CN109851776A - A kind of polyarylether ketone/carbon nanotube composite material and preparation method and polyarylether ketone/carbon nanotube composite material film - Google Patents
A kind of polyarylether ketone/carbon nanotube composite material and preparation method and polyarylether ketone/carbon nanotube composite material film Download PDFInfo
- Publication number
- CN109851776A CN109851776A CN201910003378.XA CN201910003378A CN109851776A CN 109851776 A CN109851776 A CN 109851776A CN 201910003378 A CN201910003378 A CN 201910003378A CN 109851776 A CN109851776 A CN 109851776A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- composite material
- nanotube composite
- polyarylether ketone
- ketone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to polymeric material fields, and the present invention provides a kind of polyarylether ketone/carbon nanotube composite material and preparation method and polyarylether ketone/carbon nanotube composite material films.Polyarylether ketone/carbon nanotube composite material provided by the invention has preferable heating conduction.The present invention is by the way of in-situ polymerization by carbon nano-tube filled into polyaryletherketone matrix, fluorenes conjugated structure in carbon nanotube and polymer molecular chain forms pi-pi accumulation effect, be conducive to carbon nanotube to disperse in polyaryletherketone matrix, and then make the polyarylether ketone/carbon nanotube composite material being prepared that there is preferable heating conduction.Embodiment the result shows that, the thermal coefficient of polyarylether ketone/carbon nanotube composite material provided by the invention is 0.13~0.40W/ (mK).
Description
Technical field
The present invention relates to polymeric material field more particularly to a kind of polyarylether ketone/carbon nanotube composite material and its systems
Preparation Method and polyarylether ketone/carbon nanotube composite material film.
Background technique
The fast development of modern science technology and globalised economy, so that high molecular material will be used wider and wider.
High molecular material has light, resistant to chemical etching, the advantages that easy processing forms, but most of high molecular material heating conduction compared with
Difference, which limits its applications in certain fields, and therefore, the heating conduction for improving high molecular material is of crucial importance.
Improve high molecular material thermal coefficient generally there are two types of approach, intrinsic is led first is that improving its by Molecular Design
Hot property, PVA is blended with polymeric matrix by extruder patent of invention CN103183964A is prepared for containing conjugated double bond
The heat-conductive composite material of carbon-chain structure, the composite material exhibits go out good heating conduction；Second is that by dosing high thermal conductivity coefficient
Filler improves high molecular material heating conduction.Carbon nanotube can theoretically greatly improve macromolecule material as high thermal conductivity filler
The thermal conductivity of material.However the Van der Waals force, capillarity and electrostatic effect between carbon nanotube make carbon nanotube in matrix resin
In be difficult to be uniformly dispersed.Therefore, how to realize that effective dispersion of the carbon nanotube in matrix resin is that raising composite material is thermally conductive
The key of performance.
Summary of the invention
The present invention provides a kind of polyarylether ketone/carbon nanotube composite material and preparation methods and poly(aryl ether ketone)/carbon to receive
Mitron composite material film, polyarylether ketone/carbon nanotube composite material thermal conductivity provided by the invention is preferable, and thermal coefficient is
0.13~0.40W/ (mK).
The present invention provides a kind of polyarylether ketone/carbon nanotube composite material, the carbon nanotube is dispersed in poly(aryl ether ketone)
In matrix, the poly(aryl ether ketone) has structure shown in Formulas I:
Preferably, in the polyarylether ketone/carbon nanotube composite material carbon nanotube mass fraction be 0.1%~
30%.
The present invention provides the preparation methods of polyarylether ketone/carbon nanotube composite material described in above-mentioned technical proposal, including
Following steps:
(1) by carbon nanotube, bisphenol fluorene, 4,4 '-difluoro benzophenones, bisphenol-A, catalyst, dehydrating agent and organic solvent
Mixing, obtains mixed liquor；The catalyst is one of sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate and sodium hydroxide
Or it is a variety of；
(2) under protection of argon gas, the mixed liquor step (1) obtained carries out azeotropic dehydration, then removal dehydration
Agent obtains polyarylether ketone/carbon nanotube composite material.
Preferably, in the step (1) bisphenol fluorene and bisphenol-A total mole number and 4, mole of 4 '-difluoro benzophenones
Ratio between number is 0.9~1.2:0.9~1.2.
Preferably, the quality of carbon nanotube passes through the polyarylether ketone/carbon nanotube being finally prepared in the step (1)
The mass fraction of carbon nanotube determines in composite material.
Preferably, the solid content of mixed liquor is 15%~35% in the step (1).
Preferably, the temperature of azeotropic dehydration is 120~140 DEG C in the step (2), and the time is 1~3h.
Preferably, the step (2) removes dehydrating agent by the way of reflux, and the temperature of the reflux is 150~170
℃。
It preferably, further include the precipitation by reaction product discharging in deionized water after step (2) the removal dehydrating agent
Solid, the solid is washed and dry, obtains polyarylether ketone/carbon nanotube composite material.
The present invention also provides polyarylether ketone/carbon nanotube composite material film described in above-mentioned technical proposal, the film
In polyarylether ketone/carbon nanotube composite material be above-mentioned technical proposal described in polyarylether ketone/carbon nanotube composite material, or
The polyarylether ketone/carbon nanotube composite material being prepared for above-mentioned technical proposal the method
The present invention provides a kind of polyarylether ketone/carbon nanotube composite material, poly(aryl ether ketone) provided by the invention/carbon nanometer
Pipe composite material has preferable heating conduction.The present invention also provides the systems of the polyarylether ketone/carbon nanotube composite material
Preparation Method, by the way of in-situ polymerization by carbon nano-tube filled into polyaryletherketone matrix, carbon nanotube and polymer molecule
Fluorenes conjugated structure in chain forms pi-pi accumulation effect, is conducive to carbon nanotube and disperses in polyaryletherketone matrix, and then makes to prepare
Obtained polyarylether ketone/carbon nanotube composite material has preferable heating conduction.Embodiment the result shows that, it is provided by the invention
The thermal coefficient of polyarylether ketone/carbon nanotube composite material is 0.13~0.40W/ (mK).
Detailed description of the invention
Fig. 1 is the SEM figure of polyarylether ketone/carbon nanotube composite material prepared by the embodiment of the present invention 1；
Fig. 2 is the hydrogen nuclear magnetic spectrogram of polyarylether ketone/carbon nanotube composite material prepared by the embodiment of the present invention 2；
Fig. 3 is the SEM figure for the polyarylether ketone/carbon nanotube composite material that the embodiment of the present invention 5 is prepared.
Specific embodiment
The present invention provides a kind of polyarylether ketone/carbon nanotube composite material, the carbon nanotube is dispersed in poly(aryl ether ketone)
In matrix, the poly(aryl ether ketone) has structure shown in Formulas I:
In the present invention, in Formulas I n be preferably (0,1], further preferably 0.3~0.7.
In the present invention, the mass fraction of carbon nanotube is preferably in the polyarylether ketone/carbon nanotube composite material
0.1%~30%, further preferably 1%~25%, more preferably 5%~20%, most preferably 10%~15%.
In polyarylether ketone/carbon nanotube composite material provided by the invention, the carbon nanotube is in polyaryletherketone matrix
Dispersibility preferably so that the heating conduction of polyarylether ketone/carbon nanotube composite material is preferable.
The present invention also provides the preparation method of polyarylether ketone/carbon nanotube composite material described in above-mentioned technical proposal, packets
Include following steps:
(1) by carbon nanotube, bisphenol fluorene, 4,4 '-difluoro benzophenones, bisphenol-A, catalyst, dehydrating agent and organic solvent
Mixing, obtains mixed liquor；The catalyst is one of sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate and sodium hydroxide
Or it is a variety of；
(2) under protection of argon gas, the mixed liquor step (1) obtained carries out azeotropic dehydration, then removal dehydration
Agent obtains polyarylether ketone/carbon nanotube composite material.
In the present invention, all raw materials are commercial goods.
The present invention is by carbon nanotube, bisphenol fluorene, 4,4 '-difluoro benzophenones, bisphenol-A, catalyst, dehydrating agent and organic molten
Agent mixing, obtains mixed liquor.The present invention does not specially require the size of carbon nanotube.The present invention is preferably first by carbon nanometer
Pipe, bisphenol fluorene and organic solvent mixing, then again with 4,4 '-difluoro benzophenones, bisphenol-A, catalyst and dehydrating agent mixing have
Conducive to fully dispersed between raw material.In the present invention, the total mole number and 4 of bisphenol fluorene and bisphenol-A, 4 '-difluoro benzophenones
Molal quantity between ratio be preferably 0.9~1.2:0.9~1.2, further preferably 1.0~1.1:1.0~1.1.At this
In invention, the quality of the carbon nanotube gated carbon in the polyarylether ketone/carbon nanotube composite material being finally prepared
The mass fraction of nanotube determines；The carbon nanotube mass fraction=carbon nanotube quality ÷ (quality of carbon nanotube+
The quality of polymer) × 100%, the small molecule quality that quality=raw material weight summation-reaction of the polymer is sloughed.?
In the present invention, the dehydrating agent is preferably one of benzene,toluene,xylene and hexamethylene or a variety of；The organic solvent is excellent
Choosing includes in dioxane, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, sulfolane and N-Methyl pyrrolidone
It is one or more.In the present invention, the solid content of the mixed liquor is preferably 15%~35%, and further preferably 20%
~30%.
After obtaining mixed liquor, the present invention carries out azeotropic dehydration under protection of argon gas, by the mixed liquor, then removes
Dehydrating agent obtains polyarylether ketone/carbon nanotube composite material.In the present invention, the temperature of the azeotropic dehydration be preferably 120~
140 DEG C, further preferably 125~135 DEG C；Time is preferably 1~3h, further preferably 1.5~2.5h.The present invention is altogether
It boils in dehydration, the bisphenol fluorene, 4, polycondensation reaction occurs for 4 '-difluoro benzophenones and bisphenol-A, generates poly(aryl ether ketone).
After the completion of azeotropic dehydration, the present invention removes dehydrating agent.Present invention preferably employs the modes of reflux to remove dehydrating agent, institute
The temperature for stating reflux is preferably 150~170 DEG C, and further preferably 155~165 DEG C；Time is preferably 1.5~2.5h.
After removing dehydrating agent, solid, the solid warp is precipitated preferably by reaction product discharging in deionized water in the present invention
Washing and drying, obtain polyarylether ketone/carbon nanotube composite material.The present invention is washed to solid and dry specific embodiment
It does not specially require, using mode well-known to those skilled in the art.
The present invention prepares polyarylether ketone/carbon nanotube composite material, during the reaction, carbon by the way of in-situ polymerization
Fluorenes conjugated structure in nanotube and polymer molecular chain forms pi-pi accumulation effect, is conducive to carbon nanotube in polyarylether ketone group
Disperse in body, and then is conducive to improve the heating conduction of polyarylether ketone/carbon nanotube composite material.
In the present invention, the polyarylether ketone/carbon nanotube composite material or the preparation of above-mentioned technical proposal the method
The mass fraction of fluorene group is preferably 10%~70% in obtained polyarylether ketone/carbon nanotube composite material, further preferably
It is 30%~50%, most preferably 30%.
The present invention also provides a kind of polyarylether ketone/carbon nanotube composite material films.In the present invention, in the film
Polyarylether ketone/carbon nanotube composite material be above-mentioned technical proposal described in polyarylether ketone/carbon nanotube composite material, Huo Zhewei
The polyarylether ketone/carbon nanotube composite material that above-mentioned technical proposal the method is prepared.
Present invention preferably employs solution casting method or hot pressing membrane formation process, to prepare polyarylether ketone/carbon nanotube composite material thin
The specific embodiment of the solution casting method or hot pressing membrane formation process is not particularly limited in film, the present invention, using this field skill
Mode known to art personnel.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.
Embodiment 1: the polyarylether ketone/carbon nanotube composite material that fluorenes content is 10%
Carbon nanotube (5.23g), N-Methyl pyrrolidone (129mL), bisphenol fluorene (1.75g, 0.005mol) are packed into 250mL
In three-necked flask ultrasound 1 hour after, by 4,4 '-difluoro benzophenones (10.91g, 0.05mol), bisphenol-A (10.27g,
0.045mol), Anhydrous potassium carbonate (8.293g, 0.06mol) and toluene (45mL) are fitted into flask, under an argon atmosphere, machine
Tool stirs 0.5 hour, is warming up to 140 DEG C, and azeotropic dehydration reflux, band water flows back 2 hours, excludes azeotropy dehydrant, is warming up to 180
DEG C, the reaction was continued 3 hours, and obtained polymer solution is precipitated in deionized water, and through crushing, washing, drying, fluorenes is made
The polyarylether ketone/carbon nanotube composite material that content is 10%.
Embodiment 2: the polyarylether ketone/carbon nanotube composite material that fluorenes content is 30%
Carbon nanotube (5.53g), N-Methyl pyrrolidone (133mL), bisphenol fluorene (5.25g, 0.015mol) are packed into 250mL
In three-necked flask ultrasound 1 hour after, by 4,4 '-difluoro benzophenones (10.91g, 0.05mol), bisphenol-A (7.99g,
0.035mol), Anhydrous potassium carbonate (8.293g, 0.06mol) and toluene (46mL) are fitted into flask, under an argon atmosphere, machine
Tool stirs 0.5 hour, is warming up to 145 DEG C, and azeotropic dehydration reflux, band water flows back 2.5 hours, excludes azeotropy dehydrant, is warming up to
180 DEG C, the reaction was continued 3.5 hours, and obtained polymer solution is precipitated in deionized water, through crushing, washing, drying,
The polyarylether ketone/carbon nanotube composite material that fluorenes content is 30% is made.
Embodiment 3: the polyarylether ketone/carbon nanotube composite material that fluorenes content is 50%
Carbon nanotube (5.84g), N-Methyl pyrrolidone (144mL), bisphenol fluorene (8.76g, 0.025mol) are packed into 250mL
In three-necked flask ultrasound 1 hour after, by 4,4 '-difluoro benzophenones (10.91g, 0.05mol), bisphenol-A (5.71g,
0.025mol), Anhydrous potassium carbonate (8.293g, 0.06mol) and toluene (50mL) are fitted into flask, under an argon atmosphere, machine
Tool stirs 0.5 hour, is warming up to 147 DEG C, and azeotropic dehydration reflux, band water flows back 3 hours, excludes azeotropy dehydrant, is warming up to 180
DEG C, the reaction was continued 3 hours, and obtained polymer solution is precipitated in deionized water, and through crushing, washing, drying, fluorenes is made
The polyarylether ketone/carbon nanotube composite material that content is 50%.
Embodiment 4: the polyarylether ketone/carbon nanotube composite material that fluorenes content is 70%
Carbon nanotube (6.15g), N-Methyl pyrrolidone (150mL), bisphenol fluorene (12.26g, 0.035mol) are packed into
In 250mL three-necked flask ultrasound 1 hour after, by 4,4 '-difluoro benzophenones (10.91g, 0.05mol), bisphenol-A (3.42g,
0.015mol), Anhydrous potassium carbonate (8.293g, 0.06mol) and toluene (53mL) are fitted into flask, under an argon atmosphere, machine
Tool stirs 0.5 hour, is warming up to 160 DEG C, and azeotropic dehydration reflux, band water flows back 3 hours, excludes azeotropy dehydrant, is warming up to 180
DEG C, the reaction was continued 4 hours, and obtained polymer solution is precipitated in deionized water, and through crushing, washing, drying, fluorenes is made
The polyarylether ketone/carbon nanotube composite material that content is 70%.
SEM test, test result difference are carried out to the polyarylether ketone/carbon nanotube composite material that embodiment 1 is prepared
As shown in Figure 1.In Fig. 1, white point represents carbon nanotube, as shown in Figure 1, the polyarylether ketone/carbon nanotube that embodiment 1 is prepared
The dispersion effect of carbon nanotube is preferable in composite material.The polyarylether ketone/carbon nanotube composite wood that embodiment 2~4 is prepared
The SEM spectrogram of material is similar with Fig. 1, illustrates that carbon is received in polyarylether ketone/carbon nanotube composite material that embodiment 2~4 is prepared
The dispersion effect of mitron is preferable.It is no longer repeated herein.
Proton magnetic tester is carried out to the polyarylether ketone/carbon nanotube composite material that embodiment 2 is prepared, test result is such as
It is-CH at 1.699ppm in Fig. 2 shown in Fig. 23Characteristic peak is the characteristic peak of fluorenes at 6.8-7.8ppm, shows synthesized poly- virtue
Ether ketone/carbon nano tube compound material structure is consistent with expected structure.By the integral and-CH of the hydrogen (6.7-7.8ppm) of fluorenes3's
The integral ratio of methoxy hydrogen, the content that fluorenes conjugation group in polyarylether ketone/carbon nanotube composite material can be calculated are
30%.Similarly, embodiment 1, embodiment 3 and the identical calculation method of the use of embodiment 4, obtain embodiment 1, embodiment 3 and reality
The content for applying the conjugation group of fluorenes in the polyarylether ketone/carbon nanotube composite material that example 4 is prepared is respectively 10%, 50%,
70%.
It is 30% by fluorenes content control in polyarylether ketone/carbon nanotube composite material, adjusts the content of carbon nanotube, carry out
Embodiment 5~10.
Embodiment 5: the polyarylether ketone/carbon nanotube composite material that carbon nanotube mass score is 0.1%
Carbon nanotube (0.02g), N-Methyl pyrrolidone (133mL), bisphenol fluorene (5.25g, 0.015mol) are packed into 250mL
In three-necked flask ultrasound 1 hour after, by 4,4 '-difluoro benzophenones (10.91g, 0.05mol), bisphenol-A (7.99g,
0.035mol), Anhydrous potassium carbonate (8.293g, 0.06mol) and toluene (46mL) are fitted into flask, under an argon atmosphere, machine
Tool stirs 0.5 hour, is warming up to 155 DEG C, and azeotropic dehydration reflux, band water flows back 3 hours, excludes azeotropy dehydrant, is warming up to 180
DEG C, the reaction was continued 3 hours, and obtained polymer solution is precipitated in deionized water, and through crushing, washing, drying, carbon is made
The polyarylether ketone/carbon nanotube composite material of Nanotube quality score 0.1%.
Embodiment 6: the polyarylether ketone/carbon nanotube composite material that carbon nanotube mass score is 1%
Carbon nanotube (0.22g), N-Methyl pyrrolidone (133mL), bisphenol fluorene (5.25g, 0.015mol) are packed into 250mL
In three-necked flask ultrasound 1 hour after, by 4,4 '-difluoro benzophenones (10.91g, 0.05mol), bisphenol-A (7.99g,
0.035mol), Anhydrous potassium carbonate (8.293g, 0.06mol) and toluene (46mL) are fitted into flask, under an argon atmosphere, machine
Tool stirs 1 hour, is warming up to 160 DEG C, and azeotropic dehydration reflux, band water flows back 3 hours, excludes azeotropy dehydrant, is warming up to 180
DEG C, the reaction was continued 4 hours, and obtained polymer solution is precipitated in deionized water, and through crushing, washing, drying, carbon is made
The polyarylether ketone/carbon nanotube composite material of Nanotube quality score 1%.
Embodiment 7: the polyarylether ketone/carbon nanotube composite material that carbon nanotube mass score is 5%
Carbon nanotube (1.16g), N-Methyl pyrrolidone (133mL), bisphenol fluorene (5.25g, 0.015mol) are packed into 250mL
In three-necked flask ultrasound 1 hour after, by 4,4 '-difluoro benzophenones (10.91g, 0.05mol), bisphenol-A (7.99g,
0.035mol), Anhydrous potassium carbonate (8.293g, 0.06mol) and toluene (46mL) are fitted into flask, under an argon atmosphere, machine
Tool stirs 1 hour, is warming up to 160 DEG C, and azeotropic dehydration reflux, band water flows back 3 hours, excludes azeotropy dehydrant, is warming up to 180
DEG C, the reaction was continued 3 hours, and obtained polymer solution is precipitated in deionized water, and through crushing, washing, drying, carbon is made
The polyarylether ketone/carbon nanotube composite material of Nanotube quality score 5%.
Embodiment 8: the polyarylether ketone/carbon nanotube composite material that carbon nanotube mass score is 10%
Carbon nanotube (2.46g), N-Methyl pyrrolidone (133mL), bisphenol fluorene (5.25g, 0.015mol) are packed into 250mL
In three-necked flask ultrasound 1 hour after, by 4,4 '-difluoro benzophenones (10.91g, 0.05mol), bisphenol-A (7.99g,
0.035mol), Anhydrous potassium carbonate (8.293g, 0.06mol) and toluene (46mL) are fitted into flask, under an argon atmosphere, machine
Tool stirs 1 hour, is warming up to 150 DEG C, and azeotropic dehydration reflux, band water flows back 2 hours, excludes azeotropy dehydrant, is warming up to 180
DEG C, the reaction was continued 3 hours, and obtained polymer solution is precipitated in deionized water, and through crushing, washing, drying, carbon is made
The polyarylether ketone/carbon nanotube composite material of Nanotube quality score 10%.
Embodiment 9: the polyarylether ketone/carbon nanotube composite material that carbon nanotube mass score is 15%
Carbon nanotube (3.91g), N-Methyl pyrrolidone (133mL), bisphenol fluorene (5.25g, 0.015mol) are packed into 250mL
In three-necked flask ultrasound 1 hour after, by 4,4 '-difluoro benzophenones (10.91g, 0.05mol), bisphenol-A (7.99g,
0.035mol), Anhydrous potassium carbonate (8.293g, 0.06mol) and toluene (46mL) are fitted into flask, under an argon atmosphere, machine
Tool stirs 1 hour, is warming up to 158 DEG C, and azeotropic dehydration reflux, band water flows back 2 hours, excludes azeotropy dehydrant, is warming up to 180
DEG C, the reaction was continued 2 hours, and obtained polymer solution is precipitated in deionized water, and through crushing, washing, drying, carbon is made
The polyarylether ketone/carbon nanotube composite material of Nanotube quality score 15%.
Embodiment 10: the polyarylether ketone/carbon nanotube composite material that carbon nanotube mass score is 20%
Carbon nanotube (5.53g), N-Methyl pyrrolidone (133mL), bisphenol fluorene (5.25g, 0.015mol) are packed into 250mL
In three-necked flask ultrasound 1 hour after, by 4,4 '-difluoro benzophenones (10.91g, 0.05mol), bisphenol-A (7.99g,
0.035mol), Anhydrous potassium carbonate (8.293g, 0.06mol) and toluene (46mL) are fitted into flask, under an argon atmosphere, machine
Tool stirs 1 hour, is warming up to 160 DEG C, and azeotropic dehydration reflux, band water flows back 3 hours, excludes azeotropy dehydrant, is warming up to 180
DEG C, the reaction was continued 1 hour, and obtained polymer solution is precipitated in deionized water, and through crushing, washing, drying, carbon is made
The polyarylether ketone/carbon nanotube composite material of Nanotube quality score 20%.
Comparative example 1
It is tested according to the method for embodiment 5, difference is, do not add carbon nanotube, content of carbon nanotubes 0%,
Poly(aryl ether ketone) is prepared.
Electronic Speculum test is scanned to the polyarylether ketone/carbon nanotube composite material that embodiment 5 is prepared, as a result as schemed
Shown in 3.Carbon nanotube is dispersed in polyaryletherketone matrix as shown in Figure 3.
Polyarylether ketone/carbon nanotube composite material and comparative example 1 that embodiment 6~10 is prepared are prepared poly-
Aryl ether ketone is respectively adopted solution casting method and is prepared into polyarylether ketone/carbon nanotube composite material film and polyaryletherketone film, right
The thermal conductivity of film is tested, and test result is as shown in table 1:
The thermal coefficient of 1 embodiment 6~10 of table and comparative example 1
According to 1 test result of table it is found that the polyarylether ketone/carbon nanotube composite material film that is prepared of the present invention is thermally conductive
Better performances, thermal coefficient are 0.13~0.40W/ (mK).
In conclusion the content control of fluorenes in polyarylether ketone/carbon nanotube composite material is 10%~70% by the present invention,
Content of carbon nanotubes control is 0.1%~30%, so that carbon nanotube is well dispersed in polyaryletherketone matrix, effectively mentions
The high heating conduction of polyarylether ketone/carbon nanotube composite material.
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 polyarylether ketone/carbon nanotube composite material, the carbon nanotube are dispersed in polyaryletherketone matrix, the poly- virtue
Ether ketone has structure shown in Formulas I:
2. polyarylether ketone/carbon nanotube composite material according to claim 1, which is characterized in that the poly(aryl ether ketone)/carbon
The mass percent of carbon nanotube is 0.1%~30% in nanometer tube composite materials.
3. the preparation method of polyarylether ketone/carbon nanotube composite material as claimed in claim 1 or 2, comprising the following steps:
(1) by carbon nanotube, bisphenol fluorene, 4,4 '-difluoro benzophenones, bisphenol-A, catalyst, dehydrating agent and organic solvent are mixed,
Obtain mixed liquor；The catalyst is one of sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate and sodium hydroxide or more
Kind；
(2) under protection of argon gas, the mixed liquor step (1) obtained carries out azeotropic dehydration, then removes dehydrating agent, obtains
To polyarylether ketone/carbon nanotube composite material.
4. preparation method according to claim 3, which is characterized in that bisphenol fluorene and bisphenol-A always rubs in the step (1)
Ratio between that number and the molal quantity of 4,4 '-difluoro benzophenones is 0.9~1.2:0.9~1.2.
5. preparation method according to claim 3 or 4, which is characterized in that the quality of carbon nanotube is logical in the step (1)
The mass fraction for crossing carbon nanotube in the polyarylether ketone/carbon nanotube composite material being finally prepared determines.
6. preparation method according to claim 3 or 4, which is characterized in that the solid content of mixed liquor in the step (1)
It is 15%~35%.
7. preparation method according to claim 3, which is characterized in that the temperature of azeotropic dehydration is 120 in the step (2)
~140 DEG C, the time is 1~3h.
8. preparation method according to claim 3 or 7, which is characterized in that the step (2) is removed by the way of reflux
Dehydrating agent, the temperature of the reflux are 150~170 DEG C.
9. preparation method according to claim 3, which is characterized in that after the step (2) removal dehydrating agent, further include by
Reaction product discharges in deionized water, and solid is precipitated, and the solid is washed and dry, obtains polyarylether ketone/carbon nanotube
Composite material.
10. a kind of polyarylether ketone/carbon nanotube composite material film, which is characterized in that poly(aryl ether ketone)/carbon in the film is received
Mitron composite material is polyarylether ketone/carbon nanotube composite material as claimed in claim 1 or 2, or is claim 3~8 times
The polyarylether ketone/carbon nanotube composite material that one the method is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910003378.XA CN109851776B (en) | 2019-01-03 | 2019-01-03 | Polyaryletherketone/carbon nanotube composite material, preparation method thereof and polyaryletherketone/carbon nanotube composite material film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910003378.XA CN109851776B (en) | 2019-01-03 | 2019-01-03 | Polyaryletherketone/carbon nanotube composite material, preparation method thereof and polyaryletherketone/carbon nanotube composite material film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109851776A true CN109851776A (en) | 2019-06-07 |
| CN109851776B CN109851776B (en) | 2020-07-14 |
Family
ID=66893743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910003378.XA Active CN109851776B (en) | 2019-01-03 | 2019-01-03 | Polyaryletherketone/carbon nanotube composite material, preparation method thereof and polyaryletherketone/carbon nanotube composite material film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109851776B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183647A (en) * | 2019-06-18 | 2019-08-30 | 吉林大学 | A kind of carbon nano-tube/poly ether ketone composite material and preparation method and application |
| CN110527247A (en) * | 2019-09-09 | 2019-12-03 | 吉林大学 | A kind of dual network polyether-ether-ketone composite material and its preparation method and application |
| 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 |
| CN114507356A (en) * | 2022-02-28 | 2022-05-17 | 吉林大学 | Phenolphthalein-based polyaryletherketone-carbon nanotube graft and preparation method thereof, and polyetheretherketone heat-conducting composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4889909A (en) * | 1987-07-29 | 1989-12-26 | Rohm Gmbh | Thermoplastic polyarylene ethers |
| CN103788619A (en) * | 2014-01-21 | 2014-05-14 | 西南石油大学 | Polyaryletherketone nano composite material and preparation method thereof |
-
2019
- 2019-01-03 CN CN201910003378.XA patent/CN109851776B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4889909A (en) * | 1987-07-29 | 1989-12-26 | Rohm Gmbh | Thermoplastic polyarylene ethers |
| CN103788619A (en) * | 2014-01-21 | 2014-05-14 | 西南石油大学 | Polyaryletherketone nano composite material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| D.S. BANGARUSAMPATH ET AL.: "Rheology and properties of melt-processed poly(ether ether ketone)/multi-wall carbon nanotube composites", 《POLYMER》 * |
| YINGSHUANG SHANG ET AL.: "Functionalization of multi-walled carbon nanotubes and their effect on the tribological properties of poly(ether ether ketone) composites", 《SOCIETY OF CHEMICAL INDUSTRY》 * |
| 周文英等: "《导热高分子材料》", 30 April 2014 * |
| 宋波: "《塑料改性技术》", 31 October 2016, 中国纺织出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110183647A (en) * | 2019-06-18 | 2019-08-30 | 吉林大学 | A kind of carbon nano-tube/poly ether ketone composite material and preparation method and application |
| CN110527247A (en) * | 2019-09-09 | 2019-12-03 | 吉林大学 | A kind of dual network polyether-ether-ketone composite material and its preparation method and application |
| CN110527247B (en) * | 2019-09-09 | 2020-07-03 | 吉林大学 | Double-network polyether-ether-ketone composite material and preparation method and application 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 |
| CN113480752B (en) * | 2021-07-26 | 2022-04-15 | 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 |
| CN114507356A (en) * | 2022-02-28 | 2022-05-17 | 吉林大学 | Phenolphthalein-based polyaryletherketone-carbon nanotube graft and preparation method thereof, and polyetheretherketone heat-conducting composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109851776B (en) | 2020-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109851776A (en) | A kind of polyarylether ketone/carbon nanotube composite material and preparation method and polyarylether ketone/carbon nanotube composite material film | |
| Gao et al. | High-efficiency electromagnetic interference shielding realized in nacre-mimetic graphene/polymer composite with extremely low graphene loading | |
| Wei et al. | Conductive herringbone structure carbon nanotube/thermoplastic polyurethane porous foam tuned by epoxy for high performance flexible piezoresistive sensor | |
| Bin et al. | Morphology and mechanical and electrical properties of oriented PVA–VGCF and PVA–MWNT composites | |
| Song et al. | Striking multiple synergies created by combining reduced graphene oxides and carbon nanotubes for polymer nanocomposites | |
| Wang et al. | Fibrous nanocomposites of carbon nanotubes and graphene-oxide with synergetic mechanical and actuative performance | |
| Sun et al. | Thermal properties of polyethylene glycol/carbon microsphere composite as a novel phase change material | |
| EP1789477A2 (en) | Carbon nanotube reinforced polymer nanocomposites | |
| Kim et al. | Material selection windows for hybrid carbons/poly (phenylene sulfide) composite for bipolar plates of fuel cell | |
| CN101955631A (en) | Preparation method of polyaniline modified multi-wall carbon canotube/epoxy resin composite material | |
| Zhang et al. | Enhanced thermal conductivity of polyvinyl alcohol insulation composites with m-BN@ CNW hybrid materials | |
| An et al. | A novel environmentally friendly boron nitride/lignosulfonate/natural rubber composite with improved thermal conductivity | |
| Wang et al. | Simultaneous enhancement of mechanical and electrical/thermal properties of carbon fiber/polymer composites via SiC nanowires/graphene hybrid nanofillers | |
| Yao et al. | Thermal management of electronics and thermoelectric power generation from waste heat enabled by flexible Kevlar@ SiC thermal conductive materials with liquid-crystalline orientation | |
| CN109243670A (en) | A method of enhancing three-dimensional graphene framework structure prepares three-dimensional grapheme/polymer composite material | |
| Zhu et al. | Nacre-like composite films with a conductive interconnected network consisting of graphene oxide, polyvinyl alcohol and single-walled carbon nanotubes | |
| Wang et al. | Morphological, electrical, thermal and mechanical properties of phthalocyanine/multi-wall carbon nanotubes nanocomposites prepared by masterbatch dilution | |
| Zou et al. | Low dielectric permittivity and high thermal stability composites based on crosslinkable poly (arylene ether nitrile) and hollow glass microsphere | |
| Mei et al. | Dramatic increase in electrical conductivity in epoxy composites with uni-directionally oriented laminae of carbon nanotubes | |
| Lin et al. | The effects of MWCNT length on the mechanical, crystallization and electromagnetic interference shielding effectiveness of PP/MWCNT composites | |
| CN106633373B (en) | Carbon nanotube/polypropylene composite powder material for S L S and preparation method thereof | |
| Lai et al. | Enhanced positive temperature coefficient in amorphous PS/CSPE‐MWCNT composites with low percolation threshold | |
| CN110105756A (en) | A kind of high tenacity high thermal conductivity PBONF based coextruded film and preparation method thereof | |
| Wang et al. | Synchronously enhanced thermal properties and fracture toughness of epoxy composites through melamine foam templated dispersion of carbon nanofibers | |
| Zhang et al. | Polymer nanocomposites using urchin‐shaped carbon nanotube‐silica hybrids as reinforcing fillers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |