CN104725630B - Containing pyrene PAEK, preparation method and the application in SWCN/polyether-ether-ketone composite material - Google Patents
Containing pyrene PAEK, preparation method and the application in SWCN/polyether-ether-ketone composite material Download PDFInfo
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Abstract
A kind of containing pyrene PAEK, preparation method and the application in modified SWCN/polyether-ether-ketone composite material thereof, belong to field of polymer material preparing technology.PAEK first with boracic acid esters reacts preparation PAEK Han pyrene with 1 bromine pyrene monomer under four triphenylphosphine palladium chtalyst；Then, utilization carries out physical modification containing pyrene PAEK to SWCN.Finally, the SWCN of functionalization and polyether-ether-ketone are prepared SWCN/polyether-ether-ketone composite material by the method for solution blending, owing to SWCN having been carried out surface modification containing pyrene PAEK, SWCN is uniformly dispersed in polyether-ether-ketone.Therefore, this PAEK containing pyrene is expected to become the coupling agent of the CNT of a kind of excellence, can efficiently solve CNT agglomeration traits in PAEK system.
Description
Technical field
The invention belongs to field of polymer material preparing technology, be specifically related to a kind of containing pyrene PAEK, preparation method
And the application in modified SWCN/polyether-ether-ketone composite material.
Background technology
Pyrene has typical multi-aromatic ring structure, due to its distinctive structure and Photophysics, plane condensed-nuclei aromatics
Pyrene and derivant thereof are at fluorescence probe, organic electroluminescent LED, organic field effect tube, solar energy
The fields such as battery have a wide range of applications.The number of substituent group, classification and position are affect pyrene derivatives several big heavy
Want factor.They are with the conjugated degree of pyrene chromophore, space structure, amount of rigidity and electronic induction effect etc. all
The photoelectron performance of molecule can be produced material impact.Produce it addition, pyrene can also be piled up with graphite underrun π key
The strongest raw interaction, be used for disperses SWCN more.Send out at calendar year 2001 Chen etc.
Existing pyrene has the strongest interaction with the sidewall of CNT.From that time, the different little molecule chemical combination containing pyrene
Thing is synthesized and is used for the non-covalent functionalization research of CNT.As may be expected, this functionalization
CNT all shows compared with the more preferable dispersibility of pure nano-carbon tube in water or organic solvent.But, for
For preparing Polymer/carbon Nanotubes Composites by solution methods, the concentration of CNT is the lowest, and
Dispersion stabilization is poor.Compared with little dispersal agent molecule, macromole has longer segment to be thus able to provide more
Dissolve site make that there is between CNT mutually exclusive enough spatial volumes simultaneously, ultimately facilitate carbon
The dispersion of nanotube.But apply in polyarylether system and also rarely have report.
Summary of the invention
It is an object of the invention to the PAEK by boracic acid esters and prepare the polyarylether Han pyrene with 1-bromine pyrene monomer reaction
Ketone, what recycling obtained carries out physical modification, and then preparation functionalization list containing pyrene PAEK to SWCN
Wall carbon nano tube/polyether-ether-ketone composite material.
First the present invention is to be reacted by bisphenol-A and the fluoro-benzophenone of 4,4`-bis-to obtain bisphenol A type polyaromatic ether ketone
(PAEK), then 1,5-cyclo-octadiene iridium chloride dimer and 4,4 '-di-t-butyl-2, the common work of 2 '-bipyridyl
React with connection pinacol borate generation boronation with lower, prepare the PAEK of boracic acid esters；Gathering of boracic acid esters
Aryl ether ketone reacts generation polyarylether Han pyrene with 1-bromine pyrene again under the common effect of four triphenylphosphine palladiums and potassium carbonate
Ketone.
The present invention has selected the catalysis boronation reaction of 1,5-cyclo-octadiene iridium chloride dimer and four triphenylphosphine palladium chtalyst
Borate ester and the method for bromine pyrene coupling, be successfully incorporated into pyrene monomer in PAEK, not only do not interfere with poly-
The performance of aryl ether ketone itself, and novel macromolecular material PAEK Han pyrene of stable performance can be generated.?
What rear utilization obtained carries out physical modification containing pyrene PAEK to SWCN, so obtain SWCN/
Polyether-ether-ketone composite material.
The PAEK of boracic acid esters of the present invention is by bisphenol A type polyaromatic ether ketone main chain and pinacol borate
Side chain forms, and the molar content of pinacol borate is 10%～30%, and its structural formula is as follows:
N=15～25；2x+y+z=0.1～0.3, t+ (2x+y+z)=1.
Of the present invention it is made up of bisphenol A type polyaromatic ether ketone main chain and pyrene side chain containing pyrene PAEK, wherein pyrene
The molar content of side chain is 10%～30%, and its structural formula is as follows:
Wherein m=14～23；2a+b+c=0.1～0.3, d+ (2a+b+c)=1.
The preparation method of the PAEK of boracic acid esters of the present invention, including the synthesis of bisphenol A type polyaromatic ether ketone
With the PAEK process two that boracic acid esters is prepared in bisphenol A type polyaromatic ether ketone and connection pinacol borate boronation reaction
Step.
The synthesis of described bisphenol A type polyaromatic ether ketone, is by bisphenol A-type diphenol monomer and equimolar 4,4'-difluoro
Benzophenone monomer, diphenol monomer 1.05～the Anhydrous potassium carbonate of 1.10 times of moles, reaction monomers (diphenol monomer
With 4,4`-difluoro benzophenone) quality and the organic solvent of 3～6 times amount, organic solvent volume 20～the azeotropic of 30%
Dehydrant is put in the there-necked flask equipped with nitrogen through hole, mechanical agitation and water-taker in the lump, logical nitrogen, starts stirring,
It is warmed up to azeotropy dehydrant backflow, reaction 1～3 hours, gets rid of azeotropy dehydrant, then be warmed up to 170～200 DEG C
Continue reaction 7～10 hours；After dropping to room temperature, the polymer solution obtained is separated out in deionized water, size-reduced,
Wash, be dried, obtain bisphenol A type polyaromatic ether ketone polymer.
In the synthesis of bisphenol A type polyaromatic ether ketone, organic solvent used can be dimethyl sulfoxide, sulfolane or
N-Methyl pyrrolidone, azeotropy dehydrant used can be toluene or dimethylbenzene.
Described bisphenol A type polyaromatic ether ketone and connection pinacol borate carry out boronation reaction and prepare the poly-virtue of boracic acid esters
Ether ketone, is by bisphenol A type polyaromatic ether ketone and the connection boric acid pinacol being its repetitive 0.27～0.8 times of mole
Ester (connection pinacol borate is bought from An Naiji chemical company) is together encased in the container being placed with stirrer,
Add be connection pinacol borate 0.01～the 1,5-cyclo-octadiene iridium chloride dimer of 0.03 times of mole, be connection
Pinacol borate 0.02～the 4 of 0.04 times of mole, 4 '-di-t-butyl-2,2 '-bipyridyl, it is filled with high-purity after evacuation
Nitrogen, 3～5 times repeatedly, adds organic solvent (chloroform, oxolane or dioxane) and seals afterwards,
Stirring reaction 12～48 hours under room temperature；Then decompression removes organic solvent, by the polymer crude product that obtains with third
Ketone is washed 3～5 times, filter, dry, then by obtain polymer organic solvent (chloroform, oxolane or
N,N-dimethylacetamide) dissolve after, use column layer chromatography silicone rubber post filter 1～3 time, then by polymer use
Acetone is washed 3～5 times, filters, evacuation post-drying, i.e. obtains the PAEK of boracic acid esters.
Preparation method containing pyrene PAEK of the present invention, refers to PAEK and the 1-bromine pyrene list of boracic acid esters
Body carries out the Suzuki-Miyaura coupling reaction preparation process containing pyrene PAEK, particularly by boracic acid esters
PAEK and be that the 1-bromine pyrene of its 1～2 times of mole is put in reaction vessel, adding is the poly-virtue of boracic acid esters
Four triphenylphosphine palladiums of ether ketone mesoboric acid ester mole 1%～3%, it is the PAEK mesoboric acid ester of boracic acid esters
The potassium carbonate that mole is 3 times, then evacuation be filled with high pure nitrogen, 3～5 times repeatedly；Inject organic solvent (chlorine
Imitative, oxolane or dioxane) dissolve after, then be slowly injected into the distilled water of organic solvent volume 3%～10%,
Sealing, in oil bath, 60～80 DEG C are reacted 10～20 hours；Rotation is evaporated off organic solvent, with acetone extraction 20～30h,
Dissolve with organic solvent (chloroform, oxolane or dioxane), use column layer chromatography silicone rubber post to filter,
Rotation is evaporated off organic solvent, and acetone is washed 4～6 times, filters, and dries, obtains containing pyrene PAEK.
The SWCN modified containing pyrene PAEK of the present invention, refers to containing pyrene PAEK and single wall
CNT uses ultrasonic method mixing, thus realizes the physical modification to SWCN.Specifically will contain
Pyrene PAEK solvent (oxolane, chloroform or 1,2-dichloro-benzenes) dissolves, and configuration concentration is 1～2mg/mL
Polymer solution, (SWCN with the mass ratio containing pyrene PAEK is to be subsequently adding SWCN
16:70～80), under the conditions of water-bath and 20～30 DEG C ultrasonic 2～4h, then place 8～16h, finally use glass
Glass cotton is filtered, and stands 12～24h, thus obtains the SWCN modified containing pyrene PAEK.
Functionalization SWCN/polyether-ether-ketone composite material of the present invention, is by containing pyrene PAEK, list
Wall carbon nano tube and polyether-ether-ketone use the method for solution blending to prepare.Specifically will contain pyrene PAEK first to use
Solvent (oxolane, chloroform or 1,2-dichloro-benzenes) dissolves, and configuration concentration is the polymer solution of 1～2mg/mL,
(SWCN is 16:70～80 with the mass ratio containing pyrene PAEK, ultrasonic to add SWCN
2～4h, (from Jinlin University, Te Su engineering plastics company limited is commercially available, 200～400 to add polyether-ether-ketone micropowder
Mesh；It is 1:15～25 with the mass ratio containing pyrene PAEK), ultrasonic 0.5～1h, rotation is evaporated off solvent, dries,
Obtain gray solid powder；The pressed powder obtained is joined three equipped with thermometer, mechanical agitation and drying tube
In mouth flask, add solvent (sulfolane or diphenyl sulphone (DPS)), open stirring, be heated to 250～290 DEG C,
Being stirred for 0.5～1h after solid dissolves, discharging is on iron plate；With high speed agitator, discharging afterproduct is ground into powder
End, then boil 3～5 times with acetone, dry, obtain Lycoperdon polymorphum Vitt powder, i.e. SWCN/polyether-ether-ketone composite material.
Use HAAKE minijet II type injection machine to be molded into stretching, bending batten is tested.
First of the present invention be successfully to be drawn by borate by a kind of boronation reaction containing pyrene poly aryl ether ketone polymer
Enter on PAEK main chain, anti-by palladium chtalyst coupling with 1-bromine pyrene followed by this boracic acid esters PAEK
Should obtain, this method does not interferes with the molecular weight of polymer, and the PAEK containing pyrene obtained has the most steady
Qualitative.Utilize this PAEK containing pyrene can realize the physical modification to SWCN, this modification
SWCN well can disperse in polyether-ether-ketone, can obtain mechanics, the single wall of dielectric properties excellence
Carbon nano-tube/poly polyetherether ketone composite.
Accompanying drawing explanation
Fig. 1: bisphenol A type polyaromatic ether ketone of the present invention1H-NMR spectrum；
Fig. 2: the bisphenol A type polyaromatic ether ketone of boracic acid esters of the present invention1H-NMR spectrum；
Fig. 3: of the present invention containing pyrene bisphenol A type polyaromatic ether ketone1H-NMR spectrum；
Fig. 4: the DSC curve of bisphenol A type polyaromatic ether ketone of the present invention；
Fig. 5: the DSC curve of the bisphenol A type polyaromatic ether ketone of boracic acid esters of the present invention；
Fig. 6: the DSC curve containing pyrene bisphenol A type polyaromatic ether ketone of the present invention；
Fig. 7: the UV-Vis curve containing pyrene bisphenol A type polyaromatic ether ketone of the present invention；
Fig. 8: the TGA curve containing pyrene bisphenol A type polyaromatic ether ketone of the present invention；
Fig. 9: SWCN of the present invention and pyrene molar content be 10% the PAEK physics containing pyrene change
The Raman spectrum of the SWCN of property；
Figure 10: the dielectric constant curve of SWCN/polyether-ether-ketone composite material of the present invention；
Figure 11: pyrene molar content of the present invention be 10% the single wall carbon containing pyrene PAEK physical modification receive
The stereoscan photograph of mitron.
What Fig. 1 was given is the hydrogen nuclear magnetic spectrogram of the bisphenol A type polyaromatic ether ketone (embodiment 1) of the present invention, from figure
It can be seen that each hydrogen in polymer architecture has correct ownership.
The boracic acid esters molar fraction of the present invention that what Fig. 2 was given is is respectively the boracic acid esters of 10%, 20%, 30%
Bisphenol A type polyaromatic ether ketone (embodiment 2,3,4) hydrogen nuclear magnetic spectrogram (figure (a) be that borate molar content is
The borate PAEK of 10%, figure (b) be boracic acid esters molar content be the borate PAEK of 20%, scheme (c)
Be boracic acid esters molar content be the borate PAEK of 30%), as we can see from the figure in polymer architecture
Each hydrogen has correct ownership.
The molar fraction containing pyrene of the present invention that what Fig. 3 was given is be respectively 10%, 20% containing pyrene bisphenol A-type polyarylether
The hydrogen nuclear magnetic spectrogram of ketone (embodiment 5,6) (figure (a) be pyrene molar content be 10% containing pyrene PAEK, scheme (b)
Be pyrene molar content be 20% containing pyrene PAEK), each hydrogen in polymer architecture is all as we can see from the figure
There is correct ownership.
What Fig. 4 was given is bisphenol A type polyaromatic ether ketone (embodiment 1) DSC curve of the present invention, permissible from figure
See that the Tg of the bisphenol A-type polyether sulphone of the present invention is 159 degrees Celsius.
The boracic acid esters molar fraction of the present invention that what Fig. 5 was given is respectively is respectively 10%, 20% and 30% contain
The DSC curve of borate bisphenol A type polyaromatic ether ketone (embodiment 2,3,4), boric acid as we can see from the figure
The Tg of the boracic acid esters bisphenol A type polyaromatic ether ketone that ester molar fraction is respectively 10%, 20%, 30% is respectively 162
Degree Celsius, 164 degrees Celsius and 168 degrees Celsius.
The molar fraction containing pyrene of the present invention that what Fig. 6 was given is respectively be respectively 10%, 20% and 30% double containing pyrene
The DSC curve of phenol A type PAEK (embodiment 5,6,7), as we can see from the figure the present invention containing pyrene
The Tg containing pyrene bisphenol A type polyaromatic ether ketone respectively 169 of molar fraction respectively 10%, 20% and 30% takes the photograph
Family name's degree, 177 degrees Celsius and 195 degrees Celsius.
What Fig. 7 was given is the respectively polymer with bis phenol A aryl ether ketone of the present invention and the molar fraction Han pyrene are respectively 10%, 20%
The ultraviolet-visible spectrogram containing pyrene bisphenol A type polyaromatic ether ketone (embodiment 1,5,6), as we can see from the figure
The present invention's is 285 containing pyrene bisphenol A type polyaromatic ether ketone at wavelength containing pyrene molar fraction respectively 10%, 20%
Nanometer and 350 nanometers have obvious absworption peak.
The present invention that what Fig. 8 was given is respectively containing pyrene molar fraction be 10% containing pyrene bisphenol A type polyaromatic ether ketone and contain
Pyrene molar fraction is the SWCN (embodiment 8) modified containing pyrene bisphenol A type polyaromatic ether ketone of 10%
TGA curve, as we can see from the figure containing pyrene molar fraction be 10% containing pyrene bisphenol A type polyaromatic ether ketone with containing pyrene
Molar fraction be 10% the SWCN modified containing pyrene bisphenol A type polyaromatic ether ketone have good thermally-stabilised
Property.
What Fig. 9 was given is respectively pure SWCN and the present invention containing pyrene molar fraction be 10% containing pyrene bis-phenol
The Raman spectrogram of the SWCN (embodiment 8) that A type PAEK is modified, contains as we can see from the figure
Pyrene molar fraction is the SWCN modified containing pyrene bisphenol A type polyaromatic ether ketone of 10% and pure single
Pipe is compared, and Raman shift there occurs significantly change, it was demonstrated that be 10% gather containing pyrene bisphenol A-type containing pyrene molar fraction
Pyrene in aryl ether ketone and SWCN there occurs interaction.Illustration is partial enlarged drawing.
What Figure 10 was given is the pure polyether-ether-ketone resin of the present invention respectively, and SWCN mass fraction is 1%
SWCN/polyether-ether-ketone composite material, it is poly-fragrant containing pyrene that employing HAAKE minilab II extrusion way obtains
SWCN/polyether-ether-ketone composite material that SWCN mass fraction is 1% that ether ketone is modified, uses
The single wall carbon that SWCN mass fraction be 1% modified containing pyrene PAEK that the mode of solution blending obtains
The dielectric properties scatterplot of nanotube/polyether-ether-ketone composite material (embodiment 9,10,11).
In figure, PEEK is pure polyether-ether-ketone resin, and PEEK/SCNT1% is that SWCN mass fraction is
SWCN/the polyether-ether-ketone composite material of 1%, PEEK/f-SCNT1%-Extrusion is to use
The SWCN mass fraction modified containing pyrene PAEK that HAAKE minilab II extrusion way obtains is
SWCN/the polyether-ether-ketone composite material of 1%, PEEK/f-SCNT1%-Solvation is to use solution altogether
The SWCN that SWCN mass fraction be 1% modified containing pyrene PAEK that mixed mode obtains/
Polyether-ether-ketone composite material.The SWCN modified containing pyrene PAEK obtained by the way of solution blending
Mass fraction is the dielectric constant of the SWCN/polyether-ether-ketone composite material of 1%, with SWCN matter
Amount mark is the SWCN/polyether-ether-ketone composite material of 1% and uses HAAKEminilab II extrusion way
SWCN/the polyether-ether-ketone that SWCN mass fraction be 1% modified containing pyrene PAEK obtained
Composite is compared, and improves a lot.
It is modified containing pyrene PAEK that the mode using solution blending of the present invention that what Figure 11 was given is respectively obtains
SWCN mass fraction is sweeping of SWCN/polyether-ether-ketone composite material (embodiment 11) of 1%
Retouch electromicroscopic photograph.The SWCN that SWCN mass fraction is 1% containing the modification of pyrene PAEK/poly-
SWCN in polyetherether ketone composite is uniformly dispersed.
Detailed description of the invention
Embodiment 1
By anhydrous to 13.6974g bisphenol A monomer, 13.0920g4,4`-difluoro benzophenone monomer and 9.1205g
Potassium carbonate, 107mL sulfolane, 36mL toluene, put into three equipped with nitrogen through hole, mechanical agitation and water-taker
In mouth flask, logical nitrogen, start stirring, be warming up to 135 DEG C and reflux to azeotropy dehydrant, react 2.5 hours,
Get rid of azeotropy dehydrant, be warmed up to 175 DEG C and continue reaction 8 hours；By the polymer solution that obtains at deionized water
Middle precipitation, size-reduced, washing, it is dried, obtains 23.4g bisphenol A type polyaromatic ether ketone polymer.
Molecular formula is as follows:
The wherein integer of p=13～22.
Embodiment 2
First there-necked flask is burned with gas burner under conditions of evacuation, after cooling, be filled with nitrogen, put into magnetic and stir
Mix son, add bisphenol A type polyaromatic ether ketone and 0.6772g that 4.0748g (10mmol) embodiment 1 prepares
(2.7mmol) connection pinacol borate, adds 0.0269g [IrCl (COD)]2Fourth tertiary with 0.0215g4,4'-bis-
Base-2,2'-bipyridyl, evacuation is filled with high pure nitrogen, 3 times repeatedly, injects 50mL oxolane and dissolves, seals,
In oil bath, 80 DEG C are reacted 12 hours；Dissolve with chloroform after cooling, use tlc silica gel (200～400 mesh)
Filtering, rotation is evaporated off oxolane, and acetone is washed 5 times, dries, obtains the boracic acid esters of the faint yellow bulk of 4.12g
Bisphenol A type polyaromatic ether ketone polymer.
Molecular formula is as follows:
Wherein 2x+y+z=0.1, t=0.1；N=15～25.
Embodiment 3
First there-necked flask is burned with gas burner under conditions of evacuation, after cooling, be filled with nitrogen, put into magnetic and stir
Mix son, add bisphenol A type polyaromatic ether ketone and 1.3544g that 4.0748g (10mmol) embodiment 1 prepares
(5.4mmol) connection pinacol borate, adds 0.0538g [IrCl (COD)]2Fourth tertiary with 0.0430g 4,4'-bis-
Base-2,2'-bipyridyl, evacuation is filled with high pure nitrogen, 3 times repeatedly, injects 50mL oxolane and dissolves, seals,
In oil bath, 80 DEG C are reacted 12 hours；Dissolve with chloroform after cooling, use tlc silica gel (200～400 mesh)
Filtering, rotation is evaporated off oxolane, and acetone is washed 5 times, dries, obtains the boracic acid esters of the faint yellow bulk of 4.18g
Bisphenol A type polyaromatic ether ketone polymer.
Molecular formula is as follows:
Wherein 2x+y+z=0.2, t=0.8；N=15～25.
Embodiment 4
First there-necked flask is burned with gas burner under conditions of evacuation, after cooling, be filled with nitrogen, put into magnetic and stir
Mix son, add bisphenol A type polyaromatic ether ketone and 2.0316g that 4.0748g (10mmol) embodiment 1 prepares
(8mmol) connection pinacol borate, adds 0.0806g [IrCl (COD)]2With 0.0644g 4,4'-di-t-butyl
-2,2'-bipyridyl, evacuation is filled with high pure nitrogen, 3 times repeatedly, injects 50mL oxolane and dissolves, seals,
In oil bath, 80 DEG C are reacted 12 hours；Dissolve with chloroform after cooling, use tlc silica gel (200～400 mesh) mistake
Filter, rotation is evaporated off oxolane, and acetone is washed 5 times, dries, obtains the boracic acid esters of the faint yellow bulk of 4.25g
Bisphenol A type polyaromatic ether ketone polymer.
Molecular formula is as follows:
Wherein 2x+y+z=0.3, t=0.7；N=15～25.
Embodiment 5
First there-necked flask is burned with gas burner under conditions of evacuation, after cooling, be filled with nitrogen, put into magnetic and stir
Mix son, add bisphenol A type polyaromatic ether ketone and the 0.4217g 1-of the boracic acid esters that 4.2019g embodiment 2 prepares
Bromine pyrene, adds 0.0174g tetra-triphenylphosphine palladium and 0.4146g potassium carbonate, and then evacuation is filled with High Purity Nitrogen
Gas, 3 times repeatedly, injects 100mL oxolane and dissolves, finally, be slowly injected into 5mL distilled water, seal,
80 DEG C of reaction 12h in oil bath；Rotation is evaporated off solvent, uses acetone extraction 24h, dissolves with chloroform, uses thin layer chromatography
Silica gel filters, and rotation is evaporated off solvent, and acetone is washed 5 times, filters, and dries, obtains faint yellow blocks of solid, to obtain final product
To 4.51g faint yellow pyrene molar fraction be 10% containing pyrene bisphenol A type polyaromatic ether ketone (PEEK-Py-10).
Molecular formula is as follows:
Wherein 2a+b+c=0.1, d=0.9；M=14～23.
Embodiment 6
First there-necked flask is burned with gas burner under conditions of evacuation, after cooling, be filled with nitrogen, put into magnetic and stir
Mix son, add bisphenol A type polyaromatic ether ketone and the 0.8434g 1-of the boracic acid esters that 4.3288g embodiment 3 prepares
Bromine pyrene, adds 0.0347g tetra-triphenylphosphine palladium and 0.8292g potassium carbonate, and then evacuation is filled with High Purity Nitrogen
Gas, 3 times repeatedly, injects 100mL oxolane and dissolves, finally, be slowly injected into 5mL distilled water, seal,
80 DEG C of reaction 12h in oil bath；Rotation is evaporated off solvent, uses acetone extraction 24h, dissolves with chloroform, uses thin layer chromatography
Silica gel filters, and rotation is evaporated off solvent, and acetone is washed 5 times, filters, and dries, obtains 4.81g faint yellow pyrene molar fraction
Be 20% containing pyrene bisphenol A type polyaromatic ether ketone (PEEK-Py-20).
Molecular formula is as follows:
Wherein 2a+b+c=0.2, d=0.8；M=14～23.
Embodiment 7
First there-necked flask is burned with gas burner under conditions of evacuation, after cooling, be filled with nitrogen, put into magnetic and stir
Mix son, add bisphenol A type polyaromatic ether ketone and the 1.2651g 1-of the boracic acid esters that 4.4558g embodiment 4 prepares
Bromine pyrene, adds 0.0522g tetra-triphenylphosphine palladium and 1.2438g potassium carbonate, and then evacuation is filled with High Purity Nitrogen
Gas, 3 times repeatedly, injects 100mL oxolane and dissolves, finally, be slowly injected into 5mL distilled water, seal,
80 DEG C of reaction 12h in oil bath；Rotation is evaporated off solvent, uses acetone extraction 24h, dissolves with chloroform, uses thin layer chromatography
Silica gel filters, and rotation is evaporated off solvent, and acetone is washed 5 times, filters, and dries, obtains 5.48g faint yellow pyrene molar fraction
Be 30% containing pyrene bisphenol A type polyaromatic ether ketone (PEEK-Py-30).
Molecular formula is as follows:
Wherein 2a+b+c=0.3, d=0.7；M=14～23.
Embodiment 8
Pyrene molar fraction is the preparation of the SWCN of the PAEK modification of 10%.By 1.875 grams of embodiments 5
The PEEK-Py-10 of preparation is dissolved in 1500mL chloroform, then 400 milligrams of SWCNs is joined this
In the chloroformic solution of PEEK-Py-10, ultrasonic 4h in a water bath and under the conditions of 20 DEG C, then place 12 hours, will
The 2/3 of the supernatant is poured out and is filtered with glass cotton, stands 12h, finally obtains the homogeneous solution of black.
Embodiment 9
SWCN mass fraction is that the preparation of the SWCN/polyether-ether-ketone composite material of 1% (uses
Prepared by the mode of solution blending).Weigh 0.4g SWCN and join magnetic agitation 12h in chloroformic solution,
Ultrasonic 2h under the conditions of 20 DEG C again；(400 mesh, Jinlin University, Changchun spy moulds to weigh the polyether-ether-ketone micropowder of 39.6g
Engineering research company limited) join in the dispersion liquid of above-mentioned SWCN, ultrasonic under conditions of 20 DEG C
1h, rotation is evaporated off solvent, processes 12h at 120 DEG C.Then, the 39.92g polymer solution obtained is added
In the there-necked flask of the 1000mL equipped with thermometer, mechanical agitation and drying tube, add 160g diphenyl sulphone (DPS),
Being heated to 280 DEG C, thing to be polymerized continues stirring 30min after being completely dissolved, then discharging is on iron plate, with at a high speed
Blender is pulverized, and boils 5 times with acetone, sucking filtration, puts into 120 DEG C of baking 12h in baking oven, standby.
Embodiment 10
SWCN mass fraction is the preparation of the functionalization SWCN/polyether-ether-ketone composite material of 1%
(prepared by the mode using extrusion).Taking in 1.875g embodiment 5 is the PAEK of 10% containing pyrene molar fraction
Polymer dissolves in 1500mL chloroformic solution, and then weighing 0.4g SWCN, to join polymer molten
Magnetic agitation 12h in liquid, more ultrasonic 2h under the conditions of 20 DEG C, weigh 37.725g polyether-ether-ketone micropowder and add
In the dispersion liquid of above-mentioned SWCN, ultrasonic 1h under conditions of 20 DEG C, rotation is evaporated off solvent,
120 DEG C process 12h.Then, the 39.94g polymer obtained is added HAAKE minilab II extruder,
In extruder barrel in 380 DEG C (under the conditions of fusion plastification, form polyether-ether-ketone melt, in extruder barrel again
Secondary carry out compound being blended, then extrude material strip, pelletize through head.Put into 120 DEG C of baking 12h in baking oven, standby.
Embodiment 11
SWCN mass fraction is the preparation of the functionalization SWCN/polyether-ether-ketone composite material of 1%
(prepared by the mode using solution blending).Take in 1.875g embodiment 5 containing the poly-virtue that pyrene molar fraction is 10%
Ether ketone polymer dissolves in 1500mL chloroformic solution, then weighs 0.4g SWCN and joins polymerization
Magnetic agitation 12h in thing solution, more ultrasonic 2h under the conditions of 20 DEG C, weigh 37.725g polyether-ether-ketone micropowder
Join in the dispersion liquid of above-mentioned SWCN, ultrasonic 1h under conditions of 20 DEG C, rotation is evaporated off solvent,
12h is processed at 120 DEG C.Then, the 39.94g polymer obtained is joined equipped with thermometer, mechanical agitation and
In the there-necked flask of the 1000mL of drying tube, add 160g diphenyl sulphone (DPS), be heated to 280 DEG C, thing to be polymerized
Continuing stirring 30min after being completely dissolved, then discharging is on iron plate, pulverizes by high-speed stirred, boils 5 times with acetone,
Sucking filtration, puts into 120 DEG C of baking 12h in baking oven, standby.
Embodiment 12
Product PEEK, embodiment 9,10,11 obtained uses Mini Jet II injection machine to be molded, point
(long 75mm, wide 10mm and 5mm, thick 2mm are used for stretching not to make the tensile bars of two dumbbell shapes
Performance test), a bending batten (long 80mm, wide 10mm, thick 4mm test for bending property)
And the sequin (thick 2mm, for the test of dielectric properties) of a diameter of 20mm.
Table 1: pure polyether-ether-ketone, SWCN/polyether-ether-ketone composite material, functionalized carbon nano-tube/polyether-ether-ketone composite material
Mechanical property
Note: PEEK be melt index (inserting in sulculus by polyether-ether-ketone raw material, groove end is connected to tubule, and capillary diameter is 3mm,
Pipe range is 8mm.After heating 380 DEG C, polyether-ether-ketone upper end applies load by 5 kilograms of counterweights and extrudes downwards, measures polyethers ether
The weight that ketone was extruded in 10 minutes) it is the polyether-ether-ketone resin of 19g/10min；SCNT is SWCN；f-SCNT
Be through pyrene molar content be 10% containing the SWCN after pyrene PAEK physical modification.PEEK/f-SCNT-E in table
Be the SWCN mass fraction modified containing pyrene PAEK using HAAKE minilab II extrusion way to obtain be 1%
SWCN/polyether-ether-ketone composite material (embodiment 10 product), PEEK/SCNT-S is that the mode using solution blending obtains
To SWCN/polyether-ether-ketone composite material that SWCN mass fraction is 1% (embodiment 9 product),
PEEK/f-SCNT-S is that the SWCN mass fraction modified containing pyrene PAEK using the mode of solution blending to obtain is
SWCN/the polyether-ether-ketone composite material (embodiment 11 product) of 1%.
As shown in table 1, the polyether-ether-ketone composite material (compared with pure polyether-ether-ketone resin) that SWCN is filled,
Its hot strength, bending strength, bending modulus are not significantly improved, and elongation at break reduces.And,
Through the polyethers ether filled containing the SWCN after pyrene PAEK physical modification that pyrene molar content is 10%
The mechanical property of the composite that the mode (embodiment 10) of ketone employing extrusion obtains the most does not improves and declines on the contrary.
But, through the gathering containing the SWCN filling after pyrene PAEK physical modification that pyrene molar content is 10%
The composite that the mode (embodiment 11) of ether ether ketone employing solution blending obtains is (with SWCN filling
Polyether-ether-ketone composite material is compared) its hot strength, bending strength, bending modulus and elongation at break have substantially
Raising.
The above, detailed description of the invention the most of the present invention, but protection domain of the present invention not office
Being limited to this, any those skilled in the art of being familiar with, in the technical scope that the invention discloses, can readily occur in
Change or replacement, all should contain within protection domain of the present invention.
Claims (4)
1. the PAEK Han pyrene, its structural formula is as follows:
Wherein m=14～23；2a+b+c=0.1～0.3, d+ (2a+b+c)=1.
2. the preparation method containing pyrene PAEK described in claim 1, it is characterised in that: it is that structural formula is as follows
The PAEK of shown boracic acid esters is put in reaction vessel with the 1-bromine pyrene being its 1～2 times of mole,
Add the PAEK mesoboric acid ester mole 1%～3% being boracic acid esters four triphenylphosphine palladiums,
It is the potassium carbonate of the PAEK mesoboric acid ester mole 3 times of boracic acid esters, then evacuation be filled with height
Pure nitrogen gas, 3～5 times repeatedly；After injecting organic solvents, chloroform, oxolane or dioxane dissolving, then
It is slowly injected into the distilled water of organic solvent volume 3%～10%, seals, 60～80 DEG C of reactions in oil bath
10～20 hours；Rotation is evaporated off organic solvent, with acetone extraction 20～30h, with organic solvent three chloromethane
Alkane, oxolane or dioxane dissolve, and use column layer chromatography silicone rubber post to filter, and rotation is evaporated off organic molten
Agent, acetone is washed 4～6 times, filters, and dries, obtains containing pyrene PAEK,
N=15～25；2x+y+z=0.1～0.3, t+ (2x+y+z)=1.
3. the SWCN containing the modification of pyrene PAEK, it is characterised in that: it is by described in claim 1
Containing pyrene PAEK oxolane, chloroform or 1,2-dichloro-benzenes dissolves, and configuration concentration is 1～2mg/mL
Polymer solution, be subsequently adding SWCN, SWCN and the matter containing pyrene PAEK
Amount ratio is 16:70～80, under the conditions of water-bath and 20～30 DEG C ultrasonic 2～4h, and then placement 8～16h,
Finally use glass cotton to filter, stand 12～24h, thus obtain the single wall carbon modified containing pyrene PAEK
Nanotube.
4. functionalization SWCN/polyether-ether-ketone composite material, it is characterised in that: it is by claim 1
Described first uses oxolane, chloroform or 1 containing pyrene PAEK, and 2-dichloro-benzenes dissolves, and configuration concentration is
The polymer solution of 1～2mg/mL, add SWCN, SWCN with containing pyrene polyarylether
The mass ratio of ketone is 16:70～80, ultrasonic 2～4h, and the polyether-ether-ketone adding 200～400 mesh is ultra-fine
Powder, it is 1:15～25 with the mass ratio containing pyrene PAEK, ultrasonic 0.5～1h, and rotation is evaporated off solvent,
Dry, obtain gray solid powder；The pressed powder obtained is joined equipped with thermometer, mechanical agitation
And in the there-necked flask of drying tube, add sulfolane or diphenyl sulphone (DPS), open stirring, be heated to
250～290 DEG C, being stirred for 0.5～1h after solid dissolves, discharging is on iron plate；Will with high speed agitator
Discharging afterproduct is ground into powder, then boils 3～5 times with acetone, dries, obtains Lycoperdon polymorphum Vitt powder, i.e. function
Change SWCN/polyether-ether-ketone composite material.
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| CN112063151B (en) * | 2020-09-02 | 2022-12-02 | 吉林化工学院 | Multi-walled carbon nanotube and polyaryletherketone compound thermosetting material containing furan benzene side group and preparation method thereof |
| CN113652057B (en) * | 2021-09-28 | 2022-06-21 | 吉林大学 | 3D printing high-strength high-toughness polyether-ether-ketone carbon nanotube composite material and preparation method thereof |
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