CN113636575B - Preparation of nano alkali metal carbonate and application thereof in preparation of poly (aryl ether ketone) - Google Patents

Preparation of nano alkali metal carbonate and application thereof in preparation of poly (aryl ether ketone) Download PDF

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CN113636575B
CN113636575B CN202110928567.5A CN202110928567A CN113636575B CN 113636575 B CN113636575 B CN 113636575B CN 202110928567 A CN202110928567 A CN 202110928567A CN 113636575 B CN113636575 B CN 113636575B
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谢怀杰
平仕衡
董波
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Jilin Joinature Polymer Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • 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
    • C08G65/4093—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 characterised by the process or apparatus used
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

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Abstract

The invention provides a preparation method of nano alkali metal carbonate and application thereof in preparation of poly (aryl ether ketone), belonging to the field of organic synthesis. The preparation of nano alkali metal carbonate includes reaction of alkali metal carbonate material and settling agent in liquid phase by means of bubble-liquid film interface process. The obtained nano alkali carbonate is used as a salifying catalyst of the poly (aryl ether ketone) to prepare the high molecular material poly (aryl ether ketone), and the prepared poly (aryl ether ketone) melt has more excellent tensile strength, the strength is at least 100MPa, and meanwhile, the melt viscosity of the polymer is less than 1.0kNsm‑2And simultaneously is more than 0.06kNsm‑2This results in polymers having excellent high strength and good processability.

Description

Preparation of nano alkali metal carbonate and application thereof in preparation of poly (aryl ether ketone)
Technical Field
The invention relates to a preparation method of nano alkali metal carbonate and application thereof in preparation of poly (aryl ether ketone), belonging to the field of organic synthesis.
Background
Potassium carbonate and sodium carbonate are common inorganic carbonates, have wide application in a plurality of fields, and are very important inorganic chemical products. At present, the commonly adopted method for producing potassium carbonate or sodium carbonate at home and abroad comprises a Solvay method, a Hough alkali preparation method, a combined alkali method and the like, and when the potassium carbonate or the sodium carbonate is crystallized, large-particle products are easily generated due to the high crystal growth speed; and when the crystal is crystallized in the production process of potassium carbonate or sodium carbonate, a small amount of impurities can be seen by naked eyes, and the impurities seriously affect the quality of the product.
However, it is not easy to obtain potassium carbonate or sodium carbonate with a smaller particle size, the potassium carbonate or sodium carbonate particles on the market have a large difference from the nanometer size, and the common method is to grind the potassium carbonate or sodium carbonate into products with a smaller particle size by using a grinder, and when the potassium carbonate or sodium carbonate is ground into a smaller particle size, the grinder also generates a large amount of shedding mechanical impurities to enter the potassium carbonate or sodium carbonate, so that the grinding fails, and the particle size obtained by the grinding method is also limited and cannot reach the nanometer level, so that a new method with less energy consumption and simple process needs to be found to prepare the nanometer-sized potassium carbonate or sodium carbonate.
In the field of preparing high-performance poly (aryl ether ketone) products, potassium carbonate and sodium carbonate play an important role, the reaction has higher requirements on the potassium carbonate and the sodium carbonate, and the product quality of the poly (aryl ether ketone) is directly influenced.
If the particle size of potassium carbonate or sodium carbonate is large, the reaction hardly proceeds, and poly (aryl ether ketone) having a certain molecular weight cannot be obtained because: when the poly (aryl ether ketone) is prepared, the larger the particles of potassium carbonate or sodium carbonate are, the smaller the relative area of the particles in contact with a solution during reaction is, the potassium carbonate or sodium carbonate which reacts with a nucleophilic reagent enters the solution, and along with the reaction, the particles of potassium carbonate or sodium carbonate in the solution are further distributed, so that the particles are more and more unevenly distributed, the salt forming reaction process of the nucleophilic reagent and the potassium carbonate or sodium carbonate is further influenced, the reaction time of the carbonate of the nucleophilic reagent in the solution is too long, the reaction is incomplete at a salt forming temperature, and a prepared poly (aryl ether ketone) product generates a large amount of gelatinous substances, so that the product quality is reduced.
If heavy potassium carbonate or sodium carbonate is used, the heavy potassium carbonate or sodium carbonate can sink in a suspension taking diphenyl sulfone as a solvent, and the reaction is difficult even under the condition of high-speed stirring; if the macroscopic impurities of potassium carbonate or sodium carbonate are too much, the prepared poly (aryl ether ketone) has a large amount of impurities, which directly affects the product quality.
CN104788632B discloses a preparation method of high-purity polyetheretherketone, wherein the method adopts nano-calcium carbonate and corresponding hydroquinone disodium salt to quantitatively prepare polyetheretherketone, and the product has few impurities. But has the problem of low reaction activity of the nano calcium carbonate.
Disclosure of Invention
One of the purposes of the present invention is to provide a preparation method of nanometer-scale alkali metal carbonate.
The preparation method of the nanoscale alkali metal carbonate provided by the invention comprises the following steps: the alkali metal carbonate particles with nanometer particle size are obtained by reacting alkali metal carbonate raw material and sedimentation agent in liquid phase by adopting a bubble liquid film interface method.
The preparation method of the nanometer alkali metal carbonate provided by the invention comprises the following steps:
inorganic nano particles are added into the aqueous solution of alkali carbonate as a settling agent, then a thickening agent and a foaming agent are added, a large amount of bubbles are formed under stirring, and the alkali carbonate is crystallized into nano particles on the surfaces of the bubbles, so that nano alkali carbonate particles are prepared.
The specific operation is as follows: dissolving alkali carbonate in water to obtain alkali carbonate aqueous solution, then adding inorganic nanoparticles serving as a settling agent into the alkali carbonate aqueous solution, stirring at a high speed and uniformly mixing, adding a thickening agent into the mixed solution, adding a foaming agent after the mixed solution is uniformly distributed again, stirring until a large number of bubbles stably exist, generating a large number of bubble liquid films at the moment, crystallizing the alkali carbonate on the interface of the bubble liquid films, flatly laying the bubbles on a tray, and drying to obtain the nano-composite material.
In the above method, the alkali metal carbonate may be potassium carbonate, sodium carbonate or a mixture of the two;
in the alkali metal carbonate aqueous solution, the mass concentration of the alkali metal carbonate can be 8-12 g/ml;
inorganic nanoparticles as settling agents include, but are not limited to, nano-TiO2、SiO2、Al2O3、Fe2O3、Fe3O4、 V2O5、MnO2One or more of CuO, CuO;
the mass ratio of the inorganic nano particles to the alkali metal carbonate can be 1 (2-5), and specifically can be 1:2 and 1: 5;
the thickening agent comprises but is not limited to polyethylene glycol, hydroxymethyl cellulose, methyl cellulose, polymethacrylic acid, sodium polyacrylate, polyoxyethylene, polyvinylpyrrolidone and one or more of N, N-methylene bisacrylamide;
the mass ratio of thickener to alkali metal carbonate may be 1: (50-2000), specifically 1:50, 1:200,
The foaming agent comprises but is not limited to one or more of fatty alcohol polyoxyethylene ether sodium sulfate, lauryl sodium sulfate and 4, 4' -oxo-bis-benzenesulfonyl hydrazide;
the mass ratio of the foaming agent to the alkali metal carbonate may be 1: (20-4000) may be 3:100 or 1: 125.
Because the liquid film of the bubbles is very thin and a large number of smaller bubbles exist in the liquid film, the growth of alkali carbonate crystals can be hindered, thereby achieving the aim of reducing the particle size of the alkali carbonate,
when the alkali carbonate is potassium carbonate, the drying temperature of the potassium carbonate is more than or equal to 56 ℃ and less than 891 ℃;
when the alkali carbonate is sodium carbonate, the drying temperature of the sodium carbonate is more than or equal to 56 ℃ and less than 851 ℃.
The drying time can be 8-14h, and specifically can be 12 h.
After drying, the method may further comprise an operation of grinding the dried product.
When preparing nano-scale alkali metal carbonate, Al is adopted2O3When inorganic nanoparticles which are insoluble in water are used as settling agent, Al2O3And part of the inorganic nano particles can be mixed into the prepared nano alkali metal carbonate by dissolving in the solution, so that the inorganic nano particles can be further purified by adopting a molecular sieve chromatography mode, and specifically:
adding the prepared product into a suspension (ethanol), stirring, and filtering by using a molecular sieve (such as sephadex, pumice, agar, agarose, polyvinyl alcohol, polyacrylamide and the like) with a filtering molecular weight of 100-120, wherein the nano alkali metal carbonate can pass through the molecular sieve while Al can pass through the molecular sieve during filtering2O3And the nanometer alkali metal carbonate can not pass through the molecular sieve, so that the purification of the nanometer alkali metal carbonate is realized.
The application of the nanometer alkali metal carbonate prepared by the method as a salifying catalyst of the poly (aryl ether ketone) in preparing the polymer material poly (aryl ether ketone) also belongs to the protection scope of the invention.
In the application, the poly (aryl ether ketone) can be polyether ether ketone or polyether ketone.
The poly (aryl ether ketone) is a gel-free high purity poly (aryl ether ketone) product with good molecular distribution.
The invention also aims to provide the application of the nanoscale alkali metal carbonate in preparing the poly (aryl ether ketone).
It is a further object of the present invention to provide a process for the preparation of a poly (aryl ether ketone).
The method provided by the present invention for the preparation of a poly (aryl ether ketone) having repeat units of the formula-O-Ph-CO-Ph-, which is scheme one or scheme two or scheme three below;
the first scheme comprises the following steps: preparation of poly (aryl ether ketone) s by a stepwise process:
1) firstly, glycerol is taken as a solvent, bisphenol compounds and nano alkali metal carbonate are added, the mixture is heated to 190-220 ℃ under the protection of inert gas, the mixture reacts for 1-2 hours to obtain bisphenol alkali metal salt, the mixture is cooled to room temperature under the protection of inert gas, and then the glycerol is removed through toluene extraction to obtain the bisphenol alkali metal salt;
2) in a high-boiling point inert proton solvent, under the protection of inert gas, a double-halogenated organic compound reacts with a bisphenol alkali metal salt to obtain the poly (aryl ether ketone).
In step 1) of the above method, the bisphenol compound may be hydroquinone;
the hydroquinone is photographic-grade hydroquinone;
the molar ratio of the bisphenol compound to the nano alkali carbonate may be 1: (1-1.2), specifically 1: 1;
in step 2), the high-boiling inert protic solvent may be an aromatic sulfone, specifically diphenyl sulfone or sulfolane, and more specifically diphenyl sulfone;
the double halogenated organic compound can be a double fluorinated organic compound, and specifically can be 4, 4' -difluorobenzophenone;
the molar ratio of the bishaloorganic compound to the alkali metal salt of the bisphenol may be 1: (1-1.2), specifically 1: 1;
the specific operation of step 2) is as follows: taking a three-mouth bottle, inserting a stirring paddle into a middle port, connecting a side port with a three-way pipe, placing a thermometer and connecting high-purity nitrogen, and connecting a spherical condenser pipe to the other port for exhausting; putting a three-necked bottle in an electric heating jacket, putting a high-boiling point inert protic solvent and a double-halogenated organic compound into the bottle, introducing nitrogen, adding a bisphenol alkali metal salt after the high-boiling point inert protic solvent is melted, stirring, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 220 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuously heating to 305 ℃, keeping the temperature for 2 hours, and pouring the materials into cold distilled water after the reaction is finished to obtain a white blocky loose substance.
The melting enthalpy of the prepared poly (aryl ether ketone) with a specific melting point under similar density is more than or equal to 2.60.
The prepared poly (aryl ether ketone) polymer is respectively purified by acetone and distilled water by using a fat extractor, and then is dried to obtain a pure poly (aryl ether ketone) sample, and a melting point test is carried out by a NETZSCH differential scanning calorimeter DSC-200F3 instrument according to the test standard of ISO 11357, so as to obtain the melting point Tm (DEG C). Density test of Poly (aryl Ether Ketone) Density ρ (g/cm) was obtained according to ISO 1183 test standard using a Density Meter3). We have found that poly (aryl ether ketone) polymers prepared using disodium/potassium hydroquinone salts have melting points (Tm)/densities (p) which are characterized by a melting enthalpy greater than or equal to 2.60 for a particular melting point at similar densities, which is characteristic of poly (aryl ether ketone) polymers prepared using disodium/potassium hydroquinone salts.
Scheme II: preparation of poly (aryl ether ketone) s by a stepwise process:
a) under the protection of inert gas, leading the bisphenol compound to react with the nano alkali carbonate to generate bisphenol alkali metal salt;
b) the bisphenol alkali metal salt solution obtained in a) and the heated and dissolved double-halogen organic compound and the high boiling point inert protic solvent are subjected to polycondensation reaction at the temperature of 280-330 ℃ at the heating rate of 2-8 ℃/min, thus obtaining the poly (aryl ether ketone) polymer.
In step a), the reaction temperature can be 160-180 ℃;
the bisphenol compound can be 1, 4' -hydroquinone,
the nanometer alkali metal carbonate can be nanometer sodium carbonate, nanometer potassium carbonate or the mixture of nanometer sodium carbonate and nanometer potassium carbonate;
the molar ratio of the bisphenol compound to the nano alkali metal carbonate may be 1.0:1.0-1: 1.05.
More preferably, the alkali metal carbonate used in the process is sodium carbonate and the reaction temperature is preferably from 160 ℃ to 180 ℃, more preferably from 170 ℃ to 180 ℃.
In the method, the preparation of the bisphenol alkali metal salt and the heating of the dissolved dihalogenated organic compound and the high-boiling inert protic solvent are carried out simultaneously in different reaction vessels.
When the double-halogenated organic compound and the high-boiling point inert protic solvent are dissolved and the temperature is raised to 160-180 ℃, adding the prepared bisphenol alkali metal salt solution which maintains the temperature into the system, raising the temperature to 280-330 ℃ at the temperature raising rate of 2-8 ℃/min, and maintaining the temperature for reaction for 2-3 hours;
the double-halogenated organic compound in the method can be a double-fluorinated organic compound, in particular can be 4, 4' -difluorobenzophenone,
in the method, the molar ratio of the bisphenol alkali metal salt to the 4, 4' -difluorobenzophenone can be 1.0:1.0-1.0:1.1, and specifically can be 1.0: 1.0;
the high boiling point inert protic solvent in the process may be an aryl sulfone, specifically diphenyl sulfone or sulfolane, more specifically diphenyl sulfone.
In the method, the heating rate is preferably 2-8 ℃/min, and more preferably 2-4 ℃/min in the reaction process.
The polymerization is carried out at 170 ℃ to 350 ℃ and the final reaction temperature is maintained above 300 ℃ and preferably 320 ℃.
The method has the advantage of no CO in the polymerization reaction process2The gas is generated, the polymerization reaction time is shortened by 1-2 hours, the foaming of a reaction mixture is avoided, the polymerization reaction speed is accelerated, the factory efficiency is further improved, and the production cost is reduced.
The third scheme is as follows: preparing polyether-ether-ketone by a one-step method:
in a high-boiling point inert protic solvent, in the presence of nano alkali metal carbonate, making the dihalogenated organic compound and bisphenol compound produce polycondensation reaction so as to obtain the polyether-ether-ketone.
In the above process, the high-boiling inert protic solvent in the process may be an aromatic sulfone, specifically diphenyl sulfone or sulfolane, more specifically diphenyl sulfone.
The nanometer alkali metal carbonate can be nanometer sodium carbonate, nanometer potassium carbonate or the mixture of nanometer sodium carbonate and nanometer potassium carbonate;
the bisphenol compound can be 1, 4' -hydroquinone,
the double-halogenated organic compound in the method can be a double-fluorinated organic compound, in particular can be 4, 4' -difluorobenzophenone,
the molar ratio of the bisphenol compound to the 4, 4' -difluorobenzophenone in the method can be 1.0:1.0-1.0:1.1, and specifically can be 1.0: 1.0.
The molar ratio of the bisphenol compound to the nano alkali metal carbonate may be 1.0:1.0-1: 1.05.
The specific operation of the reaction is as follows: putting a high-boiling point inert proton solvent and a double-halogenated organic compound into a three-neck flask in a nitrogen atmosphere, adding a bisphenol compound and nano alkali metal carbonate after the high-boiling point inert proton solvent is melted, starting stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 200 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuing heating to 305 ℃, keeping the temperature for 2 hours, and pouring the material into cold distilled water to obtain the grey loose substance.
The resulting poly (aryl ether ketone) polymer material has a molecular weight polydispersity index PDI of 2.5 or less, preferably PDI of 2.4 or less, more preferably PDI of 2.3 or less. The molecular weight distribution was measured using Agilent Technologies PL-GPC220 High Temperature chromatography (Agilent PL-GPC220 High Temperature gel chromatography), alpha-chloronaphthalene as solvent, and 1,2, 4-trichlorobenzene as diluent. The temperature of the chromatographic column is 115 ℃, the mobile phase adopts a mixture of alpha-chloronaphthalene and 1,2, 4-trichlorobenzene, and the mass ratio of the alpha-chloronaphthalene to the 1,2, 4-trichlorobenzene is as follows: 1,2, 4-trichlorobenzene is 1:2.2, and the test parameters are K14.1 and α 0.7.
The melt viscosity MV of the polyaryletherketone polymer material adopts a Dynisco LCR 7001 capillary rheometer, the load is 10KN under the test condition of 400 ℃, and the shear flow rate is 1000 (1/S); after injection moulding with an injection moulding machine to form standard test specimens, the tensile strength of the polymer material, measured according to ISO527 using an Shimadzu AG-Xplus Universal testing machine, test method: firstly, a standard test sample strip which is formed by injection molding through an injection molding machine is cut into sample strips with the size of 50 multiplied by 4mm by a mould, two ends of the sample are fixed on a stretching mould of a universal testing machine, the stretching speed is 2mm/min, and the average value of each sample is obtained by repeating the test three times. Wherein the polymeric material has a melt viscosity MV tensile strength in the range of 40-160, preferably 60-140, more preferably 80-120.
The prepared thermoplastic polyaryletherketone has the characteristic that the tensile strength (Ts)/molecular weight distribution width (PD) is more than or equal to 25.
The fourth object of the present invention is to provide a poly (aryl ether ketone) product having high purity, melt viscosity and tensile strength which are greatly improved compared to PEEK made from nano-sized calcium carbonate.
The invention has the following advantages:
the invention provides a preparation method of nano-scale alkali metal carbonate, which is characterized by adopting a bubble liquid film interface method for preparation, belongs to the technical field of inorganic chemistry, and is a preparation method of a novel inorganic functional material. The preparation method of the nano potassium carbonate is simple and convenient to operate, low in cost and easy to control. The prepared nano potassium carbonate or nano sodium carbonate is used as a salifying catalyst of the poly (aryl ether ketone), and a gel-free high-purity poly (aryl ether ketone) product with good molecular distribution can be prepared.
Scheme I provides a method for preparing hydroquinone disodium/potassium salt by using glycerol as a solvent and hydroquinone and sodium carbonate and/or potassium carbonate under the protection of inert gas, and an improved method for preparing poly (aryl ether ketone) by using the hydroquinone disodium/potassium salt. Belongs to the technical field of high polymer materials. The first scheme is basically nucleophilic substitution condensation reaction, and the ratio of two raw materials can be accurately controlled, so that the molecular weight can be accurately controlled. And in the first scheme, glycerol is used as a solvent, and diphenyl sulfone is not used, so that the reaction temperature can be reduced.
Scheme two proposes that bisphenol alkali metal salt solution is generated in advance by bisphenol compounds and alkali metal carbonates in nitrogen atmosphere, and nucleophilic polycondensation reaction is carried out on the bisphenol alkali metal salt solution, the heat-dissolved bis-halogenated organic compound and the high-boiling point inert protic solvent at high temperature, so as to prepare the polyaryletherketone polymer with the repeating unit of the chemical formula-O-Ph-O-Ph-CO-Ph-. The polymer has the characteristics of high quality and high strength.
The prepared poly (aryl ether ketone) has uniform molecular weight distribution, and a high-performance poly (aryl ether ketone) product is obtained. Therefore, in the field of preparing special high polymer materials, potassium carbonate and sodium carbonate play an important role. Therefore, the reduction of the particle size of the potassium carbonate or the sodium carbonate to the nanometer level plays an important role in the synthesis of the matrix material, the nanoparticles have the characteristics of surface effect, volume effect, size effect and the like, so that the nanoparticles can have stronger chemical activity and catalytic effect, and the prepared poly (aryl ether ketone) product cannot generate gel.
Drawings
FIG. 1 is a field emission Scanning Electron Microscope (SEM) image of nanometer potassium carbonate prepared in example 1 of the present invention.
Fig. 2 is a field emission Scanning Electron Microscope (SEM) image of the nano sodium carbonate prepared in example 2 of the present invention.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the hydroquinone disodium salt obtained in example 3 of the present invention.
FIG. 4 is a Scanning Electron Microscope (SEM) image of the field emission of hydroquinone dipotassium salt obtained in example 4 of the present invention.
FIG. 5 is a Scanning Electron Microscope (SEM) image of the PEEK prepared in example 5 of the present invention.
FIG. 6 is a Scanning Electron Microscope (SEM) image of the PEEK prepared in example 6 of the present invention.
FIG. 7 is a Scanning Electron Microscope (SEM) image of the PEEK prepared in example 7 of the present invention.
FIG. 8 is a Scanning Electron Microscope (SEM) image of the PEEK prepared in example 8 of the present invention.
FIG. 9 is a Scanning Electron Microscope (SEM) image of the PEEK prepared in example 9 of the present invention.
FIG. 10 is a Scanning Electron Microscope (SEM) image of the PEEK prepared in example 10 of the present invention.
FIG. 11 is a Scanning Electron Microscope (SEM) image of the PEEK prepared in example 11 of the present invention.
FIG. 12 is a Scanning Electron Microscope (SEM) image of the PEEK prepared in example 12 of the present invention.
FIG. 13 is a Scanning Electron Microscope (SEM) image of the PEEK prepared in example 13 of the present invention.
FIG. 14 is a Scanning Electron Microscope (SEM) image of the PEEK prepared in example 14 of the present invention.
FIG. 15 is a graph comparing PDIs of polyetheretherketones prepared in examples 11-14 of the present invention and comparative examples 1 and 2.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
EXAMPLE 1 preparation of Nano Potassium carbonate
Firstly weighing 10g of potassium carbonate, dissolving the potassium carbonate in 100ml of distilled water to prepare a potassium carbonate solution, then taking 5g of nano titanium dioxide, adding the nano titanium dioxide into the prepared potassium carbonate solution, uniformly stirring the nano titanium dioxide with a stirrer at a high speed, then adding 0.2g of polyethylene glycol into the mixed solution, stirring the mixed solution for 15 minutes, adding 0.3g of 4, 4' -oxo-bis-benzenesulfonyl hydrazide of a high-strength foaming agent into the mixed solution, stirring the mixed solution until a large number of bubbles exist stably, generating a large number of bubble liquid films at the moment, crystallizing the potassium carbonate on the liquid film interface, flatly paving the stable bubbles on a tray, and drying the stable bubbles in an oven at the temperature of 56-891 ℃ for 12 hours. And finally slightly grinding the obtained dried product to obtain the potassium carbonate particles with the nanometer particle size, wherein the particle size is close to spherical, and the diameter is in the range of 1-2000 nm.
FIG. 1 is a field emission Scanning Electron Microscope (SEM) image of the prepared nano potassium carbonate.
Example 2 preparation of Nano sodium carbonate
Firstly weighing 10g of sodium carbonate, dissolving the sodium carbonate in 100ml of distilled water to prepare a sodium carbonate solution, and then taking 2g of nano ferric oxide Fe2O3Adding the sodium carbonate solution into the prepared sodium carbonate solution, uniformly stirring the sodium carbonate solution at a high speed by using a stirrer, adding 0.05g of polyoxyethylene into the mixed solution, stirring the mixture for 15 minutes, adding 0.08g of high-strength foaming agent 4, 4' -oxybis-benzenesulfonylhydrazide into the mixed solution, stirring the mixture until a large number of bubbles stably exist, generating a large number of bubble liquid films at the moment, crystallizing the sodium carbonate on the liquid film interfaces, flatly paving the stable bubbles on a tray, and drying the stable bubbles in an oven at the temperature of between 56 and 851 ℃ for 12 hours. And finally slightly grinding the obtained dried product to obtain the nano-scale sodium carbonate particles with the particle size close to a sphere and the diameter of 1-2000 nm.
Fig. 2 is a field emission Scanning Electron Microscope (SEM) image of the prepared nano sodium carbonate.
When preparing nanometer potassium carbonate and nanometer sodium carbonate, Al is adopted2O3When inorganic nano particles which are difficult to dissolve in water are used as a settling agent, Al2O3And part of the inorganic nano particles can be dissolved in the solution and mixed into the prepared nano potassium carbonate and nano sodium carbonate, so that the inorganic nano particles can be further purified by adopting a molecular sieve chromatography mode, and specifically:
adding the prepared product into suspension (ethanol), stirring, and filtering with a molecular sieve (such as sephadex, pumice, agar, agarose, polyvinyl alcohol, polyacrylamide and the like) with a filtering molecular weight of 100-120, wherein the nano potassium carbonate or nano sodium carbonate can pass through the molecular sieve during filtering, and Al can pass through the molecular sieve2O3And the nanometer potassium carbonate or the nanometer sodium carbonate can not pass through the molecular sieve, so that the purification of the nanometer potassium carbonate or the nanometer sodium carbonate is realized.
EXAMPLE 3 preparation and purification of Hydroquinone disodium salt (Using Nano sodium carbonate prepared according to example 2)
Preparation: placing a 500ml three-mouth bottle in a temperature-regulating electric heating jacket, inserting a stirring paddle into the middle port, connecting a side port with a tee joint respectively with a thermometer and a high-purity electric heating jacketNitrogen gas, and the other edge port is connected with a spherical condenser pipe. 184.18g (2mol) of glycerol are weighed and added into a three-neck bottle, 110.1g (1mol) of hydroquinone and 127.188g (1.2mol) of nano-scale Na are weighed2CO3Adding into a three-neck flask, introducing high-purity nitrogen to flow rate of 200ml/min, heating until hydroquinone is molten, and starting a stirring paddle to stirring speed of 85 rpm. When the temperature rises to 220 ℃, the temperature is kept constant for 1 hour, and after the reaction is finished, the reaction product is cooled to room temperature under the protection of nitrogen with the flow rate of 200 ml/min.
And (3) purification: taking out the reactant in the three-necked bottle, adding the reactant into a 1000ml separating funnel, adding 500ml toluene into the separating funnel, shaking for extraction, taking the lower layer solution, pouring the lower layer solution into a 1000ml flask, placing the flask in an electric heating sleeve, connecting a thermometer and a straight condensing tube to the flask, connecting the tail end of the condensing tube with a vacuum tail pipe and a receiving bottle, starting a vacuum pump and a heating sleeve, controlling the heating temperature within 80 ℃, distilling out the toluene in vacuum to obtain pure hydroquinone disodium salt, taking out the hydroquinone disodium salt, weighing about 150g, and reserving for later use. The obtained hydroquinone disodium salt is white powder, has a shape close to spherical, and has a particle size of 10-1000nm, as shown in figure 3.
FIG. 3 is a field emission Scanning Electron Microscope (SEM) image of the prepared hydroquinone disodium salt.
Example 4 preparation and purification of Hydroquinone dipotassium salt (Using Nano Potassium carbonate prepared according to example 1)
Preparation: a500 ml three-mouth bottle is arranged in a temperature-adjusting electric heating jacket, a stirring paddle is inserted into a middle port, one side port is connected with a tee joint and is respectively connected with a thermometer and high-purity nitrogen, and the other side port is connected with a spherical condenser pipe. 184.18g (2mol) of glycerol are weighed into a three-mouth bottle, 110.1g (1mol) of hydroquinone and 165.852g (1.2mol) of nano-scale K are weighed2CO3Adding into a three-neck flask, introducing high-purity nitrogen to flow rate of 200ml/min, heating until hydroquinone is molten, and starting a stirring paddle to stirring speed of 85 rpm. When the temperature rises to 190 ℃, the temperature is kept constant for 1 hour, and after the reaction is finished, the reaction product is cooled to room temperature under the protection of nitrogen with the flow rate of 200 ml/min.
And (3) purification: taking out the reactant in the three-mouth bottle, adding the reactant into a 1000ml separating funnel, adding 500ml of methylbenzene into the separating funnel, shaking for extraction, taking the lower layer solution, pouring the lower layer solution into a 1000ml flask, placing the flask into an electric heating sleeve, connecting a thermometer and a straight condensing tube to the mouth of the flask, connecting the tail end of the condensing tube with a vacuum tail connecting tube and a receiving bottle, starting a vacuum pump and a heating sleeve, controlling the heating temperature to be within 80 ℃, distilling out methylbenzene in vacuum to obtain pure hydroquinone dipotassium salt, taking out the hydroquinone dipotassium salt, weighing about 185g, and reserving for later use. The obtained hydroquinone dipotassium salt is white powder, has shape close to spherical, and has particle size of 10-1000nm, as shown in figure 4.
FIG. 4 is a field emission Scanning Electron Microscope (SEM) image of the prepared hydroquinone dipotassium salt.
Examples 5-10 show the preparation of polyetheretherketone in different proportions using the dipotassium hydroquinone salt and disodium hydroquinone salt prepared according to examples 3 and 4
Example 5 (scheme one preparation of polyetheretherketone from Hydroquinone disodium salt)
A1000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle port, a side port is connected with a three-way pipe, a thermometer is placed and connected with high-purity nitrogen, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-necked bottle in an electric heating sleeve, putting 327.3g (1.5mol) of diphenyl sulfone and 109.1g (0.5mol) of 4, 4' -difluorobenzophenone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 76.05g (0.5mol) of hydroquinone disodium salt (prepared in example 3) after the diphenyl sulfone is molten, starting stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 220 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuously heating to 305 ℃, keeping the temperature for 2 hours, and pouring the materials into cold distilled water to obtain white blocky loose objects.
Crushing the white block loose substance, putting 100g of the sample into a fat extractor, adding 500ml of acetone for extraction for 2h, then pouring out the acetone, adding 500ml of distilled water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃ and drying for 8h to obtain 99.97g of pure polyether ether ketone (PEEK) sample, wherein the yield is 99.97%, and the density and melting point of the PEEK sample are measured by a densitometer, as shown in detail in FIG. 5.
Fig. 5 is a field emission Scanning Electron Microscope (SEM) image of the prepared polyetheretherketone.
Example 6 (scheme one preparation of polyetheretherketone from Hydroquinone dipotassium salt)
A1000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle port, a side port is connected with a three-way pipe, a thermometer is placed and connected with high-purity nitrogen, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-necked bottle in an electric heating jacket, putting 327.3g (1.5mol) of diphenyl sulfone and 109.1g (0.5mol) of 4, 4' -difluorobenzophenone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 93.05g (0.5mol) of hydroquinone dipotassium salt (prepared in example 4) after the diphenyl sulfone is molten, starting stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 185 ℃, keeping the temperature for 0.5 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuously heating to 305 ℃, keeping the temperature for 1 hour, and pouring the material into cold distilled water to obtain the grey block loose substance.
Crushing the white block loose substance, putting 100G of the sample into a fat extractor, adding 500ml of acetone for extraction for 2h, pouring out the acetone, adding 500ml of distilled water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃ and drying for 8h to obtain a pure Polyetheretherketone (PEEK) sample 99.99G, wherein the yield is 99.99%, and the polyetheretherketone sample is tested for density and melting point by a densitometer, which is detailed in figure 6.
Fig. 6 is a field emission Scanning Electron Microscope (SEM) image of the prepared polyetheretherketone.
Example 7 (scheme one preparation of polyetheretherketone from disodium/Potassium hydroquinone salt)
Preparation of polyether ether ketone from hydroquinone disodium salt and hydroquinone dipotassium salt in different proportions
A1000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle port, a side port is connected with a three-way pipe, a thermometer is placed and connected with high-purity nitrogen, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-necked bottle in an electric heating jacket, putting 327.3g (1.5mol) of diphenyl sulfone and 109.1g (0.5mol) of 4, 4' -difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow of 100ml/min, adding 72.43g of hydroquinone disodium salt and 4.43g of hydroquinone dipotassium salt (the molar ratio is 20:1) after the diphenyl sulfone is molten, starting stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 200 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuing heating to 305 ℃, keeping the temperature for 2 hours, and pouring the materials into cold distilled water to obtain the grey-white blocky loose substance.
Crushing the white block loose substance, putting 100g of the sample into a fat extractor, adding 500ml of acetone for extraction for 2h, then pouring out the acetone, adding 500ml of distilled water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃ and drying for 8h to obtain 99.98g of pure polyether ether ketone (PEEK) sample, wherein the yield is 99.98%, and the density and melting point of the PEEK sample are measured by a densitometer, as shown in detail in FIG. 7.
Fig. 7 is a field emission Scanning Electron Microscope (SEM) image of the prepared polyetheretherketone.
Example 8 (scheme one preparation of polyetheretherketone from disodium/Potassium Hydroquinone)
Preparation of polyether ether ketone from hydroquinone disodium salt and hydroquinone dipotassium salt in different proportions
A1000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle port, a side port is connected with a three-way pipe, a thermometer is placed and connected with high-purity nitrogen, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating jacket, putting 327.3g (1.5mol) of diphenyl sulfone and 109.1g (0.5mol) of 4, 4' -difluorobenzophenone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 71.30g of hydroquinone disodium salt and 5.82g of hydroquinone dipotassium salt (the molar ratio is 15:1) after the diphenyl sulfone is molten, starting stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 200 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuing heating to 305 ℃, keeping the temperature for 2 hours, and pouring the materials into cold distilled water to obtain the grey block loose substance.
Crushing the white block loose substance, putting 100g of the sample into a fat extractor, adding 500ml of acetone for extraction for 2h, then pouring out the acetone, adding 500ml of distilled water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃ and drying for 8h to obtain 99.97g of pure polyether ether ketone (PEEK) sample, wherein the yield is 99.97%, and the density and melting point of the PEEK sample are measured by a densitometer, as shown in detail in FIG. 8.
Fig. 8 is a field emission Scanning Electron Microscope (SEM) image of the prepared polyetheretherketone.
Example 9 (scheme one preparation of polyetheretherketone from disodium/Potassium hydroquinone salt)
Preparation of polyether ether ketone from hydroquinone disodium salt and hydroquinone dipotassium salt in different proportions
A1000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle port, a side port is connected with a three-way pipe, a thermometer is placed and connected with high-purity nitrogen, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-necked bottle in an electric heating jacket, putting 327.3g (1.5mol) of diphenyl sulfone and 109.1g (0.5mol) of 4, 4' -difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow of 100ml/min, adding 69.14g of hydroquinone disodium salt and 8.46g of hydroquinone dipotassium salt (the molar ratio is 10:1) after the diphenyl sulfone is molten, starting stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 200 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuing heating to 305 ℃, keeping the temperature for 2 hours, and pouring the materials into cold distilled water to obtain the grey-white blocky loose substance.
Crushing the white block loose substance, putting 100g of the sample into a fat extractor, adding 500ml of acetone for extraction for 2h, pouring out the acetone, adding 500ml of distilled water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃ and drying for 8h to obtain 99.98g of pure Polyetheretherketone (PEEK) sample, wherein the yield is 99.98%, and the polyetheretherketone sample is tested for density and melting point by a densitometer, which is detailed in figure 9.
Fig. 9 is a field emission Scanning Electron Microscope (SEM) image of the prepared polyetheretherketone.
Example 10 (scheme one preparation of polyetheretherketone from disodium/Potassium Hydroquinone)
Preparing polyether-ether-ketone by hydroquinone disodium salt and hydroquinone dipotassium salt in different proportions.
A1000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle port, a side port is connected with a three-way pipe, a thermometer is placed and connected with high-purity nitrogen, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-necked bottle in an electric heating jacket, putting 327.3g (1.5mol) of diphenyl sulfone and 109.1g (0.5mol) of 4, 4' -difluorobenzophenone into the bottle, introducing high-purity nitrogen at the flow rate of 100ml/min, adding 67.60g of hydroquinone disodium salt and 10.34g of hydroquinone dipotassium salt (the molar ratio is 8:1) after the diphenyl sulfone is molten, starting stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 200 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuously heating to 305 ℃, keeping the temperature for 2 hours, and pouring the materials into cold distilled water to obtain the grey lump loose object.
Crushing the white block loose substance, putting 100g of the sample into a fat extractor, adding 500ml of acetone for extraction for 2h, pouring out the acetone, adding 500ml of distilled water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃ and drying for 8h to obtain 99.99g of pure Polyetheretherketone (PEEK) sample, wherein the yield is 99.99%, and the polyetheretherketone sample is tested for density and melting point by a densitometer, which is detailed in figure 10.
Fig. 10 is a field emission Scanning Electron Microscope (SEM) image of the prepared polyetheretherketone.
Comparative example 1
Polyetheretherketone is prepared using conventional method one.
A1000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle port, a side port is connected with a three-way pipe, a thermometer is placed and connected with high-purity nitrogen, and the other side port is connected with a spherical condenser pipe for exhausting. Placing a three-neck bottle in an electric heating jacket, adding 327.3g (1.5mol) of diphenyl sulfone and 109.1g (0.5mol) of 4, 4' -difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow rate of 100ml/min, adding 55.05g of hydroquinone (0.5mol) and 53.00g of light anhydrous Na after the diphenyl sulfone is molten2CO3(0.5mol), starting stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 200 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuously heating to 305 ℃, keeping the temperature for 2 hours, and pouring the materials into cold distilled water to obtain the grey loose block.
Crushing the white block loose substance, putting 100g of the sample into a fat extractor, adding 500ml of acetone for extraction for 2h, then pouring out the acetone, adding 500ml of distilled water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃, and drying for 8h to obtain a pure polyether ether ketone (PEEK) sample, wherein the density and the melting point of the PEEK sample are measured by a densitometer.
Comparative example 2
Polyetheretherketone is prepared using conventional method one.
A1000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle port, a side port is connected with a three-way pipe, a thermometer is placed and connected with high-purity nitrogen, and the other side port is connected with a spherical condenser pipe for exhausting. Placing the three-neck bottle in an electric heating jacket, adding 327.3g (1.5mol) of diphenyl sulfone and 109.1g (0.5mol) of 4, 4' -difluorobenzophenone, introducing high-purity nitrogen gas with the flow rate of 100ml/min, adding 55.05g of hydroquinone (0.5mol) and 48.18g of light anhydrous Na after the diphenyl sulfone is molten2CO3And 6.28g of light anhydrous K2CO3(molar ratio Na2CO3：K2CO310:1), stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 200 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuously heating to 305 ℃, keeping the temperature for 2 hours, and pouring the materials into cold distilled water to obtain the grey loose substance.
Crushing the white block loose object, putting 100g of sample into a fat extractor, adding 500ml of acetone for extraction for 2h, pouring out the acetone, adding 500ml of distilled water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃, and drying for 8h to obtain a pure polyether ether ketone (PEEK) sample, wherein the density and the melting point of the PEEK sample are measured by a densitometer.
Comparative example 3 quantitative preparation of polyetheretherketone Using light anhydrous Carbonic acid Hydroquinone disodium salt
A500 ml three-mouth bottle is arranged in a temperature-regulating electric heating jacket, a stirring paddle is inserted into a middle port, one side port is connected with a tee joint and is respectively connected with a thermometer and high-purity nitrogen, and the other side port is connected with a spherical condenser tube. 184.18g (2mol) of glycerol are weighed and added into a three-neck flask, 110.1g (1mol) of hydroquinone and 127.188g (1.2mol) of light anhydrous Na are weighed2CO3Adding into a three-neck flask, introducing high-purity nitrogen to flow rate of 200ml/min, heating until hydroquinone is molten, and starting a stirring paddle to stirring speed of 85 rpm. When the temperature rises to 220 ℃, the temperature is kept constant for 1 hour, and after the reaction is finished, the reaction product is cooled to room temperature under the protection of nitrogen with the flow rate of 200 ml/min.
Purification of hydroquinone disodium salt
Taking out the reactants in the three-neck flask, adding the reactants into a 1000ml separating funnel, adding 500ml toluene into the separating funnel, vibrating and extracting, taking the lower layer solution, pouring the lower layer solution into a 1000ml flask, placing the flask into an electric heating sleeve, connecting a thermometer and a straight condensing tube to the flask, connecting the tail end of the condensing tube with a vacuum tail pipe and a receiving bottle, starting a vacuum pump and a heating sleeve, controlling the heating temperature within 80 ℃, distilling out the toluene in vacuum to obtain pure hydroquinone disodium salt, taking out the hydroquinone disodium salt, weighing about 150g, and reserving for later use.
A1000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle port, a side port is connected with a three-way pipe, a thermometer is placed and connected with high-purity nitrogen, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-necked bottle in an electric heating jacket, putting 327.3g (1.5mol) of diphenyl sulfone and 109.1g (0.5mol) of 4, 4' -difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow of 100ml/min, adding 69.14g of hydroquinone disodium salt and 8.46g of hydroquinone dipotassium salt (the molar ratio is 10:1) after the diphenyl sulfone is molten, starting stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 200 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuing heating to 305 ℃, keeping the temperature for 2 hours, and pouring the materials into cold distilled water to obtain the grey-white blocky loose substance.
Crushing the white block loose object, putting 100g of sample into a fat extractor, adding 500ml of acetone for extraction for 2h, pouring out the acetone, adding 500ml of distilled water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃, and drying for 8h to obtain a pure polyether ether ketone (PEEK) sample, wherein the density and the melting point of the PEEK sample are measured by a densitometer.
TABLE 1 results of the tests of the examples
Figure BDA0003210126320000141
Examples 5-10 PEEK was prepared using quantitative amounts of alkali metal hydroquinone salt, i.e. the molar ratio of alkali hydroquinone salt to 4, 4' -difluorobenzophenone was 1:1, comparative examples 1-2 also used alkali metal carbonate to 4, 4' -difluorobenzophenone in a molar ratio of 1:1, observing the examples 5-10 and the comparative examples 1-2, the poly (aryl ether ketone) prepared by using the hydroquinone disodium salt/potassium salt has the characteristics of high melting point and small density, and the law of the melting point and the density accords with (Tm/rho) ≥ 2.60. The poly (aryl ether ketone) with high melting point can improve the use temperature and the application range, and the poly (aryl ether ketone) with low density has the advantage of saving the unit weight cost. Compared with the traditional one-step method for preparing PEEK, excess alkali metal carbonate is generally used, the PEEK prepared in examples 5-10 has less residues, and the purity of the obtained PEEK is improved.
Further comparing example 9 with comparative example 3, except that in example 3, the nano-scale carbonate is replaced by light anhydrous carbonate, PEEK produced had a small difference in the melt break percentage at density and melting point levels, and a large difference in viscosity, indicating that the nano-scale carbonate has some effect on the viscosity of PEEK.
Comparative example 4
Preparing hydroquinone dicalcium salt from nano calcium carbonate, and preparing polyether-ether-ketone from hydroquinone dipotassium salt
110.1g (1mol) of hydroquinone and 350g of nano calcium carbonate (the grain diameter is 0.01 mu m, 3.5mol) are taken and added into a three-mouth bottle, and high-purity argon is continuously introduced for protection, wherein the flow of the argon is 2.55L/min. Heating the three-mouth bottle in an electric heating jacket, starting a stirring paddle to stir after the raw materials are completely melted, heating to 200 ℃ at the temperature of about 195 ℃, maintaining the temperature for 30min, continuing heating to 215 ℃, and then carrying out salt forming reaction on the nano calcium carbonate and hydroquinone and releasing heat. Controlling the reaction temperature is a key point, immediately turning off the heating system when the temperature reaches 215 ℃, keeping stirring, simultaneously moving the three-mouth bottle out of the electric heating jacket, putting the three-mouth bottle into heat conducting oil of 180-210 ℃ for cooling, maintaining the reaction temperature at 215 ℃, and when no bubble appears on the liquid level in the three-mouth bottle any more, taking about 1 hour for the reaction to finish. Pouring the reactant into 1L of distilled water, stirring quickly, filtering and recrystallizing after the particles are completely dissolved to obtain the hydroquinone dicalcium, adding 400ml of acetone into the recrystallized product, stirring until the particles are completely dissolved, and filtering again to obtain the refined hydroquinone dicalcium.
625.8g (2.87mol) of diphenyl sulfone and 159.29g (0.73mol) of 4, 4' -difluorobenzophenone are taken, 188g (0.73mol) of hydroquinone dicalcium are taken and added into a three-neck bottle, and high-purity argon is continuously introduced for protection, wherein the argon flow is 2.55L/min. And (3) putting the three-necked bottle into an electric heating jacket for slow heating, starting a stirring paddle for stirring after the raw materials are completely melted, continuously heating to 280 ℃, maintaining the temperature for reaction for 1 hour, quickly pouring reactants into distilled water, and continuously stirring to obtain the crude polyetheretherketone particles.
Repeatedly washing crude product of polyether-ether-ketone with acetone for 5 times, wherein 500ml of acetone is used each time to remove solvent diphenyl sulfone, then using 280ml of 35% phosphoric acid and 300ml of 58.44g of ethylenediamine tetraacetic acid and distilled water to prepare 500ml of phosphoric acid-EDTA complex solution, washing polyether-ether-ketone for 1 time to remove a small amount of calcium fluoride generated by the reaction, finally washing with distilled water for 5 times, using 500ml of distilled water each time to remove phosphoric acid, and drying to obtain 186.44g of high-purity polyether-ether-ketone with yield of 88.68%.
From comparative example 4 it can be seen that: the nano calcium carbonate has low reaction activity, and the obtained high-purity polyether-ether-ketone has low yield.
Example 11 (case two)
Preparation of hydroquinone sodium salt solution: 250g of diphenyl sulfone and 104.04g (0.95mol) of hydroquinone were charged into a 500ml three-necked flask equipped with a mechanical stirrer, air inlet and air condenser. After introducing high-purity nitrogen, heating the mixture to dissolve, starting a stirring device, raising the temperature to 170 ℃, adding 100.16g (0.95mol) of nano-grade sodium carbonate, and reacting for 30 minutes. Keeping the temperature for standby;
in a further 1000ml three-necked flask equipped with overhead stirrer, thermometer and air condenser were placed 350g of diphenyl sulfone and 202.16g of 4, 4' -difluorobenzophenone (0.95mol), dissolved after passing high-purity nitrogen and the temperature was raised to 170 ℃, immediately the hydroquinone sodium salt solution prepared above was added, stirring was continued and the temperature was raised to 320 ℃ at a rate of 2 ℃/min, and the temperature was maintained until a torque determined by the power consumption on the stirrer motor was reached. The reaction mixture was poured into a container with cold purified water to give an off-white block. Pulverizing the block with a pounder into desired powder, boiling with ethanol under reflux for 2 hr, pouring out ethanol, adding pure water, boiling under reflux for 1 hr, repeating the above steps for 5 times, and removing the diphenyl sulfone solvent and inorganic salt. The sample was placed in a vacuum oven for vacuum and heated to 120 ℃ for drying for 12h to obtain a pure Polyetheretherketone (PEEK) sample, as shown in fig. 11.
Fig. 11 is a field emission Scanning Electron Microscope (SEM) image of the prepared polyetheretherketone.
Example 12 (scheme two)
Preparation of hydroquinone sodium salt solution: 300g of diphenyl sulphone and 98.26g (0.9mol) of hydroquinone are charged into a 500ml three-necked flask equipped with a mechanical stirrer, air inlet and air condenser. After high-purity nitrogen is introduced, the mixture is heated to be dissolved, a stirring device is started, the temperature is raised to 170 ℃, and 94.59g (0.9mol) of nano sodium carbonate are added to react for 30 minutes. This temperature is maintained for future use.
In another three-necked flask equipped with an overhead stirrer, thermometer and air condenser, 325g of diphenyl sulfone and 191.52g (0.9mol) of 4, 4' -difluorobenzophenone were charged, dissolved after passing high purity nitrogen and the temperature was raised to 170 ℃, hydroquinone sodium salt prepared as described above was immediately added, stirring was continued and the temperature was raised to 320 ℃ at a rate of 2 ℃/min, and the temperature was kept reacting until a torque determined by the power consumption on the stirrer motor was reached. The reaction mixture was poured into a container with cold purified water to give an off-white block. Pulverizing the blocks with a pounder into desired powder, boiling with ethanol under reflux for 2 hr, pouring out ethanol, adding pure water, boiling under reflux for 1 hr, repeating the above steps for 5 times, and removing diphenylsulfone solvent and inorganic salt. The sample was placed in a vacuum oven for vacuum and dried at 120 ℃ for 12h to obtain a pure Polyetheretherketone (PEEK) sample, as shown in detail in fig. 12.
Fig. 12 is a field emission Scanning Electron Microscope (SEM) image of the prepared polyetheretherketone.
Example 13 (scheme two)
Preparation of hydroquinone sodium salt solution: 200g of diphenyl sulfone and 69.36g (0.63mol) of hydroquinone were charged into a 500ml three-necked flask equipped with a mechanical stirrer, air inlet and air condenser. After introducing high-purity nitrogen, the mixture is heated to be dissolved, a stirring device is started, the temperature is raised to 170 ℃, and 66.77g (0.63mol) of nano-grade sodium carbonate is added for reaction for 30 minutes. This temperature is maintained for future use.
In another three-necked flask equipped with an overhead stirrer, thermometer and air condenser, 300g of diphenyl sulfone and 134.06g (0.63mol) of 4, 4' -difluorobenzophenone were charged, dissolved after passing high purity nitrogen and the temperature was raised to 170 ℃, hydroquinone sodium salt prepared as described above was immediately added, stirring was continued and the temperature was raised to 320 ℃ at a rate of 2 ℃/min, and the temperature was kept reacting until a torque determined by the power consumption on the stirrer motor was reached. The reaction mixture was poured into a container with cold purified water to give an off-white block. Pulverizing the blocks with a pounder into desired powder, boiling with ethanol under reflux for 2 hr, pouring out ethanol, adding pure water, boiling under reflux for 1 hr, repeating the above steps for 5 times, and removing diphenylsulfone solvent and inorganic salt. The sample was placed in a vacuum oven for vacuum and dried at 120 ℃ for 12h to obtain a pure Polyetheretherketone (PEEK) sample, as shown in detail in fig. 13.
Fig. 13 is a field emission Scanning Electron Microscope (SEM) image of the polyether ether ketone obtained.
Example 14 (scheme two)
Preparation of hydroquinone sodium salt solution: 320g of diphenyl sulphone and 80.92g (0.735mol) of hydroquinone are charged to a 500ml three-necked flask equipped with a mechanical stirrer, air inlet and air condenser. After introducing high-purity nitrogen, the mixture is heated to be dissolved, a stirring device is started, the temperature is raised to 170 ℃, and 77.90g (0.735mol) of nano-sodium carbonate is added to react for 30 minutes. This temperature is maintained for future use.
In another three-necked flask equipped with an overhead stirrer, thermometer and air condenser, 300g of diphenyl sulfone and 156.41g (0.735mol) of 4, 4' -difluorobenzophenone were charged, dissolved after passing high purity nitrogen and the temperature was raised to 170 ℃, hydroquinone sodium salt prepared as described above was immediately added, stirring was continued and the temperature was raised to 320 ℃ at a rate of 2 ℃/min, and the temperature was kept reacting until a torque determined by the power consumption on the stirrer motor was reached. The reaction mixture was poured into a container of cold purified water to give off-white blocks. Pulverizing the block with a pounder into desired powder, boiling with ethanol under reflux for 2 hr, pouring out ethanol, adding pure water, boiling under reflux for 1 hr, repeating the above steps for 5 times, and removing the diphenyl sulfone solvent and inorganic salt. The sample was placed in a vacuum oven for vacuum and heated to 120 ℃ for drying for 12h to obtain a pure Polyetheretherketone (PEEK) sample, see fig. 14 for details.
Fig. 14 is a field emission Scanning Electron Microscope (SEM) image of the polyether ether ketone obtained.
Table 2: results for polymers produced according to the preparation described in the above examples are provided
Figure BDA0003210126320000171
FIG. 15 is a graph comparing PDIs of polyetheretherketones prepared in examples 11-14 of the present invention and comparative examples 1 and 2.
As can be seen from table 2 and fig. 15, the inventors found that the molecular weight polydispersity index PDI of the Polyetheretherketone (PEEK) of the present invention is less than 2.4, with much lower dispersibility (PDI), i.e. much narrower molecular mass distribution, at the same ramp rate. It is known that the theoretical PDI of polycondensation polymers is at least 2.0, whereas the PDI of the Polyetheretherketone (PEEK) of the present invention is very close to the theoretical minimum. Wherein PDI is Mw/Mn, Mw is weight average molecular weight, and Mn is number average molecular weight. This is advantageous for applications where the molecular weight of the polymeric material is critical.
Meanwhile, compared with PEEK prepared by the traditional method, the PEEK prepared by the traditional method has more excellent tensile strength in a melt, the strength is at least 100MPa, and meanwhile, the melt viscosity of the polymer is less than 1.0kNsm-2And simultaneously is more than 0.06kNsm-2This results in polymers having excellent high strength and good processability. This is very beneficial to the manufacturing industry of some parts with higher strength requirement。
Example 15 (scheme three preparation of polyetheretherketone in one step using nano-sized carbonate)
A1000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle port, a side port is connected with a three-way pipe, a thermometer is placed and connected with high-purity nitrogen, and the other side port is connected with a spherical condenser pipe for exhausting. Placing the three-neck bottle in an electric heating jacket, adding 327.3g (1.5mol) of diphenyl sulfone and 109.1g (0.5mol) of 4, 4' -difluorobenzophenone, introducing high-purity nitrogen gas with the flow rate of 100ml/min, adding 55.05g of hydroquinone (0.5mol) and 48.18g of nano-Na after the diphenyl sulfone is molten2CO3(preparation by the process of the invention) and 6.28g of nanoscale K2CO3(preparation by the Process of the invention) (molar ratio Na)2CO3： K2CO310:1), stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 200 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuously heating to 305 ℃, keeping the temperature for 2 hours, and pouring the materials into cold distilled water to obtain the grey loose substance.
Crushing the white block loose object, putting 100g of sample into a fat extractor, adding 500ml of acetone for extraction for 2h, pouring out the acetone, adding 500ml of distilled water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃, and drying for 8h to obtain a pure polyether ether ketone (PEEK) sample, wherein the density and the melting point of the PEEK sample are measured by a densitometer.
Example 16 (scheme three preparation of polyetheretherketone in one step using nano-sized carbonate)
Using only nano-scale Na2CO3Preparing the polyether-ether-ketone.
A1000 ml three-mouth bottle is taken, a stirring paddle is inserted into a middle port, a side port is connected with a three-way pipe, a thermometer is placed and connected with high-purity nitrogen, and the other side port is connected with a spherical condenser pipe for exhausting. Putting a three-neck bottle in an electric heating sleeve, putting 327.3g (1.5mol) of diphenyl sulfone and 109.1g (0.5mol) of 4, 4' -difluorobenzophenone into the bottle, introducing high-purity nitrogen with the flow rate of 100ml/min, adding 55.05g of hydroquinone (0.5mol) and 53.00g of nano-Na after the diphenyl sulfone is molten2CO3(0.5mol) (prepared by the method of the invention), starting stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 200 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuing heating to 305 ℃, keeping the temperature for 2 hours, and then finishing the reaction, pouring the materials into cold distilled water to obtain the grey white loose block.
Crushing the white block loose object, putting 100g of sample into a fat extractor, adding 500ml of acetone for extraction for 2h, pouring out the acetone, adding 500ml of distilled water for extraction for 4h, putting the sample into a vacuum drying oven for vacuumizing, heating to 120 ℃, and drying for 8h to obtain a pure polyether ether ketone (PEEK) sample, wherein the density and the melting point of the PEEK sample are measured by a densitometer.
TABLE 3 results of the tests of the examples III
Figure BDA0003210126320000181
Figure BDA0003210126320000191
Examples 15-16 use of nano-sized carbonate to prepare PEEK in a single step, demonstrate the use of nano-sized carbonate in the preparation of PEEK to improve the properties of PEEK such as density, melt break percentage, and viscosity compared to comparative examples 1-2.

Claims (7)

1. A method of preparing a poly (aryl ether ketone), comprising the steps of: in a high-boiling point inert protic solvent, in the presence of nano alkali metal carbonate, carrying out polycondensation reaction on a double-halogenated organic compound and a bisphenol compound to obtain polyether-ether-ketone;
the nanometer alkali metal carbonate is prepared by the following method:
dissolving alkali carbonate in water to obtain alkali carbonate aqueous solution, then adding inorganic nanoparticles serving as a settling agent into the alkali carbonate aqueous solution, stirring at a high speed and uniformly mixing, adding a thickening agent into the mixed solution, adding a foaming agent after the mixed solution is uniformly distributed again, stirring until a large number of bubbles stably exist, generating a large number of bubble liquid films at the moment, crystallizing the alkali carbonate on the interface of the bubble liquid films, flatly laying the bubbles on a tray, and drying to obtain the nano-particles;
wherein the mass ratio of the inorganic nano particles to the alkali metal carbonate is 1 (2-5);
the mass ratio of the thickening agent to the alkali metal carbonate is 1: (50-2000);
the mass ratio of the foaming agent to the alkali carbonate is 1: (20-4000);
when the alkali carbonate is potassium carbonate, the drying temperature of the potassium carbonate is more than or equal to 55 ℃ and less than 891 ℃;
when the alkali carbonate is sodium carbonate, the drying temperature of the sodium carbonate is more than or equal to 55 ℃ and less than 851 ℃;
the drying time is 8-14h,
when inorganic nano particles which are difficult to dissolve in water are used as a settling agent in the preparation of nano alkali carbonate,
further purifying by adopting a molecular sieve chromatography mode, namely:
and adding the prepared product into the suspension, stirring, and filtering by using a molecular sieve with the filtering molecular weight of 100-120 to purify the nano alkali metal carbonate.
2. The method of claim 1, wherein: the molar ratio of the bisphenol compound to the double-halogenated organic compound is 1.0:1.0-1.0: 1.1;
the molar ratio of the bisphenol compound to the nano alkali carbonate is 1.0:1.0-1: 1.05.
3. The method of claim 1, wherein: the alkali metal carbonate is potassium carbonate, sodium carbonate or a mixture of the potassium carbonate and the sodium carbonate;
the inorganic nanoparticles used as settling agents are: nano TiO 22、SiO2、Al2O3、Fe2O3、Fe3O4、V2O5、MnO2One or more of CuO, CuO;
the thickening agent is: one or more of polyethylene glycol, hydroxymethyl cellulose, methyl cellulose, polymethacrylic acid, sodium polyacrylate, polyoxyethylene, polyvinylpyrrolidone and N, N-methylene-bisacrylamide;
the foaming agent is as follows: one or more of fatty alcohol-polyoxyethylene ether sodium sulfate, lauryl sodium sulfate and 4, 4' -oxo-bis-benzenesulfonyl hydrazide.
4. The method of claim 1, wherein: the high-boiling point inert proton solvent is aromatic sulfone;
the bisphenol compound is 1, 4' -hydroquinone;
the double halogenated organic compound is a double fluorinated organic compound.
5. The method of claim 4, wherein: the high-boiling point inert protic solvent is diphenyl sulfone or sulfolane;
the double-halogenated organic compound is 4, 4' -difluorobenzophenone.
6. The method of claim 1, wherein: putting a high-boiling point inert proton solvent and a double-halogenated organic compound into a three-neck flask in a nitrogen atmosphere, adding a bisphenol compound and nano alkali metal carbonate after the high-boiling point inert proton solvent is melted, starting stirring to 100rpm, heating to 150 ℃, keeping the temperature for 0.5 hour, heating to 200 ℃, keeping the temperature for 1 hour, heating to 280 ℃, keeping the temperature for 1 hour, continuing heating to 305 ℃, keeping the temperature for 2 hours, and pouring the material into cold distilled water to obtain the grey loose substance.
7. A poly (aryl ether ketone) prepared by the process of any one of claims 1 to 5, having a molecular weight polydispersity index (PDI) of less than 2.4, a tensile strength of at least 100MPa, and a melt viscosity of less than 1.0kNsm-2Greater than 0.05kNsm-2。
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