CN113480752B - Polyether-ether-ketone reinforced master batch and preparation method thereof, and polyether-ether-ketone composite material and preparation method thereof - Google Patents
Polyether-ether-ketone reinforced master batch and preparation method thereof, and polyether-ether-ketone composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyether-ether-ketone reinforced master batch and a preparation method thereof, and a polyether-ether-ketone composite material and a preparation method thereof. Mixing a carbon nano tube, an organic solvent, a dispersing agent and a water-carrying agent to obtain a carbon nano tube dispersion liquid; and mixing the carbon nano tube dispersion liquid, 4' -difluorobenzophenone, a bisphenol compound and a catalyst, and carrying out polymerization reaction to obtain the polyether-ether-ketone reinforced master batch. The polyether-ether-ketone reinforced master batch provided by the invention has good compatibility with a polyether-ether-ketone pure material, so that the carbon nanotubes in the polyether-ether-ketone reinforced master batch can be more uniformly dispersed in a polyether-ether-ketone material, and the toughness of the polyether-ether-ketone composite material can be further effectively improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polyether-ether-ketone reinforced master batch and a preparation method thereof, and a polyether-ether-ketone composite material and a preparation method thereof.
Background
Polyether-ether-ketone (PEEK) is a linear aromatic semi-crystalline thermoplastic high-performance special engineering plastic and has the advantages of high strength, high temperature resistance, solvent resistance, aging resistance and light weight. PEEK has been widely used in the fields of aerospace, biomedicine, military industry, nuclear industry, electronic information, automobile industry, and daily necessities because of its excellent properties. With the increasing use of PEEK, the requirements for various properties of PEEK materials, such as high strength, toughness, and high temperature resistance, are increasing.
At present, the common method for improving the strength of the polyetheretherketone material is to directly melt and blend the polyetheretherketone and the carbon nano tube; however, the polarity difference between the polyetheretherketone and the carbon nanotubes causes more defects on the interface of the composite material, the carbon nanotubes are difficult to disperse uniformly, the local agglomeration phenomenon is obvious, the strength and the toughness are low, and the processing application of the composite material is greatly limited.
In view of the above situation, a polyetheretherketone material, carbon nanotubes and a coupling agent (such as a silane coupling agent and a titanate coupling agent) are blended to obtain a modified reinforced master batch or a compound with specific functional groups is synthesized for better dispersion of the carbon nanotubes. However, although the coupling agent improves the interfacial compatibility between the carbon nanotubes and the polyetheretherketone material, the high temperature resistance of the coupling agent is not good, and the final use performance of the product may be affected.
Disclosure of Invention
In view of the above, the invention provides a polyether-ether-ketone reinforced master batch and a preparation method thereof, and a polyether-ether-ketone composite material and a preparation method thereof. The polyether-ether-ketone reinforced master batch provided by the invention has good interface compatibility with a polyether-ether-ketone pure material, so that carbon nanotubes in the polyether-ether-ketone reinforced master batch can be uniformly distributed in the polyether-ether-ketone pure material, and the toughness of the polyether-ether-ketone composite material is further effectively improved.
In order to realize the purpose, the invention provides a preparation method of a polyether-ether-ketone reinforced master batch. And then mixing the 4,4' -difluorobenzophenone, the bisphenol compound and the catalyst with the uniformly dispersed carbon nanotube solution, and carrying out in-situ polymerization reaction to obtain the polyether-ether-ketone reinforced master batch. Different from the general post-modification method, the invention firstly prevents the re-aggregation of the carbon nano tube by adsorbing the dispersant monomer on the surface of the carbon nano tube, and simultaneously, the polymer chain segment generated by polymerizing the 4,4' -difluorobenzophenone, the bisphenol compound and the dispersant in the polymerization stage can be attached to the surface of the carbon nano tube to grow, thereby enhancing the combination of the carbon nano tube and the master batch.
The technical scheme of the polyether-ether-ketone reinforced master batch provided by the invention comprises the following steps:
mixing the carbon nano tube, an organic solvent, a dispersing agent and a water-carrying agent to obtain a carbon nano tube dispersion liquid;
dispersing the carbon nano tube into a liquid;
the dispersing agent comprises one or more of bisphenol fluorene, anthralin, phenolphthalein, 1, 6-dihydroxypyrene and 1, 5-dihydroxynaphthalene;
the bisphenol compound comprises bisphenol A and/or bisphenol AF.
Preferably, the mass ratio of the carbon nano tube to the dispersing agent is (0.1-3): 1.
preferably, the molar ratio of the bisphenol compound to the dispersant is (9-5): (1-5); the amount of the 4,4' -difluorobenzophenone is the sum of the amounts of the bisphenol compound and the dispersant.
Preferably, the catalyst comprises an alkali metal catalyst comprising one or more of sodium carbonate, potassium carbonate and cesium carbonate.
Preferably, the polymerization reaction comprises carrying out azeotropic water-carrying and continuing the polymerization in sequence; the temperature of the azeotropic entrained water is 120-150 ℃; the temperature for continuous polymerization is 160-180 ℃.
The invention also provides the polyether-ether-ketone reinforced master batch obtained by the preparation method in the technical scheme.
The invention also provides a polyether-ether-ketone composite material which comprises the following components in parts by weight:
70-90 parts of polyether-ether-ketone powder;
10-30 parts of polyether-ether-ketone reinforced master batch;
the reinforced mother material of polyether-ether-ketone as claimed in claim 6.
The invention also provides a preparation method of the polyether-ether-ketone composite material, which comprises the following steps:
mixing polyether-ether-ketone powder and polyether-ether-ketone reinforced master batch, and then sequentially carrying out melt extrusion, granulation and drying to obtain polyether-ether-ketone composite particles;
and sequentially carrying out injection molding and heat treatment on the polyether-ether-ketone composite particles to obtain the polyether-ether-ketone composite material.
Preferably, the injection molding temperature is 360-400 ℃, and the pressure is 0.4-0.8 MPa.
Preferably, the temperature of the heat treatment is 200-220 ℃, and the time is 2.0-4.0 h.
The invention provides a preparation method of a polyether-ether-ketone reinforced master batch, which comprises the following steps: mixing the carbon nano tube, an organic solvent, a dispersing agent and a water-carrying agent to obtain a carbon nano tube dispersion liquid; mixing the carbon nano tube dispersion liquid, 4' -difluorobenzophenone, bisphenol compounds and a catalyst, and carrying out polymerization reaction to obtain the polyether-ether-ketone reinforced master batch; the dispersing agent comprises one or more of bisphenol fluorene, anthralin, phenolphthalein, 1, 6-dihydroxypyrene and 1, 5-dihydroxynaphthalene; the bisphenol compound comprises bisphenol A and/or bisphenol AF. According to the invention, the carbon nano tube, the dispersing agent and the organic solvent are mixed firstly, so that the dispersing agent can be fully adsorbed on the surface of the carbon nano tube, the reaggregation of the carbon nano tube is prevented, and the uniform dispersion of the carbon nano tube is realized. Then, the dispersion liquid in which the carbon nanotubes are dispersed is mixed with 4,4' -difluorobenzophenone, a bisphenol compound and a catalyst to perform an in-situ polymerization reaction. In the invention, in the in-situ polymerization stage, because the surface of the carbon nano tube is uniformly adsorbed with the dispersing agent, the 4,4' -difluorobenzophenone and the polymerization product chain segment of the bisphenol compound can be attached to the surface of the carbon nano tube to grow, so that the combination of the carbon nano tube and the master batch is enhanced, and the good dispersion of the carbon nano tube in the master batch and the enhancement of the interface bonding force are realized. Meanwhile, the dispersing agent contains a conjugated structure, so that better dispersion can be realized through pi-pi non-covalent interaction with the carbon nano tube, the interface binding force between the carbon nano tube and a polymerization reaction chain section is further increased, and the toughness of the polyether-ether-ketone composite material is further improved.
The invention also provides a polyether-ether-ketone composite material which comprises the following components in parts by weight: 70-90 parts of polyether-ether-ketone powder and 10-30 parts of polyether-ether-ketone reinforced master batch; the polyether-ether-ketone reinforced master batch is obtained by the preparation method in the technical scheme. The polyether-ether-ketone composite material contains the polyether-ether-ketone reinforced master batch, the polyether-ether-ketone reinforced master batch and the polyether-ether-ketone pure material have good compatibility, and the polyether-ether-ketone reinforced master batch increases the amorphous area of the polyether-ether-ketone composite material, effectively improves the interface compatibility of polyether-ether-ketone powder and the carbon nano tube, and further improves the toughness of the composite material. Meanwhile, the polyether-ether-ketone composite material prepared by the invention has good high-temperature resistance. The examples show that: the polyether-ether-ketone composite material prepared by the invention is hardly decomposed at 400 ℃, has the temperature of 577 ℃ when being decomposed by 5 percent and has good high-temperature resistance.
The embodiment result shows that the tensile strength of the polyether-ether-ketone composite material prepared by the invention is 99-100 MPa, the bending strength can reach 131MPa, the bending modulus is 3800-3891 MPa, and the elongation at break is 122-133%. In addition, the polyether-ether-ketone composite material prepared by the invention has excellent high-temperature resistance, and is beneficial to the application of the polyether-ether-ketone composite material in the high-temperature field.
Drawings
FIGS. 1-2 are scanning electron micrographs of the PEEK composite material obtained in example 2 at different magnifications;
FIG. 3 is a DSC spectrum of the PEEK composite material prepared in example 2;
FIG. 4 is a graph of the mechanical properties of the PEEK composite prepared in example 2;
figure 5 is a TGA profile of the thermal analysis made in example 2.
Detailed Description
The invention provides a preparation method of a polyether-ether-ketone reinforced master batch, which comprises the following steps:
mixing the carbon nano tube, an organic solvent, a dispersing agent and a water-carrying agent to obtain a carbon nano tube dispersion liquid;
and mixing the carbon nano tube dispersion liquid, 4' -difluorobenzophenone, a bisphenol compound and a catalyst, and carrying out polymerization reaction to obtain the polyether-ether-ketone reinforced master batch.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention mixes the carbon nano tube, the organic solvent, the dispersant and the water-carrying agent to obtain the carbon nano tube dispersion liquid.
In the present invention, the length of the carbon nanotube is preferably 0.5 to 2 μm or 5 to 30 μm, and more preferably 0.5 to 2 μm.
In the present invention, the organic solvent preferably includes one or more of sulfolane, N-methylpyrrolidone and dimethylacetamide, and more preferably N-methylpyrrolidone. In the present invention, the use ratio of the carbon nanotubes to the organic solvent is preferably (1 to 50) g: (200-600) mL, more preferably (4-30) g: (400-500) mL.
In the invention, the dispersant comprises one or more of bisphenol fluorene, anthralin, phenolphthalein, 1, 6-dihydroxypyrene and 1, 5-dihydroxynaphthalene, and preferably bisphenol fluorene. In the invention, the mass ratio of the carbon nano tube to the dispersing agent is preferably (0.1-3): 1, more preferably (0.2 to 2): 1. in the present invention, the mass ratio of the dispersing agent to the carbon nanotubes is set to the above range, which contributes to achieving good dispersion of the carbon nanotubes without causing an agglomeration phenomenon.
In the present invention, the water-carrying agent preferably includes toluene and/or xylene, and more preferably toluene. The dosage ratio of the carbon nano tube to the water-carrying agent is preferably 1 g: (2-100) mL.
In the present invention, the step of mixing the carbon nanotube, the organic solvent, the dispersant and the water-carrying agent is preferably: carrying out first mixing on a carbon nano tube and an organic solvent to obtain a pre-dispersion liquid; and carrying out second mixing on the pre-dispersion liquid, the dispersing agent and the water-carrying agent to obtain the carbon nano tube dispersion liquid. In the invention, the first mixing mode is preferably ultrasonic, the frequency of the ultrasonic is preferably 45kHz, and the time of the first mixing is preferably 0.5-2 h, and more preferably 1 h.
In the present invention, the manner and setting parameters of the second mixing are preferably the same as those of the first mixing, and are not described herein again.
In the invention, the ultrasound can enable the carbon nano tubes to be uniformly distributed in the organic solvent, and the dispersing agent can also uniformly act on the carbon nano tubes, thereby providing a foundation for subsequent in-situ polymerization.
After the carbon nanotube dispersion liquid is obtained, the carbon nanotube dispersion liquid, 4' -difluorobenzophenone, bisphenol compounds and a catalyst are mixed for polymerization reaction to obtain the polyether-ether-ketone reinforced master batch.
In the present invention, the bisphenol compound includes bisphenol a and/or bisphenol AF, preferably bisphenol a. In the invention, the molar ratio of the bisphenol compound to the dispersant is preferably (9-5): (1-5), and more preferably 7: 3. In the present invention, setting the dispersant and the bisphenol compound to the above ranges contributes to an increase in fracture toughness.
In the invention, the molar weight of the 4,4' -difluorobenzophenone is the sum of the molar weight of the bisphenol compound and the molar weight of the dispersant.
In the invention, the catalyst preferably comprises an alkali metal catalyst, the alkali metal catalyst preferably comprises one or more of potassium carbonate, sodium carbonate and cesium carbonate, and further preferably potassium carbonate. In the invention, the mass ratio of the catalyst to the 4,4' -difluorobenzophenone is preferably (1.0-1.2): 1.
in the present invention, it is preferable that the method further comprises degassing the mixed feed solution before the polymerization reaction. In the present invention, the degassing method is preferably mechanical stirring, the rotation speed of the mechanical stirring is preferably 120r/min, and the time of the mechanical stirring is preferably 1 h. In the present invention, the mechanical stirring is preferably performed under a protective atmosphere, which is preferably argon. In the present invention, the degassing can prevent the bisphenol compound and the dispersant from being oxidized to generate byproducts during the polymerization reaction.
In the present invention, the polymerization reaction preferably comprises carrying out azeotropic water-carrying and continuing the polymerization in this order. In the invention, the temperature of the azeotropic entrained water is preferably 120-150 ℃, and more preferably 140 ℃; the time for carrying water in the azeotropic manner is preferably 1.8 to 3 hours, and more preferably 2 hours. In the invention, the temperature for continuous polymerization is preferably 160-180 ℃, and more preferably 170 ℃; the time for continuing the polymerization is preferably 1.8 to 2.2 hours, and more preferably 2 hours. In the present invention, the polymerization reaction is preferably carried out under a protective atmosphere. In the present invention, the polymerization is preferably carried out in a three-necked flask, and a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device is specifically used in the examples of the present invention.
After the polymerization reaction, the invention preferably further comprises the steps of separating out the obtained polymerization reaction feed liquid in deionized water, and sequentially crushing, washing and drying the separated out material to obtain the polyether-ether-ketone reinforced master batch. In the present invention, the mode of precipitation is preferably stirring, and the stirring is not particularly limited in the present invention, and the precipitates may be completely precipitated as black filaments. The pulverization operation is not particularly limited in the present invention, and the operation method known in the art may be adopted. In the invention, the washing reagent is preferably deionized water, absolute ethyl alcohol or acetone; the number of washing is preferably 5 to 10. The organic solvent used in the reaction, the micromolecular salt and the catalyst generated in the reaction process are removed by washing. In the invention, the drying temperature is preferably 110-130 ℃, and more preferably 120 ℃; the drying time is preferably 12-24 hours, and more preferably 12 hours. The drying equipment is not particularly limited, and the drying equipment in the embodiment of the invention is particularly a vacuum oven; the drying method removes the residual washing reagent in the material washing process through drying.
In the present invention, the reactants involved in the polymerization reaction include a dispersant, a bisphenol compound and 4,4' -difluorobenzophenone.
The invention also provides the polyether-ether-ketone reinforced master batch obtained by the preparation method in the technical scheme.
The invention also provides a polyether-ether-ketone composite material which comprises the following components in parts by weight: 70-90 parts of polyether-ether-ketone powder; 10-30 parts of polyether-ether-ketone reinforced master batch.
The polyether-ether-ketone composite material provided by the invention comprises 70-90 parts by weight of polyether-ether-ketone powder, preferably 75-90 parts by weight, and further preferably 80-90 parts by weight; in the invention, the melt index of the polyether-ether-ketone powder is preferably 2-90 g/10min, and more preferably 20-90 g/10 min.
The polyether-ether-ketone composite material comprises 10-30 parts by weight of polyether-ether-ketone reinforced master batch, preferably 10-20 parts by weight of polyether-ether-ketone powder. In the invention, the polyether-ether-ketone reinforced master batch is prepared by the technical scheme.
The invention also provides a preparation method of the polyether-ether-ketone composite material, which comprises the following steps:
mixing polyether-ether-ketone powder and polyether-ether-ketone reinforced master batch, and then sequentially carrying out melt extrusion and granulation to obtain polyether-ether-ketone composite particles;
and sequentially carrying out injection molding and heat treatment on the polyether-ether-ketone composite particles to obtain the polyether-ether-ketone composite material.
According to the invention, the polyether-ether-ketone powder and the polyether-ether-ketone reinforced master batch are mixed, and then are subjected to melt extrusion and granulation in sequence to obtain the polyether-ether-ketone composite particles.
In the present invention, the mixing is preferably carried out in a high-speed stirrer.
In the present invention, the melt extrusion preferably includes sequentially performing the first melting, the second melting, the third melting, and the extrusion; the first melting temperature is preferably 320-340 ℃, and more preferably 320 ℃; the second melting temperature is preferably 360-380 ℃, and more preferably 370 ℃; the temperature of the third melting is preferably 380 to 400 ℃, and more preferably 360 ℃. In the present invention, the rotation speed of the extrusion is preferably 30 r/min.
In the present invention, the melt extrusion is preferably performed in a twin-screw extruder, and in the embodiment of the present invention, the first melting temperature is specifically a zone temperature in the twin-screw extruder, the second melting temperature is specifically a zone temperature in the twin-screw extruder, and the third melting temperature is specifically a zone temperature in the twin-screw extruder.
After the polyether-ether-ketone composite particles are obtained, the polyether-ether-ketone composite particles are subjected to injection molding and heat treatment in sequence to obtain the polyether-ether-ketone composite material.
In the invention, the injection molding temperature is preferably 360-400 ℃, and more preferably 380 ℃. In the present invention, the pressure for the injection molding is 0.4 to 0.8MPa, and more preferably 0.6 MPa.
In the invention, the temperature of the heat treatment is 200-220 ℃, and more preferably 200 ℃; the time of the heat treatment is preferably 2.0-4.0 h, and more preferably 2.0 h. In the present invention, the heat treatment apparatus is not particularly limited, and in the embodiment of the present invention, the heat treatment is specifically performed in a vacuum oven.
The reinforced polyether-ether-ketone masterbatch and the preparation method thereof, the polyether-ether-ketone composite material and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 4.35g of carbon nano tube into 480mL of N-methyl pyrrolidone for ultrasonic treatment for 1h, then adding 18.92g of bisphenol fluorene and 100mL of toluene into the mixed solution for ultrasonic treatment for 1h to obtain carbon nano tube dispersion liquid;
28.76g of bisphenol A, 39.27g of 4,4' -difluorobenzophenone, 29.85g of potassium carbonate and the carbon nanotube dispersion were added to a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device, mechanically stirred and degassed for 1 hour, then heated to 140 ℃ for azeotropic water carrying for 2 hours, and further heated to 170 ℃ for further polymerization for 2 hours.
Continuously stirring the continuous polymerization feed liquid in deionized water to precipitate the continuous polymerization feed liquid into filaments, and sequentially crushing, washing and drying the precipitates; and the washing is carried out for 10 times in deionized water, and the drying is carried out for 12 hours in a vacuum oven at the temperature of 120 ℃ to obtain the polyether-ether-ketone reinforced master batch.
Adding 10g of polyether-ether-ketone reinforced master batch and 90g of polyether-ether-ketone pure material with the melt index of 29g/10min into a high-speed stirrer for blending, and then carrying out melt extrusion in a double-screw extruder, wherein the temperature of a first zone is 320 ℃, the temperature of a second zone is 370 ℃, the temperature of a third zone is 360 ℃, and the extrusion speed is 30 r/min. And granulating the extruded product, performing injection molding under the conditions that the injection molding temperature is 380 ℃ and the injection molding pressure is 0.6MPa, and performing heat treatment on the injection molded product in a vacuum oven at 200 ℃ for 2 hours to obtain the polyether-ether-ketone composite material.
Example 2
Adding 8.86g of carbon nano tube into 480mL of N-methyl pyrrolidone for ultrasonic treatment for 1h, then adding 18.92g of bisphenol fluorene and 100mL of toluene into the mixed solution, and further performing ultrasonic dispersion for 1h to obtain a carbon nano tube dispersion solution;
28.76g of bisphenol A, 39.27g of 4,4' -difluorobenzophenone, 29.85g of potassium carbonate and the carbon nanotube dispersion were added to a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device, mechanically stirred and degassed for 1 hour, then heated to 140 ℃ for azeotropic water carrying for 2 hours, and further heated to 170 ℃ for further polymerization for 2 hours.
Continuously stirring the continuous polymerization feed liquid in deionized water to precipitate a filamentous precipitate, and sequentially crushing, washing and drying the precipitate. And the washing is carried out for 10 times in deionized water, and the drying is carried out for 12 hours in a vacuum oven at the temperature of 120 ℃ to obtain the polyether-ether-ketone reinforced master batch.
Adding 10g of polyether-ether-ketone reinforced master batch and 90g of polyether-ether-ketone pure material with the melt index of 29g/10min into a high-speed stirrer for blending, and then carrying out melt extrusion in a double-screw extruder, wherein the temperature of a first zone is 320 ℃, the temperature of a second zone is 370 ℃, the temperature of a third zone is 360 ℃, and the extrusion speed is 30 r/min. And granulating the extruded product, performing injection molding under the conditions that the injection molding temperature is 380 ℃ and the injection molding pressure is 0.6MPa, and performing heat treatment on the injection molded product in a vacuum oven at 200 ℃ for 2 hours to obtain the polyether-ether-ketone composite material.
Example 3
Adding 17.38g of carbon nano tube into 480mL of N-methylpyrrolidone, carrying out ultrasonic dispersion for 1h, then adding 18.92g of bisphenol fluorene and 100mL of toluene into the mixed solution, and carrying out ultrasonic dispersion for 1h to obtain a carbon nano tube dispersion liquid;
28.76g of bisphenol A, 39.27g of 4,4' -difluorobenzophenone, 29.85g of potassium carbonate and the carbon nanotube dispersion were added to a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device, mechanically stirred and degassed for 1 hour, then heated to 140 ℃ for azeotropic water carrying for 2 hours, and further heated to 170 ℃ for further polymerization for 2 hours.
Continuously stirring the continuous polymerization feed liquid in deionized water to precipitate a filamentous precipitate, and sequentially crushing, washing and drying the precipitate. And the washing is carried out for 10 times in deionized water, and the drying is carried out for 12 hours in a vacuum oven at the temperature of 120 ℃ to obtain the polyether-ether-ketone reinforced master batch.
Weighing 10g of the prepared master batch and 90g of pure polyetheretherketone material with the melt index of 29g/10min, adding into a high-speed stirrer, blending, and performing melt extrusion in a double-screw extruder, wherein the temperature of a first zone is 320 ℃, the temperature of a second zone is 370 ℃, the temperature of a third zone is 360 ℃, and the extrusion speed is 30 r/min. And granulating the extruded product, performing injection molding under the conditions that the injection molding temperature is 380 ℃ and the injection molding pressure is 0.6MPa, and performing heat treatment on the injection molded product in a vacuum oven at 200 ℃ for 2 hours to obtain the polyether-ether-ketone composite material.
Example 4
26.08g of carbon nano tube is added into 480mL of N-methyl pyrrolidone for ultrasonic treatment for 1h, and then 18.92g of bisphenol fluorene and 100mL of toluene are added into the mixed solution for further ultrasonic dispersion for 1h to obtain carbon nano tube dispersion liquid.
28.76g of bisphenol A, 39.27g of 4,4' -difluorobenzophenone, 29.85g of potassium carbonate and the carbon nanotube dispersion were added to a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device, mechanically stirred and degassed for 1 hour, then heated to 140 ℃ for azeotropic water carrying for 2 hours, and further heated to 170 ℃ for further polymerization for 2 hours.
Continuously stirring the continuous polymerization reaction feed liquid in deionized water to precipitate a filamentous material, and sequentially crushing, washing and drying the precipitate. And the washing is carried out for 10 times in deionized water, and the drying is carried out for 12 hours in a vacuum oven at the temperature of 120 ℃ to obtain the polyether-ether-ketone reinforced master batch.
10g of the prepared master batch and 90g of pure polyetheretherketone material with the melt index of 29g/10min are added into a high-speed stirrer for blending, and then melt extrusion is carried out in a double-screw extruder, wherein the temperature of a first zone is 320 ℃, the temperature of a second zone is 370 ℃, the temperature of a third zone is 360 ℃, and the extrusion speed is 30 r/min. And granulating the extruded product, performing injection molding under the conditions that the injection molding temperature is 380 ℃ and the injection molding pressure is 0.6MPa, and performing heat treatment on the injection molded product in a vacuum oven at 200 ℃ for 2 hours to obtain the polyether-ether-ketone composite material.
Example 5
Adding 8.86g of carbon nano tube into 480mL of N-methyl pyrrolidone for ultrasonic treatment for 1h, then adding 18.92g of bisphenol fluorene and 100mL of toluene into the mixed solution, and further performing ultrasonic dispersion for 1h to obtain a carbon nano tube dispersion solution;
28.76g of bisphenol A, 39.27g of 4,4' -difluorobenzophenone, 29.85g of potassium carbonate and the carbon nanotube dispersion were added to a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device, mechanically stirred and degassed for 1 hour, then heated to 140 ℃ for azeotropic water carrying for 2 hours, and further heated to 170 ℃ for further polymerization for 1 hour.
Continuously stirring the continuous polymerization reaction feed liquid in deionized water to precipitate a filamentous material, and sequentially crushing, washing and drying the precipitate. And the washing is carried out for 10 times in deionized water, and the drying is carried out for 12 hours in a vacuum oven at the temperature of 120 ℃ to obtain the polyether-ether-ketone reinforced master batch.
Weighing 10g of the prepared master batch and 90g of pure polyetheretherketone material with the melt index of 29g/10min, adding into a high-speed stirrer, blending, and performing melt extrusion in a double-screw extruder, wherein the temperature of a first zone is 320 ℃, the temperature of a second zone is 370 ℃, the temperature of a third zone is 360 ℃, and the extrusion speed is 30 r/min. And granulating the extruded product, performing injection molding under the conditions that the injection molding temperature is 380 ℃ and the injection molding pressure is 0.6MPa, and performing heat treatment on the injection molded product in a vacuum oven at 200 ℃ for 2 hours to obtain the polyether-ether-ketone composite material.
Example 6
Adding 8.86g of carbon nano tube into 480mL of N-methyl pyrrolidone for ultrasonic treatment for 1h, then adding 18.92g of bisphenol fluorene and 100mL of toluene into the mixed solution, and further performing ultrasonic dispersion for 1h to obtain a carbon nano tube dispersion solution;
28.76g of bisphenol A, 39.27g of 4,4' -difluorobenzophenone, 29.85g of potassium carbonate and the carbon nanotube dispersion were added to a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device, mechanically stirred and degassed for 1 hour, then heated to 140 ℃ for azeotropic water carrying for 2 hours, and further heated to 170 ℃ for further polymerization for 3 hours.
Continuously stirring the continuous polymerization reaction feed liquid in deionized water to precipitate a filamentous material, and sequentially crushing, washing and drying the precipitate. And the washing is carried out for 10 times in deionized water, and the drying is carried out for 12 hours in a vacuum oven at the temperature of 120 ℃ to obtain the polyether-ether-ketone reinforced master batch.
Adding 10g of polyether-ether-ketone reinforced master batch and 90g of polyether-ether-ketone pure material with the melt index of 29g/10min into a high-speed stirrer for blending, and then carrying out melt extrusion in a double-screw extruder, wherein the temperature of a first zone is 320 ℃, the temperature of a second zone is 370 ℃, the temperature of a third zone is 360 ℃, and the extrusion speed is 30 r/min. And granulating the extruded product, performing injection molding under the conditions that the injection molding temperature is 380 ℃ and the injection molding pressure is 0.6MPa, and performing heat treatment on the injection molded product in a vacuum oven at 200 ℃ for 2 hours to obtain the polyether-ether-ketone composite material.
Example 7
Adding 8.86g of carbon nano tube into 480mL of N-methyl pyrrolidone for ultrasonic treatment for 1h, then adding 18.92g of bisphenol fluorene and 100mL of toluene into the mixed solution, and further performing ultrasonic dispersion for 1h to obtain a carbon nano tube dispersion solution;
28.76g of bisphenol A, 39.27g of 4,4' -difluorobenzophenone, 29.85g of potassium carbonate and the carbon nanotube dispersion were added to a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device, mechanically stirred and degassed for 1 hour, then heated to 140 ℃ for azeotropic water carrying for 2 hours, and further heated to 170 ℃ for further polymerization for 2 hours.
Continuously stirring the continuous polymerization reaction feed liquid in deionized water to precipitate a filamentous material, and sequentially crushing, washing and drying the precipitate. And the washing is carried out for 10 times in deionized water, and the drying is carried out for 12 hours in a vacuum oven at the temperature of 120 ℃ to obtain the polyether-ether-ketone reinforced master batch.
Adding 10g of polyether-ether-ketone reinforced master batch and 90g of polyether-ether-ketone pure material with the melt index of 12g/10min into a high-speed stirrer for blending, and then carrying out melt extrusion in a double-screw extruder, wherein the temperature of a first zone is 320 ℃, the temperature of a second zone is 370 ℃, the temperature of a third zone is 360 ℃, and the extrusion speed is 30 r/min. And granulating the extruded product, performing injection molding under the conditions that the injection molding temperature is 380 ℃ and the injection molding pressure is 0.6MPa, and performing heat treatment on the injection molded product in a vacuum oven at 200 ℃ for 2 hours to obtain the polyether-ether-ketone composite material.
Example 8
Adding 8.86g of carbon nano tube into 480mL of N-methyl pyrrolidone for ultrasonic treatment for 1h, then adding 18.92g of bisphenol fluorene and 100mL of toluene into the mixed solution, and further performing ultrasonic dispersion for 1h to obtain a carbon nano tube dispersion solution;
28.76g of bisphenol A, 39.27g of 4, 4-difluorobenzophenone, 29.85g of potassium carbonate and the carbon nanotube dispersion were added to a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device, mechanically stirred and degassed for 1 hour, then heated to 140 ℃ for azeotropic water carrying for 2 hours, and further heated to 170 ℃ for further polymerization for 2 hours.
Continuously stirring the continuous polymerization reaction feed liquid in deionized water to precipitate a filamentous material, and sequentially crushing, washing and drying the precipitate. And the washing is carried out for 10 times in deionized water, and the drying is carried out for 12 hours in a vacuum oven at the temperature of 120 ℃ to obtain the polyether-ether-ketone reinforced master batch.
Adding 10g of polyether-ether-ketone reinforced master batch and 90g of polyether-ether-ketone pure material with the melt index of 21g/10min into a high-speed stirrer for blending, and then carrying out melt extrusion in a double-screw extruder, wherein the temperature of a first zone is 320 ℃, the temperature of a second zone is 370 ℃, the temperature of a third zone is 360 ℃, and the extrusion speed is 30 r/min. And granulating the extruded product, performing injection molding under the conditions that the injection molding temperature is 380 ℃ and the injection molding pressure is 0.6MPa, and performing heat treatment on the injection molded product in a vacuum oven at 200 ℃ for 2 hours to obtain the polyether-ether-ketone composite material.
Example 9
Adding 8.86g of carbon nano tube into 480mL of N-methyl pyrrolidone for ultrasonic treatment for 1h, then adding 18.92g of bisphenol fluorene and 100mL of toluene into the mixed solution, and further performing ultrasonic dispersion for 1h to obtain a carbon nano tube dispersion solution;
28.76g of bisphenol A, 39.27g of 4,4' -difluorobenzophenone, 29.85g of potassium carbonate and the carbon nanotube dispersion were added to a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device, mechanically stirred and degassed for 1 hour, then heated to 140 ℃ for azeotropic water carrying for 2 hours, and further heated to 170 ℃ for further polymerization for 2 hours.
Continuously stirring the continuous polymerization reaction feed liquid in deionized water to precipitate a filamentous material, and sequentially crushing, washing and drying the precipitate. And the washing is carried out for 10 times in deionized water, and the drying is carried out for 12 hours in a vacuum oven at the temperature of 120 ℃ to obtain the polyether-ether-ketone reinforced master batch.
Adding 10g of polyether-ether-ketone reinforced master batch and 90g of polyether-ether-ketone pure material with the melt index of 40g/10min into a high-speed stirrer for blending, and then carrying out melt extrusion in a double-screw extruder, wherein the temperature of a first zone is 320 ℃, the temperature of a second zone is 370 ℃, the temperature of a third zone is 360 ℃, and the extrusion speed is 30 r/min. And granulating the extruded product, performing injection molding under the conditions that the injection molding temperature is 380 ℃ and the injection molding pressure is 0.6MPa, and performing heat treatment on the injection molded product in a vacuum oven at 200 ℃ for 2 hours to obtain the polyether-ether-ketone composite material.
Example 10
Adding 8.86g of carbon nano tube into 480mL of N-methyl pyrrolidone for ultrasonic treatment for 1h, then adding 18.92g of bisphenol fluorene and 100mL of toluene into the mixed solution, and further performing ultrasonic dispersion for 1h to obtain a carbon nano tube dispersion solution;
28.76g of bisphenol A, 39.27g of 4,4' -difluorobenzophenone, 29.85g of potassium carbonate and the carbon nanotube dispersion were added to a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device, mechanically stirred and degassed for 1 hour, then heated to 140 ℃ for azeotropic water carrying for 2 hours, and further heated to 170 ℃ for further polymerization for 2 hours.
Continuously stirring the continuous polymerization reaction feed liquid in deionized water to precipitate a filamentous material, and sequentially crushing, washing and drying the precipitate. And the washing is carried out for 10 times in deionized water, and the drying is carried out for 12 hours in a vacuum oven at the temperature of 120 ℃ to obtain the polyether-ether-ketone reinforced master batch.
Adding 10g of polyether-ether-ketone reinforced master batch and 90g of polyether-ether-ketone pure material with the melt index of 60g/10min into a high-speed stirrer for blending, and then carrying out melt extrusion in a double-screw extruder, wherein the temperature of a first zone is 320 ℃, the temperature of a second zone is 370 ℃, the temperature of a third zone is 360 ℃, and the extrusion speed is 30 r/min. And granulating the extruded product, performing injection molding under the conditions that the injection molding temperature is 380 ℃ and the injection molding pressure is 0.6MPa, and performing heat treatment on the injection molded product in a vacuum oven at 200 ℃ for 2 hours to obtain the polyether-ether-ketone composite material.
Example 11
Adding 8.86g of carbon nano tube into 480mL of N-methyl pyrrolidone for ultrasonic treatment for 1h, then adding 18.92g of bisphenol fluorene and 100mL of toluene into the mixed solution, and further performing ultrasonic dispersion for 1h to obtain a carbon nano tube dispersion solution;
28.76g of bisphenol A, 39.27g of 4, 4-difluorobenzophenone, 29.85g of potassium carbonate and the carbon nanotube dispersion were added to a three-necked flask equipped with an argon port, a mechanical stirrer and a water-carrying device, mechanically stirred and degassed for 1 hour, then heated to 140 ℃ for azeotropic water carrying for 2 hours, and further heated to 170 ℃ for further polymerization for 2 hours.
Continuously stirring the continuous polymerization reaction feed liquid in deionized water to precipitate a filamentous material, and sequentially crushing, washing and drying the precipitate. And the washing is carried out for 10 times in deionized water, and the drying is carried out for 12 hours in a vacuum oven at the temperature of 120 ℃ to obtain the polyether-ether-ketone reinforced master batch.
Adding 10g of polyether-ether-ketone reinforced master batch and 90g of polyether-ether-ketone pure material with the melt index of 85g/10min into a high-speed stirrer for blending, and then carrying out melt extrusion in a double-screw extruder, wherein the temperature of a first zone is 320 ℃, the temperature of a second zone is 370 ℃, the temperature of a third zone is 360 ℃, and the extrusion speed is 30 r/min. And granulating the extruded product, performing injection molding under the conditions that the injection molding temperature is 380 ℃ and the injection molding pressure is 0.6MPa, and performing heat treatment on the injection molded product in a vacuum oven at 200 ℃ for 2 hours to obtain the polyether-ether-ketone composite material.
The polyetheretherketone composite material obtained in example 2 is subjected to electron microscope scanning, and fig. 1-2 are scanning electron microscope images of the polyetheretherketone composite material obtained in example 2 under different magnifications. As can be seen from fig. 1 and 2: the carbon nano tube and the pure material of the polyether-ether-ketone have good interface compatibility and good dispersion effect.
The invention carries out DSC test on the polyetheretherketone composite material obtained in the example 2, and the test result is shown in figure 3, and can be seen from figure 3: only one glass transition temperature exists in the polyether-ether-ketone prepared in the example 2, which shows that the compatibility of the polyether-ether-ketone reinforced master batch and the polyether-ether-ketone is good.
For the purpose of performance measurement, the polyetheretherketone composite materials prepared in examples 2 and 4 and the pure polyetheretherketone material were injection molded into a bar having a length of 75mm, a width of 5mm and a thickness of 2mm and a curved bar having a length of 80mm, a width of 10mm and a thickness of 4mm using a JIANDA-70 injection molding machine, 5 bars were used for each material, and then mechanical properties were measured according to GB/T1040.1 and GB/T9431, as shown in Table 1 and FIG. 4:
TABLE 1 mechanical Property test results
The test results of table 1 and fig. 4 show that the high-strength and high-toughness polyetheretherketone composite material provided by the invention can effectively improve the flexural modulus, tensile strength, elongation at break and flexural strength of polyetheretherketone, and has good mechanical properties.
The invention also carries out thermal analysis performance test on the polyetheretherketone composite material obtained in the embodiment 2, the test result is shown in figure 5, and according to the figure 5, the temperature of the polyetheretherketone composite material prepared by the invention is 577 ℃ when the polyetheretherketone composite material is decomposed by 5%, the polyetheretherketone composite material is hardly decomposed at 400 ℃, the polyetheretherketone composite material can be stably used at the thermal processing temperature of the polyetheretherketone and the polyetheretherketone composite material, and the polyetheretherketone composite material has good high temperature resistance.
It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. The polyether-ether-ketone composite material is characterized by comprising the following components in parts by weight:
70-90 parts of polyether-ether-ketone powder;
10-30 parts of polyether-ether-ketone reinforced master batch;
the preparation method of the polyether-ether-ketone reinforced master batch comprises the following steps:
mixing the carbon nano tube, an organic solvent, a dispersing agent and a water-carrying agent to obtain a carbon nano tube dispersion liquid;
mixing the carbon nano tube dispersion liquid, 4' -difluorobenzophenone, bisphenol compounds and a catalyst, and carrying out in-situ polymerization reaction to obtain the polyether-ether-ketone reinforced master batch;
the dispersing agent comprises one or more of bisphenol fluorene, anthralin, phenolphthalein, 1, 6-dihydroxypyrene and 1, 5-dihydroxynaphthalene;
the bisphenol compound comprises bisphenol A and/or bisphenol AF.
2. The polyetheretherketone composite material of claim 1, wherein the mass ratio of the carbon nanotubes to the dispersant is (0.1-3): 1.
3. the polyetheretherketone composite material of claim 1 or 2, wherein the molar ratio of the bisphenol compound to the dispersant is (9-5): (1-5); the amount of the 4,4' -difluorobenzophenone is the sum of the amounts of the bisphenol compound and the dispersant.
4. The polyetheretherketone composite of claim 1, wherein the catalyst comprises an alkali metal catalyst comprising one or more of sodium carbonate, potassium carbonate and cesium carbonate.
5. The polyetheretherketone composite of claim 1, wherein the polymerization reaction comprises sequential azeotropic entrainment and continued polymerization; the temperature of the azeotropic entrained water is 120-150 ℃; the temperature for continuous polymerization is 160-180 ℃.
6. The preparation method of the polyetheretherketone composite material according to any one of claims 1 to 5, comprising the steps of:
mixing polyether-ether-ketone powder and polyether-ether-ketone reinforced master batch, and then sequentially carrying out melt extrusion, granulation and drying to obtain polyether-ether-ketone composite particles;
and sequentially carrying out injection molding and heat treatment on the polyether-ether-ketone composite particles to obtain the polyether-ether-ketone composite material.
7. The method according to claim 6, wherein the injection molding temperature is 360 to 400 ℃ and the pressure is 0.4 to 0.8 MPa.
8. The method according to claim 6, wherein the heat treatment is carried out at a temperature of 200 to 220 ℃ for 2.0 to 4.0 hours.
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