CN105801837A - Purification method of polyaryletherketone material - Google Patents
Purification method of polyaryletherketone material Download PDFInfo
- Publication number
- CN105801837A CN105801837A CN201610245965.6A CN201610245965A CN105801837A CN 105801837 A CN105801837 A CN 105801837A CN 201610245965 A CN201610245965 A CN 201610245965A CN 105801837 A CN105801837 A CN 105801837A
- Authority
- CN
- China
- Prior art keywords
- washing
- solvent
- wash
- organic solvent
- time
- 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
Links
Classifications
-
- 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
Abstract
The invention relates to a purification method of a polyaryletherketone material. The method comprises the steps that organic solvent with a high flash point is adopted to conduct washing purification on polyetheretherketone crude products, one solvent can be used alone, multiple solvents can be used alternatively or mixedly, and diphenyl sulfone, unreacted monomers and oligomers in the production process are removed. By means of the purification method, organic small molecular weight impurities in the polyetheretherketone crude products are removed, and the purity of final products is guaranteed.
Description
Technical field:
The purification process of a kind of poly aryl ether ketone material of disclosure, further there is provided a kind of to the thick product washing purification process of PAEK, belongs to the technical field of purification of high molecular polymer.
Background technology:
nullThe commercial production of PAEK generally adopts 4,Sodium (or potassium) salt of 4 '-difluoro benzophenone and hydroquinone is polycondensation synthesis in the high-temperature solvents such as diphenyl sulphone (DPS)，In the course of the polymerization process can from raw material、Equipment、Environment etc. introduce ferrum、Aluminum、Calcium、Manganese、Copper、The metallic elements such as nickel，These metal ion content height can affect the heat stability of polyether-ether-ketone，Therefore each company adopts diverse ways deduction with regard to polyether-ether-ketone (Jilin Jinzheng Macromolecule Materials Research Co., Ltd effectively reduces the method application number of metal content in polyetheretherketone: 200910009128.3 publication numbers: CN1011486784A) (the purification process application number of Sichuan University's polyether-ether-ketone: 200410081436.4 publication numbers: CN1640911A)，These patents are only referred to the purification of metal ion，Be not directed to other side-products removing method.
PAEK is in polycondensation process, product can not obtain the polymer of whole high molecular completely, difference due to reaction condition, in system, the residual list of reactant and low-molecular-weight (molecular weight is less than 2000) prepolymer by-product can be retained in system, adopt common organic solvent (methanol, ethanol, acetone) wash, can not remove it clean, especially low-molecular-weight performed polymer by-product also can remain in the product, although this low-molecular-weight performed polymer content is seldom (constituting about between ten thousand/1-5 of gross product amount), but it is very big on polyether-ether-ketone hot property and processing impact, the final performance of product is impacted.The purification process of such impurity currently there are no patent and reports.
Due to the organic solvent such as ethanol, acetone there is low boiling, volatile and flash-point is very low; belong to inflammable and explosive high-risk chemical; there is certain security risk, therefore at field of industrial production, equipment and environmental requirement is higher, so needing the cleaning solvent that a kind of stable chemical nature, flash-point are higher.
Summary of the invention:
The present invention is the purification process of a kind of poly aryl ether ketone material, polyether-ether-ketone is gone out product and carries out washing purification by the organic solvent adopting flash-point high, can be used alone by a kind of solvent, can also be used alternatingly or mix use by multi-solvents, remove diphenyl sulphone (DPS), unreacted monomer and oligomer in production process, by this purification process, the organic molecule impurity in thick for polyether-ether-ketone product is removed, it is ensured that the purity of final products.
The purification process of a kind of poly aryl ether ketone material of the present invention, comprises the following steps:
1) thick for PAEK (PAEK) product is added the washing organic solvent of 2 ~ 3 times of quality, stirs；
2) by the heating washing of step 1) mixture, stop when 80 DEG C-100 DEG C heating, constant temperature 0.5-2 hour, stop stirring, remove washing organic solvent；Again adding 2 ~ 3 times of new washing organic solvents of quality, carry out second time washing, wash temperature and time ibid, remove washing organic solvent；The operation of such cyclic washing carries out 5-7 time, treats that in organic solvent, diphenyl sulphone (DPS) content is less than≤0.03%, and solvent wash terminates；
3) by step 2) the complete material of solvent wash adds the deionized water of 2 ~ 3 times of quality, heated and stirred, and 80-100 DEG C is washed 0.5-2 hour, removes water lotion；The deionized water again adding 2 ~ 3 times of quality carries out washing next time, and wash temperature and time are ibid；Water washing operation carries out row 6-10 time so repeatedly, when electrical conductivity is less than≤50 μm/cm in deionized water, takes out dry materials, to obtain final product.
The purification process of a kind of poly aryl ether ketone material of the present invention, described washing organic solvent is selected from: N, N dimethyl acetylamide (DMAc) or N, N dimethylformamide (DMF) or N-Methyl pyrrolidone (NMP).
The positive effect of the present invention is in that:
Utilize N, N dimethyl acetylamide or N, the excellent dissolution ability of the organic solvents such as N dimethylformamide, N-Methyl pyrrolidone and the characteristic of high-flash, the molecular weight polymers produced in polyether-ether-ketone polymerization process and some monomers are dissolved and washed away removing, thick purifying products process improves the quality of product, the little molecule oligomer of the PAEK purity after purification and other organic impurities content≤0.1 ‰；Meanwhile, their high-flash characteristic is utilized, it is ensured that purge process safety, avoid bring in use procedure higher and fire risk, utilize multi-solvents alternately washing or mixing, washing, it is possible to small organic molecule washing is more thorough, and due to N, N dimethyl acetylamide or N, N dimethylformamide cost is relatively low, it is possible to first carry out early stage washing with both solvents, organic solvent washing several times after carrying out with N-Methyl pyrrolidone, all cleaning solvents are all recyclable, reduce cost.
Detailed description of the invention
Illustrated further the description present invention by following example, and do not limit the present invention in any way, under the premise without departing substantially from the technical solution of the present invention, any change or change that those of ordinary skill in the art made for the present invention easily realize fall within scope of the presently claimed invention.
Embodiment 1
Precise PAEK (PAEK) crude product 500 kilograms, is pumped in solvent wash still, adds N, N dimethyl acetylamide (DMAC) 1000 kilograms in solvent Material-washing kettle；Starting stirring and firing equipment, when temperature in the kettle reaches 80 DEG C, constant temperature stirs 1 hour, releases solvent and injects new N, N dimethyl acetylamide (DMAC) 1000 kilograms and wash, and wash temperature and time ibid, remove washing organic solvent；This solvent wash need to carry out 7 times altogether, and in N, N dimethyl acetylamide (DMAC) to be dissolved and washed away during diphenyl sulphone (DPS) content≤0.03% in solvent, solvent wash terminates.Being transferred in washing kettle by crude product, at the pure water carrying out 8 times with deionized water, washing temperature controls at 80 DEG C, and wash time controlled at 1 hour, and during electrical conductivity≤50 μm in deionized water/cm, washing terminates.Material is put in drying equipment and dries, when moisture≤0.5% in material, stop drying, it is thus achieved that required PAEK product, organic impurities content≤0.1 ‰ in product after purification.
Embodiment 2:
Precise PAEK (PAEK) crude product 500 kilograms, is pumped in solvent wash still, adds N, N dimethylformamide (DMF) 1000 kilograms in solvent Material-washing kettle；Starting stirring and firing equipment, when temperature in the kettle reaches 90 DEG C, constant temperature stirs 1 hour, releases solvent and injects new N, N dimethylformamide (DMF) 1000 kilograms and wash, and wash temperature and time ibid, remove washing organic solvent；This solvent wash need to carry out 7 times altogether, and in N, N dimethylformamide (DMF) to be dissolved and washed away during diphenyl sulphone (DPS) content≤0.03% in solvent, solvent wash terminates.Being transferred in washing kettle by crude product, at the pure water carrying out 8 times with deionized water, washing temperature controls at 80 DEG C, and wash time controlled at 1 hour, and during electrical conductivity≤50 μm in deionized water/cm, washing terminates.Material is put in drying equipment and dries, when moisture≤0.5% in material, stop drying, it is thus achieved that required PAEK product, organic impurities content≤0.1 ‰ in product after purification.
Embodiment 3:
Precise PAEK (PAEK) crude product 500 kilograms, is pumped in solvent wash still, adds N-Methyl pyrrolidone (NMP) 1000 kilograms in solvent Material-washing kettle.Starting stirring and firing equipment, when temperature in the kettle reaches 100 DEG C, constant temperature stirs 1 hour, releases solvent and injects new N-Methyl pyrrolidone (NMP) 1000 kilograms and wash, and wash temperature and time ibid, remove washing organic solvent；This solvent wash need to carry out 7 times altogether, and during diphenyl sulphone (DPS) content≤0.03% in N-Methyl pyrrolidone (NMP) solvent dissolved and washed away, solvent wash terminates.Being transferred in washing kettle by crude product, at the pure water carrying out 8 times with deionized water, washing temperature controls at 80 DEG C, and wash time controlled at 1 hour, and during electrical conductivity≤50 μm in deionized water/cm, washing terminates.Material is put in drying equipment and dries, when moisture≤0.5% in material, stop drying, it is thus achieved that required PAEK product, organic impurities content≤0.1 ‰ in product after purification.
Embodiment 4:
Precise PAEK (PAEK) crude product 500 kilograms, is pumped in solvent wash still, adds N, N dimethyl acetylamide (DMAC) 1000 kilograms in solvent Material-washing kettle.Starting stirring and firing equipment, when temperature in the kettle reaches 100 DEG C, constant temperature stirs 1 hour, releases solvent and injects new N, N dimethyl acetylamide (DMAC) 1000 kilograms and wash, and wash temperature and time ibid, remove washing organic solvent；This solvent wash need to carry out 5 times altogether, changes N-Methyl pyrrolidone (NMP) solvent into and repeats above washing operation 2 times, and during diphenyl sulphone (DPS) content≤0.03% in N-Methyl pyrrolidone (NMP) solvent dissolved and washed away, solvent wash terminates.Being transferred in washing kettle by crude product, at the pure water carrying out 8 times with deionized water, washing temperature controls at 80 DEG C, and wash time controlled at 1 hour, and during electrical conductivity≤50 μm in deionized water/cm, washing terminates.Material is put in drying equipment and dries, when moisture≤0.5% in material, stop drying, it is thus achieved that required PAEK product, organic impurities content≤0.1 ‰ in product after purification.
Embodiment 5:
Precise PAEK (PAEK) crude product 500 kilograms, is pumped in solvent wash still, adds N, N dimethylformamide (DMF) 1000 kilograms in solvent Material-washing kettle.Starting stirring and firing equipment, when temperature in the kettle reaches 100 DEG C, constant temperature stirs 1 hour, releases solvent and injects new N, N dimethylformamide (DMF) 1000 kilograms and wash, and wash temperature and time ibid, remove washing organic solvent；This solvent wash need to carry out 5 times altogether, changes N-Methyl pyrrolidone (NMP) solvent into and repeats above washing operation 2 times, and during diphenyl sulphone (DPS) content≤0.03% in N-Methyl pyrrolidone (NMP) solvent dissolved and washed away, solvent wash terminates.Being transferred in washing kettle by crude product, at the pure water carrying out 8 times with deionized water, washing temperature controls at 80 DEG C, and wash time controlled at 1 hour, and during electrical conductivity≤50 μm in deionized water/cm, washing terminates.Material is put in drying equipment and dries, when moisture≤0.5% in material, stop drying, it is thus achieved that required PAEK product, organic impurities content≤0.1 ‰ in product after purification.
Claims (2)
1. a purification process for poly aryl ether ketone material, comprises the following steps:
1) thick for PAEK (PAEK) product is added the washing organic solvent of 2 ~ 3 times of quality, stirs；
2) by the heating washing of step 1) mixture, stop when 80 DEG C-100 DEG C heating, constant temperature 0.5-2 hour, stop stirring, remove washing organic solvent；Again adding 2 ~ 3 times of new washing organic solvents of quality, carry out second time washing, wash temperature and time ibid, remove washing organic solvent；The operation of such cyclic washing carries out 5-7 time, treats that in organic solvent, diphenyl sulphone (DPS) content is less than≤0.03%, and solvent wash terminates；
3) by step 2) the complete material of solvent wash adds the deionized water of 2 ~ 3 times of quality, heated and stirred, and 80-100 DEG C is washed 0.5-2 hour, removes water lotion；The deionized water again adding 2 ~ 3 times of quality carries out washing next time, and wash temperature and time are ibid；Water washing operation carries out row 6-10 time so repeatedly, when electrical conductivity is less than≤50 μm/cm in deionized water, takes out dry materials, to obtain final product.
2. the purification process of a kind of poly aryl ether ketone material described in claim 1, it is characterised in that: described washing organic solvent is selected from: N, N dimethyl acetylamide or N, N dimethylformamide or N-Methyl pyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610245965.6A CN105801837A (en) | 2016-04-20 | 2016-04-20 | Purification method of polyaryletherketone material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610245965.6A CN105801837A (en) | 2016-04-20 | 2016-04-20 | Purification method of polyaryletherketone material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105801837A true CN105801837A (en) | 2016-07-27 |
Family
ID=56458145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610245965.6A Pending CN105801837A (en) | 2016-04-20 | 2016-04-20 | Purification method of polyaryletherketone material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105801837A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461932A (en) * | 2021-07-29 | 2021-10-01 | 浙江大学 | Preparation method of polyaryletherketone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1473314A1 (en) * | 2000-07-06 | 2004-11-03 | Gharda Chemicals Limited | Melt processible polyether ether ketone polymer |
| CN1640911A (en) * | 2004-12-09 | 2005-07-20 | 四川大学 | Method for purifying poly ether-ether-ketone |
| 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 |
| CN105175714A (en) * | 2015-09-23 | 2015-12-23 | 中橡集团炭黑工业研究设计院 | Process method for preparing cyano polyetherketoneketone resin |
-
2016
- 2016-04-20 CN CN201610245965.6A patent/CN105801837A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1473314A1 (en) * | 2000-07-06 | 2004-11-03 | Gharda Chemicals Limited | Melt processible polyether ether ketone polymer |
| CN1640911A (en) * | 2004-12-09 | 2005-07-20 | 四川大学 | Method for purifying poly ether-ether-ketone |
| 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 |
| CN105175714A (en) * | 2015-09-23 | 2015-12-23 | 中橡集团炭黑工业研究设计院 | Process method for preparing cyano polyetherketoneketone resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461932A (en) * | 2021-07-29 | 2021-10-01 | 浙江大学 | Preparation method of polyaryletherketone |
| CN113461932B (en) * | 2021-07-29 | 2022-08-09 | 浙江大学 | Preparation method of polyaryletherketone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6110385B2 (en) | Process for preparing polysulfone | |
| Dimitrov et al. | Polysulfone functionalized with phosphonated poly (pentafluorostyrene) grafts for potential fuel cell applications | |
| CN104530419A (en) | Industrial synthesis method of high-thermal-stability terminated polysulfone resin | |
| CN111433254B (en) | Preparation method of polyether ketone and prepared polyether ketone | |
| CN107778486B (en) | Post-treatment method of soluble polyarylethersulfone resin | |
| KR20170107031A (en) | De-chlorination of polyaryl ethers by melt polymerization | |
| CN104497239A (en) | Industrial synthetic method of low-chromaticity high-thermal-stability end capped polyether-ether-ketone resin | |
| CN103626999A (en) | Industrial synthesis method of polyarylether sulfone resin | |
| CN104479089A (en) | Industrial synthesis method of high-thermal-stability blocked binphenyl-structure-containing polyaryletherketone resin | |
| Takamuku et al. | Fully aromatic block copolymers for fuel cell membranes with densely sulfonated nanophase domains | |
| Yang et al. | Synthesis of poly [arylene ether sulfone-b-vinylidene fluoride] block copolymers | |
| CN108948343B (en) | Polymer containing sulfoxide group and preparation method thereof | |
| CN101220163B (en) | Method for producing polybenzimidazole crosslinked membrane with epoxy compound | |
| CN107936244B (en) | Post-treatment method of soluble polyaryletherketone resin | |
| CN109054019A (en) | A kind of polyarylether sulfoxide polymer and preparation method thereof | |
| CN107428932B (en) | Desalting of polyaryl ethers by melt extraction | |
| CN105801837A (en) | Purification method of polyaryletherketone material | |
| CN105348512A (en) | Polyarylether materials containing imide side groups and preparation method therefor | |
| CN104558586A (en) | Allyl containing crosslinkable azo polyarylether and preparation method thereof | |
| CN113512161A (en) | Sulfonate phenolic resin and preparation method and application thereof | |
| CN104003861B (en) | Hexaphenyl terminated monomer and preparation method and application thereof in preparation of hexa-benzene ring terminated polyether ketone | |
| CN102492132A (en) | Polyaryletherketone copolymers containing cyano group and preparation method for polyaryletherketone copolymers | |
| CN109096485A (en) | The novel crystallizable polyether-ether-ketone keto-resin and preparation method that can dissolve the side group containing phthalein | |
| CN105175714A (en) | Process method for preparing cyano polyetherketoneketone resin | |
| CN101538366B (en) | Polyarylene imide sulfide polymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160727 |