CN110183647B - Carbon nanotube/polyether ketone composite material and preparation method and application thereof - Google Patents
Carbon nanotube/polyether ketone composite material and preparation method and application thereof Download PDFInfo
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- 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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- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
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Abstract
The invention provides a carbon nano tube/polyether ketone composite material and a preparation method and application thereof, belonging to the field of polymers. The carbon nano tube/polyether ketone composite material provided by the invention comprises polyether ketone and carbon nano tubes dispersed in the polyether ketone; according to the invention, bisphenol fluorene is added into polyether ketone, so that the polyether ketone has a unique structure, and is beneficial to forming a strong pi-pi bond with the carbon nano tube added in situ, and the carbon nano tube can be uniformly dispersed in the polyether ketone through pi-pi accumulation, so that the interface compatibility of the carbon nano tube and polyether ketone matrix resin is effectively improved, and the mechanical property and the wear resistance of the composite material are improved.
Description
Technical Field
The invention relates to the field of polymers, in particular to a carbon nano tube/polyether ketone composite material and a preparation method and application thereof.
Background
Polyether ketone (PEK) as a semi-crystalline thermoplastic polymer material has excellent flame retardance, radiation resistance and high temperature resistance, so that the PEK is widely applied to the fields of aerospace, instruments, automobile industry and the like, but the mechanical property of the PEK is still to be improved.
Carbon nanotubes are considered ideal fillers for the preparation of high performance nanocomposites due to their excellent mechanical properties. However, van der waals force and electrostatic effect between the carbon nanotubes make it difficult to disperse them uniformly in the matrix resin, so that the carbon nanotubes cannot effectively improve the mechanical properties of the resin matrix.
Disclosure of Invention
The carbon nanotube/polyether ketone composite material provided by the invention has good mechanical properties, and has the tensile strength of 111.76-126.43 MPa, the tensile modulus of 1406.15-1828.56 MPa, the bending strength of 127.63-148.00 MPa, the bending modulus of 3669.98-4375.41 MPa and the elongation at break of 71.06-94.15%.
The invention provides a carbon nano tube/polyether ketone composite material, which comprises polyether ketone and carbon nano tubes dispersed in the polyether ketone;
the polyether ketone has a structural unit shown in a formula I:
wherein x + y is 1, and x is 1-10%;
the mass fraction of the carbon nano tube in the composite material is 0.1-10%.
The invention provides a preparation method of the carbon nanotube/polyether ketone composite material in the technical scheme, which comprises the following steps:
(1) mixing 4,4' -difluorobenzophenone, bisphenol fluorene, p-hydroxybenzophenone, a carbon nano tube, a catalyst, a dehydrating agent and a reaction solvent to obtain a reaction raw material; the catalyst comprises one or two of potassium carbonate and sodium carbonate;
(2) and (2) carrying out azeotropic dehydration, dehydrating agent removal and polymerization reaction on the reaction raw materials obtained in the step (1) in sequence to obtain the carbon nano tube/polyether ketone composite material.
Preferably, the molar ratio of 4,4' -difluorobenzophenone, bisphenol fluorene and p-hydroxybenzophenone is 0.8-1.2: 0.01-0.10: 0.9-0.99; the mass ratio of the carbon nano tube to the bisphenol fluorene is 0.1-5: 1-10.
Preferably, the carbon nanotubes comprise single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
Preferably, the azeotropic dehydration, the removal of the dehydrating agent and the polymerization reaction are carried out under a protective atmosphere.
Preferably, the temperature of azeotropic dehydration is 140-180 ℃, and the time is 1-2 h.
Preferably, the temperature for removing the dehydrating agent is 210-230 ℃ and the time is 2-3 h.
Preferably, the polymerization reaction comprises a first polymerization reaction and a second polymerization reaction which are sequentially carried out; the temperature of the first polymerization reaction is 240-280 ℃, and the time is 2-3 h; the temperature of the second polymerization reaction is 300-310 ℃, and the time is 0.5-1 h.
The invention provides an application of the carbon nanotube/polyether ketone composite material or the carbon nanotube/polyether ketone composite material prepared by the method in the technical scheme as a thermoplastic high polymer material.
Preferably, the application method of the carbon nanotube/polyether ketone composite material as the thermoplastic polymer material comprises the following steps:
(a) sequentially carrying out extrusion, granulation and drying treatment on the carbon nanotube/polyether ketone composite material to obtain composite material particles;
(b) and (b) sequentially carrying out injection molding and annealing treatment on the composite material particles obtained in the step (a) to obtain the thermoplastic polymer material.
The invention provides a carbon nano tube/polyether ketone composite material, which comprises polyether ketone and carbon nano tubes dispersed in the polyether ketone; according to the invention, bisphenol fluorene is added into polyether ketone, so that the polyether ketone has a unique structure, and is beneficial to forming a strong pi-pi bond with the carbon nano tube added in situ, and the carbon nano tube can be uniformly dispersed in the polyether ketone through pi-pi accumulation, so that the interface compatibility of the carbon nano tube and polyether ketone matrix resin is effectively improved, and the mechanical property and the wear resistance of the composite material are improved. As shown in the embodiment, the carbon nanotube/polyether ketone composite material provided by the invention has the tensile strength of 111.76-126.43 MPa, the tensile modulus of 1406.15-1828.56 MPa, the bending strength of 127.63-148.00 MPa, the bending modulus of 3669.98-4375.41 MPa and the elongation at break of 71.06-94.15%.
Detailed Description
The invention provides a carbon nano tube/polyether ketone composite material, which comprises polyether ketone and carbon nano tubes dispersed in the polyether ketone;
the polyether ketone has a structural unit shown in a formula I:
wherein x + y is 1; x is 1% to 10%, preferably 2% to 8%, and more preferably 4% to 6%.
In the present invention, the mass fraction of the carbon nanotubes in the composite material is 0.1% to 10%, preferably 0.1% to 8%, more preferably 0.1% to 6%, more preferably 0.1% to 4%, and most preferably 0.1% to 2%. The invention preferably controls the mass fraction of the carbon nano tube in the composite material within the range, and is beneficial to improving the mechanical property and the wear resistance of the carbon nano tube/polyether ketone composite material.
The carbon nano tube/polyether ketone composite material provided by the invention comprises polyether ketone and carbon nano tubes dispersed in the polyether ketone; according to the invention, bisphenol fluorene is added into polyether ketone, so that the polyether ketone has a unique structure, and is beneficial to forming a strong pi-pi bond with a carbon nano tube added in situ, and the carbon nano tube can be uniformly dispersed in the polyether ketone through the pi-pi accumulation effect, so that the interface compatibility of the carbon nano tube and polyether ketone matrix resin is effectively improved; in addition, the carbon nano tubes can be uniformly dispersed in the polyether ketone matrix through in-situ polymerization of the carbon nano tubes, so that the carbon nano tubes can be fully exerted, and the mechanical property and the wear resistance of the composite material are improved.
The invention also provides a preparation method of the carbon nanotube/polyether ketone composite material in the technical scheme, which comprises the following steps:
(1) mixing 4,4' -difluorobenzophenone, bisphenol fluorene, p-hydroxybenzophenone, a carbon nano tube, a catalyst, a dehydrating agent and a reaction solvent to obtain a reaction raw material; the catalyst comprises one or two of potassium carbonate and sodium carbonate;
(2) and (2) carrying out azeotropic dehydration, dehydrating agent removal and polymerization reaction on the reaction raw materials obtained in the step (1) in sequence to obtain the carbon nano tube/polyether ketone composite material.
The invention mixes 4,4' -difluorobenzophenone, bisphenol fluorene, p-hydroxybenzophenone, carbon nano tube, catalyst, dehydrating agent and reaction solvent to obtain the reaction raw material.
In the present invention, the mixing method is preferably: dispersing carbon nano tubes in trichloromethane, and then dispersing bisphenol fluorene in trichloromethane dispersion liquid of the carbon nano tubes to obtain a mixed solution. According to the invention, the mixed solution is preferably subjected to rotary evaporation treatment, and the solvent chloroform is removed, so that the mixed powder with uniformly dispersed bisphenol fluorene and carbon nano tubes is obtained. After the mixed powder with uniformly dispersed bisphenol fluorene and carbon nano is obtained, the mixed powder is mixed with 4,4' -difluorobenzophenone, p-hydroxybenzophenone, a catalyst, a dehydrating agent and a reaction solvent. In the present invention, the dispersion is preferably ultrasonic dispersion and/or mechanical stirring. The invention preferably adopts the mixing mode, which is beneficial to uniformly dispersing the carbon nano tube in the polyether ketone resin matrix and further beneficial to improving the mechanical property of the carbon nano tube/polyether ketone composite material.
In the present invention, the molar ratio of 4,4' -difluorobenzophenone, bisphenol fluorene and p-hydroxybenzophenone is preferably 0.8 to 1.2:0.01 to 0.10:0.9 to 0.99, more preferably 0.9 to 1.1:0.02 to 0.08:0.92 to 0.98, and still more preferably 1:0.04 to 0.06:0.94 to 0.96. In the invention, the mass ratio of the carbon nano tube to the bisphenol fluorene is preferably 0.1-5: 1-10, more preferably 1-4: 2-8, and even more preferably 2-3: 4-6. In the present invention, the carbon nanotubes preferably include single-walled carbon nanotubes and/or multi-walled carbon nanotubes. The invention preferably controls the quality of 4,4' -difluorobenzophenone, bisphenol fluorene, p-hydroxybenzophenone and carbon nano tube in the above range, which is beneficial to preparing the carbon nano tube/polyether ketone composite material with good mechanical property.
In the present invention, the molar ratio of the catalyst to 4,4' -difluorobenzophenone is preferably 0.01 to 1.3:1 to 1.1, more preferably 0.05 to 1.0:1 to 1.1, and still more preferably 0.1 to 0.8:1 to 1.1. In the invention, the catalyst comprises one or two of potassium carbonate and sodium carbonate, the catalyst potassium carbonate and sodium carbonate are preferably added at the same time, the molar ratio of the potassium carbonate to the sodium carbonate is preferably 0.01:1.2, and the catalyst is controlled within the range, so that the method is favorable for more fully catalyzing the reaction and further is favorable for preparing the carbon nanotube/polyether ketone composite material. In the present invention, the dehydrating agent preferably comprises xylene; the reaction solvent preferably comprises diphenyl sulfone. In the invention, the ratio of the total mass of the 4,4' -difluorobenzophenone, the bisphenol fluorene, the p-hydroxybenzophenone, the carbon nanotube and the catalyst to the amount of the reaction solvent is preferably 25-50 g:100mL, and more preferably 30-45 g:100 mL. In the present invention, the mass of the dehydrating solvent is preferably 15% to 30%, and more preferably 20% to 25% of the mass of the reaction solvent.
After reaction raw materials are obtained, the invention carries out azeotropic dehydration, dehydrating agent removal and polymerization reaction on the reaction raw materials in sequence to obtain the carbon nano tube/polyether ketone composite material.
In the present invention, the azeotropic dehydration, the removal of the dehydrating agent and the polymerization reaction are preferably all carried out under a protective atmosphere, which is preferably an argon atmosphere or a nitrogen atmosphere.
In the invention, the temperature of the azeotropic dehydration is preferably 140-180 ℃, more preferably 150-170 ℃, and the time of the azeotropic dehydration is preferably 1-2 h. According to the invention, through azeotropic dehydration reaction, water in the system is removed, and the influence on the subsequent polymerization reaction is avoided.
After the azeotropic dehydration reaction is finished, the invention continuously raises the reaction temperature and removes the dehydrating agent. In the invention, the temperature for removing the dehydrating agent is preferably 210-230 ℃, and the time is preferably 2-3 h.
After the dehydrating agent is removed, the reaction temperature is continuously raised to carry out polymerization reaction. In the present invention, the polymerization reaction preferably includes a first polymerization reaction and a second polymerization reaction which are carried out in this order; the temperature of the first polymerization reaction is preferably 240-280 ℃, more preferably 250-270 ℃, and the time is preferably 2-3 h; the temperature of the second polymerization reaction is preferably 300-310 ℃, and the time is preferably 0.5-1 h. The invention preferably divides the polymerization reaction into two steps, which is beneficial to leading the reaction raw materials to be capable of fully reacting to generate the carbon nano tube/polyether ketone composite material.
After the polymerization reaction is completed, the reaction solution obtained after the polymerization reaction is preferably discharged into deionized water to precipitate a solid. According to the invention, the solid is preferably dried and then crushed, and then washed and dried in sequence to obtain the carbon nanotube/polyether ketone composite material. In the invention, the washing is preferably carried out by sequentially adopting acetone and hot water, and the temperature of the hot water is preferably 90-100 ℃. The present invention preferably removes impurities in the target product sufficiently by the above-mentioned manner.
The invention also provides the application of the carbon nano tube/polyether ketone composite material in the technical scheme or the carbon nano tube/polyether ketone composite material prepared by the method in the technical scheme as a thermoplastic high polymer material.
In the present invention, the method for applying the carbon nanotube/polyether ketone composite material as a thermoplastic polymer material preferably comprises the following steps:
(a) sequentially carrying out extrusion, granulation and drying treatment on the carbon nanotube/polyether ketone composite material to obtain composite material particles;
(b) and (b) sequentially carrying out injection molding and annealing treatment on the composite material particles obtained in the step (a) to obtain the thermoplastic polymer material.
The carbon nano tube/polyether ketone composite material is sequentially subjected to extrusion, granulation and drying treatment to obtain composite material particles. In the invention, the extrusion temperature is preferably 390-400 ℃, and the extrusion rotating speed is preferably 40-50 r/min; the extrusion apparatus is preferably a twin screw extruder. In the invention, the drying temperature is preferably 100-120 ℃, and the drying time is preferably 10-14 h.
After the composite material particles are obtained, the invention sequentially carries out injection molding and annealing treatment on the composite material particles to obtain the thermoplastic polymer material.
In the invention, the injection molding temperature is preferably 390-400 ℃, and more preferably 392-398 ℃; the pressure of the injection molding is preferably 750-850 bar, more preferably 760-840 bar, and even more preferably 770-820 bar. In the invention, the temperature of the annealing treatment is preferably 230-240 ℃; the time is preferably 3.5-4.5 h. The thermoplastic polymer material with better mechanical property is obtained through injection molding and annealing treatment.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
Weighing 0.44g of multi-walled carbon nanotube, adding the multi-walled carbon nanotube into 500mL of chloroform, and carrying out ultrasonic treatment for 2h to obtain a chloroform dispersion liquid of the multi-walled carbon nanotube; weighing 7g of bisphenol fluorene (0.02mol) and adding the bisphenol fluorene into the chloroform dispersion liquid of the multi-walled carbon nano tube, carrying out ultrasonic treatment for 2 hours, mechanically stirring for 1 hour, and carrying out rotary evaporation to obtain bisphenol fluorene dispersed multi-walled carbon nano tube powder.
222.56g of 4,4' -difluorobenzophenone (1.02mol), bisphenol fluorene dispersed multi-wall carbon nanotube powder, 210g of p-hydroxybenzophenone monomer (0.98mol), 1.38g of anhydrous potassium carbonate (0.01mol), 127.19g of anhydrous sodium carbonate (1.2mol), 1317g of diphenyl sulfone and 200mL of xylene are put into a three-neck flask with an argon port, mechanical stirring and a water-carrying device, heated to 140 ℃ under argon atmosphere for reflux, reacted for 2h, then heated to 210 ℃ for reaction for 3h, xylene is removed, then heated to 240 ℃ for reaction for 2h, and then heated to 300 ℃ for reaction for 0.5h, the obtained reaction liquid is discharged into deionized water, solids are separated out, and the carbon nanotube/polyether ketone composite material with the carbon nanotube mass fraction of 0.1% is obtained after crushing, washing and drying.
Example 2
Weighing 1.77g of multi-walled carbon nanotube, adding the multi-walled carbon nanotube into 1000mL of chloroform, and carrying out ultrasonic treatment for 2h to obtain a chloroform dispersion liquid of the multi-walled carbon nanotube; weighing 8g of bisphenol fluorene, adding the bisphenol fluorene into the chloroform dispersion liquid of the multi-walled carbon nano tube, carrying out ultrasonic treatment for 2 hours, mechanically stirring for 1 hour, and carrying out rotary evaporation to obtain bisphenol fluorene dispersed multi-walled carbon nano tube powder.
4,4' -difluorobenzophenone (178g, 0.816mol), the powder of bisphenol fluorene dispersed multi-walled carbon nanotubes described above, (166g, 0.776mol) p-hydroxybenzophenone monomer, (1.3g, 0.008mol) anhydrous potassium carbonate, (101g, 0.96mol) anhydrous sodium carbonate, 1061g diphenylsulfone and 250mL xylene were charged into a three-necked flask with argon port, mechanical stirring and water-carrying device, heated to 150 ℃ under argon atmosphere for reflux, reacted for 2h, then heated to 220 ℃ for 3h, and xylene was excluded. And then heating to 250 ℃ for reaction for 2h, continuously heating to 300 ℃ for reaction for 0.5h, discharging the obtained reaction liquid into deionized water, separating out solids, and crushing, washing and drying to obtain the carbon nanotube/polyether ketone composite material with the mass fraction of the carbon nanotube of 0.5%.
Example 3
Weighing 8.12g of multi-walled carbon nanotube, adding the multi-walled carbon nanotube into 8000mL of chloroform, carrying out ultrasonic treatment for 2h, weighing 15g of bisphenol fluorene, adding the bisphenol fluorene into the multi-walled carbon nanotube dispersion liquid, carrying out ultrasonic treatment for 2h, mechanically stirring for 1h, and carrying out rotary evaporation to obtain bisphenol fluorene dispersed multi-walled carbon nanotube powder.
Putting (200g, 0.918mol)4,4' -difluorobenzophenone, the bisphenol fluorene dispersion multi-wall carbon nanotube powder, (183g, 0.855mol) p-hydroxybenzophenone monomer, (1.2g, 0.009mol) anhydrous potassium carbonate, (114g, 1.08mol) anhydrous sodium carbonate, 1198g diphenyl sulfone and 235mL dimethylbenzene into a three-neck flask with an argon port, a mechanical stirrer and a water-carrying device, heating to 180 ℃ under argon atmosphere for reflux, reacting for 2h, then heating to 230 ℃, reacting for 3h, removing dimethylbenzene, heating to 260 ℃ for reaction for 2h, further heating to 310 ℃ for reaction for 0.5h, discharging the obtained reaction feed liquid into deionized water, separating out a solid, crushing, washing and drying to obtain the carbon nanotube/polyether ketone composite material with the carbon nanotube mass fraction of 2%.
Example 4
Weighing 3.64g of single-walled carbon nanotube, adding the single-walled carbon nanotube into 4000mL of chloroform, carrying out ultrasonic treatment for 2h, weighing 28g of bisphenol fluorene, adding the bisphenol fluorene into the single-walled carbon nanotube dispersion liquid, carrying out ultrasonic treatment for 2h, mechanically stirring for 1h, and carrying out rotary evaporation to obtain bisphenol fluorene dispersed single-walled carbon nanotube powder.
Putting (178g, 0.816mol)4,4' -difluorobenzophenone, the powder of the bisphenol fluorene dispersed single-walled carbon nanotube, (154g, 0.72mol) p-hydroxybenzophenone monomer, (1.4g, 0.008mol) anhydrous potassium carbonate, (101g, 0.96mol) anhydrous sodium carbonate, 1084g diphenylsulfone and 288mL dimethylbenzene into a three-neck flask with an argon port, mechanical stirring and a water-carrying device, heating to 170 ℃ under argon atmosphere for reflux, reacting for 2h, then heating to 220 ℃, reacting for 3h, removing dimethylbenzene, heating to 270 ℃ for reaction for 2h, further heating to 305 ℃ for reaction for 0.5h, discharging the obtained reaction feed liquid into deionized water, separating out a solid, crushing, washing and drying to obtain the carbon nanotube/polyether ketone composite material with the mass fraction of 1% of the carbon nanotube.
Application example 1
The carbon nanotube/polyether ketone composite material prepared in the embodiment 1 is sequentially subjected to extrusion, granulation and drying treatment to obtain composite material particles, then the composite material particles are subjected to injection molding at 390 ℃ and 850bar, and then annealing is carried out for 4 hours at 230 ℃ to obtain the thermoplastic polymer material.
Application example 2
The carbon nanotube/polyether ketone composite material prepared in the embodiment 2 is sequentially subjected to extrusion, granulation and drying treatment to obtain composite material particles, and then the composite material particles are subjected to injection molding at 395 ℃ and 850bar and then are annealed at 230 ℃ for 4 hours to obtain the thermoplastic polymer material.
Application example 3
And (2) sequentially carrying out extrusion, granulation and drying treatment on the carbon nanotube/polyether ketone composite material prepared in the embodiment 3 to obtain composite material particles, then carrying out injection molding on the composite material particles at 395 ℃ under 850bar, and annealing for 4 hours at 230 ℃ to obtain the thermoplastic polymer material.
Application example 4
The carbon nanotube/polyether ketone composite material prepared in the embodiment 4 is sequentially subjected to extrusion, granulation and drying treatment to obtain composite material particles, and then the composite material particles are subjected to injection molding at 395 ℃ and 850bar and then are annealed at 230 ℃ for 4 hours to obtain the thermoplastic polymer material.
Comparative example 1
Putting 2.01g of multi-walled carbon nanotube, 222.56g of 4,4' -difluorobenzophenone (1.02mol), 210g of p-hydroxybenzophenone monomer (0.98mol), 1.38g of anhydrous potassium carbonate (0.01mol), 127.19g of anhydrous sodium carbonate (1.2mol), 1317g of diphenyl sulfone and 200mL of xylene into a three-neck flask with an argon port, mechanical stirring and a water carrying device, heating to 140 ℃ under argon atmosphere for reflux, reacting for 2h, heating to 210 ℃, reacting for 3h, removing xylene, heating to 240 ℃ for reaction for 2h, further heating to 300 ℃ for reaction for 0.5h, discharging the obtained reaction product into deionized water, separating out solids, crushing, washing and drying to obtain the carbon nanotube/pure polyether ketone composite material.
Comparative application example 1
And (2) sequentially carrying out extrusion, granulation and drying treatment on the carbon nanotube/pure polyether ketone composite material prepared in the comparative example 1 to obtain composite material particles, then carrying out injection molding on the composite material particles at 395 ℃ under 850bar, and annealing for 4 hours at 230 ℃ to obtain the thermoplastic polymer material.
Performance testing
The mechanical properties of the thermoplastic polymer materials prepared in the application examples 1-4 and the comparative application example 1 were tested, and the test method was: a JIANDA-70 injection molding machine (Shenzhen Jianda mechanical Co., Ltd.) is adopted to respectively prepare dumbbell-shaped tensile sample strips (with the length of 75 mm/the width of 5 mm/the thickness of 2mm) and bending sample strips (with the length of 80 mm/the width of 10 mm/the thickness of 4mm), and the mechanical properties of the thermoplastic polymer material are tested. The test results are shown in table 1:
TABLE 1 application examples 1 to 4 and comparative application example 1 mechanical properties of thermoplastic Polymer Material
The test results in table 1 show that the carbon nanotube/polyether ketone composite material provided by the present invention has good mechanical properties, and the mechanical properties of the carbon nanotube/polyether ketone composite material provided by the present invention are superior to the mechanical properties of the carbon nanotube/pure polyether ketone composite material, which indicates that the carbon nanotube and bisphenol fluorene in the present invention both have important effects on improving the mechanical properties of the composite material. The carbon nanotube/polyether ketone composite material provided by the invention has the tensile strength of 111.76-126.43 MPa, the tensile modulus of 1406.15-1828.56 MPa, the bending strength of 127.63-148.00 MPa, the bending modulus of 3669.98-4375.41 MPa and the elongation at break of 71.06-94.15%.
The friction performance of the thermoplastic polymer material prepared in the application examples 1-4 is tested, and the test method comprises the following steps: a JIANDA-70 type injection molding machine (Shenzhen Jianda mechanical Co., Ltd.) is adopted to respectively prepare friction sample strips (length is 16.5 mm/width is 9.6 mm/thickness is 6.8mm), and a UMT-2 type multifunctional friction testing machine (Bruker, Germany) is adopted to test the friction performance of the thermoplastic polymer material, and the test standard is GB-T3960-1983. The test results are shown in table 2:
TABLE 2 Friction Properties of thermoplastic Polymer materials in application examples 1 to 4
| Performance index | Application example 1 | Application example 2 | Application example 3 | Application example 4 |
| Coefficient of friction | 0.44 | 0.41 | 0.37 | 0.32 |
| Wear rate (mm)3/Nm) | 1.25×10-6 | 9.98×10-7 | 7.90×10-7 | 6.88×10-7 |
As can be seen from Table 2, the carbon nanotube/polyether ketone composite material provided by the invention has a low friction coefficient and a low wear rate. The carbon nanotube/polyether ketone composite material provided by the invention has the friction coefficient of 0.32-0.44 and the wear rate of 6.88 multiplied by 10-7～1.25×10-6mm3/Nm。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The carbon nanotube/polyether ketone composite material is characterized by comprising polyether ketone and carbon nanotubes dispersed in the polyether ketone;
the polyether ketone has a structural unit shown in a formula I:
wherein x + y is 1, and x is 1-10%;
the mass fraction of the carbon nano tube in the composite material is 0.1-10%;
the preparation method of the carbon nanotube/polyether ketone composite material comprises the following steps:
(1) mixing 4,4' -difluorobenzophenone, bisphenol fluorene, p-hydroxybenzophenone, a carbon nano tube, a catalyst, a dehydrating agent and a reaction solvent to obtain a reaction raw material; the catalyst comprises one or two of potassium carbonate and sodium carbonate;
(2) carrying out azeotropic dehydration, dehydrating agent removal and polymerization reaction on the reaction raw materials obtained in the step (1) in sequence to obtain a carbon nano tube/polyether ketone composite material;
the molar ratio of the 4,4' -difluorobenzophenone, the bisphenol fluorene and the p-hydroxybenzophenone is 0.8-1.2: 0.01-0.10: 0.9 to 0.99; the mass ratio of the carbon nano tube to the bisphenol fluorene is 0.1-5: 1-10;
the polymerization reaction comprises a first polymerization reaction and a second polymerization reaction which are sequentially carried out; the temperature of the first polymerization reaction is 240-280 ℃, and the time is 2-3 h; the temperature of the second polymerization reaction is 300-310 ℃, and the time is 0.5-1 h.
2. The method for preparing the carbon nanotube/polyether ketone composite material as claimed in claim 1, comprising the steps of:
(1) mixing 4,4' -difluorobenzophenone, bisphenol fluorene, p-hydroxybenzophenone, a carbon nano tube, a catalyst, a dehydrating agent and a reaction solvent to obtain a reaction raw material; the catalyst comprises one or two of potassium carbonate and sodium carbonate;
(2) carrying out azeotropic dehydration, dehydrating agent removal and polymerization reaction on the reaction raw materials obtained in the step (1) in sequence to obtain a carbon nano tube/polyether ketone composite material;
the molar ratio of the 4,4' -difluorobenzophenone, the bisphenol fluorene and the p-hydroxybenzophenone is 0.8-1.2: 0.01-0.10: 0.9 to 0.99; the mass ratio of the carbon nano tube to the bisphenol fluorene is 0.1-5: 1-10;
the polymerization reaction comprises a first polymerization reaction and a second polymerization reaction which are sequentially carried out; the temperature of the first polymerization reaction is 240-280 ℃, and the time is 2-3 h; the temperature of the second polymerization reaction is 300-310 ℃, and the time is 0.5-1 h.
3. The method of claim 2, wherein the carbon nanotubes comprise single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
4. The method according to claim 2, wherein the azeotropic dehydration, the removal of the dehydrating agent and the polymerization are carried out under a protective atmosphere.
5. The method according to claim 2 or 4, wherein the azeotropic dehydration is carried out at a temperature of 140 to 180 ℃ for 1 to 2 hours.
6. The method according to claim 2 or 4, wherein the temperature for removing the dehydrating solvent is 210 to 230 ℃ and the time is 2 to 3 hours.
7. Use of the carbon nanotube/polyether ketone composite material according to claim 1 or the carbon nanotube/polyether ketone composite material prepared by the method according to any one of claims 2 to 6 as a thermoplastic polymer material.
8. The application of the carbon nanotube/polyether ketone composite material as a thermoplastic polymer material is characterized by comprising the following steps of:
(a) sequentially carrying out extrusion, granulation and drying treatment on the carbon nanotube/polyether ketone composite material to obtain composite material particles;
(b) and (b) sequentially carrying out injection molding and annealing treatment on the composite material particles obtained in the step (a) to obtain the thermoplastic polymer material.
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