CN110183647A - A kind of carbon nano-tube/poly ether ketone composite material and preparation method and application - Google Patents
A kind of carbon nano-tube/poly ether ketone composite material and preparation method and application Download PDFInfo
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- CN110183647A CN110183647A CN201910525267.5A CN201910525267A CN110183647A CN 110183647 A CN110183647 A CN 110183647A CN 201910525267 A CN201910525267 A CN 201910525267A CN 110183647 A CN110183647 A CN 110183647A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The present invention provides a kind of carbon nano-tube/poly ether ketone composite material and preparation method and applications, belong to polymer arts.Carbon nano-tube/poly ether ketone composite material provided by the invention includes polyether-ketone and the carbon nanotube that is dispersed in polyether-ketone；The present invention in polyether-ketone by adding bisphenol fluorene, so that polyether-ketone has unique structure, be conducive to form stronger pi-pi bond between the carbon nanotube added in situ, it is acted on by pi-pi accumulation, carbon nanotube is set to be dispersed in polyether-ketone, the interface compatibility of carbon nanotube Yu polyether-ketone matrix resin is effectively improved, the mechanical performance and wear-resisting property of composite material are improved.
Description
Technical field
The present invention relates to polymer arts more particularly to a kind of carbon nano-tube/poly ether ketone composite material and preparation methods
And application.
Background technique
Polyether-ketone (PEK) is used as a kind of hemicrystalline thermoplastic macromolecule material, has excellent anti-flammability, radiation resistance
And heat-resisting quantity, so that it is widely used in the fields such as aerospace, instrument and meter and auto industry, however the mechanicalness of polyether-ketone
It can need to be improved.
Carbon nanotube is considered as the ideal filler for preparing High performance nanometer composite material because of its excellent mechanical performance.So
And the Van der Waals force and electrostatic effect between carbon nanotube make it be difficult to be uniformly dispersed in matrix resin, cause carbon nanotube without
Method effectively improves the mechanical performance of resin matrix.
Summary of the invention
The present invention provides a kind of carbon nano-tube/poly ether ketone composite material, carbon nano-tube/poly ether ketone provided by the invention is multiple
Condensation material better mechanical property, tensile strength is 111.76~126.43MPa, stretch modulus be 1406.15~1828.56MPa,
Bending strength is 127.63~148.00MPa, bending modulus is 3669.98~4375.41MPa, elongation at break be 71.06~
94.15%.
The present invention provides a kind of carbon nano-tube/poly ether ketone composite material, the carbon nano-tube/poly ether ketone composite material packet
The carbon nanotube for including polyether-ketone and being dispersed in polyether-ketone；
The polyether-ketone has structural unit shown in Formulas I:
Wherein x+y=1, x=1%~10%；
The mass fraction of the carbon nanotube in the composite is 0.1%~10%.
The present invention provides the preparation methods of carbon nano-tube/poly ether ketone composite material described in above-mentioned technical proposal, including with
Lower step:
(1) by 4,4'- difluoro benzophenone, bisphenol fluorene, to dihydroxy benaophenonel, carbon nanotube, catalyst, dehydrating agent and
Reaction dissolvent mixing, obtains reaction raw materials；The catalyst includes one or both of potassium carbonate and sodium carbonate；
(2) reaction raw materials that the step (1) obtains successively are subjected to azeotropic dehydration, exclude dehydrating agent and polymerization reaction,
Obtain carbon nano-tube/poly ether ketone composite material.
Preferably, 4,4'- difluoro benzophenone, bisphenol fluorene and be 0.8~1.2 to the molar ratio of dihydroxy benaophenonel:
0.01~0.10:0.9~0.99；The mass ratio of the carbon nanotube and bisphenol fluorene is 0.1~5:1~10.
Preferably, the carbon nanotube includes single-walled carbon nanotube and/or multi-walled carbon nanotube.
Preferably, the azeotropic dehydration, exclusion dehydrating agent and polymerization reaction carry out under protective atmosphere.
Preferably, the temperature of the azeotropic dehydration is 140~180 DEG C, and the time is 1~2h.
Preferably, the temperature for excluding dehydrating agent is 210~230 DEG C, and the time is 2~3h.
Preferably, the polymerization reaction includes the first polymerization reaction and the second polymerization reaction successively carried out；Described first
The temperature of polymerization reaction is 240~280 DEG C, and the time is 2~3h；The temperature of second polymerization reaction is 300~310 DEG C, when
Between be 0.5~1h.
The present invention provides carbon nano-tube/poly ether ketone composite material described in above-mentioned technical proposal or above-mentioned technical proposal institutes
Application of the carbon nano-tube/poly ether ketone composite material that the method for stating is prepared as thermoplastic macromolecule material.
Preferably, the carbon nano-tube/poly ether ketone composite material includes as the application method of thermoplastic macromolecule material
Following steps:
(a) carbon nano-tube/poly ether ketone composite material is successively squeezed out, is granulated and is dried, obtain composite material
Particle；
(b) composite material granular that the step (a) obtains successively is subjected to injection molding and annealing, obtains thermoplastic
Property high molecular material.
The present invention provides a kind of carbon nano-tube/poly ether ketone composite material, carbon nano-tube/poly ether ketone provided by the invention is multiple
Condensation material includes polyether-ketone and the carbon nanotube that is dispersed in polyether-ketone；The present invention is made by adding bisphenol fluorene in polyether-ketone
Polyether-ketone has unique structure, be conducive to form stronger pi-pi bond between the carbon nanotube added in situ, pass through π-π
Sedimentation enables carbon nanotube to be dispersed in polyether-ketone, effectively improves carbon nanotube and polyether-ketone matrix resin
Interface compatibility, improve the mechanical performance and wear-resisting property of composite material.As shown in the Examples, carbon provided by the invention is received
Mitron/polyether-ketone composite material tensile strength is 111.76~126.43MPa, stretch modulus be 1406.15~
1828.56MPa, bending strength are 127.63~148.00MPa, bending modulus is 3669.98~4375.41MPa, extension at break
Rate is 71.06~94.15%.
Specific embodiment
The present invention provides a kind of carbon nano-tube/poly ether ketone composite material, the carbon nano-tube/poly ether ketone composite material packet
The carbon nanotube for including polyether-ketone and being dispersed in polyether-ketone；
The polyether-ketone has structural unit shown in Formulas I:
Wherein x+y=1；X is 1%~10%, preferably 2%~8%, further preferably 4%~6%.
In the present invention, the mass fraction of the carbon nanotube in the composite is 0.1%~10%, preferably
0.1%~8%, further preferably 0.1%~6%, more preferably 0.1%~4%, most preferably 0.1%~2%.This hair
It is bright preferably to control the mass fraction of carbon nanotube in the composite within the above range, be conducive to improve carbon nano-tube/poly
The mechanical performance and wear-resisting property of ether ketone composite material.
Carbon nano-tube/poly ether ketone composite material provided by the invention includes polyether-ketone and the carbon nanometer that is dispersed in polyether-ketone
Pipe；The present invention in polyether-ketone by adding bisphenol fluorene, so that polyether-ketone has unique structure, is conducive to and adds in situ
Stronger pi-pi bond is formed between carbon nanotube, is acted on by pi-pi accumulation, and carbon nanotube is enable to be dispersed in polyether-ketone,
Effectively improve the interface compatibility of carbon nanotube Yu polyether-ketone matrix resin；In addition, the present invention is poly- in situ by carbon nanotube
It closes, is conducive to that carbon nanotube is enable to be dispersed in polyether-ketone matrix, and then be conducive to give full play to the work of carbon nanotube
With improving the mechanical performance and wear-resisting property of composite material.
The present invention also provides the preparation methods of carbon nano-tube/poly ether ketone composite material described in above-mentioned technical proposal, including
Following steps:
(1) by 4,4'- difluoro benzophenone, bisphenol fluorene, to dihydroxy benaophenonel, carbon nanotube, catalyst, dehydrating agent and
Reaction dissolvent mixing, obtains reaction raw materials；The catalyst includes one or both of potassium carbonate and sodium carbonate；
(2) reaction raw materials that the step (1) obtains successively are subjected to azeotropic dehydration, exclude dehydrating agent and polymerization reaction,
Obtain carbon nano-tube/poly ether ketone composite material.
The present invention by 4,4'- difluoro benzophenone, bisphenol fluorene, to dihydroxy benaophenonel, carbon nanotube, catalyst, dehydration
Agent and reaction dissolvent mixing, obtain reaction raw materials.
In the present invention, the hybrid mode is preferred are as follows: disperses carbon nanotube in chloroform, then again by bis-phenol
Fluorenes is scattered in the chloroform dispersion liquid of carbon nanotube, obtains mixed solution.The present invention preferably rotates mixed solution
Processing removes solvent chloroform, obtains bisphenol fluorene and the evenly dispersed mixed-powder of carbon nanotube.It obtains bisphenol fluorene and carbon is received
After evenly dispersed mixed-powder, the present invention is again by above-mentioned mixed-powder and 4,4'- difluoro benzophenone, to hydroxy benzophenone
Ketone, catalyst, dehydrating agent and reaction dissolvent mixing.In the present invention, the dispersion is preferably that ultrasonic disperse and/or machinery stir
It mixes.Present invention preferably employs above-mentioned hybrid mode, be conducive to be dispersed in carbon nanotube in polyether ketone resin matrix, in turn
Be conducive to improve the mechanical performance of carbon nano-tube/poly ether ketone composite material.
In the present invention, 4, the 4'- difluoro benzophenone, bisphenol fluorene and it is preferably to the molar ratio of dihydroxy benaophenonel
0.8~1.2:0.01~0.10:0.9~0.99, further preferably 0.9~1.1:0.02~0.08:0.92~0.98, it is more excellent
It is selected as 1:0.04~0.06:0.94~0.96.In the present invention, the mass ratio of the carbon nanotube and bisphenol fluorene is preferably 0.1
~5:1~10, further preferably 1~4:2~8, more preferably 2~3:4~6.In the present invention, the carbon nanotube is preferred
Including single-walled carbon nanotube and/or multi-walled carbon nanotube.The present invention is preferably by 4,4'- difluoro benzophenone, bisphenol fluorene, to hydroxyl
The quality of benzophenone and carbon nanotube control be conducive to be prepared within the above range the carbon nanotube of good mechanical property/
Polyether-ketone composite material.
In the present invention, the catalyst and 4, the molar ratio of 4'- difluoro benzophenone be preferably 0.01~1.3:1~
1.1, further preferably 0.05~1.0:1~1.1, more preferably 0.1~0.8:1~1.1.In the present invention, the catalysis
Agent includes one or both of potassium carbonate and sodium carbonate, and the present invention preferably adds catalyst potassium carbonate and sodium carbonate, institute simultaneously
The molar ratio for stating potassium carbonate and sodium carbonate is preferably 0.01:1.2, and catalyst is controlled within this range, is conducive to more by the present invention
Fully catalysis reaction carries out, and then is conducive to that carbon nano-tube/poly ether ketone composite material is prepared.In the present invention, described
Dehydrating agent preferably includes dimethylbenzene；The reaction dissolvent preferably includes diphenyl sulphone (DPS).In the present invention, 4, the 4'- difluorodiphenyl
Ketone, bisphenol fluorene are preferably to the quality summation of dihydroxy benaophenonel, carbon nanotube and catalyst and the amount ratio of reaction dissolvent
25~50g:100mL, further preferably 30~45g:100mL.In the present invention, the quality of the dehydrating agent is preferably reacted
The 15%~30% of solvent quality, further preferably 20%~25%.
After obtaining reaction raw materials, the reaction raw materials are successively carried out azeotropic dehydration, exclude dehydrating agent and polymerization by the present invention
Reaction, obtains carbon nano-tube/poly ether ketone composite material.
In the present invention, the azeotropic dehydration, exclusion dehydrating agent and polymerization reaction preferably carry out under protective atmosphere, institute
Stating protective atmosphere is preferably argon atmosphere or nitrogen atmosphere.
In the present invention, the temperature of the azeotropic dehydration is preferably 140~180 DEG C, and further preferably 150~170 DEG C,
The time of the azeotropic dehydration is preferably 1~2h.The present invention is reacted by azeotropic dehydration, the moisture in exclusion system, is avoided pair
Subsequent polymerisation reaction has an impact.
After the reaction was completed, the present invention continues to increase reaction temperature azeotropic dehydration, excludes dehydrating agent.In the present invention, it excludes
The temperature of dehydrating agent is preferably 210~230 DEG C, and the time is preferably 2~3h.
After excluding dehydrating agent, the present invention continues to increase reaction temperature, carries out polymerization reaction.In the present invention, the polymerization
Reaction preferably includes the first polymerization reaction and the second polymerization reaction successively carried out；The temperature of first polymerization reaction is preferably
240~280 DEG C, further preferably 250~270 DEG C, the time is preferably 2~3h；The temperature of second polymerization reaction is preferred
It is 300~310 DEG C, the time is preferably 0.5~1h.Polymerization reaction is preferably divided into two steps and carried out by the present invention, is conducive to make to react
It can sufficiently react between raw material, generate carbon nano-tube/poly ether ketone composite material.
After the completion of polymerization reaction, the present invention is preferably by the reaction solution obtained after polymerization reaction discharging in deionized water, analysis
Solid out.The present invention crushes after preferably drying the solid, is then successively washed and is dried, and carbon nanometer is obtained
Pipe/polyether-ketone composite material.In the present invention, the washing is preferably successively washed using acetone and hot water, the hot water
Temperature be preferably 90~100 DEG C.The present invention preferably sufficiently removes the impurity in target product through the above way.
The present invention also provides carbon nano-tube/poly ether ketone composite material or above-mentioned technical proposals described in above-mentioned technical proposal
Application of the carbon nano-tube/poly ether ketone composite material that the method is prepared as thermoplastic macromolecule material.
In the present invention, application method of the carbon nano-tube/poly ether ketone composite material as thermoplastic macromolecule material
Preferably include following steps:
(a) carbon nano-tube/poly ether ketone composite material is successively squeezed out, is granulated and is dried, obtain composite material
Particle；
(b) composite material granular that the step (a) obtains successively is subjected to injection molding and annealing, obtains thermoplastic
Property high molecular material.
Carbon nano-tube/poly ether ketone composite material is successively squeezed out, be granulated and is dried by the present invention, obtains composite wood
Expect particle.In the present invention, the temperature of the extrusion is preferably 390~400 DEG C, and the revolving speed of the extrusion is preferably 40~50r/
min；The extrusion is preferably double screw extruder with equipment.In the present invention, the temperature of the drying is preferably 100~120
DEG C, the time is preferably 10~14h.
After obtaining composite material granular, the present invention successively carries out the composite material granular at injection molding and annealing
Reason, obtains thermoplastic macromolecule material.
In the present invention, the temperature of the injection molding is preferably 390~400 DEG C, and further preferably 392~398 DEG C；
The pressure of the injection molding is preferably 750~850bar, further preferably 760~840bar, more preferably 770~
820bar.In the present invention, the temperature of the annealing is preferably 230~240 DEG C；Time is preferably 3.5~4.5h.This hair
It is bright by injection molding and annealing, obtain the thermoplastic macromolecule material of better mechanical property.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.
Embodiment 1
It weighs 0.44g multi-walled carbon nanotube to be added in 500mL chloroform, ultrasonic 2h obtains multi-walled carbon nanotube
Chloroform dispersion liquid；It weighs 7g bisphenol fluorene (0.02mol) to be added in the chloroform dispersion liquid of multi-walled carbon nanotube, ultrasound
2h, mechanical stirring 1h, by rotating the powder for obtaining bisphenol fluorene and dispersing multi-walled carbon nanotube.
By 222.56g 4,4'- difluoro benzophenone (1.02mol), the powder of above-mentioned bisphenol fluorene dispersion multi-walled carbon nanotube
End, 210g are to hydroxy benzophenone one monomers (0.98mol), 1.38g Anhydrous potassium carbonate (0.01mol), 127.19g natrium carbonicum calcinatum
(1.2mol), 1317g diphenyl sulphone (DPS) and 200mL dimethylbenzene are packed into three mouthfuls of burnings with argon gas port, mechanical stirring and water-taker
In bottle, it is warming up to 140 DEG C of reflux under argon atmosphere, reacts 2h, is then warming up to 210 DEG C, reacts 3h, excludes dimethylbenzene, after
And 240 DEG C of reaction 2h are warming up to, it is further continued for being warming up to 300 DEG C of reaction 0.5h, obtained reaction material liquid is discharged in deionized water
In, solid is precipitated, through crushing, washing, drying, it is compound to obtain the carbon nano-tube/poly ether ketone that carbon nanotube mass score is 0.1%
Material.
Embodiment 2
It weighs 1.77g multi-walled carbon nanotube to be added in 1000mL chloroform, ultrasonic 2h obtains multi-walled carbon nanotube
Chloroform dispersion liquid；It weighs 8g bisphenol fluorene to be added in the chloroform dispersion liquid of multi-walled carbon nanotube, ultrasonic 2h, machinery stirs
1h is mixed, by rotating the powder for obtaining bisphenol fluorene and dispersing multi-walled carbon nanotube.
By (178g, 0.816mol) 4,4'- difluoro benzophenone, above-mentioned bisphenol fluorene dispersion multi-walled carbon nanotube powder,
(166g, 0.776mol) is to hydroxy benzophenone one monomers, (1.3g, 0.008mol) Anhydrous potassium carbonate, (101g, 0.96mol) nothing
Aqueous sodium carbonate, 1061g diphenyl sulphone (DPS) and 250mL dimethylbenzene are packed into three mouthfuls of burnings with argon gas port, mechanical stirring and water-taker
In bottle, it is warming up to 150 DEG C of reflux under argon atmosphere, reacts 2h, is then warming up to 220 DEG C, reacts 3h, excludes dimethylbenzene.After
And 250 DEG C of reaction 2h are warming up to, and continue to be warming up to 300 DEG C of reaction 0.5h, by the discharging of obtained reaction material liquid in deionized water,
Solid is precipitated, through crushing, washing, drying, obtains the carbon nano-tube/poly ether ketone composite wood that carbon nanotube mass score is 0.5%
Material.
Embodiment 3
It weighs 8.12g multi-walled carbon nanotube to be added in 8000mL chloroform, ultrasonic 2h, weighs the addition of 15g bisphenol fluorene
Into multi-walled carbon nanotube dispersion liquid, ultrasonic 2h, mechanical stirring 1h obtain bisphenol fluorene dispersion multi-walled carbon nanotube by rotating
Powder.
By (200g, 0.918mol) 4,4'- difluoro benzophenone, above-mentioned bisphenol fluorene dispersion multi-walled carbon nanotube powder,
(183g, 0.855mol) is to hydroxy benzophenone one monomers, (1.2g, 0.009mol) Anhydrous potassium carbonate, (114g, 1.08mol) nothing
Aqueous sodium carbonate, 1198g diphenyl sulphone (DPS) and 235mL dimethylbenzene are packed into three mouthfuls of burnings with argon gas port, mechanical stirring and water-taker
In bottle, it is warming up to 180 DEG C of reflux under argon atmosphere, reacts 2h, is then warming up to 230 DEG C, reacts 3h, excludes dimethylbenzene, after
And 260 DEG C of reaction 2h are warming up to, it is further continued for being warming up to 310 DEG C of reaction 0.5h, obtained reaction material liquid is discharged in deionization
In water, solid is precipitated, through crushing, washing, drying, it is compound to obtain the carbon nano-tube/poly ether ketone that carbon nanotube mass score is 2%
Material.
Embodiment 4
It weighs 3.64g single-walled carbon nanotube to be added in 4000mL chloroform, ultrasonic 2h, weighs the addition of 28g bisphenol fluorene
Into single-walled carbon nanotube dispersion liquid, ultrasonic 2h, mechanical stirring 1h obtain bisphenol fluorene dispersion single-walled carbon nanotube by rotating
Powder.
By the powder of (178g, 0.816mol) 4,4'- difluoro benzophenone, above-mentioned the bisphenol fluorene single-walled carbon nanotube dispersed
End, (154g, 0.72mol) are to hydroxy benzophenone one monomers, (1.4g, 0.008mol) Anhydrous potassium carbonate, (101g, 0.96mol)
Natrium carbonicum calcinatum, 1084g diphenyl sulphone (DPS) and 288mL dimethylbenzene are packed into three mouthfuls with argon gas port, mechanical stirring and water-taker
In flask, it is warming up to 170 DEG C of reflux under argon atmosphere, reacts 2h, is then warming up to 220 DEG C, reacts 3h, excludes dimethylbenzene,
Then 270 DEG C of reaction 2h are warming up to, are further continued for being warming up to 305 DEG C of reaction 0.5h, obtained reaction material liquid is discharged in deionization
In water, solid is precipitated, through crushing, washing, drying, it is compound to obtain the carbon nano-tube/poly ether ketone that carbon nanotube mass score is 1%
Material.
Application examples 1
The carbon nano-tube/poly ether ketone composite material that embodiment 1 is prepared successively is squeezed out, is granulated and dried place
Reason, obtains composite material granular, then by composite material granular under conditions of 390 DEG C, 850bar after injection molding, 230
Anneal 4h at DEG C, obtains thermoplastic macromolecule material.
Application examples 2
The carbon nano-tube/poly ether ketone composite material that embodiment 2 is prepared successively is squeezed out, is granulated and dried place
Reason, obtains composite material granular, then by composite material granular under conditions of 395 DEG C, 850bar after injection molding, 230
Anneal 4h at DEG C, obtains thermoplastic macromolecule material.
Application examples 3
The carbon nano-tube/poly ether ketone composite material that embodiment 3 is prepared successively is squeezed out, is granulated and dried place
Reason, obtains composite material granular, then by composite material granular under conditions of 395 DEG C, 850bar after injection molding, 230
Anneal 4h at DEG C, obtains thermoplastic macromolecule material.
Application examples 4
The carbon nano-tube/poly ether ketone composite material that embodiment 4 is prepared successively is squeezed out, is granulated and dried place
Reason, obtains composite material granular, then by composite material granular under conditions of 395 DEG C, 850bar after injection molding, 230
Anneal 4h at DEG C, obtains thermoplastic macromolecule material.
Comparative example 1
By 2.01g multi-walled carbon nanotube, 222.56g 4,4'- difluoro benzophenone (1.02mol), 210g to hydroxyl hexichol
Ketone monomer (0.98mol), 1.38g Anhydrous potassium carbonate (0.01mol), 127.19g natrium carbonicum calcinatum (1.2mol), 1317g bis-
Benzene sulfone and 200mL dimethylbenzene are fitted into the three-necked flask with argon gas port, mechanical stirring and water-taker, in argon atmosphere
Under be warming up to 140 DEG C of reflux, react 2h, be then warming up to 210 DEG C, react 3h, exclude dimethylbenzene, be then warming up to 240 DEG C it is anti-
2h is answered, is further continued for being warming up to 300 DEG C of reaction 0.5h, by the discharging of obtained reaction material liquid in deionized water, solid is precipitated, through powder
Broken, washing, drying, obtain carbon nanotube/pure polyether-ketone composite material.
Compare application examples 1
Carbon nanotube/pure polyether-ketone composite material that comparative example 1 is prepared successively is squeezed out, is granulated and dried place
Reason, obtains composite material granular, then by composite material granular under conditions of 395 DEG C, 850bar after injection molding, 230
Anneal 4h at DEG C, obtains thermoplastic macromolecule material.
Performance test
The mechanical performance for the thermoplastic macromolecule material that application examples 1~4 and comparison application examples 1 are prepared is surveyed
Examination, test method are as follows: the stretching of dumbbell shape is respectively prepared using JIANDA-70 type injection molding machine (Shenzhen heavily fortified point reaches Machinery Co., Ltd.)
Batten (long 75mm/ wide 5mm/ thickness 2mm), bending batten (long 80mm/ wide 10mm/ thickness 4mm), test thermoplastic macromolecule material
Mechanical performance.Test result is as shown in table 1:
1 application examples 1~4 of table and the mechanical performance for comparing 1 thermoplastic macromolecule material of application examples
By 1 test result of table it is found that carbon nano-tube/poly ether ketone composite material provided by the invention has preferable mechanicalness
Can, and the mechanical performance of carbon nano-tube/poly ether ketone composite material provided by the invention is better than carbon nanotube/pure polyether-ketone composite wood
The mechanical performance of material illustrates that carbon nanotube and bisphenol fluorene all have weight for the mechanical performance of raising composite material in the present invention
It acts on.The tensile strength of carbon nano-tube/poly ether ketone composite material provided by the invention is 111.76~126.43MPa, stretching
Modulus is 1406.15~1828.56MPa, bending strength is 127.63~148.00MPa, bending modulus be 3669.98~
4375.41MPa, elongation at break are 71.06~94.15%.
The frictional behaviour for the thermoplastic macromolecule material that application examples 1~4 is prepared is tested, test method are as follows:
Friction batten (long 16.5mm/ wide 9.6mm/ is respectively prepared using JIANDA-70 type injection molding machine (Shenzhen heavily fortified point reaches Machinery Co., Ltd.)
Thick 6.8mm), using the frictional property of UMT-2 type Multifunctional friction testing machine (Bruker, Germany) test thermoplastic macromolecule material
Can, testing standard GB-T3960-1983.Test result is as shown in table 2:
The frictional behaviour of 2 application examples of table, 1~4 thermoplastic macromolecule material
| Performance indicator | Application examples 1 | Application examples 2 | Application examples 3 | Application examples 4 |
| Coefficient of friction | 0.44 | 0.41 | 0.37 | 0.32 |
| Wear rate (mm3/Nm) | 1.25×10-6 | 9.98×10-7 | 7.90×10-7 | 6.88×10-7 |
As shown in Table 2, carbon nano-tube/poly ether ketone friction coefficient of composite material provided by the invention is smaller, and wear rate is lower.
The coefficient of friction of carbon nano-tube/poly ether ketone composite material provided by the invention is 0.32~0.44, and wear rate is 6.88 × 10-7~
1.25×10-6mm3/Nm。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of carbon nano-tube/poly ether ketone composite material, which is characterized in that the carbon nano-tube/poly ether ketone composite material includes
Polyether-ketone and the carbon nanotube being dispersed in polyether-ketone；
The polyether-ketone has structural unit shown in Formulas I:
Wherein x+y=1, x=1%~10%；
The mass fraction of the carbon nanotube in the composite is 0.1%~10%.
2. the preparation method of carbon nano-tube/poly ether ketone composite material described in claim 1, comprising the following steps:
(1) by 4,4'- difluoro benzophenone, bisphenol fluorene, to dihydroxy benaophenonel, carbon nanotube, catalyst, dehydrating agent and reaction
Solvent mixing, obtains reaction raw materials；The catalyst includes one or both of potassium carbonate and sodium carbonate；
(2) reaction raw materials that the step (1) obtains successively are subjected to azeotropic dehydration, exclude dehydrating agent and polymerization reaction, obtained
Carbon nano-tube/poly ether ketone composite material.
3. preparation method according to claim 2, which is characterized in that 4,4'- difluoro benzophenones, bisphenol fluorene and to hydroxyl
The molar ratio of benzophenone is 0.8~1.2:0.01~0.10:0.9~0.99；The mass ratio of the carbon nanotube and bisphenol fluorene
For 0.1~5:1~10.
4. preparation method according to claim 2, which is characterized in that the carbon nanotube include single-walled carbon nanotube and/
Or multi-walled carbon nanotube.
5. preparation method according to claim 2, which is characterized in that the azeotropic dehydration excludes dehydrating agent and polymerization instead
It should be carried out under protective atmosphere.
6. preparation method according to claim 2 or 5, which is characterized in that the temperature of the azeotropic dehydration is 140~180
DEG C, the time is 1~2h.
7. preparation method according to claim 2 or 5, which is characterized in that it is described exclude dehydrating agent temperature be 210~
230 DEG C, the time is 2~3h.
8. preparation method according to claim 2 or 5, which is characterized in that the polymerization reaction includes successively carried out
One polymerization reaction and the second polymerization reaction；The temperature of first polymerization reaction is 240~280 DEG C, and the time is 2~3h；It is described
The temperature of second polymerization reaction is 300~310 DEG C, and the time is 0.5~1h.
9. the method preparation of any one of carbon nano-tube/poly ether ketone composite material described in claim 1 or claim 2~8
Application of the obtained carbon nano-tube/poly ether ketone composite material as thermoplastic macromolecule material.
10. application according to claim 9, which is characterized in that the carbon nano-tube/poly ether ketone composite material is as thermoplastic
The application method of property high molecular material the following steps are included:
(a) carbon nano-tube/poly ether ketone composite material is successively squeezed out, is granulated and is dried, obtain composite material granular；
(b) composite material granular that the step (a) obtains successively is subjected to injection molding and annealing, obtains thermoplasticity height
Molecular material.
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| CN112063151A (en) * | 2020-09-02 | 2020-12-11 | 吉林化工学院 | Multi-walled carbon nanotube and polyaryletherketone compound thermosetting material containing furan benzene side group and preparation method thereof |
| CN113480752A (en) * | 2021-07-26 | 2021-10-08 | 吉林大学 | Polyether-ether-ketone reinforced master batch and preparation method thereof, and polyether-ether-ketone composite material and preparation method thereof |
| CN113652057A (en) * | 2021-09-28 | 2021-11-16 | 吉林大学 | 3D printing high-strength high-toughness polyether-ether-ketone carbon nanotube composite material and preparation method thereof |
| CN117024873A (en) * | 2023-06-15 | 2023-11-10 | 广州力合新材料科技有限公司 | Preparation method of modified polypropylene plastic |
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| CN117024873A (en) * | 2023-06-15 | 2023-11-10 | 广州力合新材料科技有限公司 | Preparation method of modified polypropylene plastic |
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