product；Primary product washs 3 times with the backflow of 600g water respectively, then through filtering, being dried, obtains white PEKK sterling, Detect through ICP, its Al³⁺Content is 32ppm, 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, the rear aqueous solution 400g adding the dimethyl sulfoxide that mass concentration is 5%, rise high-temperature and be stirred at reflux 8 hours；It is cooled to 20 DEG C of filtrations, obtain PEKK primary product；Primary product washs 3 times with the backflow of 600g water respectively, then through filtering, being dried, To 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, 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 2,3 dihydroxybutanedioic acid aqueous solution 300g of 5%, return stirring 5 hours, is cooled to 25 DEG C of filtrations, obtains 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, 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 2,3 dihydroxybutanedioic acid aqueous solution 200g of 8%, return stirring 4 hours, be cooled to 20 DEG C of filtrations, 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

1. one kind uses the method that PEKK crude product is refined by 2,3 dihydroxybutanedioic acid, it is characterised in that include following step Rapid:

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: in step (2), 2,3 dihydroxybutanedioic acid is water-soluble The mass concentration of liquid is 5～10%.

Process for purification the most according to claim 1, it is characterised in that: in step (2), 2,3 dihydroxybutanedioic acid is water-soluble The addition of liquid is 10～20 times of PEKK crude product quality.

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 Hour.

Process for purification 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.

Process for purification the most according to claim 9, it is characterised in that: in step (3), washing times is 3～5 times.