CN101721944B - Polymer-base carbon nanotube dispersing auxiliary, synthesis method and application thereof - Google Patents
Polymer-base carbon nanotube dispersing auxiliary, synthesis method and application thereof Download PDFInfo
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- CN101721944B CN101721944B CN2009102313705A CN200910231370A CN101721944B CN 101721944 B CN101721944 B CN 101721944B CN 2009102313705 A CN2009102313705 A CN 2009102313705A CN 200910231370 A CN200910231370 A CN 200910231370A CN 101721944 B CN101721944 B CN 101721944B
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Abstract
The invention relates to a polymer-base carbon nanotube dispersing auxiliary, a synthesis method and application thereof. The polymer-base carbon nanotube dispersing auxiliary is an amorphous polystyrene homopolymer with the function of pyrene, wherein the structural formula is a polymer that one end of the polystyrene main chain is sealed by 0.9-1.05 pyrene units, the number-average molar mass ranges from 5000 to 30000, and the molecular weight distribution index ranges from 1.10 to 1.21. The polymer-base carbon nanotube dispersing auxiliary is synthesized by an anion polymerization method, reactivity pyrene-containing compound is added in the later period of living polymerization of the styrene, and the reaction is terminated with methanol at the end of polymerization. The polymer-base carbon nanotube dispersing auxiliary can remarkably improve the dispersing ability in the normal organic solvent, and even carbon nanotube dispersing liquid with high concentration can be prepared. The dispersing liquid can be used for preparing styryl polymer (polystyrene or styryl copolymer)/carbon nanotube composite material of the carbon nanotube evenly dispersed in the matrix resin.
Description
Technical field
The present invention relates to polymer and field of nanometer technology, more particularly relate to the innovation of a kind of polymer-base carbon nanotube dispersing auxiliary and preparation method and use thereof.
Background technology
CNT (CNT) is regarded as preparing the ideal filler of high-performance, multifunctional polymer nano composite material because of its superelevation draw ratio, lower density, excellent physical and mechanical performance and high heat, conductivity.Although theoretical and experimental study has proved that CNT has above-mentioned outstanding properties, desire in polymer matrix composite, to realize these performances, still need material scholar, chemist and physicist's effort.Because CNT particularly SWCN (SWNT) has huge specific area, so it exists with the form of tube bank usually.When CNT is scattered in the matrix resin with this form, very unfavorable undoubtedly for effective transmission of load.In addition, the CNT surface is extremely smooth and show extremely strong chemical inertness, and its dispersing or dissolving in most organic solvents and polymer is limited in one's ability, and promptly the surface wettability of CNT is poor.For composite, realize that even dispersion and enhancing between the two the interfacial adhesion of filler in matrix resin is the important prerequisite of the excellent composite of processability.Therefore, for addressing the above problem, CNT is carried out controlled surface modification, when keeping proper properties such as its excellent heat, electricity, mechanics, guarantee that as far as possible it is scattered in the matrix resin with individual tubes or less tube bank or form that the two is total is very necessary.
Whether participate in chemical reaction directly according to CNT itself, the CNT surface modifying method can be divided into chemical method and physics method two big classes.Through the CNT of chemical method modification, its dispersed in matrix resin and all be significantly improved with the bonding force of matrix resin.The mechanical property of prepared composite also correspondingly is improved.But obtaining of these achievements is that loss with other excellent properties of CNT (as performances such as heat, electricity) is a cost.This is because in the chemical modification process, the chemistry of CNT and electronic structure destroy integrity.Under the extreme condition, as in strong oxidation environment (concentrated sulfuric acid/red fuming nitric acid (RFNA) mixed liquor) commonly used, CNT can be cut off, and has significantly reduced its draw ratio.This just makes the CNT loss even has lost its rely realization composite high performance and polyfunctional architecture basics.Compare with chemical method, the physics method has not only kept the nearly all excellent properties of CNT, and the difference of looking modified additive can also additionally give CNT other performance, has therefore caused people's attention in recent years gradually.For the research work of this respect, Fujigaya and Nakashima nearest one piece of summary paper (T.Fujigaya, N.Nakashima Polymer Journal, 2008,40, carried out good summary in 577-589).In numerous physical modification methods, particularly noticeable based on the interactional physical modification technology of extremely strong pi-pi accumulation between pyrene or derivatives thereof and CNT.This intermolecular strong interaction is mainly derived from extremely similar chemical constitution (pyrene can be regarded as the part of CNT on chemical constitution) between the two.
Styrene-based polymer, particularly homopolymers-polystyrene (PS) are one of the most frequently used commercialization polymer.Itself and the compound composite with the processability excellence of CNT have been evoked researchers' interest greatly naturally.For realizing goal in research, must at first solve dispersion and the interfacial adhesion problem of CNT in the polystyrene matrix as previously mentioned.The solution of having reported comprises optimizes fabrication process condition, chemistry or physical modification CNT etc.Wherein, utilize the intermolecular strong interaction of pyrene and CNT that the report that CNT carries out physical modification is had three examples.The employed pyrene polymer that contains is styrene-based copolymers, synthetic through the radical living polymerization method, chemical constitution is styrene-pyrene functionalized styrene di-block copolymer (G.J.Bahun, C.Wang, A.Adronov Journal of Polymer Science Part A:Polymer Chemistry, 2006,44,1941-1951) and the functionalized copolymer-maleic anhydride of phenylethylene-maleic anhydride-pyrene (D.Wang, W.X.Ji, Z.C.Li, L.Chen Journal of the American Chemical Society, 2006,128,6556-6557; I.H.Choi, M.Park, S.S.Lee, S.C.Hong European Polymer Journal, 2008,44,3087-3095).
In sum, realize that even dispersion and enhancing between the two the interfacial adhesion of CNT in matrix resin is the important prerequisite of the polymer-base carbon nanotube composite of processability excellence.CNT is carried out the effective means that controlled surface modification has been proved to be to realize above-mentioned target.Wherein, chemical modification method can destroy chemistry and the electronic structure of CNT, damages performances such as its heat, electricity; Physical modification method then can keep the most excellent properties of CNT.Important a kind of as in the physical modification method, therefore the method for utilizing π-π interaction partners CNT between pyrene and CNT to carry out modification causes people's very big concern.Be preparation PS/CNT composite, Recent study person have synthesized some and have contained the pyrene styrene-based polymer.But in these reports, the researcher all is not optimized the molecular structure that contains the pyrene polymer, specifically be exactly position and the content of pyrene unit on macromolecular chain not to be regulated and control, thereby polymer can not be maximized in the adsorbance on CNT surface, and then dispersion (dissolving) usefulness of the modification CNT that weakened.
Summary of the invention
Purpose of the present invention just is to overcome above-mentioned shortcoming and defect, and a kind of polymer-base carbon nanotube dispersing auxiliary and preparation method and use thereof are provided.This dispersing aid is an intermolecular strong interaction of utilizing pyrene and CNT, that is pi-pi accumulation effect and special MOLECULE DESIGN, the synthetic a kind of novel pyrene polymer that contains.Its adopts anionic polymerisation process synthetic, and it is controlled that its stoichiometry polymerization property can guarantee to be keyed to the pyrene number of unit of polystyrene molecule chain end.Synthetic work is once finished in same reactor, need not middle product is carried out extra separation, purification, and process window is wide in range, and is simple to operate, and synthesis cycle is short, the productive rate height.It has solved CNT low problem of dispersion amount in organic solvent commonly used, has significantly improved the dispersion amount of CNT in organic solvent, thereby lays a good foundation for the polymer-base carbon nanotube composite of solwution method processability excellence.
In order to achieve the above object, polymer-base carbon nanotube dispersing auxiliary of the present invention is represented by following general formula (A)
R in the general formula
1Be CH
3(CH
2)
3-, (CH
3)
2CHCH
2-, C
6H
5-, C
6H
5CH
2-or CH
2=CHCH
2One of-; R
2For-(CH
2)
x-, x=1～4 wherein; N=40～300; M=0.9～1.05; Be a kind of pyrene functionalized amorphous polystyrene homopolymer on its chemical constitution, the pyrene unit is positioned at the polymer molecule chain end, and content is 0.9～1.05 per 1 macromolecular chain in pyrene unit; Its number-average molecular weight is between 5,000～30, and 000, molecular weight distributing index is 1.10～1.21.
Polymer-base carbon nanotube dispersing auxiliary of the present invention adopts anionic polymerisation process to synthesize.In the presence of catalyst, styrene monomer is carried out living polymerization in hydrocarbon organic solvent, cinnamic anionic polymerisation temperature is 10～70 ℃, polymerization time is 0.5～4 hour; Polymerization later stage adding reactivity contains pyrene compound and carries out end-blocking, and the polymerization temperature that adding contains behind the pyrene compound is 30～90 ℃, and polymerization time is 2～6 hours; Polymerization finishes back with methyl alcohol or ethanol stopped reaction; Synthetic work is finished in same reactor, need not middle product is carried out extra separation, purification.
Catalyst adopts one of n-BuLi, s-butyl lithium, phenyl lithium, benzyl lithium or pi-allyl lithium, and consumption is the every 100ml styrene monomer of 3～20mmol.
Hydrocarbon organic solvent adopts the mixture of toluene, benzene, cyclohexane, n-hexane or above-mentioned two or more solvents, and consumption is the every 1ml styrene monomer of 5～15ml.
Reactivity contains pyrene compound for adopting the compound of general formula (B) expression
R wherein
2For-(CH
2)
x-, x=1～4, consumption is the every 1mol catalyst of 1.2～1.5mol.
Optimized reaction conditions is: catalyst adopts n-BuLi, and hydrocarbon organic solvent adopts toluene or cyclohexane, and cinnamic anionic polymerisation temperature is 30～70 ℃, and polymerization time is 1～2 hour; The polymerization temperature that adding contains behind the pyrene compound is 50～70 ℃, and polymerization time is 4～5 hours.After adopting this optimized reaction conditions, effect is best.
Polymer-base carbon nanotube dispersing auxiliary of the present invention can improve the dispersibility of CNT in organic solvent commonly used, prepares the even carbon nanotube dispersion liquid of high concentration.This moment, CNT can be the mixture of SWCN, double-walled carbon nano-tube, multi-walled carbon nano-tubes or above-mentioned two or three CNT; Organic solvent commonly used is toluene, oxolane, chloroform, dimethyl formamide or dimethyl sulfoxide (DMSO).
Polymer-base carbon nanotube dispersing auxiliary of the present invention can be used for preparing CNT finely dispersed styrene-based polymer/carbon nano tube compound material in matrix resin, and wherein styrene-based polymer is polystyrene, s-B-S copolymer or acrylonitrile-butadiene-styrene copolymer.
Polymer base CNT dispersing aid of the present invention has adopted polystyrene macromolecular chain one end by the unit terminated MOLECULE DESIGN of pyrene.This MOLECULE DESIGN, can guarantee to contain pyrene polystyrene (PyPS) strand is adsorbed on the CNT surface securely by the pi-pi accumulation effect on the one hand; Its backbone structure that is similar to polystyrene can impel the CNT/PyPS hybrid to be dispersed in styrene-based polymer commonly used (comprising styryl homopolymers and the copolymer) good solvent on the other hand, and guarantees and the matrix resin similar compatibility.So, by PyPS this " bridge ", CNT not only can be dispersed in the matrix resin and realize seamless connection between the two.
Why polymer base CNT dispersing aid PyPS of the present invention adopts macromolecular chain one end by 1 MOLECULE DESIGN that pyrene is unit terminated, mainly based on following consideration: in dispersing aid PyPS, the pyrene unit is the unique functional group of macromolecular chain holdfast in the CNT surface, there is and has only 1 pyrene unit can guarantee holdfast, thereby make the dispersion usefulness of CNT significantly improve in the maximization of the PyPS on CNT surface strand number.
Polymer base CNT dispersing aid PyPS of the present invention adopts anionic polymerisation process to synthesize.In the styrene living polymerization later stage, add the reactive pyrene thing of metering, the stoichiometry polymerization property of anionic polymerisation process has been guaranteed the exploitativeness of above-mentioned MOLECULE DESIGN.Therefore the gained styrene-based polymer can be regarded as containing the homopolymers of functional pyrene end group.This is different from obviously that document reported contains the pyrene styrene-based polymer: (1) these polymer are copolymer; (2) these polymer adopt the preparation of radical living polymerization method; (3) the average pyrene content on every polymer chain is much larger than 1.
This polymerizate PyPS is a kind of polystyrene homopolymer by the unit terminated amorphous of 0.9～1.05 pyrene, and density is 1.02～1.05g/cm
3, number-average molecular weight is between 5,000～30, and between 000, molecular weight distributing index is 1.10～1.21.Polymerizate PyPS is a kind of atactic polymer, does not have crystalline melt point (molten limit), and its glass transition temperature is between 85～95 ℃.
CNT dispersing aid PyPS among the present invention can be dissolved in the organic solvents commonly used such as toluene, oxolane, chloroform, dimethyl formamide, dimethyl sulfoxide (DMSO), forms uniform solution.The dispersion amount of CNT in these organic solutions is significantly higher than the dispersion amount in the pure organic solvent of correspondence.Related CNT is the mixture of SWCN (SWNT), double-walled carbon nano-tube (DWNT), multi-walled carbon nano-tubes (MWNT) or above-mentioned two or three CNT.With the chloroform is example, earlier 12.5mg PyPS is dissolved in the 10ml chloroform, then 5.0mg SWNT is scattered in wherein (concrete dispersion step is referring to embodiment 11), look the number-average molecular weight difference (30 of PyPS, 000～5,000), records the content of SWNT in the even dispersion liquid at last between 140～400mg/L.To in the pure chloroform in the same old way, the even dispersion amount of the SWNT 30mg/L that then only has an appointment.For significantly improving of explanation SWNT dispersibility is not PS backbone structure or the pyrene cellular construction that only derives from PyPS, at two other in the same old way, PS and low-molecular-weight are contained pyrene compound (shown in Formula B) be dissolved in the solution that is mixed with in the chloroform with the PyPS same concentrations respectively, then each 5mg SWNT is scattered in wherein according to identical dispersion step, the even dispersion amount of measured SWNT is respectively 27mg/L and 58mg/L.
CNT dispersing aid PyPS among the present invention has significantly improved the dispersion amount of CNT in organic solvent, and this lays a good foundation for solwution method prepares styrene-based polymer/CNT composite.Related commercialization styrene-based polymer is polystyrene (PS), s-B-S copolymer (SBS), acrylonitrile-butadiene-styrene copolymer (ABS) or above two or three mixture of polymers.With PS is example, earlier PS is dissolved in the solution that is made into 0.1～0.3g/ml in the chloroform, then with the even dispersion liquid blend of above-mentioned SWNT, homogenize, after decompression removes solvent, vacuum drying, obtain composite, it can be molded into the sample (concrete preparation section is referring to embodiment 13) of required form as required again.
Dispersing aid of the present invention is an intermolecular strong interaction of utilizing pyrene and CNT, that is pi-pi accumulation effect and special MOLECULE DESIGN, the synthetic a kind of novel pyrene polymer that contains.Its adopts anionic polymerisation process synthetic, and it is controlled that its stoichiometry polymerization property can guarantee to be keyed to the pyrene number of unit of polystyrene molecule chain end.Synthetic work is once finished in same reactor, need not middle product is carried out extra separation, purification, and process window is wide in range, and is simple to operate, and synthesis cycle is short, the productive rate height.It has solved CNT low problem of dispersion amount in organic solvent commonly used, has significantly improved the dispersion amount of CNT in organic solvent, thereby lays a good foundation for the polymer-base carbon nanotube composite of solwution method processability excellence.
Description of drawings
Fig. 1 is the FTIR spectrogram of dispersing aid PyPS prepared among the embodiment 8.
Fig. 2 is dispersing aid PyPS prepared among the embodiment 8
1The H-NMR spectrogram.
See figures.1.and.2.Use fourier infrared (FTIR) spectrometer and nuclear magnetic resonance (NMR) instrument that the chemical constitution that polymer samples (PyPS) carries out is characterized explanation.On the FTIR spectrogram, the absworption peak of C-H stretching vibration appears at 3057 and 3024cm on the corresponding phenyl ring
-1The place; The absworption peak of corresponding phenyl ring stretching vibration appears at 1597,1543,1491 and 1447cm
-1The place; The absworption peak of C=O stretching vibration appears at 1723cm on the corresponding pyrene unit
-1The place, the C-O-C absworption peak appears at 1150 and 1181cm
-1The place.In addition, at 1620～1680cm
-1Between, there is not the characteristic absorption of the two keys of corresponding C=C.This shows in the sample styrene monomer, and polymerization is complete, and reactivity contains pyrene compound and also successfully is keyed on the main polymer chain.
1On the H-NMR spectrogram, except that the proton peak of corresponding polystyrene architectural feature, the proton peak of corresponding pyrenyl group has appearred also at the 8.04-8.31ppm place, but intensity a little less than, show that the pyrene unit of introducing is less.In conjunction with
1Pyrene content on H-NMR and GPC (gel permeation chromatography) test result, every PyPS macromolecular chain is defined as 0.9～1.05.
Fig. 3 is the electron scanning micrograph of composite prepared among the embodiment 13.
Fig. 4 is the electron scanning micrograph of composite prepared in the reference examples of embodiment 13.
With reference to Fig. 1 and Fig. 4.With PS is example, earlier PS is dissolved in the solution that is made into 0.1～0.3g/ml in the chloroform, then with the even dispersion liquid blend of above-mentioned SWNT, homogenize, after decompression removes solvent, vacuum drying, obtain composite, it can be molded into the sample (concrete preparation section is referring to embodiment 13) of required form as required again.No matter be to use light microscope to carry out macroscopic observation and also be to use electron microscope to carry out microscopic observation, its result shows that all SWNT disperses in the PS matrix resin very even.The conductivity threshold of composite is 0.097wt%SWNT; And not using the composite of dispersing aid PyPS, its conductivity threshold is 0.28wt%SWNT.
The specific embodiment
Below listed embodiment be for being described more specifically the present invention, but the present invention and not only be confined to this place row embodiment.
Embodiment 1
A kind of polymer-base carbon nanotube dispersing auxiliary.It is represented by following general formula (A)
R in the general formula
1Be CH
3(CH
2)
3-; R
2For-CH
2-; N=46; M=0.89; Be a kind of pyrene functionalized amorphous polystyrene homopolymer on its chemical constitution, the pyrene unit is positioned at the polymer molecule chain end, and content is 0.89 per 1 macromolecular chain in pyrene unit; Its number-average molecular weight is 5,200, and molecular weight distributing index is 1.21.
A kind of polymer-base carbon nanotube dispersing auxiliary.It can be by general formula (A) expression, and general formula (A) is with embodiment 1.R in the general formula
1Be (CH
3)
2CHCH
2-; R
2For-CH
2-; N=80; M=0.96; Be a kind of pyrene functionalized amorphous polystyrene homopolymer on its chemical constitution, the pyrene unit is positioned at the polymer molecule chain end, and content is 0.96 per 1 macromolecular chain in pyrene unit; Its number-average molecular weight is 8,800, and molecular weight distributing index is 1.20.
Embodiment 3
A kind of polymer-base carbon nanotube dispersing auxiliary.It can be by general formula (A) expression, and general formula (A) is with embodiment 1.R in the general formula
1Be C
6H
5-; R
2For-CH
2-; N=180; M=0.97; Be a kind of pyrene functionalized amorphous polystyrene homopolymer on its chemical constitution, the pyrene unit is positioned at the polymer molecule chain end, and content is 0.97 per 1 macromolecular chain in pyrene unit; Its number-average molecular weight is 19,100, and molecular weight distributing index is 1.17.
A kind of polymer-base carbon nanotube dispersing auxiliary.It can be by general formula (A) expression, and general formula (A) is with embodiment 1.R in the general formula
1Be C
6H
5CH
2-; R
2For-CH
2-; N=280; M=1.05; Be a kind of pyrene functionalized amorphous polystyrene homopolymer on its chemical constitution, the pyrene unit is positioned at the polymer molecule chain end, and content is 1.05 per 1 macromolecular chains in pyrene unit; Its number-average molecular weight is 29,200, and molecular weight distributing index is 1.13.
Embodiment 5
A kind of polymer-base carbon nanotube dispersing auxiliary.It can be by general formula (A) expression, and general formula (A) is with embodiment 1.R in the general formula
1Be CH
2=CHCH
2-; R
2For-(CH
2)
4-; N=240; M=0.92; Be a kind of pyrene functionalized amorphous polystyrene homopolymer on its chemical constitution, the pyrene unit is positioned at the polymer molecule chain end, and content is 0.92 per 1 macromolecular chain in pyrene unit; Its number-average molecular weight is 25,400, and molecular weight distributing index is 1.10.
A kind of synthetic method of polymer-base carbon nanotube dispersing auxiliary.This polymer-base carbon nanotube dispersing auxiliary can be by general formula (A) expression, and general formula (A) is with embodiment 1.Synthetic method is as follows:
Get 1 500ml there-necked flask, 300ml anhydrous tetrahydro furan (THF), 10.7ml (76.8mmol) triethylamine, 6.0170g (25.9mmol) pyrene methyl alcohol are successively added wherein.Then, under magnetic agitation, ice-water bath, nitrogen protection condition, slowly drip 7.5ml (76.8mmol) methacrylic chloride.After 30 minutes, remove ice-water bath.Reaction system is warming up to room temperature, reacts 24 hours, with reacting liquid filtering, removes the THF in the filtrate under reduced pressure, gets solids.This solids is dissolved in the 300ml carrene again, and solution is through 1 1M HCl (1 * 150ml), 2 saturated NaHCO
3Solution (2 * 150ml), 3 ultra-pure waters (after 3 * 150ml) washings, organic facies MgSO
4Dry 1 hour, filter, remove solvent under reduced pressure, get crude product.Be further separation and purification, crude product is dissolved among the hot THF of 6ml, add 12ml methyl alcohol then and be recrystallized.Mixture places-20 ℃ of refrigerators, after 12 hours, and the solid collected by filtration thing.Again after other twice recrystallization operation, with solid collection thing in 50 ℃ of vacuum drying ovens dry 6 hours, at last the reactive pyrene compound [(1-pyrene) methyl 2-methyl-2-propylene ester, PyMMP] that contains, productive rate is greater than 70%.
Get two mouthfuls of flasks of 1 250ml, after at least 3 " vacuum extraction-nitrogen injects " cyclings, the air displacement in the flask is become high pure nitrogen.In above operating process, flask is continued, heats equably with the 1500W air-heater.With syringe 100ml dry toluene and 10ml (87.3mmol) styrene monomer are successively injected flask.After reaction system is cooled to 0 ℃, the n-BuLi hexane solution that adds several 2.5M with in and remaining proton impurity in the system.The disposable injection reaction system of n-BuLi hexane solution (1.9mmol n-BuLi) with 0.76ml 2.5M removes ice-water bath, is warming up to 35 ℃, polymerisation 1 hour.And then 0.7420g (2.47mmol) PyMMP (being dissolved among the anhydrous THF of 2ml) is added reaction system, be warming up to 50 ℃, continue polymerization 5 hours.After polymerization finishes,, deposit polymerizate with a large amount of methyl alcohol again with 10ml methyl alcohol stopped reaction.After the filtration, solids is put into 70 ℃ of vacuum drying ovens and is dried to constant weight, must contain pyrene polystyrene (PyPS) at last.Calculate with the monomer molar number, productive rate is greater than 95%.Number-average molecular weight is 5,200; Molecular weight distributing index is 1.21; Pyrene content is 0.89 per 1 PyPS macromolecular chain in pyrene unit.
Embodiment 7
Catalyst n-BuLi among the embodiment 6 is substituted with s-butyl lithium, and catalyst amount is adjusted into 1.08mmol, and the consumption of PyMMP is adjusted into the cinnamic polymerization temperature of 0.4216g (1.4mmol) and is adjusted into 65 ℃, and polymerization time extends to 2 hours; After adding PyMMP, the temperature that continues polymerization is adjusted into 70 ℃, and polymerization time is 4 hours; Other operating condition is identical with embodiment 6.The productive rate of PyPS is greater than 98%.Number-average molecular weight is 8,800; Molecular weight distributing index is 1.20; Pyrene content is 0.96 per 1 PyPS macromolecular chain in pyrene unit.
Catalyst n-BuLi among the embodiment 6 is substituted with phenyl lithium, and catalyst amount is adjusted into 0.49mmol, and the consumption of PyMMP is adjusted into 0.1772g (0.59mmol), and other condition is identical with embodiment 6.The productive rate of PyPS is greater than 95%.Number-average molecular weight is 19,100; Molecular weight distributing index is 1.17; Pyrene content is 0.97 per 1 PyPS macromolecular chain in pyrene unit.
In the present embodiment FTIR spectrogram of prepared dispersing aid PyPS and
1The H-NMR spectrogram is seen Fig. 1 and Fig. 2 respectively.
Embodiment 9
Catalyst s-butyl lithium among the embodiment 7 is substituted with the benzyl lithium, and catalyst amount is adjusted into 0.32mmol, and the consumption of PyMMP is adjusted into 0.1441g (0.48mmol); Other condition is identical with embodiment 7.The productive rate of PyPS is greater than 98%.Number-average molecular weight is 29,200; Molecular weight distributing index is 1.13; Pyrene content is 1.05 per 1 PyPS macromolecular chains in pyrene unit.
Embodiment 10
With the pyrene methyl alcohol in the pyrene butanols alternate embodiment 6, other synthesis condition is identical with embodiment 6, synthetic the reactive pyrene compound [(1-pyrene) butyl 2-methyl-2-propylene ester, PyBMP] that contains, and productive rate is greater than 70%.
Catalyst n-BuLi among the embodiment 6 is substituted with the pi-allyl lithium, and catalyst amount is adjusted into 0.36mmol; Substitute PyMMP with PyBMP, its consumption is adjusted into 0.1472g (0.43mmol); Other condition is identical with embodiment 6.The productive rate of PyPS is greater than 95%.Number-average molecular weight is 25,400; Molecular weight distributing index is 1.10; Pyrene content is 0.92 per 1 PyPS macromolecular chain in pyrene unit.
Embodiment 11
Get the test tube of 5 50ml, add the 10ml chloroform respectively, add each 12.5mg of PyPS of preparation among the embodiment 6～10 then successively.After treating that PyPS dissolves fully, add 5.0mg SWNT respectively, the test tube mouth was placed in 0～30 ℃ of water-bath ultrasonic processing 1 hour with polyethylene film sealing.Gained dispersion liquid standing over night is taken out 3/4ths supernatant liquids with dropper, after filtering via the glass fiber of closely piling up, collect and obtain the even dispersion liquid of black SWNT.Spectral technique (the J.L.Bahr that utilizes people such as Smalley and Tour to set up, E.T.Mickelson, M.J.Bronikowski, R.E.Smalley, J.M.Tour Chemical Communication, 2001,193-194), record in the dispersion liquid that the content of SWNT is respectively 372.5,224.3,162.4,140.1,141.6mg/L.
Other gets the test tube of 3 50ml, is labeled as A-C, adds the 10ml chloroform respectively, adds PS (number-average molecular weight is 17,500, and molecular weight distributing index is 1.06, Polysciences Inc.) and each 12.5mg of PyMMP then in B and C test tube respectively.After treating that PS and PyMMP dissolve fully, add 5.0mg SWNT respectively in 3 test tubes, dispersion step is the same.Record in the dispersion liquid that the content of SWNT is respectively 31.0,26.5,58.0mg/L.
Embodiment 12
Get the test tube of 8 50ml, add the 10ml chloroform respectively, add PyPS 2.5,5.0,7.5,10.0,12.5,25.0,37.5, the 50.0mg of preparation among the embodiment 8 then successively.After treating that PyPS dissolves fully, add 5.0mg SWNT respectively, dispersion step is identical with embodiment 11.Record in the dispersion liquid that the content of SWNT is respectively 34.8,78.5,116.2,192.1,224.3,255.2,270.7,279.6g/L.
Embodiment 13
Get the test tube of 5 50ml, be labeled as A-E, other gets each 1 of 100ml and 200ml Boiling tube, is labeled as F and G.In test tube, add 6.5,12.5,19,25,37.5,62.5 respectively, the 125ml chloroform; Add the PyPS 8.2,15.7,23.8,31.3,46.9,78.2, the 156.3mg that prepare among the embodiment 8 then successively, be mixed with the PyPS chloroformic solution of 1.25mg/ml.Add 1.3,2.5,3.8,5.0,7.5,12.5 successively, behind the 25.0mg SWNT, the test tube mouth sealed with polyethylene film, place 0～30 ℃ of ultrasonic processing of water-bath 1 hour, obtain the even dispersion liquid of SWNT.Get the single port flask of 7 250ml, be labeled as A-G, take by weighing 2.50,2.49,2.48,2.47,2.46,2.42 respectively, 2.35g PS (BASF
143E) and be mixed with the PS chloroformic solution of 10wt%.The even dispersion liquid of above-mentioned SWNT is added in the corresponding single port flask magnetic agitation 30 minutes, ultrasonic processing 15 minutes in 0～30 ℃ of water-bath then respectively.Use Rotary Evaporators that solvent is steamed and remove, in 80 ℃ of vacuum drying ovens dry 3 hours, make SWNT content at last and be 0.05,0.1,0.15,0.2,0.3,0.5, the PS/PyPS/SWNT composite of 1.0wt%.On moulding press, adopt the technology of 200 ℃/70bar/1min, with the above-mentioned composite material moulded one-tenth specification thin slice that is 100mm * 100mm * 0.30mm.The electrical conductivity that records is respectively 2.68 * 10
-18, 7.94 * 10
-13, 3.45 * 10
-10, 2.75 * 10
-8, 9.49 * 10
-8, 1.62 * 10
-7, 1.60 * 10
-6S/cm.According to test result, it is 0.095wt% that application exceedes the electrical conductivity percolation threshold that oozes theoretical calculating composite.
The electron scanning micrograph of the composite that present embodiment is prepared is seen Fig. 3.
Reference examples
Get the single port flask of 1 100ml, take by weighing 2.50g PS and be mixed with the PS chloroformic solution of 10wt%.After the magnetic agitation 30 minutes, ultrasonic processing is 15 minutes in 0～30 ℃ of water-bath, uses Rotary Evaporators to steam and desolventizes, and drying is 3 hours in 80 ℃ of vacuum drying ovens.Adopt the mold pressing procedure identical then, PS is molded into the thin slice of 100mm * 100mm * 0.30mm with embodiment 13.Electrical conductivity is 8.26 * 10
-19S/cm.
Do not use dispersing aid PyPS, adopt the operation identical to prepare the PS/SWNT composite with embodiment 13.SWNT content is 0.1,0.2,0.3,0.5,1.0,1.5, during 2.0wt%, the electrical conductivity of composite is respectively 5.43 * 10
-18, 7.38 * 10
-16, 2.91 * 10
-12, 7.82 * 10
-11, 2.81 * 10
-8, 5.32 * 10
-7, 5.35 * 10
-7S/cm.The electrical conductivity percolation threshold is 0.28wt%.
The electron scanning micrograph of prepared composite is seen Fig. 4 in this reference examples.
Claims (5)
1. polymer-base carbon nanotube dispersing auxiliary is characterized in that it is represented by following general formula (A)
R in the general formula
1Be CH
3(CH
2)
3-, (CH
3)
2CHCH
2-, C
6H
5-, C
6H
5CH
2-or CH
2=CHCH
2One of-; R
2For-(CH
2)
x-, x=1～4 wherein; N=40～300; M=0.9～1.05; Be a kind of pyrene functionalized amorphous polystyrene homopolymer on its chemical constitution, the pyrene unit is positioned at the polymer molecule chain end, and content is 0.9～1.05 per 1 macromolecular chain in pyrene unit; Its number-average molecular weight is between 5,000～30, and 000, molecular weight distributing index is 1.10～1.21; Above-mentioned pyrene unit is for adopting the compound of general formula (B) expression
R wherein
2For-(CH
2)
x-, x=1～4.
2. the synthetic method of polymer-base carbon nanotube dispersing auxiliary according to claim 1, it is characterized in that adopting anionic polymerisation process to synthesize, in the presence of catalyst, styrene monomer carries out living polymerization in hydrocarbon organic solvent, cinnamic anionic polymerisation temperature is 10～70 ℃, and polymerization time is 0.5～4 hour; Polymerization later stage adding reactivity contains pyrene compound and carries out end-blocking, and the polymerization temperature that adding contains behind the pyrene compound is 30～90 ℃, and polymerization time is 2～6 hours; Polymerization finishes back with methyl alcohol or ethanol stopped reaction; Synthetic work is finished in same reactor, need not middle product is carried out extra separation, purification; Above-mentioned reactivity contains pyrene compound for adopting the compound of general formula (B) expression
R wherein
2For-(CH
2)
x-, x=1～4, consumption is the every 1mol catalyst of 1.2～1.5mol; Catalyst adopts one of n-BuLi, s-butyl lithium, phenyl lithium, benzyl lithium or pi-allyl lithium, and consumption is the every 100ml styrene monomer of 3～20mmol; Hydrocarbon organic solvent adopts the mixture of toluene, benzene, cyclohexane, n-hexane or above-mentioned two or more solvents, and consumption is the every 1ml styrene monomer of 5～15ml.
3. the synthetic method of polymer-base carbon nanotube dispersing auxiliary according to claim 2, it is characterized in that catalyst adopts n-BuLi, hydrocarbon organic solvent adopts toluene or cyclohexane, and cinnamic anionic polymerisation temperature is 30～70 ℃, and polymerization time is 1～2 hour; The polymerization temperature that adding contains behind the pyrene compound is 50～70 ℃, and polymerization time is 4～5 hours.
4. the purposes of polymer-base carbon nanotube dispersing auxiliary according to claim 1 is characterized in that the dispersing aid as CNT, to improve the dispersibility of CNT in organic solvent commonly used, the even carbon nanotube dispersion liquid of preparation high concentration; CNT is the mixture of SWCN, double-walled carbon nano-tube, multi-walled carbon nano-tubes or above-mentioned two or three CNT; Organic solvent commonly used is toluene, oxolane, chloroform, dimethyl formamide or dimethyl sulfoxide (DMSO).
5. the purposes of polymer-base carbon nanotube dispersing auxiliary according to claim 4, it is characterized in that the even dispersion liquid of said high-concentration carbon nano tube can be used for preparing CNT finely dispersed styrene-based polymer/carbon nano tube compound material in matrix resin, wherein styrene-based polymer is polystyrene, s-B-S copolymer or acrylonitrile-butadiene-styrene copolymer.
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| CN102627727B (en) * | 2012-03-29 | 2017-05-31 | 江南大学 | A kind of preparation method and purposes of photosensitive polymers base carbon nanotube dispersing auxiliary |
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| WO2016078664A1 (en) | 2014-11-11 | 2016-05-26 | Lundorf Pedersen Materials Aps | Design of composite materials with desired characteristics |
| CN104725630B (en) * | 2015-02-03 | 2016-09-21 | 吉林大学 | Containing pyrene PAEK, preparation method and the application in SWCN/polyether-ether-ketone composite material |
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