CN104725630A - Pyrene-containing polyaryletherketone and preparation method thereof as well as application of pyrene-containing polyaryletherketone in single-wall carbon nanometer tube/polyether-ether-ketone composite material - Google Patents
Pyrene-containing polyaryletherketone and preparation method thereof as well as application of pyrene-containing polyaryletherketone in single-wall carbon nanometer tube/polyether-ether-ketone composite material Download PDFInfo
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Abstract
The invention discloses pyrene-containing polyaryletherketone and a preparation method thereof as well as application of the pyrene-containing polyaryletherketone in a single-wall carbon nanometer tube/polyether-ether-ketone composite material and belongs to the technical field of preparation of a high-molecular material. The preparation method comprises the following steps: firstly, preparing the pyrene-containing polyaryletherketone by reaction of borate-containing polyaryletherketone and a 1-bromopyrene monomer under the catalysis of tetrakis (triphenylphosphine) palladium; secondly, physically modifying single-wall carbon nanometer tubes by utilizing the pyrene-containing polyaryletherketone; finally, preparing the single-wall carbon nanometer tube/polyether-ether-ketone composite material by means of solution blending of the functionalized single-wall carbon nanometer tubes and polyether-ether-ketone, wherein the single-wall carbon nanometer tubes are uniformly dispersed in the polyether-ether-ketone due to surface modification of the single-wall carbon nanometer tubes by using the pyrene-containing polyaryletherketone. Therefore, the pyrene-containing polyaryletherketone is expected to become an excellent carbon nanometer tube coupling agent and can be used for effectively solving the problem of agglomeration of the carbon nanometer tubes in a polyaryletherketone system.
Description
Technical field
The invention belongs to field of polymer material preparing technology, be specifically related to a kind of containing pyrene polyaryletherketone, preparation method and the application in modification Single Walled Carbon Nanotube/polyether-ether-ketone composite material thereof.
Background technology
Pyrene has typical multi-aromatic ring structure, due to its distinctive structure and Photophysics, plane condensed-nuclei aromatics pyrene and derivative thereof have a wide range of applications in fields such as fluorescence probe, organic electroluminescent LED, organic field effect tube, solar cells.Substituent number, classification and position are several large important factors affecting pyrene derivatives.The conjugated degree of they and pyrene chromophore, space structure, amount of rigidity and electronic induction effect etc. all can produce material impact to the photoelectron performance of molecule.In addition, pyrene can also be piled up with graphite underrun π key and produce very strong interaction, multiplexly recently disperses Single Walled Carbon Nanotube.Just have been found that the sidewall of pyrene and carbon nanotube has very strong interaction at calendar year 2001 Chen etc.From that time, the different micromolecular compounds containing pyrene is synthesized and is used to the non-covalent functionalization research of carbon nanotube.As may be expected, the carbon nanotube of this functionalization all shows in water or organic solvent comparatively that pure nano-carbon tube is better dispersed.But prepare Polymer/carbon Nanotubes Composites for by solution methods, the concentration of carbon nanotube is still very low, and dispersion stabilization is poor.Compared with small molecules dispersion agent, macromole has longer segment that more site of dissolving thus can be provided to make to have mutually exclusive enough spatial volumes between carbon nanotube simultaneously, is finally conducive to the dispersion of carbon nanotube.But apply in polyarylether system and also rarely have report.
Summary of the invention
The object of the invention is to prepare containing pyrene polyaryletherketone by the polyaryletherketone of boracic acid esters and 1-bromine pyrene monomer reaction, what recycling obtained carries out physically modified containing pyrene polyaryletherketone to Single Walled Carbon Nanotube, and then preparation functionalization Single Walled Carbon Nanotube/polyether-ether-ketone composite material.
First the present invention is by dihydroxyphenyl propane and 4, the fluoro-benzophenone of 4`-bis-is obtained by reacting bisphenol A type polyaromatic ether ketone (PAEK), then 1,5-cyclooctadiene iridium chloride dimer and 4,4 '-di-t-butyl-2, react with connection pinacol borate generation boronation under the acting in conjunction of 2 '-dipyridyl, prepare the polyaryletherketone of boracic acid esters; The polyaryletherketone of boracic acid esters reacts with 1-bromine pyrene and generates containing pyrene polyaryletherketone under the acting in conjunction of four triphenylphosphine palladiums and salt of wormwood.
The present invention has selected 1, the method of the reaction of 5-cyclooctadiene iridium chloride dimer catalysis boronation and four triphenylphosphine palladium chtalyst borate esters and the coupling of bromine pyrene, successfully pyrene monomer is incorporated in polyaryletherketone, not only can not affect the performance of polyaryletherketone itself, and the novel macromolecular material of stable performance can be generated containing pyrene polyaryletherketone.Finally utilize the pyrene polyaryletherketone that contains obtained to carry out physically modified to Single Walled Carbon Nanotube, and then obtain Single Walled Carbon Nanotube/polyether-ether-ketone composite material.
The polyaryletherketone of boracic acid esters of the present invention is made up of bisphenol A type polyaromatic ether ketone main chain and pinacol borate side chain, 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。
The pyrene polyaryletherketone that contains of the present invention is made up of bisphenol A type polyaromatic ether ketone main chain and pyrene side chain, and wherein the molar content of pyrene 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 polyaryletherketone of boracic acid esters of the present invention, comprises the synthesis of bisphenol A type polyaromatic ether ketone and bisphenol A type polyaromatic ether ketone and connection pinacol borate boronation and reacts polyaryletherketone process two steps preparing boracic acid esters.
The synthesis of described bisphenol A type polyaromatic ether ketone, by bisphenol A-type diphenol monomer and equimolar 4, 4'-difluoro benzophenone monomer, the Anhydrous potassium carbonate of diphenol monomer 1.05 ~ 1.10 times of molar weights, reaction monomers (diphenol monomer and 4, 4`-difluoro benzophenone) organic solvent of quality and 3 ~ 6 times amount, the azeotropy dehydrant of organic solvent volume 20 ~ 30% is put in the lump and nitrogen through hole is housed, in the there-necked flask of mechanical stirring and water-taker, logical nitrogen, start stirring, be warmed up to azeotropy dehydrant backflow, react 1 ~ 3 hour, get rid of azeotropy dehydrant, be warmed up to 170 ~ 200 DEG C again and continue reaction 7 ~ 10 hours, after dropping to room temperature, the polymers soln obtained is separated out in deionized water, through pulverizing, washing, drying, obtain bisphenol A type polyaromatic ether ketone polymkeric substance.
In the synthesis of bisphenol A type polyaromatic ether ketone, organic solvent used can be dimethyl sulfoxide (DMSO), tetramethylene sulfone or N-Methyl pyrrolidone, and azeotropy dehydrant used can be toluene or dimethylbenzene.
Described bisphenol A type polyaromatic ether ketone and connection pinacol borate carry out the polyaryletherketone that boracic acid esters is prepared in boronation reaction, bisphenol A type polyaromatic ether ketone is together encased in the connection pinacol borate (joining pinacol borate to buy from An Naiji chemical company) being its repeating unit 0.27 ~ 0.8 times of molar weight be placed with the container of stirrer, adding is 1 of connection pinacol borate 0.01 ~ 0.03 times of molar weight again, 5-cyclooctadiene iridium chloride dimer, 4 of connection pinacol borate 0.02 ~ 0.04 times of molar weight, 4 '-di-t-butyl-2, 2 '-dipyridyl, high pure nitrogen is filled with after vacuumizing, 3 ~ 5 times repeatedly, add organic solvent (trichloromethane, tetrahydrofuran (THF) or dioxane) seal afterwards, at room temperature stirring reaction 12 ~ 48 hours, then decompression removing organic solvent, the polymkeric substance crude product acetone obtained is washed 3 ~ 5 times, filter, dry, then polymkeric substance organic solvent (trichloromethane, tetrahydrofuran (THF) or the N that will obtain, N-N,N-DIMETHYLACETAMIDE) dissolve after, adopt column layer chromatography silicone rubber post to filter 1 ~ 3 time, then polymkeric substance acetone is washed 3 ~ 5 times, filter, vacuumize post-drying, namely obtain the polyaryletherketone of boracic acid esters.
Preparation method containing pyrene polyaryletherketone of the present invention, refer to that polyaryletherketone and the 1-bromine pyrene monomer of boracic acid esters carry out the process of Suzuki-Miyaura linked reaction preparation containing pyrene polyaryletherketone, particularly the polyaryletherketone of boracic acid esters and the 1-bromine pyrene being its 1 ~ 2 times of molar weight are put into reaction vessel, add four triphenylphosphine palladiums of the polyaryletherketone mesoboric acid ester molar weight 1% ~ 3% being boracic acid esters again, be the salt of wormwood of the polyaryletherketone mesoboric acid ester molar weight 3 times of boracic acid esters, then vacuumize and be filled with high pure nitrogen, 3 ~ 5 times repeatedly; After injecting organic solvent (chloroform, tetrahydrofuran (THF) or dioxane) dissolving, more slowly inject the distilled water of organic solvent volume 3% ~ 10%, sealing, in oil bath, 60 ~ 80 DEG C are reacted 10 ~ 20 hours; Revolve and steam removing organic solvent, with acetone extraction 20 ~ 30h, dissolve with organic solvent (trichloromethane, tetrahydrofuran (THF) or dioxane), adopt column layer chromatography silicone rubber post to filter, revolve and steam removing organic solvent, acetone washes 4 ~ 6 times, filter, dry, obtain containing pyrene polyaryletherketone.
Single Walled Carbon Nanotube containing the modification of pyrene polyaryletherketone of the present invention, refers to and adopts ultrasonic method to mix containing pyrene polyaryletherketone with Single Walled Carbon Nanotube, thus realizes the physically modified to Single Walled Carbon Nanotube.Specifically will containing pyrene polyaryletherketone solvent (tetrahydrofuran (THF), chloroform or 1,2-dichlorobenzene) dissolve, configuration concentration is the polymers soln of 1 ~ 2mg/mL, then Single Walled Carbon Nanotube (Single Walled Carbon Nanotube is 16:70 ~ 80 with the mass ratio containing pyrene polyaryletherketone) is added, ultrasonic 2 ~ 4h under water-bath and 20 ~ 30 DEG C of conditions, then places 8 ~ 16h, finally adopts glass wool to filter, leave standstill 12 ~ 24h, thus obtain the Single Walled Carbon Nanotube containing the modification of pyrene polyaryletherketone.
Functionalization Single Walled Carbon Nanotube/polyether-ether-ketone composite material of the present invention adopts the method for solution blending to prepare by containing pyrene polyaryletherketone, Single Walled Carbon Nanotube and polyether-ether-ketone.Specifically will first use solvent (tetrahydrofuran (THF), chloroform or 1 containing pyrene polyaryletherketone, 2-dichlorobenzene) dissolve, configuration concentration is the polymers soln of 1 ~ 2mg/mL, (Single Walled Carbon Nanotube is 16:70 ~ 80 with the mass ratio containing pyrene polyaryletherketone to add Single Walled Carbon Nanotube, ultrasonic 2 ~ 4h, add polyether-ether-ketone ultrafine powder again (to buy from Jinlin University Te Su engineering plastics company limited and obtain, 200 ~ 400 orders; It is 1:15 ~ 25 with the mass ratio containing pyrene polyaryletherketone), ultrasonic 0.5 ~ 1h, revolves and steams except desolventizing, dry, obtain gray solid powder; The pressed powder obtained is joined in the there-necked flask that thermometer, mechanical stirring and drying tube are housed, add solvent (tetramethylene sulfone or sulfobenzide), open and stir, be heated to 250 ~ 290 DEG C, after dissolution of solid, stir 0.5 ~ 1h again, discharging is on iron plate; With high speed agitator, discharging after product is ground into powder, then boils 3 ~ 5 times with acetone, dry, obtain grey powder, i.e. Single Walled Carbon Nanotube/polyether-ether-ketone composite material.Employing HAAKE minijet II type injection moulding machine is injection molded into stretching, bending batten is tested.
First of the present invention be successfully be incorporated into by boric acid ester on polyaryletherketone main chain by a kind of boronation reaction containing pyrene poly aryl ether ketone polymer, then this boracic acid esters polyaryletherketone and 1-bromine pyrene is utilized to be obtained by palladium catalysed cross coupling reaction, this method can not affect the molecular weight of polymkeric substance, and what obtain has stability preferably containing pyrene polyaryletherketone.Utilize the physically modified that this polyaryletherketone containing pyrene can realize Single Walled Carbon Nanotube, the Single Walled Carbon Nanotube of this modification well can be disperseed in polyether-ether-ketone, can obtain the Single Walled Carbon Nanotube/polyether-ether-ketone composite material of mechanics, dielectric properties excellence.
Accompanying drawing explanation
Fig. 1: bisphenol A type polyaromatic ether ketone of the present invention
1h-NMR spectrogram;
Fig. 2: the bisphenol A type polyaromatic ether ketone of boracic acid esters of the present invention
1h-NMR spectrogram;
Fig. 3: of the present invention containing pyrene bisphenol A type polyaromatic ether ketone
1h-NMR spectrogram;
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: Single Walled Carbon Nanotube of the present invention and pyrene molar content are the Raman spectrum of the Single Walled Carbon Nanotube containing pyrene polyaryletherketone physically modified of 10%;
Figure 10: the specific inductivity curve of Single Walled Carbon Nanotube/polyether-ether-ketone composite material of the present invention;
Figure 11: pyrene molar content of the present invention is the stereoscan photograph of the Single Walled Carbon Nanotube containing pyrene polyaryletherketone physically modified of 10%.
The hydrogen nuclear magnetic spectrogram of bisphenol A type polyaromatic ether ketone of the present invention (embodiment 1) that what Fig. 1 provided is, each hydrogen as we can see from the figure in polymer architecture has correct ownership.
Boracic acid esters molar fraction of the present invention that what Fig. 2 provided is be respectively the bisphenol A type polyaromatic ether ketone (embodiment 2,3,4) of the boracic acid esters of 10%, 20%, 30% hydrogen nuclear magnetic spectrogram (figure (a) to be boric acid ester molar content be 10% boric acid ester polyaryletherketone, figure (b) to be boracic acid esters molar content be 20% boric acid ester polyaryletherketone, figure (c) to be boracic acid esters molar content be 30% boric acid ester polyaryletherketone), each hydrogen as we can see from the figure in polymer architecture has correct ownership.
What Fig. 3 provided is of the present invention containing pyrene molar fraction be respectively 10%, 20% the hydrogen nuclear magnetic spectrogram containing pyrene bisphenol A type polyaromatic ether ketone (embodiment 5,6) (figure (a) to be pyrene molar content be 10% containing pyrene polyaryletherketone, figure (b) to be pyrene molar content be 20% containing pyrene polyaryletherketone), each hydrogen as we can see from the figure in polymer architecture has correct ownership.
What Fig. 4 provided is bisphenol A type polyaromatic ether ketone of the present invention (embodiment 1) DSC curve, and the Tg of bisphenol A-type polyether sulphone of the present invention is 159 degrees Celsius as we can see from the figure.
What Fig. 5 provided is the DSC curve that boracic acid esters molar fraction of the present invention is respectively the boracic acid esters bisphenol A type polyaromatic ether ketone (embodiment 2,3,4) of 10%, 20% and 30% respectively, and the Tg that boric acid ester molar fraction is respectively the boracic acid esters bisphenol A type polyaromatic ether ketone of 10%, 20%, 30% is as we can see from the figure respectively 162 degrees Celsius, 164 degrees Celsius and 168 degrees Celsius.
What Fig. 6 provided is respectively of the present invention be respectively containing pyrene molar fraction 10%, 20% and 30% the DSC curve containing pyrene bisphenol A type polyaromatic ether ketone (embodiment 5,6,7), the Tg containing pyrene bisphenol A type polyaromatic ether ketone being respectively 10%, 20% and 30% containing pyrene molar fraction of the present invention is respectively 169 degrees Celsius, 177 degrees Celsius and 195 degrees Celsius as we can see from the figure.
What Fig. 7 provided is respectively polymer with bis phenol A aryl ether ketone of the present invention and be respectively containing pyrene molar fraction 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 of the present invention containing pyrene molar fraction be respectively 10%, 20% be that 285 nanometers and 350 nanometers have obvious absorption peak containing pyrene bisphenol A type polyaromatic ether ketone at wavelength.
What Fig. 8 provided is respectively of the present invention containing pyrene molar fraction be 10% containing pyrene bisphenol A type polyaromatic ether ketone and containing pyrene molar fraction be 10% the TGA curve of the Single Walled Carbon Nanotube (embodiment 8) containing the modification of pyrene bisphenol A type polyaromatic ether ketone, as we can see from the figure containing pyrene molar fraction be 10% have good thermostability containing pyrene bisphenol A type polyaromatic ether ketone with containing the Single Walled Carbon Nanotube containing the modification of pyrene bisphenol A type polyaromatic ether ketone that pyrene molar fraction is 10%.
Pure Single Walled Carbon Nanotube that what Fig. 9 provided is respectively and of the present invention be the Raman spectrogram of the Single Walled Carbon Nanotube (embodiment 8) containing the modification of pyrene bisphenol A type polyaromatic ether ketone of 10% containing pyrene molar fraction, containing pyrene molar fraction is as we can see from the figure that the Single Walled Carbon Nanotube containing the modification of pyrene bisphenol A type polyaromatic ether ketone of 10% is compared with pure Single Walled Carbon Nanotube, Raman shift there occurs obvious change, prove containing pyrene molar fraction be 10% there occurs interaction containing the pyrene in pyrene bisphenol A type polyaromatic ether ketone and Single Walled Carbon Nanotube.Illustration is partial enlarged drawing.
What Figure 10 provided is pure polyether-ether-ketone resin of the present invention respectively, Single Walled Carbon Nanotube massfraction is the Single Walled Carbon Nanotube/polyether-ether-ketone composite material of 1%, the Single Walled Carbon Nanotube massfraction containing the modification of pyrene polyaryletherketone adopting HAAKE minilab II extrusion way to obtain is the Single Walled Carbon Nanotube/polyether-ether-ketone composite material of 1%, and the Single Walled Carbon Nanotube massfraction containing the modification of pyrene polyaryletherketone adopting the mode of solution blending to obtain is the dielectric properties scatter diagram of the Single Walled Carbon Nanotube/polyether-ether-ketone composite material (embodiment 9,10,11) of 1%.
In figure, PEEK is pure polyether-ether-ketone resin, PEEK/SCNT1% to be Single Walled Carbon Nanotube massfraction be 1% Single Walled Carbon Nanotube/polyether-ether-ketone composite material, PEEK/f-SCNT1%-Extrusion to be the Single Walled Carbon Nanotube massfraction containing the modification of pyrene polyaryletherketone adopting HAAKE minilab II extrusion way to obtain be 1% Single Walled Carbon Nanotube/polyether-ether-ketone composite material, PEEK/f-SCNT1%-Solvation to be the Single Walled Carbon Nanotube massfraction containing the modification of pyrene polyaryletherketone adopting the mode of solution blending to obtain be 1% Single Walled Carbon Nanotube/polyether-ether-ketone composite material.The Single Walled Carbon Nanotube massfraction containing the modification of pyrene polyaryletherketone obtained by the mode of solution blending is the specific inductivity of the Single Walled Carbon Nanotube/polyether-ether-ketone composite material of 1%, with Single Walled Carbon Nanotube massfraction be 1% Single Walled Carbon Nanotube/polyether-ether-ketone composite material with adopt HAAKEminilab II extrusion way to obtain be 1% containing the Single Walled Carbon Nanotube massfraction of pyrene polyaryletherketone modification Single Walled Carbon Nanotube/polyether-ether-ketone composite material is compared, improve a lot.
The Single Walled Carbon Nanotube massfraction containing the modification of pyrene polyaryletherketone that the mode of what Figure 11 provided is respectively employing solution blending of the present invention obtains is the stereoscan photograph of the Single Walled Carbon Nanotube/polyether-ether-ketone composite material (embodiment 11) of 1%.Single Walled Carbon Nanotube massfraction containing the modification of pyrene polyaryletherketone is that the Single Walled Carbon Nanotube in the Single Walled Carbon Nanotube/polyether-ether-ketone composite material of 1% is disperseed equably.
Embodiment
Embodiment 1
By 13.6974g bisphenol A monomer, 13.0920g4,4`-difluoro benzophenone monomer and 9.1205g Anhydrous potassium carbonate, 107mL tetramethylene sulfone, 36mL toluene, puts into the there-necked flask that nitrogen through hole, mechanical stirring and water-taker are housed, logical nitrogen, start stirring, be warming up to 135 DEG C to azeotropy dehydrant backflow, react 2.5 hours, get rid of azeotropy dehydrant, be warmed up to 175 DEG C and continue reaction 8 hours; The polymers soln obtained is separated out in deionized water, through pulverizing, washing, dry, obtain 23.4g bisphenol A type polyaromatic ether ketone polymkeric substance.
Molecular formula is as follows:
The wherein integer of p=13 ~ 22.
Embodiment 2
First there-necked flask is burned with gaslight under the condition vacuumized, nitrogen is filled with after cooling, put into magnetic stirring, add bisphenol A type polyaromatic ether ketone that 4.0748g (10mmol) embodiment 1 prepares and 0.6772g (2.7mmol) joins pinacol borate, then add 0.0269g [IrCl (COD)]
2and 0.0215g4,4'-di-t-butyl-2,2'-dipyridyl, vacuumize and be filled with high pure nitrogen, 3 times repeatedly, inject 50mL tetrahydrofuran (THF) and dissolve, sealing, in oil bath, 80 DEG C are reacted 12 hours; Dissolve with chloroform after cooling, adopt tlc silica gel (200 ~ 400 order) to filter, revolve and steam removing tetrahydrofuran (THF), acetone washes 5 times, dries, obtains the bisphenol A type polyaromatic ether ketone polymkeric substance of the boracic acid esters of the faint yellow bulk of 4.12g.
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 gaslight under the condition vacuumized, nitrogen is filled with after cooling, put into magnetic stirring, add bisphenol A type polyaromatic ether ketone that 4.0748g (10mmol) embodiment 1 prepares and 1.3544g (5.4mmol) joins pinacol borate, then add 0.0538g [IrCl (COD)]
2with 0.0430g 4,4'-di-t-butyl-2,2'-dipyridyl, vacuumize and be filled with high pure nitrogen, 3 times repeatedly, inject 50mL tetrahydrofuran (THF) and dissolve, sealing, in oil bath, 80 DEG C are reacted 12 hours; Dissolve with chloroform after cooling, adopt tlc silica gel (200 ~ 400 order) to filter, revolve and steam removing tetrahydrofuran (THF), acetone washes 5 times, dries, obtains the bisphenol A type polyaromatic ether ketone polymkeric substance of the boracic acid esters of the faint yellow bulk of 4.18g.
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 gaslight under the condition vacuumized, nitrogen is filled with after cooling, put into magnetic stirring, add bisphenol A type polyaromatic ether ketone that 4.0748g (10mmol) embodiment 1 prepares and 2.0316g (8mmol) joins pinacol borate, then add 0.0806g [IrCl (COD)]
2with 0.0644g 4,4'-di-t-butyl-2,2'-dipyridyl, vacuumize and be filled with high pure nitrogen, 3 times repeatedly, inject 50mL tetrahydrofuran (THF) and dissolve, sealing, in oil bath, 80 DEG C are reacted 12 hours; Dissolve with chloroform after cooling, adopt tlc silica gel (200 ~ 400 order) to filter, revolve and steam removing tetrahydrofuran (THF), acetone washes 5 times, dries, obtains the bisphenol A type polyaromatic ether ketone polymkeric substance of the boracic acid esters of the faint yellow bulk of 4.25g.
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 gaslight under the condition vacuumized, be filled with nitrogen after cooling, put into magnetic stirring, add bisphenol A type polyaromatic ether ketone and the 0.4217g 1-bromine pyrene of the boracic acid esters that 4.2019g embodiment 2 prepares, add 0.0174g tetra-triphenylphosphine palladium and 0.4146g salt of wormwood again, then vacuumize and be filled with high pure nitrogen, 3 times repeatedly, inject 100mL tetrahydrofuran (THF) and dissolve, finally, slow injection 5mL distilled water, sealing, 80 DEG C of reaction 12h in oil bath; Revolve and steam except desolventizing, use acetone extraction 24h, dissolve with chloroform, employing tlc silica gel filters, and revolve and steam except desolventizing, acetone washes 5 times, filter, dry, obtain faint yellow blocks of solid, namely obtain the faint yellow pyrene molar fraction of 4.51g 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 gaslight under the condition vacuumized, be filled with nitrogen after cooling, put into magnetic stirring, add bisphenol A type polyaromatic ether ketone and the 0.8434g 1-bromine pyrene of the boracic acid esters that 4.3288g embodiment 3 prepares, add 0.0347g tetra-triphenylphosphine palladium and 0.8292g salt of wormwood again, then vacuumize and be filled with high pure nitrogen, 3 times repeatedly, inject 100mL tetrahydrofuran (THF) and dissolve, finally, slow injection 5mL distilled water, sealing, 80 DEG C of reaction 12h in oil bath; Revolve and steam except desolventizing, use acetone extraction 24h, dissolve with chloroform, employing tlc silica gel filters, and revolve and steam except desolventizing, acetone washes 5 times, filter, dry, obtain the faint yellow pyrene molar fraction of 4.81g 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 gaslight under the condition vacuumized, be filled with nitrogen after cooling, put into magnetic stirring, add bisphenol A type polyaromatic ether ketone and the 1.2651g 1-bromine pyrene of the boracic acid esters that 4.4558g embodiment 4 prepares, add 0.0522g tetra-triphenylphosphine palladium and 1.2438g salt of wormwood again, then vacuumize and be filled with high pure nitrogen, 3 times repeatedly, inject 100mL tetrahydrofuran (THF) and dissolve, finally, slow injection 5mL distilled water, sealing, 80 DEG C of reaction 12h in oil bath; Revolve and steam except desolventizing, use acetone extraction 24h, dissolve with chloroform, employing tlc silica gel filters, and revolve and steam except desolventizing, acetone washes 5 times, filter, dry, obtain the faint yellow pyrene molar fraction of 5.48g 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 Single Walled Carbon Nanotube of the polyaryletherketone modification of 10%.PEEK-Py-10 prepared by 1.875 grams of embodiments 5 is dissolved in 1500mL chloroform, then 400 milligrams of Single Walled Carbon Nanotube are joined in the chloroformic solution of this PEEK-Py-10, ultrasonic 4h in a water bath and under 20 DEG C of conditions, then place 12 hours, pour out 2/3 of supernatant liquid and filter with glass wool, leave standstill 12h, finally obtain the homogeneous solution of black.
Embodiment 9
Single Walled Carbon Nanotube massfraction is the preparation (adopting the mode of solution blending to prepare) of the Single Walled Carbon Nanotube/polyether-ether-ketone composite material of 1%.Take 0.4g Single Walled Carbon Nanotube and join magnetic agitation 12h in chloroformic solution, then under 20 DEG C of conditions ultrasonic 2h; The polyether-ether-ketone ultrafine powder (400 orders, Changchun Jida special plastic engineering Co., Ltd) taking 39.6g joins in the dispersion liquid of above-mentioned Single Walled Carbon Nanotube, ultrasonic 1h under the condition of 20 DEG C, revolves and steams except desolventizing, at 120 DEG C of process 12h.Then, the 39.92g polymers soln obtained is joined in the there-necked flask of the 1000mL that thermometer, mechanical stirring and drying tube are housed, add 160g sulfobenzide again, be heated to 280 DEG C, thing to be polymerized dissolves rear continuation completely and stirs 30min, then discharging is on iron plate, pulverize with homogenizer, boil 5 times with acetone, suction filtration, put into 120 DEG C, baking oven and dry 12h, for subsequent use.
Embodiment 10
Single Walled Carbon Nanotube massfraction is the preparation (employing extrude mode prepare) of the functionalization Single Walled Carbon Nanotube/polyether-ether-ketone composite material of 1%.Get in 1.875g embodiment 5 containing pyrene molar fraction be 10% poly aryl ether ketone polymer dissolve in 1500mL chloroformic solution, then take 0.4g Single Walled Carbon Nanotube and join magnetic agitation 12h in polymers soln, ultrasonic 2h under 20 DEG C of conditions again, taking 37.725g polyether-ether-ketone ultrafine powder joins in the dispersion liquid of above-mentioned Single Walled Carbon Nanotube, ultrasonic 1h under the condition of 20 DEG C, revolve and steam except desolventizing, at 120 DEG C of process 12h.Then, the 39.94g polymkeric substance obtained is added HAAKE minilab II forcing machine, in 380 DEG C of (fusion plastifications under condition in extruder barrel, form polyether-ether-ketone melt, in extruder barrel, again carry out compound blended, then extrude material strip through head, granulation.Put into 120 DEG C, baking oven and dry 12h, for subsequent use.
Embodiment 11
Single Walled Carbon Nanotube massfraction is the preparation (adopting the mode of solution blending to prepare) of the functionalization Single Walled Carbon Nanotube/polyether-ether-ketone composite material of 1%.Get in 1.875g embodiment 5 containing pyrene molar fraction be 10% poly aryl ether ketone polymer dissolve in 1500mL chloroformic solution, then take 0.4g Single Walled Carbon Nanotube and join magnetic agitation 12h in polymers soln, ultrasonic 2h under 20 DEG C of conditions again, taking 37.725g polyether-ether-ketone ultrafine powder joins in the dispersion liquid of above-mentioned Single Walled Carbon Nanotube, ultrasonic 1h under the condition of 20 DEG C, revolve and steam except desolventizing, at 120 DEG C of process 12h.Then, the 39.94g polymkeric substance obtained is joined in the there-necked flask of the 1000mL that thermometer, mechanical stirring and drying tube are housed, add 160g sulfobenzide again, be heated to 280 DEG C, thing to be polymerized dissolves rear continuation completely and stirs 30min, then discharging is on iron plate, pulverize by high-speed stirring, boil 5 times with acetone, suction filtration, put into 120 DEG C, baking oven and dry 12h, for subsequent use.
Embodiment 12
Product PEEK, embodiment 9,10,11 obtained uses Mini Jet II injection moulding machine to carry out injection moulding, make tensile bars (the long 75mm of two dumbbell shapes respectively, wide 10mm and 5mm, thick 2mm, for tensile property test), bending batten (long 80mm, wide 10mm, a thick 4mm, for bending property test) and diameter be the sequin (thick 2mm, the test for dielectric properties) of 20mm.
Table 1: the mechanical property of pure polyether-ether-ketone, Single Walled Carbon Nanotube/polyether-ether-ketone composite material, functionalized carbon nano-tube/polyether-ether-ketone composite material
Note: PEEK is that (insert in sulculus by polyether-ether-ketone raw material, groove end is connected to tubule to melting index, and capillary diameter is 3mm, and pipe range is 8mm.After heating 380 DEG C, extrude downwards by 5 kilograms of counterweight applying loads in polyether-ether-ketone upper end, measures the weight that was extruded in 10 minutes of polyether-ether-ketone) be the polyether-ether-ketone resin of 19g/10min; SCNT is Single Walled Carbon Nanotube; F-SCNT be through pyrene molar content be 10% containing the Single Walled Carbon Nanotube after pyrene polyaryletherketone physically modified.In table PEEK/f-SCNT-E to be the Single Walled Carbon Nanotube massfraction containing the modification of pyrene polyaryletherketone adopting HAAKE minilab II extrusion way to obtain be 1% Single Walled Carbon Nanotube/polyether-ether-ketone composite material (embodiment 10 product), PEEK/SCNT-S to be the Single Walled Carbon Nanotube massfraction adopting the mode of solution blending to obtain be 1% Single Walled Carbon Nanotube/polyether-ether-ketone composite material (embodiment 9 product), PEEK/f-SCNT-S to be the Single Walled Carbon Nanotube massfraction containing the modification of pyrene polyaryletherketone adopting the mode of solution blending to obtain be 1% Single Walled Carbon Nanotube/polyether-ether-ketone composite material (embodiment 11 product).
As shown in table 1, the polyether-ether-ketone composite material (compared with pure polyether-ether-ketone resin) that Single Walled Carbon Nanotube is filled, its tensile strength, flexural strength, modulus in flexure are not significantly improved, and elongation at break reduces.And the mechanical property of the matrix material adopting the mode (embodiment 10) extruded to obtain through the pyrene molar content polyether-ether-ketone of filling containing the Single Walled Carbon Nanotube after pyrene polyaryletherketone physically modified that is 10% does not only improve and declines on the contrary.But the matrix material (compared with the polyether-ether-ketone composite material of filling with Single Walled Carbon Nanotube) its tensile strength, flexural strength, modulus in flexure and the elongation at break that adopt the mode (embodiment 11) of solution blending to obtain through the pyrene molar content polyether-ether-ketone of filling containing the Single Walled Carbon Nanotube after pyrene polyaryletherketone physically modified that is 10% are all significantly improved.
The above; be only embodiment of the present invention; but protection domain of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection domain of the present invention.
Claims (4)
1., containing pyrene polyaryletherketone, 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 polyaryletherketone according to claim 1, it is characterized in that: be that the polyaryletherketone of boracic acid esters as follows for structural formula and the 1-bromine pyrene being its 1 ~ 2 times of molar weight are put into reaction vessel, add four triphenylphosphine palladiums of the polyaryletherketone mesoboric acid ester molar weight 1% ~ 3% being boracic acid esters again, be the salt of wormwood of the polyaryletherketone mesoboric acid ester molar weight 3 times of boracic acid esters, then vacuumize and be filled with high pure nitrogen, 3 ~ 5 times repeatedly; After injecting the dissolving of organic solvents, chloroform, tetrahydrofuran (THF) or dioxane, more slowly inject the distilled water of organic solvent volume 3% ~ 10%, sealing, in oil bath, 60 ~ 80 DEG C are reacted 10 ~ 20 hours; Revolve and steam removing organic solvent, with acetone extraction 20 ~ 30h, dissolve with organic solvent trichloromethane, tetrahydrofuran (THF) or dioxane, adopt column layer chromatography silicone rubber post to filter, revolve and steam removing organic solvent, acetone washes 4 ~ 6 times, filters, and dries, and obtains containing pyrene polyaryletherketone,
n＝15～25；2x+y+z＝0.1～0.3，t+(2x+y+z)＝1。
3. the Single Walled Carbon Nanotube containing the modification of pyrene polyaryletherketone, it is characterized in that: be containing pyrene polyaryletherketone tetrahydrofuran (THF), chloroform or 1 by according to claim 1,2-dichlorobenzene dissolves, configuration concentration is the polymers soln of 1 ~ 2mg/mL, then Single Walled Carbon Nanotube is added, Single Walled Carbon Nanotube is 16:70 ~ 80 with the mass ratio containing pyrene polyaryletherketone, ultrasonic 2 ~ 4h under water-bath and 20 ~ 30 DEG C of conditions, then 8 ~ 16h is placed, glass wool is finally adopted to filter, leave standstill 12 ~ 24h, thus obtain the Single Walled Carbon Nanotube containing the modification of pyrene polyaryletherketone.
4. functionalization Single Walled Carbon Nanotube/polyether-ether-ketone composite material, it is characterized in that: be first use tetrahydrofuran (THF) by according to claim 1 containing pyrene polyaryletherketone, chloroform or 1, 2-dichlorobenzene dissolves, configuration concentration is the polymers soln of 1 ~ 2mg/mL, add Single Walled Carbon Nanotube, Single Walled Carbon Nanotube is 16:70 ~ 80 with the mass ratio containing pyrene polyaryletherketone, ultrasonic 2 ~ 4h, add 200 ~ 400 object polyether-ether-ketone ultrafine powders again, it is 1:15 ~ 25 with the mass ratio containing pyrene polyaryletherketone, ultrasonic 0.5 ~ 1h, revolve and steam except desolventizing, dry, obtain gray solid powder, joined in the there-necked flask that thermometer, mechanical stirring and drying tube are housed by the pressed powder obtained, add tetramethylene sulfone or sulfobenzide, open and stir, be heated to 250 ~ 290 DEG C, after dissolution of solid, stir 0.5 ~ 1h again, discharging is on iron plate, with high speed agitator, discharging after product is ground into powder, then boils 3 ~ 5 times with acetone, dry, obtain grey powder, i.e. functionalization Single Walled Carbon Nanotube/polyether-ether-ketone composite material.
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