CN116120540B - Method for preparing polyether-ether-ketone at low temperature - Google Patents
Method for preparing polyether-ether-ketone at low temperature Download PDFInfo
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- CN116120540B CN116120540B CN202310308769.9A CN202310308769A CN116120540B CN 116120540 B CN116120540 B CN 116120540B CN 202310308769 A CN202310308769 A CN 202310308769A CN 116120540 B CN116120540 B CN 116120540B
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- dihydroxybenzophenone
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 33
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 111
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 96
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- QUGUFLJIAFISSW-UHFFFAOYSA-N 1,4-difluorobenzene Chemical compound FC1=CC=C(F)C=C1 QUGUFLJIAFISSW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 32
- 239000002244 precipitate Substances 0.000 claims description 31
- 239000003513 alkali Substances 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000007344 nucleophilic reaction Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 239000012153 distilled water Substances 0.000 description 30
- 239000007788 liquid Substances 0.000 description 30
- 239000007787 solid Substances 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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
- C08G65/38—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyethers (AREA)
Abstract
The invention provides a method for preparing polyether-ether-ketone at low temperature, belonging to the technical field of high polymer materials. The method uses p-difluorobenzene and 4,4' -dihydroxybenzophenone as raw materials to react in potassium hydroxide or sodium hydroxide aqueous solution, and the potassium hydroxide or sodium hydroxide is used as a reactant and a catalyst for nucleophilic reaction, so that the reaction can be carried out at a lower temperature without a large amount of organic solvents, and the method is beneficial to environmental protection. The method has very complete reaction process, and the purity of the prepared product can reach 99.9%.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a method for preparing polyether-ether-ketone at low temperature.
Background
The polyether-ether-ketone is an aromatic linear polymer material, is a novel semi-crystalline aromatic thermoplastic engineering plastic which is successfully researched and developed in the last 70 th century, has high temperature resistance, chemical corrosion resistance, high strength, high modulus, high fracture toughness, excellent dimensional stability and other physical and chemical properties. The glass transition temperature (Tg) of the polyetheretherketone is 143 ℃, the melting point (Tm) is 334 ℃, and the maximum crystallinity theoretically achievable is 48%, typically 20% -30%. The density in the amorphous state was 1.265g/cm3, and the density at the maximum crystallinity was 1.32g/cm3. The crystal form of the material has outstanding heat resistance and mechanical properties, the continuous use temperature is 260 ℃, the instant use temperature can reach 300 ℃, and the material is not decomposed in a short time at 400 ℃. The polyether-ether-ketone has excellent comprehensive performance, so that the polyether-ether-ketone has wide application in various fields.
Polyetheretherketone is a high-end product in specialty engineering plastics, which was developed in 1978 by the company ICI of the imperial chemical industry in the United kingdom, after which PEEK from the company ICI had been converted to that from VICTREX in the United kingdom. In China, due to the excellent performance of PEEK, research thereof has been put into the seventy-fifteen national major technological project of attack and the "863 program". The current synthetic methods of polyether-ether-ketone are synthesized by gradual polymerization of alkylated bisphenol salts. Typical reaction is to use 4,4' -difluorobenzophenone and hydroquinone to react with sodium carbonate or potassium carbonate, the reaction is carried out in aprotic solvents such as diphenyl sulfone or sulfolane, the reaction temperature is above 300 ℃, the polyether-ether-ketone products on the market at present are all synthesized based on the method, and the reaction method has the defects of high reaction temperature, large amount of organic solvents of diphenyl sulfone, easy oxidation in the reaction process, inert gas protection, high price of raw materials and the like.
Disclosure of Invention
The object of the present invention is to provide a process for preparing polyetheretherketone at low temperature, which process is carried out at relatively low temperatures and does not require large amounts of organic solvents.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing polyether-ether-ketone at low temperature, comprising:
Taking p-difluorobenzene and 4,4' -dihydroxybenzophenone as raw materials, and reacting in an alkali solution to obtain polyether-ether-ketone; the reaction temperature is 40-80 ℃.
Preferably, the alkali solution is potassium hydroxide or sodium hydroxide.
Preferably, the concentration of the alkali solution is 10% -50%.
Preferably, the concentration of the alkali solution is 17% -34%.
Preferably, the reaction time is 1.5-2 hours.
Preferably, the molar ratio of the 4,4' -dihydroxybenzophenone to the p-difluorobenzene is 1:1.
Preferably, the molar ratio of the alkali in the alkali solution to the 4,4' -dihydroxybenzophenone is 2-2.5:1.
Preferably, the method specifically comprises the following steps: adding an alkali solution into a reaction container, maintaining the temperature of the alkali solution in the reaction container at 40-50 ℃, adding 4,4 '-dihydroxybenzophenone under stirring, raising the temperature in the reaction container to 55-80 ℃ after the 4,4' -dihydroxybenzophenone is completely dissolved, dropwise adding p-difluorobenzene, generating precipitate, and carrying out suction filtration, washing and drying after the dropwise adding is finished to obtain polyether-ether-ketone.
The beneficial effects of the invention are that
The invention provides a method for preparing polyether-ether-ketone at low temperature, which uses p-difluorobenzene and 4,4' -dihydroxybenzophenone as raw materials to react in potassium hydroxide or sodium hydroxide aqueous solution, wherein potassium hydroxide or sodium hydroxide is used as a reactant and a catalyst for nucleophilic reaction, so that the reaction can be carried out at a lower temperature without a large amount of organic solvents, and the method is beneficial to environmental protection. The method has complete reaction process, the purity of the prepared product can reach 99.9 percent, and the molecular weight of the minimum repeated unit of the generated polyether-ether-ketone is 288.
Detailed Description
The invention is described in further detail below in connection with specific examples, wherein the starting materials are all commercially available.
Example 1
500Ml of distilled water is poured into a beaker, 123.4g of KOH (the excess amount of the KOH is 10 percent relative to the 4,4 '-dihydroxybenzophenone in terms of the molar ratio reaction) is weighed, KOH is slowly added into the beaker under the stirring condition, the temperature of KOH aqueous solution in the beaker is maintained to be 45 ℃ after the KOH is completely dissolved, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitate is generated, and the liquid in the beaker is filtered after 1.5-2h of dropwise addition is completed. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested.
Example 2
500Ml of distilled water is weighed and poured into a beaker, 134.6g of KOH (20% excess) is weighed, KOH is slowly added into the beaker under the stirring condition, after the KOH is completely dissolved, the temperature of a KOH aqueous solution in the beaker is maintained at 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitates are generated, and after the dropwise addition is completed for 1.5-2 hours, the liquid in the beaker is filtered in a suction manner. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested.
Example 3
500Ml of distilled water is weighed and poured into a beaker, 157.1g of KOH (40% excess) is weighed, KOH is slowly added into the beaker under the stirring condition, after the KOH is completely dissolved, the temperature of a KOH aqueous solution in the beaker is maintained to be 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitates are generated, and after the dropwise addition is completed for 1.5-2 hours, the liquid in the beaker is filtered in a suction manner. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested.
Example 4
500Ml of distilled water is weighed and poured into a beaker, 168.3g of KOH (50% excess) is weighed, KOH is slowly added into the beaker under the stirring condition, after the KOH is completely dissolved, the temperature of a KOH aqueous solution in the beaker is maintained to be 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitates are generated, and after the dropwise addition is completed for 1.5-2 hours, the liquid in the beaker is filtered in a suction manner. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested.
Example 5
500Ml of distilled water is weighed and poured into a beaker, 88g of NaOH (10% excess) is weighed, naOH is slowly added into the beaker under the stirring condition, after the NaOH is completely dissolved, the temperature of an aqueous solution of NaOH in the beaker is maintained to be 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitate is generated, and after the dropwise addition of 1.5-2h, the liquid in the beaker is filtered in a suction manner. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested.
Example 6
500Ml of distilled water is weighed and poured into a beaker, 96g of NaOH (20% excess) is weighed, naOH is slowly added into the beaker under the stirring condition, after the NaOH is completely dissolved, the temperature of an aqueous solution of NaOH in the beaker is maintained to be 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitate is generated, and after the dropwise addition of 1.5-2h, the liquid in the beaker is filtered in a suction manner. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested.
Example 7
500Ml of distilled water is weighed and poured into a beaker, 112g of NaOH (40% excess) is weighed, naOH is slowly added into the beaker under the stirring condition, after the NaOH is completely dissolved, the temperature of an aqueous solution of NaOH in the beaker is maintained to be 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitate is generated, and after the dropwise addition of 1.5-2h, the liquid in the beaker is filtered in a suction manner. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested.
Example 8
500Ml of distilled water is weighed and poured into a beaker, 120g of NaOH (50% excess) is weighed, naOH is slowly added into the beaker under the stirring condition, after the NaOH is completely dissolved, the temperature of an aqueous solution of NaOH in the beaker is maintained to be 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitate is generated, and after the dropwise addition of 1.5-2h, the liquid in the beaker is filtered in a suction manner. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested.
Example 9
Weighing 1000ml of distilled water, pouring the distilled water into a beaker, weighing 112g of NaOH, slowly adding NaOH into the beaker under the stirring condition, maintaining the temperature of an aqueous solution of NaOH in the beaker to be 45 ℃ after the NaOH is completely dissolved, slowly adding 212.2g of 4,4' -dihydroxybenzophenone under the stirring condition, heating the liquid in the beaker to 65 ℃ after the solid in the beaker is completely dissolved, slowly dripping 114.1g of p-difluorobenzene into the beaker, generating precipitate, and carrying out suction filtration on the liquid in the beaker after 1.5-2h of dripping is completed. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested.
Example 10
400Ml of distilled water is weighed and poured into a beaker, 112g of NaOH is weighed, naOH is slowly added into the beaker under the stirring condition, after the NaOH is completely dissolved, the temperature of an aqueous solution of NaOH in the beaker is maintained to be 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitate is generated, and after the dropwise addition is completed for 1.5-2h, the liquid in the beaker is filtered in a suction manner. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested.
Example 11
300Ml of distilled water is weighed and poured into a beaker, 112g of NaOH is weighed, naOH is slowly added into the beaker under the stirring condition, after the NaOH is completely dissolved, the temperature of an aqueous solution of NaOH in the beaker is maintained to be 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitate is generated, and after the dropwise addition is completed for 1.5-2h, the liquid in the beaker is filtered in a suction manner. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested.
Comparative example 1
1000Ml of distilled water is weighed and poured into a beaker, 177.84g of Ca (OH) 2 is weighed, ca (OH) 2 is slowly added into the beaker under the stirring condition, after all Ca (OH) 2 is added, sediment exists at the bottom of the beaker, ca (OH) 2 cannot be completely dissolved, the temperature of an aqueous solution in the beaker is maintained to be 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, the reaction is continued for 1h, a large amount of solid sediment still exists in the beaker, and the reaction is incomplete. The temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added dropwise into the beaker, and after the dropwise addition is completed for 1.5-2 hours, the liquid in the beaker is filtered by suction. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. Physical properties of the precipitate were tested, and the precipitate contained a large amount of Ca (OH) 2 and 4,4' -difluorobenzophenone, confirming that the reaction did not proceed.
Comparative example 2
500Ml of distilled water is poured into a beaker, 157.1g of KOH (40% excess) is weighed, KOH is slowly added into the beaker under the stirring condition, after the KOH is completely dissolved, the temperature of a KOH aqueous solution in the beaker is maintained to be 25 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is dissolved, the temperature of the liquid in the beaker is raised to 35 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, after the dropwise addition is completed for 1.5-2h, the liquid in the beaker is filtered in a suction manner, no solid is left on filter paper, and the reaction is proved to be not carried out.
Comparative example 3
500Ml of distilled water is poured into a beaker, 157.1g of KOH (40% excess) is weighed, KOH is slowly added into the beaker under the stirring condition, after the KOH is completely dissolved, the temperature of a KOH aqueous solution in the beaker is maintained to be 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 85 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitates are generated, after the dropwise addition is completed for 1.5-2h, the liquid in the beaker is filtered, and sticky solids are left on filter paper. The solid is washed by ethanol for three times, dried after being washed by distilled water for three times, and still has partial caking and cannot be dispersed in ethanol and water. The melting point of the precipitate was 319.73 ℃ and the melting point range of the polyetheretherketone was not reached, demonstrating that the precipitate was not pure polyetheretherketone but a mixture.
Comparative example 4
500Ml of distilled water is weighed and poured into a beaker, 101g of KOH (10% of the shortage) is weighed, KOH is slowly added into the beaker under the stirring condition, after the KOH is completely dissolved, the temperature of a KOH aqueous solution in the beaker is maintained to be 45 ℃, 212.2g of 4,4' -dihydroxybenzophenone is slowly added under the stirring condition, after the solid in the beaker is completely dissolved, the temperature of the liquid in the beaker is raised to 65 ℃, 114.1g of p-difluorobenzene is slowly added into the beaker in a dropwise manner, precipitates are generated, and after the dropwise addition is completed for 1.5-2 hours, the liquid in the beaker is filtered in a suction manner. The suction filtration is washed by ethanol for three times, washed by distilled water for three times and dried. The physical properties of the precipitate were tested. When the amount of potassium carbonate is insufficient, the reaction is insufficient, the yield is lower than 60%, and the purity of the generated polyether-ether-ketone is low.
The samples of the above examples were tested for melting point and viscosity as shown in the following table:
| Melting point (. Degree. C.) | Viscosity (Pa, S) | |
| Example 1 | 345.73 | 212.4 |
| Example 2 | 343.97 | 290.5 |
| Example 3 | 346.13 | 174.2 |
| Example 4 | 347.84 | 112.8 |
| Example 5 | 347.15 | 121.4 |
| Example 6 | 346.29 | 185.3 |
| Example 7 | 343.62 | 310.3 |
| Example 8 | 347.53 | 118.7 |
| Example 9 | 348.48 | 87.2 |
| Example 10 | 344.0 | 273.6 |
| Example 11 | 343.17 | 342.5 |
| Comparative example 4 | 324.34 | 65.8 |
According to the invention, polyether-ether-ketone with certain molecular weight is prepared at relatively low reaction temperature by the method for preparing polyether-ether-ketone by the embodiment and analyzing and testing results, the reaction is complete due to the fact that the excessive potassium hydroxide or sodium hydroxide is different, in addition, the reaction process is influenced by the concentration of the aqueous solution of potassium hydroxide or the concentration of the aqueous solution of sodium hydroxide, the length of a molecular chain is determined, and the molecular weight of the polyether-ether-ketone can be controlled.
Claims (6)
1. A method for preparing polyether-ether-ketone at low temperature, which is characterized by comprising the following steps:
Taking p-difluorobenzene and 4,4' -dihydroxybenzophenone as raw materials, and reacting in an alkali solution to obtain polyether-ether-ketone; the reaction temperature is 40-80 ℃;
The alkali solution is aqueous solution of potassium hydroxide or sodium hydroxide;
the mole ratio of the alkali in the alkali solution and the 4,4' -dihydroxydiphenyl ketone is (2-2.5): 1.
2. The method for preparing polyether-ether-ketone at low temperature according to claim 1, wherein the concentration of the alkali solution is 10% -50%.
3. The method for preparing polyether-ether-ketone at low temperature according to claim 2, wherein the concentration of the alkali solution is 17% -34%.
4. The method for preparing polyether-ether-ketone at low temperature according to claim 1, wherein the reaction time is 1.5-2h.
5. The method for preparing polyether-ether-ketone at low temperature according to claim 1, wherein the molar ratio of 4,4' -dihydroxybenzophenone to p-difluorobenzene is 1:1.
6. The method for preparing polyether-ether-ketone at low temperature according to claim 1, wherein the method specifically comprises the following steps: adding an alkali solution into a reaction container, maintaining the temperature of the alkali solution in the reaction container at 40-50 ℃, adding 4,4 '-dihydroxybenzophenone under stirring, raising the temperature in the reaction container to 55-80 ℃ after the 4,4' -dihydroxybenzophenone is completely dissolved, dropwise adding p-difluorobenzene, generating precipitate, and carrying out suction filtration, washing and drying after the dropwise adding is finished to obtain polyether-ether-ketone.
Priority Applications (1)
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