CN105838086A - Preparation method of sulfonated carbon nano tube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material - Google Patents
Preparation method of sulfonated carbon nano tube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
Abstract
The invention discloses a preparation method of a sulfonated carbon nano tube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material. The preparation method includes: performing surface modification on polyether-ether-ketone to enable carbonyl on the surface to be reduced to be hydroxyl to form hydroxylated polyether-ether-ketone; oxidizing a carbon nano tube to obtain an oxidized carbon nano tube containing carboxyl, and sulfonating the oxidized carbon nano tube containing carboxyl to obtain a sulfonated carbon nano tube; enabling a sulfonic group on the surface of the sulfonated carbon nano tube and hydroxyl on the surface of the hydroxylated polyether-ether-ketone to react to generate sulfonated carbon nano tube grafted hydroxylated polyether-ether-ketone; mixing the sulfonated carbon nano tube grafted hydroxylated polyether-ether-ketone with polyether-ether-ketone well to form a mixed raw material, and performing hot-press forming to form the sulfonated carbon nano tube grafted hydroxylated polyether-ether-ketone/polyether-ether-ketone composite material, wherein the mass percentage of polyether-ether-ketone in the mixed raw material is 2-5%. The composite material prepared by the method has the advantages of high strength, high modulus, high hardness and high heat deformation temperature.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of CNT and strengthen the preparation side of polyethers ether composite
Method, particularly relates to the preparation method of a kind of Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone/polyether-ether-ketone composite material.
Background technology
Polyether-ether-ketone resin is a kind of thermoplastic special engineering plastic, and it has temperature classification height, radiation hardness, impact strength
The features such as height, rub resistance and good, fire-retardant, the excellent electrical property of fatigue durability, in Aero-Space, automobile, electric, change
Work, the field such as mechanical and medical obtain relatively broad application.But, the glass transition temperature of pure polyether-ether-ketone resin is
143 DEG C, fusing point is 334 DEG C, and fragility is big, cutting performance is poor, limits its range of application.
CN104804373A discloses a kind of amination carbon nano-tube/poly polyetherether ketone composite, and it uses amination carbon nanometer
Pipe is combined by simple intermolecular force with original polyether-ether-ketone, but its compatibility is poor.This patent simultaneously
Use the preparation carrying out composite at solution mixing method, by amination CNT and the DMF dissolved with certain polyether-ether-ketone
Solution carries out mixing ultrasonic disperse, the at a certain temperature volatilization of fall solvent, to obtain composite.But solution mixing method is easy
Cause amination CNT at bottom deposit, cause its dispersiveness poor, simultaneously with the volatilization of solvent, cause prepared material
Material is internal there is less hole, makes the mechanical property of material and heat endurance decline.
Summary of the invention
In order to solve the deficiencies in the prior art, the invention discloses a kind of Sulfonated carbon nanotube grafting hydroxylating and gather
The preparation method of ether ether ketone/polyether-ether-ketone composite material, it is desirable to provide one has high intensity, high-modulus, high rigidity, high heat change
Shape temperature, the composite of high-corrosion resistance.
The present invention is achieved through the following technical solutions:
The preparation method of a kind of Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone/polyether-ether-ketone composite material, including walking as follows
Rapid:
(1) polyether-ether-ketone is carried out surface modification so that it is the carbonyl reduction on surface is hydroxyl, form hydroxylating polyether-ether-ketone；
(2) CNT oxidation being obtained carboxylic oxide/carbon nanometer tube, further sulfonation obtains Sulfonated carbon nanotube；
(3) Sulfonated carbon nanotube and hydroxylating polyether-ether-ketone react generation Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone；
(4) Sulfonated carbon nanotube is grafted hydroxylating polyether-ether-ketone be mixed to form with polyether-ether-ketone and mix raw material, hot-forming system
Become Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone/polyether-ether-ketone composite material, wherein, the matter of polyether-ether-ketone in mixing raw material
Amount mark is 2-5%.
Preferably, the mixing raw material in step (4) is at 378-382 DEG C, hot-forming under the conditions of 3-5MPa；Step
(2) carboxyl in carboxylic oxide/carbon nanometer tube in obtains sulfonation carbon with the amino dehydrating condensation in p-aminobenzene sulfonic acid and receives
Mitron.
As a kind of preferred embodiment, the preparation method of described carboxylic oxide/carbon nanometer tube is: by CNT
Join mass concentration and be 98% concentrated sulfuric acid and mass concentration is in the mixed solution that 65% red fuming nitric acid (RFNA) volume ratio is 3:1, at 45-55
Ultrasonic disperse 100-140min at DEG C,
Now anti-raw reaction is:
In formula: C-COOH: carboxylic oxide/carbon nanometer tube
Suction filtration obtains filter cake, and cleans filter cake to neutral, after filter cake is vacuum dried 11-13h at 88-92 DEG C by deionized water
Obtain the carboxylic oxide/carbon nanometer tube being dried.
The preparation method of described Sulfonated carbon nanotube is:
Now anti-raw reaction is:
The concrete preparation method of described Sulfonated carbon nanotube is:
(1) carboxylic oxide/carbon nanometer tube is placed in the DCC ethanol solution mixed by DCC and absolute ethyl alcohol, in 28-
At 32 DEG C, ultrasonic disperse 20-40min obtains carbon nano-tube solution；
(2) p-aminobenzene sulfonic acid is dissolved in deionized water, obtains p-aminobenzene sulfonic acid solution；
(3) carbon nano-tube solution and p-aminobenzene sulfonic acid solution are mixed, at 28-32 DEG C after ultrasonic disperse 20-40min,
Magnetic agitation reaction 5-7h under the conditions of 48-52 DEG C, suction filtration obtains filter cake, and cleans to neutral by absolute ethyl alcohol or deionized water,
Filter cake is vacuum dried at 88-92 DEG C 12h, obtains the Sulfonated carbon nanotube being dried；
Wherein, in step (3), in carbon nano-tube solution and p-aminobenzene sulfonic acid solution, the amount of solute is equal.
The preferred preparation method of described hydroxylating polyether-ether-ketone is: by polyether-ether-ketone, sodium borohydride and DMSO at 118-122
Reaction time 7-9h at DEG C, obtains hydroxylating polyether-ether-ketone, and suction filtration obtains filter cake, and successively with absolute ethyl alcohol, deionized water, salt
Acid is washed, and filter cake is dried at 78-82 DEG C 10-14h, obtains the hydroxylating polyether-ether-ketone being dried.It is preferred that polyethers ether
Ketone is (4-6) with the mass ratio of sodium borohydride: 1, and polyether-ether-ketone is (0.03-0.05) g/mL with the mass volume ratio of DMSO.
Its reaction equation is:
As a kind of preferred embodiment, described Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone can be made as follows
For forming:
(1) Sulfonated carbon nanotube is joined in DMF, ultrasonic disperse 20-40min at 48-52 DEG C, form solution A；
(2) hydroxylating polyether-ether-ketone is added in the DMF solution containing DCC and DMAP, ultrasonic disperse 20-at 48-52 DEG C
40min, forms B solution；
(3), after solution A and B solution being mixed, ultrasonic disperse 25-35min at 48-52 DEG C, the most under an inert atmosphere in 48-
Form C solution after 52 DEG C of back flow reaction 7-9h, in C solution, add absolute ethyl alcohol, locate under the conditions of the stirring in water bath of 48-52 DEG C
Reason 25-35min, carries out gained material suction filtration and obtains just filter cake, will adsorb DCC and DMAP on first filter cake with absolute ethyl alcohol
Obtain filter cake after Xi Jinging, filter cake is vacuum dried at 48-52 DEG C 11-13h, obtain Sulfonated carbon nanotube grafting hydroxylating polyethers
Ether ketone.
Its reaction equation is:
It is preferred that in step (1), Sulfonated carbon nanotube is 0.004g/mL with the mass volume ratio of DMF；In step (2), hydroxyl
Change polyether-ether-ketone, the mass ratio of DCC and DMAP is 6:8:1, hydroxylating polyether-ether-ketone and the mass body of DMF
Long-pending ratio is 0.05 g/mL.
The preferred preparation method of described Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone/polyether-ether-ketone composite material is:
(1) mixing raw material is joined in absolute ethyl alcohol, at normal temperatures after ultrasonic disperse 25-35min, vacuum at 48-52 DEG C
It is dried 18-22min, then proceedes to ultrasonic disperse 25-35min at normal temperatures, repeat above-mentioned vacuum drying, ultrasonic disperse 3-5 time
After, at 48-52 DEG C, it is vacuum dried 3-5h, wherein, Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone and the matter of absolute ethyl alcohol
Amount volume ratio is 0.001g/mL；
(2) the mixing raw material after step (1) being processed joins in mould and is compacted, and to mould low-temperature prewarming to 148-152 DEG C；
(3) vulcanizing press is heated to 378-382 DEG C, preheated mould is placed between the heating plate of vulcanizing press,
Matched moulds, heats 2h between heating plate by mould, and exhaust number of times, at 3-5MPa, is set to 3 times, will be vented distance by Stress control
It is set to 2s；
(4) by Stress control at 14-16MPa, vulcanize 10min, obtain Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone/polyethers
Ether ketone composite.
Certainly, use vulcanizing press simply a kind of embodiment, hot press, extruder, injection machine etc. other be hot pressed into
Type equipment, at 378-382 DEG C, can also obtain Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone/polyether-ether-ketone multiple under 3-5MPa
Condensation material.
As common knowledge, chemicals is dried before use, also needs to if desired be ground, certain present invention
Chemicals used by is no exception.
The present invention uses Sulfonated carbon nanotube and hydroxylating polyether-ether-ketone to carry out graft reaction, makes two kinds of materials by chemistry
Key is attached, with promote CNT in the dispersion on hydroxylating polyether-ether-ketone surface, with promote its in the composite point
Dissipate.Add Sulfonated carbon nanotube compatibility in parent polyether-ether-ketone.Use hot-forming method by sulfonation carbon simultaneously
Nanotube/hydroxylating polyether-ether-ketone is shaped with original polyether-ether-ketone, comparative solution mixed-forming, makes the inside of material not have
Hole, adds the stablizing of structure of material, can increase substantially the Chemical Physics performance of polyether-ether-ketone, strengthen acidproof,
Alkali resistance and crocking resistance, expand the range of application of polyether-ether-ketone.
Figure of description
Fig. 1 is the infrared spectrum of modified CNT.
Fig. 2 is the infrared spectrum of modified polyether-ether-ketone.
Fig. 3 is the thermal multigraph of modified CNT.
The thermal multigraph that the polyether-ether-ketone that Fig. 4 is modified is sent out.
Fig. 5 is the scanning electron microscope (SEM) photograph of modified CNT.
Fig. 6 is the scanning electron microscope (SEM) photograph of modified polyether-ether-ketone.
Fig. 7 is the storage modulus figure of material.
Fig. 8 is the fissipation factor figure of material.
Detailed description of the invention
Hereinafter describe and be used for disclosing the present invention so that those skilled in the art are capable of the present invention.Below describe in excellent
Select embodiment to be only used as citing, it may occur to persons skilled in the art that other obvious modification.
Embodiment
The preparation method of a kind of Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone/polyether-ether-ketone composite material, including such as
Lower step:
(1) oxidation processes CNT
1) CNT is placed in glass dish, places it in the vacuum drying chamber of 70 DEG C ± 2 DEG C and be dried 12h；
2) weigh dried CNT 3 g ± 0.001 g, be poured in the there-necked flask of 500mL, measure respectively
The concentrated sulfuric acid of 180mL ± 1mL and the red fuming nitric acid (RFNA) of 60mL ± 1mL, pour in there-necked flask；
3) there-necked flask is placed in dispersion Ultrasound Instrument, carries out ultrasonic disperse, dispersion temperature 50 DEG C ± 2 DEG C is set；Disperse ultrasonic
2h,
Now anti-raw reaction is:
In formula: C-COOH: carboxylic oxide/carbon nanometer tube；
4), after oxidation reaction, ultrasonic wave separating apparatus is closed, the room temperature that the oxide in there-necked flask is cooled down, the most past
The beaker of 2000mL adds the deionized water of 1000mL, then the solution after oxidation is poured in beaker, form mixed solution,
By its static 24h；
5) suction filtration, carries out suction filtration under the effect of water circulating pump with Buchner funnel and micropore filter paper, is discarded by its supernatant, protects
Stay filter cake；
6) by filter cake as in beaker, it is being rinsed by the deionized water of 300mL, is stirring 5min simultaneously, then leak with Bu Shi
Bucket and micropore filter paper carry out suction filtration, wash in Buchner funnel by deionized water after obtaining filter cake, until by the carbon of oxidation
Nanotube washes neutrality；
7) it is dried, the filter cake after washing is placed in glass dish, puts in the vacuum drying chamber of 90 DEG C ± 2 DEG C and be dried, dry
Dry 12h, take out, preserve, i.e. can be aoxidized after CNT.
(2) preparation of Sulfonated carbon nanotube
1) accurately weigh acidified rear oxide/carbon nanometer tube 0.3g ± 0.001g containing carboxyl, CNT is poured into three mouthfuls
In flask；
2) measure the absolute ethyl alcohol of 75mL ± 0.1mL with graduated cylinder, then absolute ethyl alcohol is poured in the beaker of 100mL, more accurate
Really weighing 0.5g ± 0.001g DCC, the N that will weigh up, N-dicyclohexyl carbon diamines is in pouring ethanol solution into, by beaker
Being placed in Ultrasound Instrument, arranging ultrasonic temperature is 30 DEG C ± 2 DEG C, carries out sonic oscillation, to accelerate DCC dissolving；
3) the DCC ethanol solution after dissolving pours there-necked flask into, there-necked flask is placed on Ultrasound Instrument, arranges ultrasonic temperature
Spending 30 DEG C ± 2 DEG C, ultrasonic disperse 30min, to promote CNT dispersion in absolute ethyl alcohol；
4) accurately weigh 0.3g ± 0.001g p-aminobenzene sulfonic acid, p-aminobenzene sulfonic acid is poured in the beaker of 100mL, consumption
Cylinder measures the deionized water of 75mL ± 0.1mL, deionized water is poured in beaker, is placed in Ultrasound Instrument by beaker, arranges ultrasonic
Temperature 30 DEG C ± 2 DEG C, carries out ultrasonic vibration, to accelerate the dissolving of p-aminobenzene sulfonic acid；
5) aqueous solution of p-aminobenzene sulfonic acid after dissolving is poured in there-necked flask, now continues to be placed on there-necked flask super
On sound instrument, ultrasonic temperature 30 DEG C ± 2 DEG C, ultrasonic disperse 20min are set；
6) being fixed on water-bath by there-necked flask, arranging water-bath temperature is 50 DEG C ± 2 DEG C, puts into magneton simultaneously, makes it anti-
6h should be reacted under certain rotating speed,
Now anti-raw reaction is:
7) after question response completes, it is cooled to room temperature, then carries out suction filtration with micropore filter paper, give up filtrate, obtain filter cake
After；
8) filter cake is placed in glass dish, is rinsed with substantial amounts of ethanol solution, then carrying out suction filtration with micropore filter paper,
Give up filtrate, obtain clean filter cake；
9) again filter cake is placed in glass dish, is rinsed by deionized water in large quantities, use micropore the most on a buchner funnel
Filter paper carries out suction filtration, again obtains filter cake, discards filtrate.Continuation deionized water is rinsed, until the pH value of solid is close
7；
10) putting it to, in clean glass dish, put in vacuum drying chamber, arranging baking temperature is 90 DEG C ± 2 DEG C, dry
Dry case continues drying out 12h, obtains dried Sulfonated carbon nanotube.
(3) preparation of hydroxylating polyether-ether-ketone
1) being dried, the polyether-ether-ketone weighing about 150g is placed in glass dish, is placed in vacuum drying chamber by glass dish, arranges
Baking temperature is 80 DEG C ± 2 DEG C, is dried 12 h；
2) take a certain amount of dried polyether-ether-ketone, be placed in high speed disintegrator and pulverize, gathering after then pulverizing
The ether ether ketone sieve (aperture is 0.6mm) of 30 mesh screens；
3) DMSO measuring 100mL ± 1mL is placed in 500mL there-necked flask, and the polyether-ether-ketone 4g after weighing pulverizing ±
0.001g pours in there-necked flask, weighs the sodium borohydride of 0.8g ± 0.001g afterwards, moves in there-necked flask；
4) there-necked flask is put in oil bath (dimethicone), makes in 1/2 immersion oil bath of there-necked flask.Oil bath temperature is set
Degree is 120 DEG C ± 2 DEG C, is stirred at certain rotating speed, and reaction carries out 8h；
Its reaction equation is:
5) after reaction completes, allow the temperature of there-necked flask drop to room temperature, carry out suction filtration with micropore filter paper, and successively with anhydrous
Ethanol, deionized water, and hydrochloric acid solution wash；
6) after suction filtration completes, discard filtrate, the filter cake obtained is placed in glass dish, then glass dish is placed on vacuum drying
In case, arranging baking temperature is 80 DEG C ± 2 DEG C, is dried 12h；
7) grinding, move on to, in mortar, simply grind by dried polyether-ether-ketone, the hydroxylating after grinding is gathered
Ether ether ketone leaves in inside plastic bag standby.
(4) Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone is prepared
1) Sulfonated carbon nanotube of 0.2g ± 0.001g is joined the DMF(N containing 50mL ± 1mL, dinethylformamide)
There-necked flask in, ultrasonic disperse 30min ± 2min at 50 DEG C ± 2 DEG C, formed A aaerosol solution；
2) 3g ± 0.001g hydroxylating polyether-ether-ketone is joined containing 60mL ± 1mL's that DCC and DMAP mass ratio is 8:1
In DMF solution beaker, being placed in Ultrasound Instrument by beaker, arranging ultrasonic temperature is 50 DEG C ± 2 DEG C, ultrasonic disperse 30min, forms B
Aaerosol solution.Wherein the mass volume ratio of DCC Yu DMF is 2/30 g/mL；
3) after excusing from death dispersion completes, B aaerosol solution is poured into completely in the there-necked flask of A aaerosol solution, continue there-necked flask
Being placed in Ultrasound Instrument, arranging ultrasonic temperature is 50 DEG C ± 2 DEG C, ultra-dispersed sound 30min ± 2min；
4) moving on to there-necked flask, on magnetic force heating and stirring device, be fixed stirring, arranging water-bath temperature is 50 DEG C ± 2
DEG C, open agitating device, add reflux, be filled with nitrogen simultaneously, persistently nitrogen be filled with 30min ± 2min, allow reaction exist
Carry out in the case of anoxybiotic, react 8h, form C aaerosol solution；
Its reaction equation is:
5) by during in there-necked flask, C aaerosol solution pours the beaker of 1000mL into, simultaneously toward addition 300mL ± 10mL in beaker without
Water-ethanol, is placed on beaker on stirring in water bath device, is stirred, and makes DMF and absolute ethyl alcohol be sufficiently mixed；
6) suspension micropore filter paper is carried out suction filtration on a buchner funnel, be rinsed with absolute ethyl alcohol, absorption is being suspended
DCC and DMAP on thing rinses well, then discards filtrate, is placed in glass dish by filter cake；
7) glass dish that will be equipped with filter cake is placed in vacuum drying chamber dry, and arranging baking temperature is 50 DEG C ± 2 DEG C, when being dried
Between 12h.
(5) composite shaping
1) Sulfonated carbon nanotube is grafted hydroxylating polyether-ether-ketone and weighs certain content, be simultaneously introduced original polyether-ether-ketone, make carbon
Nanotube content is adjusted to 3%, pours in the beaker containing absolute ethyl alcohol by the mixing raw material of 3%, and Sulfonated carbon nanotube is with anhydrous
The mass volume ratio of ethanol is 0.001g/mL, then carries out ultrasonic disperse, when after dispersion 30min, is placed on 50 DEG C ± 2 DEG C
Vacuum drying chamber in be dried 20min ± 2min；
2) beaker is taken out, continue to be placed on ultrasonic 30min ± 2min in Ultrasound Instrument, continue to put in vacuum drying chamber dry
20min±2min；
3) then take out beaker and continue ultrasonic disperse, after being so repeated 4 times, beaker is placed in vacuum drying chamber, 50 DEG C ± 2
DEG C vacuum drying chamber in, mix raw material drying 4h；
4) dried mixing raw material added in mould cold pressing, raw material is compacted, after mould is placed on 150 DEG C ± 2 DEG C
Vacuum drying chamber in heat, make mould carry out low-temperature prewarming temperature and reach 150 DEG C ± 2 DEG C；
5) vulcanizing press is heated to 380 DEG C ± 2 DEG C, the mould after low-temperature prewarming is put between heating plate, matched moulds, will pressure
Power controls at 3-5MPa, and then mould heats 2h on hot plate；
6) exhaust number of times is set to 3 times；
7) exhaust distance is set to 2s；
8) by Stress control at 15MPa, vulcanize 10min, then its moulding material is taken out.
Fig. 1 is the infrared spectrum of modified CNT, the infrared curve of various CNTs during modifying process, wherein
1 is the infrared spectrum of CNT, and 2 is the infrared spectrum of carboxylic oxide/carbon nanometer tube, and 3 is the infrared of Sulfonated carbon nanotube
Spectrogram, by the analysis of 1 and 2 two kind of spectrogram being drawn, carbon nano tube surface occurs in that carboxyl, the analysis to 2 and 3 obtains containing carboxylic
The oxide/carbon nanometer tube surface of base occurs in that amide group, and the sulfonic acid group of correspondence, it was demonstrated that CNT sulfonation success.
Fig. 2 is the infrared spectrum of modified polyether-ether-ketone, the infrared curve of various polyether-ether-ketones in modifying process, wherein
1 is the infrared spectrum of polyether-ether-ketone, and 2 is the infrared spectrum of hydroxylating polyether-ether-ketone, and 3 is Sulfonated carbon nanotube graft polyether ether ketone
Infrared spectrum, by 1 and 2 contrast obtain occurring in that on polyether-ether-ketone hydroxyl, it was demonstrated that hydroxylating modification success, 2 and 3 contrast
To the success of hydroxylating polyether-ether-ketone surface grafting Sulfonated carbon nanotube.
Fig. 3 is the thermal multigraph of modified CNT, the thermogravimetric curve figure of various CNTs in modifying process, wherein
1 is CNT, and 2 is carboxylic oxide/carbon nanometer tube, and 3 is Sulfonated carbon nanotube, is demonstrated by the contrast of three kinds of curves
The weight-loss ratio of CNT is zero, and carboxylic oxide/carbon nanometer tube is more than 90%, and Sulfonated carbon nanotube then demonstrates weightlessness
Rate is about 50%.And the only upper p-aminobenzene sulfonic acid of grafting just there will be the biggest weightlessness for modified carbon nano-tube
Rate.
The thermal multigraph that the polyether-ether-ketone that Fig. 4 is modified is sent out, the thermogravimetric curve figure of polyether-ether-ketone in modifying process, wherein 1
Being polyether-ether-ketone, 2 is hydroxylating polyether-ether-ketone, and 3 is the polyether-ether-ketone of graft sulfonation CNT.There are 1 and 2 analyses can obtain polyethers
The decomposition temperature of ether ketone is at 550 DEG C, and due to surface texture, modified polyether-ether-ketone there occurs that change causes decomposition temperature to drop
Low.During by 2 and 3 are compared beginning, hydroxylated polyether-ether-ketone is weightless fast, and the polyether-ether-ketone of Sulfonated carbon nanotube grafting loses
Weight is slow, and when arriving about 480 DEG C, weightlessness speed is essentially the same.
Fig. 5 is the scanning electron microscope (SEM) photograph of modified CNT, and wherein A is CNT, and B is carboxylic carbonoxide
Nanotube C is Sulfonated carbon nanotube, the various consistent even thickness of CNT length in A, and ligament is relatively big, surface more light
Sliding.And CNT thickness is uneven in B, and the winding degree of CNT substantially reduces, and the accumulation of CNT is serious, pipe
Gap is substantially reduced, and between CNT, adhesion is serious.And CNT even thickness in C, pipe end has slight destruction, and divides
Dissipating uniformly, simultaneously it can be seen that carbon nano tube surface coarse, there is organic matter on reality surface.
Fig. 6 is the scanning electron microscope (SEM) photograph of modified polyether-ether-ketone, and wherein A is polyether-ether-ketone, and B is hydroxylating polyether-ether-ketone, C
For Sulfonated carbon nanotube graft polyether ether ketone, wherein A is it can be seen that original polyether-ether-ketone smooth surface, and B surface is comparatively
Coarse, and some hollow of surface, it was demonstrated that in modifying process, create hydroxyl, can be seen that polyether-ether-ketone surface carbon nanometer for C
Pipe distribution is more uniform, and CNT and polyether-ether-ketone present the state contacted with each other.
Fig. 7 is the storage modulus figure preparing composite and original polyetheretherketonematerials materials, and wherein 1 is the energy storage mould of pure PEEK
Amount, the storage modulus that 2 is CNT grafting hydroxylating polyether-ether-ketone with pure polyether-ether-ketone composite material, as seen from the figure
When-120 DEG C, the storage modulus of 2 storage modulus than 1 exceeds 20%.And be also to exceed tens percent at normal temperature, it was demonstrated that its
Modified mechanical property improves a lot.
Fig. 8 is fissipation factor, and wherein 1 is the fissipation factor of pure polyether-ether-ketone, and 2 gather for Sulfonated carbon nanotube grafting hydroxylating
Ether ether ketone and original polyether-ether-ketone composite material, make the vitrification point of material due to the addition of CNT as can be seen
Improve 30 DEG C, further expand the temperature limit of material.
The general principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The technology of the industry
The personnel simply present invention it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and specification
Principle, the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, these change and
Improvement both falls within the range of claimed invention.The protection domain of application claims by appending claims and
Equivalent defines.
Claims (10)
1. a preparation method for Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone/polyether-ether-ketone composite material, its feature exists
In comprising the steps:
(1) polyether-ether-ketone is carried out surface modification so that it is the carbonyl reduction on surface is hydroxyl, form hydroxylating polyether-ether-ketone；
(2) CNT oxidation being obtained carboxylic oxide/carbon nanometer tube, further sulfonation obtains Sulfonated carbon nanotube；
(3) Sulfonated carbon nanotube and hydroxylating polyether-ether-ketone react generation Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone；
(4) Sulfonated carbon nanotube is grafted hydroxylating polyether-ether-ketone be mixed to form with polyether-ether-ketone and mix raw material, hot-forming system
Become Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone/polyether-ether-ketone composite material, wherein, the matter of polyether-ether-ketone in mixing raw material
Amount mark is 2-5%.
2. the preparation method of as claimed in claim 1 composite, it is characterised in that: the mixing raw material in step (4) be
378-382 DEG C, hot-forming under the conditions of 3-5MPa.
3. the preparation method of composite as claimed in claim 2, it is characterised in that: the carboxylic carbonoxide in step (2)
Carboxyl in nanotube obtains Sulfonated carbon nanotube with the amino dehydrating condensation in p-aminobenzene sulfonic acid.
4. the preparation method of composite as claimed in claim 1, it is characterised in that: described carboxylic oxide/carbon nanometer tube
Preparation method is: CNT is joined mass concentration 98% concentrated sulfuric acid and mass concentration be 65% red fuming nitric acid (RFNA) volume ratio be 3:1
Mixed solution in, ultrasonic disperse 100-140min at 45-55 DEG C, suction filtration obtains filter cake, and cleans filter cake by deionized water
To neutral, after filter cake is vacuum dried 12h at 88-92 DEG C, obtain the carboxylic oxide/carbon nanometer tube being dried.
5. the preparation method of composite as claimed in claim 4, it is characterised in that: the preparation method of described Sulfonated carbon nanotube
For:
(1) carboxylic oxide/carbon nanometer tube is placed in the DCC ethanol solution mixed by DCC and absolute ethyl alcohol, in 28-
At 32 DEG C, ultrasonic disperse 20-40min obtains carbon nano-tube solution；
(2) p-aminobenzene sulfonic acid is dissolved in deionized water, obtains p-aminobenzene sulfonic acid solution；
(3) carbon nano-tube solution and p-aminobenzene sulfonic acid solution are mixed, at 28-32 DEG C after ultrasonic disperse 20-40min,
Magnetic agitation reaction 5-7h under the conditions of 48-52 DEG C, suction filtration obtains filter cake, in cleaning extremely by absolute ethyl alcohol and deionized water successively
Property, filter cake is vacuum dried at 88-92 DEG C 12h, obtains the Sulfonated carbon nanotube being dried；
Wherein, in step (3), in carbon nano-tube solution and p-aminobenzene sulfonic acid solution, the amount of solute is equal.
6. the preparation method of composite as claimed in claim 1, it is characterised in that: the preparation side of described hydroxylating polyether-ether-ketone
Method is: by polyether-ether-ketone, sodium borohydride and DMSO reaction time 7-9h at 118-122 DEG C, suction filtration obtains filter cake, and uses successively
Absolute ethyl alcohol, deionized water, hydrochloric acid wash, and filter cake is dried at 78-82 DEG C 10-14h, and the hydroxylating obtaining being dried is gathered
Ether ether ketone.
7. the preparation method of composite as claimed in claim 6, it is characterised in that: polyether-ether-ketone and the mass ratio of sodium borohydride
For (4-6): 1, polyether-ether-ketone is (0.03-0.05) g/mL with the mass volume ratio of DMSO.
8. the preparation method of composite as claimed in claim 1, it is characterised in that: described Sulfonated carbon nanotube grafting hydroxylating
Being made by the steps of polyether-ether-ketone forms:
(1) Sulfonated carbon nanotube is joined in DMF, ultrasonic disperse 20-40min at 48-52 DEG C, form solution A；
(2) hydroxylating polyether-ether-ketone is added in the DMF solution containing DCC and DMAP, ultrasonic disperse 20-at 48-52 DEG C
40min, forms B solution；
(3), after solution A and B solution being mixed, ultrasonic disperse 25-35min at 48-52 DEG C, the most under an inert atmosphere in 48-
Form C solution after 52 DEG C of back flow reaction 7-9h, in C solution, add absolute ethyl alcohol, locate under the conditions of the stirring in water bath of 48-52 DEG C
Reason 25-35min, carries out gained material suction filtration and obtains just filter cake, will adsorb DCC and DMAP on first filter cake with absolute ethyl alcohol
Obtain filter cake after Xi Jinging, filter cake is vacuum dried at 48-52 DEG C 11-13h, obtain Sulfonated carbon nanotube grafting hydroxylating polyethers
Ether ketone.
9. the preparation method of as claimed in claim 8 composite, it is characterised in that: in step (1), Sulfonated carbon nanotube with
The mass volume ratio of DMF is 0.004g/mL；In step (2), hydroxylating polyether-ether-ketone, the mass ratio of DCC and DMAP are 6:8:1,
Hydroxylating polyether-ether-ketone is 0.05 g/mL with the mass volume ratio of DMF.
10. the preparation method of composite as described in arbitrary in claim 1-9, it is characterised in that: described Sulfonated carbon nanotube
The preparation method of grafting hydroxylating polyether-ether-ketone/polyether-ether-ketone composite material is:
(1) mixing raw material is joined in absolute ethyl alcohol, at normal temperatures after ultrasonic disperse 25-35min, vacuum at 48-52 DEG C
It is dried 18-22min, then proceedes to ultrasonic disperse 25-35min at 40-50 DEG C, repeat above-mentioned vacuum drying, ultrasonic disperse 3-5
After secondary, at 48-52 DEG C, it is vacuum dried 3-5h, wherein, Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone and absolute ethyl alcohol
Mass volume ratio is 0.001g/mL；
(2) the mixing raw material after step (1) being processed joins in mould and is compacted, and to mould low-temperature prewarming to 148-152 DEG C；
(3) vulcanizing press is heated to 378-382 DEG C, preheated mould is placed between the heating plate of vulcanizing press,
Matched moulds, heats 2h between heating plate by mould, and exhaust number of times, at 3-5MPa, is set to 3 times, will be vented distance by Stress control
It is set to 2s；
(4) by Stress control at 14-16MPa, vulcanize 10min, obtain Sulfonated carbon nanotube grafting hydroxylating polyether-ether-ketone/polyethers
Ether ketone composite.
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