CN115353617A - Polyether-ether-ketone material and preparation method and application thereof - Google Patents
Polyether-ether-ketone material and preparation method and application thereof Download PDFInfo
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- CN115353617A CN115353617A CN202211088329.9A CN202211088329A CN115353617A CN 115353617 A CN115353617 A CN 115353617A CN 202211088329 A CN202211088329 A CN 202211088329A CN 115353617 A CN115353617 A CN 115353617A
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- 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
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24F—SMOKERS' REQUISITES; MATCH BOXES; SIMULATED SMOKING DEVICES
- A24F40/00—Electrically operated smoking devices; Component parts thereof; Manufacture thereof; Maintenance or testing thereof; Charging means specially adapted therefor
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention provides a polyether-ether-ketone material and a preparation method and application thereof, belonging to the technical field of high polymer materials. The material comprises repeating units shown as a formula I and a formula II, wherein the crystallinity of the polyether-ether-ketone material is 30-40%, and the melting point of the polyether-ether-ketone material is 345-355 ℃. The invention also provides a polyether-ether-ketone material and a preparation method thereof. The structure of the material is partially changed in a PEEK chain segment, so that the regularity and flexibility of the part are improved, and the crystallinity, the crystallization temperature and the melting point are improved; in addition, because a large amount of inorganic filler is not added in the processing process, the damage to an extruder during extrusion is extremely small, the abrasion and corrosion to a screw and a chamber caused by the inorganic filler are avoided, and the service life of equipment is prolonged. The polyetheretherketone material has higher crystallization temperature and melting point, so that the polyetheretherketone material can be applied to the field of electronic cigarettes.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyether-ether-ketone material as well as a preparation method and application thereof.
Background
Polyetheretherketone is a thermoplastic with high performance for applications where excellent physical and chemical properties are required, such as long term high temperature use.
Polyether-ether-ketone is widely applied to high-temperature application scenes such as engines and electronic cigarettes, but the heat resistance of polyether-ether-ketone cannot completely meet the use requirement in a fashionable manner, and inorganic filler is added to improve the heat resistance of polyether-ether-ketone so as to meet the use requirement of the electronic cigarettes. This creates additional requirements and difficulties for processing, for example, most inorganic fillers can cause severe wear and corrosion to the extruder bore and screws, which is detrimental to processing and production. Therefore, the method is a feasible method for improving the use temperature of the polyether-ether-ketone without adding inorganic filler.
Disclosure of Invention
The invention aims to provide a polyetheretherketone material, and a preparation method and application thereof.
The invention firstly provides a polyether-ether-ketone material which comprises repeating units shown as a formula I and a formula II,
the crystallinity of the polyether-ether-ketone material is 30-40%, and the melting point is 345-355 ℃.
Preferably, the polyetheretherketone material comprises 98 to 99 mol% of the repeating unit of formula I and 1 to 2 mol% of the repeating unit of formula II.
The invention also provides a preparation method of the polyether-ether-ketone material, which comprises the following steps:
the method comprises the following steps: in a closed reaction container, adding hydroquinone and organic halide into an aqueous solution containing alkali, and heating to 65-75 ℃ to obtain a product I;
step two: adding the product I, the organic dihalide and hydroquinone in the step I into an aromatic sulfone solvent containing alkali metal carbonate in a closed reaction vessel, heating the mixture to 180-300 ℃, and carrying out nucleophilic polycondensation reaction to obtain a product II;
step three: adding organic halide with a monofluoro end group into the product II obtained in the step II, and keeping the temperature of the mixed system at 300-305 ℃ for reacting for 10-30min to obtain a product III;
step four: and cooling the product III obtained in the step III, and purifying to obtain the polyether-ether-ketone material.
Preferably, the molar ratio of the organic halide to the hydroquinone in the first step is (1-1.005): 1.
preferably, the organic halide in the first step is p-difluorobenzene, 3-biphenyldifluoro-benzene or 4, 4-difluorobiphenyl.
Preferably, the molar ratio of the organic dihalide to hydroquinone in the second step is 1.005 to 1.03: the molar ratio of organic dihalide to product I is (50-100): 1.
Preferably, in the second step, the alkali metal carbonate is a mixture of sodium carbonate and potassium carbonate, wherein the molar ratio of potassium carbonate to sodium carbonate is (1-2): (98-99);
preferably, in the second step, the molar ratio of the total moles of the alkali metal carbonate to the hydroquinone is (1.002-1.15): 1.
preferably, the molar ratio of the organic dihalide to monofluoro terminated organic halide is 1: (0.008-0.025).
Preferably, the organic dihalide in the second step is 4,4' -difluorobenzophenone and the aromatic sulfone solvent is diphenyl sulfone.
Preferably, the monofluoro-terminated organic halide of step three is 4-fluorobenzophenone.
The invention also provides application of the polyether-ether-ketone material in the field of electronic cigarettes.
The invention has the advantages of
The invention aims to provide a polyetheretherketone material and a preparation method and application thereof, wherein the polyetheretherketone material comprises repeating units shown as a formula I and a formula II, and the structure of the material is partially changed in a PEEK chain segment, so that the regularity and flexibility of the part are improved, and the crystallinity, the crystallization temperature and the melting point are improved; in addition, the invention enables the pure PEEK raw material to reach higher use temperature under the condition of carrying out composite modification without adding filler, and because a large amount of inorganic filler is not added in the processing process, the damage to an extruder is extremely small during extrusion, the abrasion and corrosion to a screw and a chamber caused by the inorganic filler are avoided, and the service life of equipment is prolonged.
The polyetheretherketone material has higher crystallization temperature and melting point, so that the polyetheretherketone material can be applied to the field of electronic cigarettes.
Detailed Description
The invention firstly provides a polyether-ether-ketone material which comprises repeating units shown as a formula I and a formula II,
the crystallinity of the polyetheretherketone material is 30-40%, preferably 31-37%, and the melting point is 345-355 ℃, preferably 348-353 ℃.
According to the invention, the polyether-ether-ketone material comprises 98-99 mol% of the repeating unit shown in the formula I and 1-2 mol% of the repeating unit shown in the formula II.
According to the invention, when the number of ether bonds in the chain segment in the structure is more, the whole chain segment is closer to a straight chain and has higher regularity, so that the orientation of the whole molecular chain is easier to be consistent during crystallization, the whole chain has higher crystallinity during complete cooling, and the melting point of the material is improved.
The invention also provides a preparation method of the polyether-ether-ketone material, which comprises the following steps:
the method comprises the following steps: adding hydroquinone and organic halide into an aqueous solution containing alkali in a closed reaction vessel, heating to 65-75 ℃, wherein the reaction temperature is preferably 70 ℃, and the reaction time is preferably 30min, so as to obtain a product I; the molar ratio of the organic halide to hydroquinone is preferably (1-1.005): 1, more preferably 1: the organic halide is preferably p-difluorobenzene, 3-biphenyldifluoro-benzene or 4, 4-difluorobiphenyl, more preferably p-difluorobenzene, and the base in the aqueous solution containing the base is preferably sodium hydroxide, calcium hydroxide or potassium hydroxide, more preferably sodium hydroxide.
Step two: adding the product I, the organic dihalide and hydroquinone in the step I into an aromatic sulfone solvent containing alkali metal carbonate in a closed reaction vessel, heating the mixture to 180-300 ℃, and carrying out nucleophilic polycondensation reaction to obtain a product II; the molar ratio of said organic dihalide to hydroquinone is preferably (1.005-1.03): 1, more preferably 1.02; the molar ratio of organic dihalide to product I is preferably from 50 to 100; the alkali metal carbonate is a mixture of sodium carbonate and potassium carbonate, wherein the molar ratio of the potassium carbonate to the sodium carbonate is preferably (1-2): (98-99); the molar ratio of the total moles of alkali metal carbonate to hydroquinone is preferably (1.002-1.15): 1; the organic dihalide is preferably 4,4' -difluorobenzophenone and the aromatic sulfone solvent is preferably diphenyl sulfone.
Preferably, the temperature rise in the second step is to firstly use high-purity nitrogen to continuously purge and protect for 30min at the rate of 0.16L/min and exhaust the air in the bottle. Then the temperature is slowly raised to 140 ℃ within 1h, at which time the material begins to melt, and the stirring device is started to stir the material. Raising the temperature to 180 ℃ at a temperature raising rate of 2 ℃/min, and keeping the constant temperature for 60min; then increasing the temperature to 190 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 30min; then heating to 200 ℃ at the heating rate of 0.5 ℃, and keeping the temperature for 30min; subsequently, the temperature was increased to 280 ℃ at a rate of 1 ℃/min, and the temperature was maintained at this temperature for 60min. Finally, the temperature is raised to 300 ℃ at a heating rate of 1 ℃/min and is kept for 60min.
Step three: adding organic halide with a monofluoro end group into the product II obtained in the step II, and keeping the temperature of the mixed system at 300-305 ℃ for reacting for 10-30min to obtain a product III; the monofluoro-terminated organic halide is preferably 4-fluorobenzophenone, and the molar ratio of the organic dihalide to the monofluoro-terminated organic halide is preferably 1: (0.008-0.025).
Step four: cooling the product III obtained in the step III, and purifying to obtain a polyether-ether-ketone material;
according to the invention, the cooling in the fourth step is preferably carried out by placing the product III obtained in the third step on a stainless steel plate for cooling, after cooling, crushing and grinding the cooled product into coarse powder, extracting with a water-miscible organic solvent, preferably acetone, washing the water-miscible organic solvent with ultrapure water or deionized water, and heating the blend, preferably at 50-60 ℃, rinsing again with deionized water or pure water, and washing for five times to remove water-soluble residues such as alkali metal carbonate, wherein the process can be controlled by detecting the conductivity of the washing water, once the required range is reached, the product can be immediately filtered from the washing water, and then the filtered solid particles are dried, i.e. the PEEK which can be used.
The invention also provides application of the polyether-ether-ketone material in the field of electronic cigarettes.
The performance test of the polyether-ether-ketone material prepared by the invention comprises the following specific test processes:
1. crystallization test
Crystallization tests were tested using Differential Scanning Calorimetry (DSC).
DSC measurements were made according to GB/T19466.1-2004, ISO11357-1:2016 on a NETZSCH DSC200F3 instrument with nitrogen as the carrier gas (99.999% purity, 50 ml/min). Temperature and heat flux calibration was performed using indium. The weight of the sample is 8-12mg, accurate to +/-0.01 mg.
The heating cycle is as follows:
1 st heating cycle: keeping the temperature of 30.0-400.0 deg.C at 10.0 deg.C/min for 5min at 400.0 deg.C;
1 st cooling cycle: from 400.0 ℃ to 80.0 ℃ at 10.0 ℃/min;
heating cycle 2: from 80.0 ℃ to 400.0 ℃ at 10.0 ℃/min;
the enthalpy of fusion was determined for the 2 nd heating scan. The melting of PEEK is chosen as the area above a linear baseline extending from 220 ℃ to a temperature above the last endotherm (typically a temperature interval of 270 ℃ to 380 ℃ is chosen).
2. Method for measuring viscosity
Viscosity is the ratio of shear stress to shear rate in pa.s.
A method for determining the flowability of plastics using a capillary rheometer, also known as the apparent viscosity test, is carried out according to GB/T25278-2010, ISO 11443, ASTM D3835 using the Dynisco laboratory capillary rheometer LCR 7001. The method involves extruding a plastic melt through a capillary die of known dimensions and testing the test pressure at a specified volumetric flow rate.
The die of the apparatus used had the following dimensions: 1mm in diameter and 20mm in length, and the aspect ratio (L/D) of the die was 20.
Prior to the assay, the test samples should be conditioned as specified in GB/T2918-1998 at a temperature of 23. + -. 2 ℃ and a humidity of 50. + -. 10% for a period of 24. + -. 0.5 hours.
Before testing, the parts were allowed to equilibrate thermally at the test temperature, after which loading was commenced, samples were added to the barrel in small portions and immediately compacted with a plunger to prevent entrainment of air. The charge was brought to about 12.5mm from the top of the barrel, and the charge was completed in 2 minutes using typically 10-15 g of polymer as measured for the material.
Immediately after feeding, preheating timing is started, preheating is carried out for 5 minutes, the test conditions are 400 ℃, and the shearing rates are respectively 100s-1, 200s-1, 500s-1, 1000s-1, 2000s-1, 5000s-1 and 10000s-1.
3. Measurement of melt index
Melt mass flow rate was according to ASTM D1238-04, ISO1133: 2005. GB/T3682.1-2018 standard, the mass extruded in a specified time is taken as the melt mass flow rate, and the unit is g/10min. The measurements were carried out using a melt flow rate meter model SRZ-400E from changchun city intelligent instruments equipment ltd, using equipment with a die having the following dimensions: 2.095 + -0.005 mm diameter and 8.000 + -0.025 mm length.
The material is measured and used 3-8g polymer, before testing, the charging barrel and the piston are kept at the constant temperature for at least 15 minutes, during testing, charging is completed within 1 minute, after charging is completed, preheating is started immediately, the preheating time is 5 minutes, and during preheating, the temperature is confirmed to be recovered to the set temperature value. Testing under the test conditions of 380 ℃ and 5kg of load; .
When in test, the length of the cut material strip is 10-20mm. All the strands with visible bubbles were discarded, after cooling, the remaining strands (3 or more) were weighed one by one to 1mg accuracy, their average mass calculated and input into the machine for melt mass flow rate calculation.
4. Die adhesion detection
Heating the tablet press to test the demoulding effect, taking 2 20cm-20cm polyimide films, placing 0.1kg of material in the middle, and testing the demoulding performance under the conditions that the upper side and the lower side of the tablet press are heated to 400 ℃, the pressure is 200MP, and the tabletting time is 1 min.
And tearing off the polyimide films on the two sides, judging whether the sticking property is good or not by observing the residual quantity of the polyimide films, and when the residual quantity of the polyimide films is less than or equal to 10 percent, the sample is qualified.
The present invention is further illustrated by reference to the following specific examples, in which the starting materials are all commercially available.
Example 1
A250 ml open reactor was used and equipped with three port caps, stirrer paddles, nitrogen blanket input, open closed clamps, heated in a water bath at 70 ℃. 50ml of pure water, 2.48g (0.062 mol) of NaOH,6.81g (0.06185 mol) of hydroquinone and 7.05g (0.06185 mol) of p-difluorobenzene were added thereto, and the mixture was sufficiently stirred to bring the p-difluorobenzene into contact with the aqueous phase, followed by reaction for half an hour. Filtering the obtained 4-fluoro-4-hydroxydiphenyl ether, and drying in a vacuum drying oven at 70 ℃ for 2h.
A10L open reactor was used and equipped with four ports, stirrer, stirring paddle, nitrogen blanket input, thermocouple temperature probe, and open closed clamp. 4275g (19.587 mol) of diphenyl sulfone, 1349.85g (6.185 mol) of 4, 4-difluorobenzophenone, 12.6174g (0.06185 mol) of 4-fluoro, 4-hydroxydiphenyl ether prepared in the preceding step, 670.05g (6.087 mol) of hydroquinone, 735.22g (6.936 mol) of finely ground sodium carbonate and 19.46g (0.141 mol) of finely ground potassium carbonate are added thereto in this order. The bottle was purged of air using high purity nitrogen at a rate of 0.16L/min for 30min. Then the temperature is slowly raised to 140 ℃ within 1h, at which time the material begins to melt, and the stirring device is started to stir the material. Raising the temperature to 180 ℃ at a temperature raising rate of 2 ℃/min, and keeping the constant temperature for 60min; then increasing the temperature to 190 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 30min; then heating to 200 ℃ at the heating rate of 0.5 ℃, and keeping the temperature for 30min; subsequently, the temperature was increased to 280 ℃ at a rate of 1 ℃/min, and the temperature was maintained at this temperature for 60min. Finally, the temperature is raised to 300 ℃ at a heating rate of 1 ℃/min and is kept for 60min. 18.65g (0.093 mol) of 4-fluorobenzophenone were added and the temperature was maintained at 300-305 ℃ for 30min.
The resulting mixture was then poured flat onto a stainless steel plate, and the mixture was allowed to cool to room temperature while it solidified. And crushing the obtained reactant by using a crusher, sieving, and selecting powder with the mixture particles of 15-60 meshes. A Soxhlet extractor is used, acetone is taken as a solvent, a reaction solvent diphenyl sulfone and other residual organic impurities in the powder particles are extracted, and the extraction is repeated for 1 hour. And then, stirring and washing the filtered particles by using purified water, pouring out deionized water after the temperature is raised to 60 ℃ during heating, rinsing by using ultrapure water, heating and stirring again, and repeating for more than 4 times until the conductivity is 2-10 muA. And (4) putting the product after water washing into a vacuum drying oven, setting the temperature in the cavity to be 150 ℃, and drying for 8 hours at constant temperature.
Comparative example 1
This example is similar to example 1, and differs in the kind of raw material.
A10L open reactor was used and equipped with four ports, stirrer, stirring paddle, nitrogen blanket input, thermocouple temperature probe, and open closed clamp. 4275g (19.587 mol) of diphenyl sulfone, 1349.85g (6.185 mol) of 4, 4-difluorobenzophenone, 670.05g (6.087 mol) of hydroquinone, 735.22g (6.936 mol) of finely ground sodium carbonate and 19.48g (0.141 mol) of finely ground potassium carbonate are added thereto in this order. The bottle was purged of air using high purity nitrogen at a rate of 0.16L/min for 30min. Then the temperature is slowly raised to 140 ℃ within 1h, at which time the material begins to melt, and the stirring device is started to stir the material. Heating to 180 deg.C at a heating rate of 2 deg.C/min, and maintaining at constant temperature for 60min; then increasing the temperature to 190 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 30min; then heating to 200 ℃ at the heating rate of 0.5 ℃, and keeping the temperature for 30min; subsequently, the temperature was increased to 280 ℃ at a rate of 1 ℃/min, and the temperature was maintained at this temperature for 60min. Finally, the temperature is raised to 300 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 60min, 18.65g (0.093 mol) of 4-fluorobenzophenone is added, and the temperature is kept at 300-305 ℃ for 30min.
The resulting mixture was then poured flat onto a stainless steel plate, and the mixture was allowed to cool to room temperature while waiting for the mixture to solidify. And crushing the obtained reactant by using a crusher, sieving, and selecting powder with the mixture particles of 15-60 meshes. Using a Soxhlet extractor, extracting reaction solvent diphenyl sulfone and other residual organic impurities in the powder particles by taking acetone as a solvent, and repeatedly extracting for 1 hour. And then, stirring and washing the filtered particles by using purified water, pouring out deionized water after the temperature is raised to 60 ℃ during heating, rinsing by using ultrapure water, heating and stirring again, and repeating for more than 4 times until the conductivity is 2-10 muA. Putting the washed product into a vacuum drying oven, setting the temperature in the cavity to be 150 ℃, and drying for 8 hours at constant temperature
Example 2
The procedure and conditions were the same as in example 1 except that the amount of 4-fluoro, 4-hydroxydiphenyl ether added was changed to add 25.234g (0.1237 mol) of 4-fluoro, 4-hydroxydiphenyl ether thereto.
Example 3
The dried products of examples 1-2 and comparative example 1 were subjected to extrusion granulation,
a co-rotating parallel double-screw extruder is used, the diameter of a screw is 32mm, the length-diameter ratio is 32. The melt filtering device is arranged in front of the machine head, and the extruder is provided with a negative pressure device for discharging gases such as water vapor and the like in the material chamber. The extruded material strip is placed on a metal conveying belt with an air cooling device arranged above, so that the temperature of the material strip is proper when the material strip enters a granulator, the particle size of the cut material particles is uniform, and the end opening is smooth.
And (4) performing sample injection molding on the product obtained by granulation.
And (4) observing the injection molding sample plate during demolding, and carrying out DSC, viscosity, melt index and other related tests.
Table 1 DSC results
| Examples | Melting Point (. Degree.C.) | Degree of crystallinity | Crystallization temperature (. Degree. C.) |
| Example 1 | 347.9 | 31.2％ | 309.1 |
| Comparative example 1 | 343.7 | 25.8％ | 301.2 |
| Example 2 | 353.2 | 37.6％ | 310.8 |
DSC tests show that the melting point, the crystallinity and the crystallization temperature of the example added with the 4-fluoro, 4-hydroxydiphenyl ether are obviously improved, and the melting point, the crystallinity and the crystallization temperature are further improved along with the increase of the addition amount of the 4-fluoro, 4-hydroxydiphenyl ether.
TABLE 2 flowability test results
| Examples | Melt index (g/10 min) | Viscosity (pa s) |
| Example 1 | 13.24 | 371.2 |
| Comparative example 1 | 10.21 | 417.9 |
| Example 2 | 15.73 | 343.1 |
As can be seen from the fluidity, the example to which 4-fluoro, 4-hydroxydiphenyl ether was added had better fluidity than the example to which 4-fluoro, 4-hydroxydiphenyl ether was not added, and the example to which 4-fluoro, 4-hydroxydiphenyl ether was added had a lower viscosity than the conventional product in the corresponding relation of melt index and viscosity.
When the sticking detection is carried out, the residual quantity of the PEEK in the polyimide film is found to be less than or equal to 10 percent, which shows that the electronic cigarette product prepared from the PEEK is easier to demould, the yield of the electronic cigarette product is improved, and the manual demoulding time is saved.
From the above data, we can see that the PEEK manufactured by the invention has higher melting point, crystallinity and crystallization temperature, so that the PEEK has higher use temperature, and can meet the use requirement of products such as electronic cigarettes without adding other inorganic fillers, thereby reducing the damage (abrasion and corrosion of a screw and a bore) to machines such as extrusion and the like in the processing process. And due to the increase of the flexible part in the molecular chain, the mobility of the PEEK is improved, so that the PEEK is more beneficial to processing.
Claims (10)
1. A polyetheretherketone material is characterized by comprising a repeating unit shown as a formula I and a formula II,
the crystallinity of the polyether-ether-ketone material is 30-40%, and the melting point is 345-355 ℃.
2. The polyetheretherketone material of claim 1, wherein the polyetheretherketone material comprises from 98 to 99 mole% of the recurring unit of formula i and from 1 to 2 mole% of the recurring unit of formula ii.
3. The method of preparing a polyetheretherketone material according to claim 1, comprising:
the method comprises the following steps: in a closed reaction container, adding hydroquinone and organic halide into an aqueous solution containing alkali, and heating to 65-75 ℃ to obtain a product I;
step two: adding the product I, the organic dihalide and hydroquinone in the step I into an aromatic sulfone solvent containing alkali carbonate in a closed reaction vessel, heating the mixture to 180-300 ℃, and carrying out nucleophilic polycondensation reaction to obtain a product II;
step three: adding organic halide with a monofluoro end group into the product II obtained in the step II, and keeping the temperature of the mixed system at 300-305 ℃ for reaction for 10-30min to obtain a product III;
step four: and cooling the product III obtained in the step III, and purifying to obtain the polyether-ether-ketone material.
4. The method for preparing polyetheretherketone material according to claim 3, wherein the molar ratio of organic halide to hydroquinone in the first step is (1-1.005): 1.
5. the method of claim 3, wherein the organic halide in step one is p-difluorobenzene, 3-biphenyldifluoro-benzene or 4, 4-difluorobiphenyl.
6. The method for preparing polyetheretherketone material of claim 3, wherein the molar ratio of organic dihalide to hydroquinone in step two is (1.005-1.03): 1, the molar ratio of organic dihalide to product I is (50-100): 1.
7. The method according to claim 3, wherein the alkali metal carbonate in step two is a mixture of sodium carbonate and potassium carbonate, wherein the molar ratio of potassium carbonate to sodium carbonate is (1-2): (98-99).
8. The method for preparing polyetheretherketone material of claim 3, wherein the molar ratio of the total moles of alkali metal carbonate to hydroquinone in step two is (1.002-1.15): 1;
the molar ratio of the organic dihalide to the organic halide with a monofluorine end group is 1: (0.008-0.025).
9. The method for preparing polyetheretherketone material of claim 3, wherein the organic dihalide in step two is 4,4' -difluorobenzophenone, the aromatic sulfone solvent is diphenyl sulfone;
and the organic halide with monofluoro end group in the third step is 4-fluorobenzophenone.
10. Use of a polyetheretherketone material according to claim 1 in the field of electronic cigarettes.
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| US5001200A (en) * | 1987-04-16 | 1991-03-19 | Amoco Corporation | Poly(phenylene oxide)-poly(aryl ether ketone) blends |
| CN1910222A (en) * | 2004-01-13 | 2007-02-07 | 约翰逊马西有限公司 | Ion-conducting polymers and membranes comprising them |
| CN110903597A (en) * | 2020-02-14 | 2020-03-24 | 九江天赐高新材料有限公司 | Polyether-ether-ketone composite material and preparation method and application thereof |
| CN111943831A (en) * | 2020-08-18 | 2020-11-17 | 山东非金属材料研究所 | Preparation method of polyether-ether-ketone oligomer with high flame retardance |
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2022
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001200A (en) * | 1987-04-16 | 1991-03-19 | Amoco Corporation | Poly(phenylene oxide)-poly(aryl ether ketone) blends |
| CN1910222A (en) * | 2004-01-13 | 2007-02-07 | 约翰逊马西有限公司 | Ion-conducting polymers and membranes comprising them |
| CN110903597A (en) * | 2020-02-14 | 2020-03-24 | 九江天赐高新材料有限公司 | Polyether-ether-ketone composite material and preparation method and application thereof |
| CN111943831A (en) * | 2020-08-18 | 2020-11-17 | 山东非金属材料研究所 | Preparation method of polyether-ether-ketone oligomer with high flame retardance |
Non-Patent Citations (1)
| Title |
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| YEN-ZEN WANG, ET AL.: "Synthesis and properties of thio-containing poly(ether ether ketone)s", 《POLYMER INTERNATIONAL》, vol. 53, no. 3, pages 320 - 325 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116120540A (en) * | 2023-03-28 | 2023-05-16 | 吉林省科众高分子材料股份有限公司 | Method for preparing polyether-ether-ketone at low temperature |
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