CN101280064A - Preparation of carbonaceous inorganic material-polymer composite material - Google Patents
Preparation of carbonaceous inorganic material-polymer composite material Download PDFInfo
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Abstract
Disclosed is a method for preparing carbon-containing inorganic materials-polymer composite materials, which has the following steps: a. preparation of organic phase, 0.01-100 portions of polymer monomers by weight are added into organic solvent to form the organic solution of polymer monomers; b. preparation of inorganic phase, 1 portion of carbon-containing inorganic material is dispersed or dissolved in water to form aqueous solution, and then the polymerization agent of polymer monomers in step a is added into the aqueous solution to form inorganic solution; the polymerization agent is non-reactive with water and the addition amount of the agent enables full polymerization of the polymer monomers in step a; c. the inorganic solution in step b is slowly added to the organic solution in step a, and the two solutions are fully mixed and reacted to generate complex colloid; the colloid is then filtered, washed and dried so as to get the polymer composite materials. The method is simple to operate and has high yield, which is suitable for large-scale industrial production; the prepared composite materials are of good performance.
Description
Affiliated field
The present invention relates to a kind of inorganic---the preparation method of organic composite material relates in particular to a kind of preparation method of carbon containing inorganic materials-polymer composites.
Background technology
Matrix material be material by two or more different in kinds by physics and chemically composited, form material with two or more phase structures.Such material any one independent material during not only performance is better than forming, but also can have the special performance that component does not have separately.
A kind of in the organic composite material of carbon material--polymer composites is inorganic---, its purposes has following several respects.1. aerospace field: because its Heat stability is good, specific tenacity, specific rigidity height can be used for making housing, motor body, space shuttle structural part of aircraft wing and forebody, satellite antenna and supporting structure thereof, the solar cell wing and shell, large-scale launch vehicle etc.2. automotive industry: because matrix material has special vibration damping characteristic, damping and reduce noise, anti-fatigue performance is good, easily repair the damage back, is convenient to monolithic molding, so can be used for making body of a motor car, primary structure member, transmission shaft, engine mount and internals thereof.3. chemical industry, weaving and mechanical manufacturing field: the carbon fiber of good corrosion resistance and the material that resin matrix is composited are arranged, can be used for making chemical industry equipment, weaving loom, paper machine, duplicating machine, high-speed machine tool, precision instrument etc.4. medical field: carbon-fibre composite has excellent mechanical property and does not absorb the X ray characteristic, can be used for making medical x-ray machine and orthopedic frame etc.; Carbon-fibre composite also has biological tissue's consistency and blood compatibility, and good stability under the coenocorrelation is also as biomedical material.5. energy devices field: carbon material and conducting polymer materials are carried out compound electrode materials as secondary cell or ultracapacitor, can bring into play the energy storage advantage of two kinds of materials, obtain excellent chemical property, application prospect is good.
Carbon material used in such matrix material mainly includes: activated carbon, graphite carbon, carbon fiber, carbon nanotube, soccerballene and activation products separately thereof etc., wherein activated carbon (AC) is based on carbon, combine with hydrogen, oxygen, nitrogen etc., have the good adsorption effect.Be characterized in that specific surface area is big especially.Activated carbon fiber (ACF) is a kind of novel adsorption functional material that grows up early 1970s, and it is a raw material with xylogen, Mierocrystalline cellulose, phenolic fibre, polypropylene fibre, pitch fibers etc., makes through carbonization and activation.Compare with granular, powdered activated carbon, ACF has distinctive microvoid structure, higher outer surface area and specific surface area and multiple functional group, average pore diameter is also littler, has obtained widespread use by modes such as physical adsorption, chemisorption and physical and chemical adsorption in fields such as waste water, off gas treatment, solvent recuperation, water purifications.Since the NEC Electronic Speculum expert Iijima of Japan in 1991 finds carbon nanotube during with vacuum arc evaporation Graphite Electrodes once more, be the forward position and the focus of international field of new to the research of carbon nanotube always.Carbon nanotube is meant the pipe of being made up of the hexagonal mesh of similar graphite, and pipe generally is made up of single or multiple lift, and the branch of Single Walled Carbon Nanotube (SWNT) and multiple-wall carbon nanotube (MWNT) is therefore arranged.To between tens nanometers, length can reach several microns to the diameter of carbon nanotube in several nanometers.Carbon nanotube can be regarded the result of two-dimension graphite sheet layer convolution as, and at a distance of 0.34nm, this is apart from the radius that is equivalent to gap between the carbon atomic layer in the graphite or Nano carbon balls between layer and the layer.And soccerballene is the general name of the cluster of a series of pure carbons compositions.They are the closed hollow ball shape that is made of nonplanar five-ring, six-ring etc. or the conjugation alkene of elliposoidal structure.Now separated obtaining wherein several, as C60 and C70 etc.C60 in some possible fullerene structures, C240, C540 and diameter ratio are 1: 2: 3.The molecular structure of C60 is spherical 32 bodies really, and it is with 20 six-rings and 12 hollow symmetrical molecules of football shaped with 30 carbon-carbon double bonds (C=C) that five-ring is formed by connecting, so soccerballene is also referred to as football alkene by 60 carbon atoms.Sphere diameter is about 710pm, promptly is made up of 12 pentagons and 20 hexagons.
Existing prepare that carbon material--the method for polymer composites is a lot, for example physical doping, in-situ polymerization, electrochemical deposition etc.Physical doping is earlier carbon material and polymer materials to be prepared, and then by a certain percentage, mixes mutually.Advantage is easy to make, simple; Shortcoming is not interconnect the poor-performing that matrix material showed between carbon material and the polymkeric substance.Situ aggregation method earlier through series of chemical treatments (as acid treatment for a long time, filter, clean, cryodrying), make carbon material surface produce organic group, allow the carbon material that is insoluble to organic solvent be dissolved in the organic solvent, and then by serial organic reaction or other means, allow the polymer monomer molecule be connected to carbon material surface, generate inorganic through the polyreaction polymerization again---organic composite material.The advantage of this method be carbon material with polymkeric substance between be connected closely, performance of composites is good; Shortcoming is that reactions steps is many, and complex operation is inconvenient to control, and the treatment time is long, is difficult for suitability for industrialized production.Electrochemical deposition method by the modification to carbon material, invests its surface charge, by electrochemical deposition technique, makes polymer deposition to carbon material surface then.The advantage of this method is more or less freelyly to come the controlling polymers deposit thickness by the control electrodeposition condition; But it is lower that shortcoming is a productive rate.In a word, in the existing method, also do not have a kind of productive rate height, be fit to large-scale industrial production, the good again method of Zhi Bei composite property simultaneously.
Summary of the invention
Purpose of the present invention just provides a kind of method for preparing carbon containing inorganic materials-polymer composites, and this method is simple to operate, and the productive rate height is fit to large-scale industrial production; The composite property of preparation is good.
The present invention realizes that the technical scheme that its goal of the invention adopts is: a kind of method for preparing carbon containing inorganic materials-polymer composites, and its concrete practice is:
A, the preparation organic phase polymer monomer that 0.01-100 part is heavy add in its organic solvent, form the organic solution of polymer monomer;
B, the inorganic carbon containing inorganic materials with 1 part of weight of preparation are dissolved or dispersed in and form the aqueous solution in the water, in the aqueous solution, add again a step polymer monomer polymerizing agent, form inorganic solution; The polymerizing agent of this polymerizing agent for not reacting with water, and its add-on is for making a complete polymeric amount of polymer monomer in step;
C, the inorganic solution that b is gone on foot slowly add in a organic solution in step, and abundant stirring reaction, generate composite colloids, to the colloid after filtering, and cleaning, drying, promptly.
Compared with prior art, the invention has the beneficial effects as follows:
One, the polymerizing agent of carbon material and polymer monomer is dissolved in the water forms mutually inorganicly, polymer monomer is dissolved in and forms organic phase in the organic solvent, so just polymerizing agent and polymkeric substance is separated, and is present in respectively in inorganic phase and the organic phase.When organic phase with inorganic when mixing mutually, polymer monomer and polymerizing agent meet at the two-phase intersection, polymerization reaction take place.Simultaneously, because the polymerizing agent uniform mixing is in carbon material, the small polymer that is generated under its effect will be adsorbed by the bigger carbon material of specific surface area, thereby cover or be wrapped in the surface of carbon material equably, form the layer of even polymkeric substance, both made the inventive method productive rate height, and also made to be connected well between carbon material and the polymkeric substance that the inorganics of generation---the organism matrix material had good performance.
Two, since organic phase with inorganic mutually immiscible, can only occur in polymerizing agent and the contacted zone of polymer monomer by the caused polyreaction of polymerizing agent, this zone is in two kinds of solution mixing processes, the boundary part of formed oil droplet of organic phase and inorganic mutually formed water droplet.Because these zones are very limited, polymerizing agent is not that big area contacts with polymer monomer, can not generate bulky polymer immediately, it also is the polymkeric substance agglomeration that the inventive method can be avoided the general polymerization method, make polyreaction in limited contact area, slowly take place, be combined between carbon material and the polymkeric substance, be evenly distributed, performance of composites is good.
Three, present method does not need carbon material is carried out modified chemical processing in advance and monomer molecule is connected carbon material surface; Get final product and only need prepare two phase liquid and mix, simple, convenient, the monomeric addition of controlling polymers promptly can be controlled in the thickness of polymkeric substance carbon material surface growth, is fit to scale operation.
Sem observation also proves the matrix material of the inventive method preparation, and polymkeric substance is even and fine and close covers carbon material surface.The matrix material of the inventive method preparation is made the electrode of ultracapacitor, carry out electrochemical property test, the result shows that also prepared matrix material has excellent electrochemical properties.
Above-mentioned carbon containing inorganic materials is: the mixture of one or more in graphite, activated carbon, active graphite carbon, carbon fiber, activated carbon fiber, carbon nanotube, activated carbon nanotube, soccerballene, the active soccerballene.。These are commonly used and well behaved carbonaceous material.
Above-mentioned polymer monomer is: a kind of in aniline, pyrroles, thiophene, polyisocyanates, vinyl cyanide, vinylchlorid, tetrafluoroethylene, divinyl, propylene, vinylbenzene, the isoprene.
The well-beaten concrete practice was when above-mentioned inorganic solution slowly added organic solution: adopt magnetic agitation, mechanical stirring, sonic oscillation to stir or the mechanical oscillation stirring.Can make blending dispersion more even like this, more help compound mutually between inorganic phase and the organic phase.
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) figure of employed carbon nanotube in the embodiment of the invention one.
Fig. 2 is for adopting scanning electronic microscope (SEM) figure of the prepared carbon nano-tube/poly aniline matrix material of the embodiment of the invention one method.
Fig. 3 changes infrared spectra (FTIR) figure for the fourier of the carbon nano-tube/poly aniline matrix material that the method that adopts the embodiment of the invention one prepares.Wherein, transverse axis is a wavelength, and unit is cm
-1, the longitudinal axis is a specific absorption.
Fig. 4 is assembled into behind the ultracapacitor constant current charge-discharge graphic representation at 0～2.5V voltage range for the carbon nano-tube/poly aniline matrix material of the method preparation of adopting the embodiment of the invention one as electrode materials.Transverse axis is a time T, and unit is s, and the longitudinal axis is a voltage U, the V of unit.
Fig. 5 changes infrared spectra (FTIR) figure for the fourier of the carbon nano-tube/poly pyrroles matrix material that the method that adopts the embodiment of the invention two prepares.Wherein, transverse axis is a wavelength, and unit is cm
-1, the longitudinal axis is a specific absorption.
Fig. 6 is assembled into cyclic voltammetry curve figure behind the ultracapacitor as electrode materials respectively for the carbon nano-tube/poly pyrroles matrix material of the method preparation of adopting the embodiment of the invention two and pure polypyrrole material.Wherein solid line is the cyclic voltammetry curve figure of carbon nano-tube/poly pyrroles matrix material, and dotted line is the cyclic voltammetry curve figure of pure polypyrrole material.Transverse axis is a voltage, the mV of unit; The longitudinal axis is an electric current, and unit is mA.
Embodiment
Embodiment one
A, preparation organic phase add the polymer monomer aniline of 9 parts of weights in the organic solvent toluene, form the organic solution of aniline;
B, the inorganic carbonaceous inorganic materials carbon nanotube powder with 1 part of weight of preparation are dissolved or dispersed in and form the aqueous solution in the water, add the polymerizing agent ammonium persulphate that the aniline that can make a step aggregates into polyaniline fully again in the aqueous solution, form inorganic solution.
C, the inorganic solution in b step is slowly added in a organic solution in step, carrying out polyreaction under constantly stirring, question response is complete, form colloid after, with product filter colloid.And being the water white transparency shape until washings with ethanol, distilled water repetitive scrubbing, vacuum dehydrating at lower temperature promptly gets carbon nano-tube/poly aniline matrix material.
Fig. 1 is transmission electron microscope (TEM) figure of employed carbon nanotube in the example method.Fig. 2 schemes for the scanning electronic microscope (SEM) of the carbon nano-tube/poly aniline matrix material that this routine method of employing makes.By Fig. 1,2 as seen, mainly all some nano level tubulose materials among two figure, the size of the nanotube among Fig. 2 is obviously greater than the nanotube among Fig. 1.Thereby the proof carbon nanotube in its surface coverage material is arranged, and these covertures is to grow along carbon nanotube uniformly after the example method is handled.
Fig. 3 makes examination of infrared spectrum (FTIR) figure of carbon nano-tube/poly aniline matrix material for adopting this routine method.As shown in Figure 3, the FTIR figure of the matrix material that this example is prepared is the infrared spectrogram of typical polyaniline, thereby the polymkeric substance that proof is generated is a polyaniline.
Chemical property for the matrix material that further specifies this example preparation, matrix material is carried out following processing: make conductive agent and 5% polyvinylidene difluoride (PVDF) (PVDF) is made caking agent with 10% acetylene black, with the nickel foam is collector electrode, with scraping the even electrode coated material of wiping manipulation in the above, oven dry is beaten behind the sheet as positive and negative two electrodes of electrical condenser.(VEC: VDEC=1: 1) make electrolytic solution, U.S. Celgard2400 is a barrier film, is assembled into electric chemical super capacitor in being full of the argon gas glove box with 1.0mol/l LiClO4/EC+DEC.Carry out the constant current charge-discharge test on the upright DC-5 type full-automatic battery controlled testing instrument of Shanghai, charging and discharging currents density is 3.4A/m
2Fig. 4 is the constant current charge-discharge graphic representation that the ultracapacitor of this assembling is tested at 0～2.5V voltage range.Can calculate the unipolar specific storage of this matrix material in view of the above and in organic electrolyte, be 117.7F/g, show good electroactive volumetric properties.
Embodiment two
This example is basic identical with embodiment one, different is: the carbon containing inorganic materials of use is 1 a part heavy carbon nano-tube material, polymer monomer is 4 parts heavy pyrrole monomers, iron(ic) chloride is polymerizing agent, organic solvent is a chloroform, the mode that stirs is a mechanical stirring, and prepared matrix material is the carbon nano-tube/poly pyrroles.
Fig. 5 is examination of infrared spectrum (FTIR) figure of the carbon nano-tube/poly pyrroles matrix material of this routine method preparation of employing.As seen from Figure 5, the FTIR figure of the matrix material that this example is prepared is the infrared spectrogram of typical polypyrrole, thereby the polymkeric substance that proof is generated is a polypyrrole.
Fig. 6 is assembled into the cyclic voltammetry curve figure that is tested behind the ultracapacitor as electrode materials respectively for this routine method prepared carbon nano-tube/poly pyrroles matrix material of employing and pure polypyrrole material.As seen from Figure 6, the electrochemistry capacitance performance of carbon nano-tube/poly pyrroles matrix material is apparently higher than pure polypyrrole material.
Embodiment three
This example is basic identical with embodiment one, different is: the active carbon material of 1 part of weight of use is as the carbon containing inorganic materials, 100 parts heavy thiophene monomers are as polymer monomer, iron trichloride is a polymerizing agent, organic solvent is an acetone, the mode that stirs is a sonic oscillation, and the matrix material of preparation is activated carbon/Polythiophene.
Embodiment four
This example is basic identical with embodiment one, different is: use 1 part of scheelite China ink carbon material as the carbon containing inorganic materials, 0.01 part heavy polyisocyanates is as polymer monomer, water is polymerizing agent, organic solvent is a tetracol phenixin, the mode that stirs is a mechanical oscillation, and prepared matrix material is graphite carbon/urethane.
Embodiment five
This example is basic identical with embodiment one, and different is: 1 part heavy soccerballene carbon material is as the carbon containing inorganic materials, and 50 parts heavy vinyl cyanide are as polymer monomer, with sodium chlorate NaClO
3And Sodium Pyrosulfite Na
2S
2O
5Be polymerizing agent, organic solvent is a benzene, and the mode of stirring is mechanical stirring and magnetic agitation mode, and prepared matrix material is soccerballene/polyacrylonitrile.
Embodiment six
This example is basic identical with embodiment one, and different is: 1 part of taskwork carbon fiber carbon material is as carbon material, and 1.5 parts weigh vinylchlorid as polymer monomer, mercury salt HgCl
2Make polymerizing agent, organic solvent is a hexanaphthene, and the mode of stirring is mechanical stirring and sonic oscillation, and prepared matrix material is activated carbon fiber/polyvinyl chloride.
Embodiment seven
This example is basic identical with embodiment one, different is: 1 part of taskwork graphite carbon material is as carbon material, 0.25 part heavy divinyl is as polymer monomer, hydrogen peroxide is as polymerizing agent, organic solvent is an ether, the mode that stirs is mechanical stirring and mechanical oscillation, and prepared matrix material is active graphite carbon/polyhutadiene.
Embodiment eight
This example is basic identical with embodiment one, different is: 1 part of taskwork carbon nano-tube material is as carbon material, 3 parts heavy propylene are as polymer monomer, propylene is dissolved in the mixed solution of tetracol phenixin and normal hexane, triethyl aluminum is a polymerizing agent, the mode that stirs is magnetic agitation and sonic oscillation, and prepared matrix material is active carbon nanotube/polypropylene.
Embodiment nine
This example is basic identical with embodiment one, different is: 0.5 part of heavy activated carbon and 0.5 part of taskwork graphite carbon material are as carbon material, polymer monomer is 2.1 parts of heavy benzol ethene, hydrogen peroxide is a polymerizing agent, organic solvent is ether and sherwood oil, the mode that stirs is that mechanical stirring adds magnetic agitation, and prepared matrix material is graphite carbon/polystyrene.
Embodiment ten
This example is basic identical with embodiment one, different is: the carbon material of use is 1 part of taskwork soccerballene carbon material, polymer monomer is 1.94 parts heavy methyl methacrylates, benzoyl peroxide is a polymerizing agent, organic solvent is an EC, the mode that stirs is that magnetic agitation adds the mechanical oscillation mode, and prepared matrix material is soccerballene/polymethylmethacrylate.
Embodiment 11
This example is basic identical with embodiment one, different is: the carbon material of use is 0.5 part of taskwork carbon nanotube and 0.5 part heavy carbon fibre material, polymer monomer is 0.92 a part heavy isoprene, the aluminium titanium compound is a polymerizing agent, organic solvent is benzene and dimethylbenzene, the mode that stirs is that sonic oscillation adds the mechanical oscillation mode, and prepared matrix material is activated carbon nanotube/carbon fiber/polyisoprene.
Embodiment 12
This example is basic identical with embodiment one, different is: the carbon material of use is the soccerballene carbon material of 0.3 part of heavy carbon nanotube and 0.7 part of weight, polymer monomer is 0.27 part of semidine and 0.27 part heavy pyrroles, ammonium persulphate and iron trichloride are polymerizing agent, organic solvent is toluene or chloroform or acetone, the mode that stirs is the mechanical stirring mode, and prepared matrix material is carbon nanotube/soccerballene/polyaniline/polypyrrole.
Embodiment 13
This example is basic identical with embodiment one, different is: the carbon material of use is the soccerballene carbon material of 0.3 part of heavy carbon nanotube and 0.7 part of weight, polymer monomer is 80 parts heavy tetrafluoroethylene, Sodium Persulfate is a polymerizing agent, organic solvent is a tetracol phenixin, use the mechanical stirring mode to handle, prepared matrix material is carbon nanotube/soccerballene/tetrafluoroethylene.
The present invention prepares the method for organic-inorganic composite material, and wherein stirring means is not limited to magnetic agitation, mechanical stirring, sonic oscillation and mechanical oscillation, and other can make the abundant dispersive method of two phase liquid use.
The employed polymer monomer of the inventive method is not limited to material cited among the embodiment, and can is its various derivatives, and the polymer monomer that its polymerizing agent does not react with water during all polymerization reaction take places.Employed organic solvent also is not limited to cited organic solvent, so long as water insoluble and can to dissolve the polymer monomer of selecting for use just passable; As: all also available benzene of aniline, pyrroles, thiophene or ether etc. are as its organic solvent; The also available ether of vinylchlorid, acetone, ethylene dichloride etc. are as its organic solvent.
Organic-inorganic composite material with the present invention preparation can be used as energy and material, electromagnetic shielding material, conductive coating material, heating material, anti-electrostatic/destatic material, engineering plastics etc.
Claims (4)
1, a kind of method for preparing carbon containing inorganic materials-polymer composites, its concrete practice is:
A, the preparation organic phase polymer monomer that 0.01-100 part is heavy add in its organic solvent, form the organic solution of polymer monomer;
B, the inorganic carbon containing inorganic materials with 1 part of weight of preparation are dissolved or dispersed in and form the aqueous solution in the water, in the aqueous solution, add again a step polymer monomer polymerizing agent, form inorganic solution; The polymerizing agent of this polymerizing agent for not reacting with water, and its add-on is for making a complete polymeric amount of polymer monomer in step;
C, the inorganic solution that b is gone on foot slowly add in a organic solution in step, and abundant stirring reaction, generate composite colloids, to the colloid after filtering, and cleaning, drying, promptly.
2, a kind of method for preparing carbon containing inorganic materials-polymer composites as claimed in claim 1, it is characterized in that: described carbon containing inorganic materials is: the mixture of one or more in graphite, activated carbon, active graphite carbon, carbon fiber, activated carbon fiber, carbon nanotube, activated carbon nanotube, soccerballene, the active soccerballene.
3, a kind of method for preparing carbon containing inorganic materials-polymer composites as claimed in claim 1, it is characterized in that: described polymer monomer is: a kind of in aniline, pyrroles, thiophene, polyisocyanates, vinyl cyanide, vinylchlorid, tetrafluoroethylene, divinyl, propylene, vinylbenzene, the isoprene.
4, a kind of method for preparing carbon containing inorganic materials-polymer composites as claimed in claim 1, it is characterized in that: the well-beaten concrete practice was when described inorganic solution slowly added organic solution: adopt magnetic agitation, mechanical stirring, sonic oscillation to stir or the mechanical oscillation stirring.
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| CN112960815A (en) * | 2021-02-23 | 2021-06-15 | 中国石油大学(北京) | Recycling treatment method and device for fracturing flowback fluid |
| CN113186565A (en) * | 2021-04-14 | 2021-07-30 | 天津大学 | Preparation method of novel nitrogen-doped carbon material for electrocatalytic reduction of carbon dioxide |
| CN114478884A (en) * | 2022-03-24 | 2022-05-13 | 山东大学 | Method for preparing PAN-fullerene nano composite particles through aqueous suspension polymerization |
| CN114478884B (en) * | 2022-03-24 | 2022-10-14 | 山东大学 | Method for preparing PAN-fullerene nano composite particles through aqueous suspension polymerization |
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