CN100443401C - Method of synthesizing nanometer carbon pipe by cracking polymer - Google Patents
Method of synthesizing nanometer carbon pipe by cracking polymer Download PDFInfo
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- CN100443401C CN100443401C CNB200610016733XA CN200610016733A CN100443401C CN 100443401 C CN100443401 C CN 100443401C CN B200610016733X A CNB200610016733X A CN B200610016733XA CN 200610016733 A CN200610016733 A CN 200610016733A CN 100443401 C CN100443401 C CN 100443401C
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Abstract
The present invention belongs to a method for synthesizing carbon nanotubes by cracking polymers, which provides a new method for preparing carbon nanotubes by using organic polymers as carbon sources and halogen containing compounds as synergistic catalysts under the existence of carbon forming catalysts. Polymer blends in a certain proportion are combusted at high temperature in the air or are cracked at high temperature by isolating the air, wherein the polymer blends contain halogen and the carbon forming catalysts, carbon residues are collected to serve as carbon nanotubes. In addition, hydrochloric acid, hydrobromic acid, etc. can also be obtained by high-temperature cracking. The more important thing is that waste is changed into valuables, the carbon nanotubes are obtained, a large amount of gas rich in hydrogen can be obtained as a hydrogen source, and the method has important significance. Carbon source materials used for the synthesis of the carbon nanotubes of the present invention can be polyolefin and recovered polyolefin with complicated constituents, even polyvinyl chloride unfavorable to the recovery of the polyolefin, and the raw materials have the advantages of low price and rich source.
Description
Technical field
The invention belongs to a kind of technical field of synthesize nano carbon tube material.Disclosing a kind of is promotor with the halide-containing, is char forming catalyst with iron, cobalt, nickel, is the novel method of carbon source synthesizing carbon nanotubes with the alkene main polymer.
Background technology
Carbon nanotube is the C that continues
60Another great discovery afterwards, its feature are that it typically has a diameter from several dusts to tens nanometers, and length-to-diameter ratio is tens to several thousand.Because carbon nanotube has excellent physical and mechanical performance and conductivity, is widely used.
Usually, carbon nanotube adopts arc process, laser evaporation method, electrochemical vapor deposition, catalysis synthesis process and the preparation of plasma synthesis method.The normally organic hydrocarbon small molecules of carbon source in these methods, as: methane, acetylene, ethene or the like.Adopt the fluidized bed cracking reactor as the ZL01118349.7 report; with CO and the following lower carbon number hydrocarbons of 7 carbon is carbon source; with hydrogen is reducing gas; all adopt protection of inert gas in the preparation process; reaction unit comprises main reactor, catalyst activator, gas distributor, gas-solid separator and product degassing stages, the equipment complexity that is adopted.In recent years, as the patent of carbon source synthesizing carbon nanotubes report is arranged also with polymkeric substance.Chinese patent application has been reported with polyolefine as carbon source, modified montmorillonoid (CN200410011179.7, CN200510016849.9) and nickel-containing catalyst (CN200510016849.9, CN200510119084.1) exist down, in air burning or under inert atmosphere pyrolytic decomposition (CN200510017038.0) obtain carbon nanotube and montmorillonite composite.Because the existence of polynite makes the purification of the thick product of this carbon nanotube have to use hydrofluoric acid, brings pollution to environment.In addition, the price of modified montmorillonoid and expanding material is also higher, adds hydrofluoric acid, makes that the raw materials cost of the carbon nanotube that this method obtains and Environmental costs are all higher.Chinese patent application 200410011337.9 expands to molecular sieve to polynite, but uses hydrofluoric acid inevitable.
Summary of the invention
The object of the present invention is to provide a kind of method of synthesizing nanometer carbon pipe by cracking polymer, relating to the halide-containing is promotor, is char forming catalyst with iron, cobalt, nickel, is the novel method of carbon source synthesizing carbon nanotubes with the alkene main polymer.
Step and condition that the present invention prepares carbon nanotube are as follows:
I. the preparation of the blend polymer of promotor and char forming catalyst
One of method is exactly that at least a promotor, at least a alkene main polymer and at least a char forming catalyst are mixed, and prepares halogen-containing and blend polymer char forming catalyst.
Promotor is:
Polyvinyl chloride, sovprene, fluorinated ethylene propylene, polyvinylidene chloride, chlorinatedpolyethylene, brominated Polystyrene, chlorinated butyl rubber, chlorinated natural rubber, vinyl chloride-ethylene copolymer, vinyl chloride-ethylene-vinyl acetate copolymer, chlorinated polyvinyl chloride, acrylonitrile-chlorianted polyethylene-styrene terpolymer, ethylene-vinyl chloride copolymer, VCP, vinylbenzene-brominated styrene multipolymer, vinylbenzene-Benzene Chloride ethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer, vinylbenzene-trieline multipolymer, propylene-metachloroethylene copolymer, the polyoxygenated dibromobenzene, brominated epoxy resin, politef, voltalef or brominated polyphenylether eight bromo ether; Or
Decabromodiphenyl oxide, ten tetrabromos, two phenoxy group benzene, decabromodiphenyl, DCRP, the special acid in sea, extra large special acid anhydrides, hexachlorocyclopentadiene, tetrachlorophthalic tetrachlorophthalic anhydrid, perchloropentacyclodecane, tribromo-benzene, tribromophenol, TDE, tetrabromo-bisphenol diglycidylether, clorafin or tetrachlorobisphenol A; Or
The crystalline hydrate of aluminum chloride, iron(ic) chloride, iron protochloride, cupric chloride, cuprous chloride, nickelous chloride, cobalt chloride, zinc chloride, gallium chloride, antimony chloride, tin chloride, zirconium chloride, chromium chloride, Manganous chloride tetrahydrate, cupric bromide, polymerize aluminum chloride, aluminium iron polychloride, ammonium chloride, brometo de amonio, ammonium iodide or above compound;
The alkene main polymer is to be the homopolymer or the multipolymer of principal monomer with ethene, alpha-olefin, iso-butylene, cycloolefin and diolefine, or the chemical modification of polymer of these homopolymer and multipolymer, has:
(1) olefin polymer has: polyethylene, polypropylene, ethylene-octene copolymer, ethylene-butene copolymer, ethene-hexene copolymer, ethylene-propylene rubber(EPR), terpolymer EP rubber, polystyrene, polyisobutene, polyhutadiene, natural rubber, styrene-butadiene rubber(SBR) or styrene-butadiene-styrene block copolymer; Or
(2) ethene, alpha-olefin, iso-butylene, cycloolefin and diolefine and other monomeric multipolymers have: acrylonitrile-butadiene-styrene copolymer, acrylonitrile ethylene styrene copolymer, ethylene-vinyl acetate copolymer or perbutan; Or
(3) olefin polymer by the chemical modification of polymer that grafting, replacement, crosslinking reaction obtain is: polypropylene/Ethylene Propylene Terpolymer thermoplastic elastomer that chlorinated polyethylene is rare, Chlorinated Polypropylene III, brominated Polystyrene, chlorinated butyl rubber, maleic anhydride inoculated polypropylene, maleic anhydride graft polystyrene, methyl methacrylate-grafted terpolymer EP rubber, maleic anhydride graft polystyrene or dynamic vulcanization obtain.
Char forming catalyst is the catalyzer of active site with iron, cobalt or nickel, and it is:
(1) iron, cobalt or the nickel with 0 valency is the catalyzer of main active site, and it is nano level iron, cobalt or nickel and loads on iron, cobalt or nickel catalyzator on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or the carbon nanotube;
(2) oxide compound of iron, cobalt or nickel and the oxide compound that loads on iron, cobalt or nickel on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or the carbon nanotube;
(3) oxyhydroxide of iron, cobalt or nickel, subcarbonate, oxalate or formate and these compound loaded loaded catalysts that on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or carbon nanotube, forms; Or iron, cobalt or nickel are a kind of or any two or three houghite that forms with aluminium element;
Two of method is exactly that at least a Halogen organic polymer and at least a char forming catalyst are mixed, and prepares halogen-containing and blend polymer char forming catalyst.
Described Halogen organic polymer has: (1) vinylchlorid, vinylidene chloride, trifluorochloroethylene, chloro-styrene, trieline and bromstyrol and ethene, propylene, cinnamic multipolymer.Mainly comprise ethylene-vinyl chloride copolymer, VCP, vinylbenzene-brominated styrene multipolymer, vinylbenzene-Benzene Chloride ethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer, vinylbenzene-trieline multipolymer or propylene-metachloroethylene copolymer; Or the homopolymer or the multipolymer of (2) ethene, iso-butylene, alpha-olefin, diolefine introduce the halogen containing polymers that halogen obtains by high molecular weight reactive on molecular chain, comprises that chlorinated polyethylene is rare, Chlorinated Polypropylene III, brominated Polystyrene, chlorinated natural glue or chlorinated butyl rubber.
Char forming catalyst is identical with one of above-mentioned method.
Above-mentioned two kinds of methods obtain blend polymer, and raw-material proportioning is:
The weight ratio that the weight of halogen accounts for blend polymer is 0.01%-10%, and preferred weight ratio is 0.1-8%, and optimum weight percent is 0.5-5%; Playing the weight ratio that metallic element weight into the charcoal katalysis accounts for blend polymer is 0.05%-40%, and preferred weight ratio is 0.1%-25%, and optimum weight percent is 1%-10%.Said ratio does not comprise following additive.
The blend polymer that obtains by said ratio adds with at least a inert material in potter's clay, talcum powder, titanium dioxide, carbon black, white carbon black, mica powder and the glass fibre and mixes, and/or with mineral oil and paraffin at least a petroleum product add and mix, be used as the raw material for preparing carbon nanotube.Wherein the inert material addition is no more than above-mentioned polymer blending raw material gross weight 50%, and the petroleum product addition is no more than above-mentioned polymer blending raw material gross weight 10%.
Above-mentioned two kinds of methods obtain blend polymer, and the hybrid mode of employing is: mechanical stirring blend, solution blending or melt blending, preferred solution blend or melt blending, most preferably melt blending.
II. the preparation of carbon nanotube
Above-mentioned blend polymer is burnt in air, treat that naked light extinguishes the back and collects carbon residue, be carbon nanotube product; Or
At secluding air, 600 ℃ of-950 ℃ of decomposition, the carbon residue of collection is carbon nanotube product with above-mentioned blend; Collect the gas that discharges and be hydrogen-rich gas.Gained gas is demarcated hydrogen content through cooled with liquid nitrogen and alkali cleaning with gas-chromatography.
III. the purification of carbon nanotube
The method of purification of siliceous system is: with mass concentration is that the hydrofluoric acid of 10-30% joins in the carbon nanotube product that Step II makes, and places 20-30 hour, separates obtaining black carbon powder; Adding volume ratio again is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxed 0.5-4 hour, after the separation, with washed with de-ionized water to pH=7, the carbon nanotube that obtains purifying; Or
The method of purification of not siliceous system is: directly carbon nanotube product is joined the vitriol oil and concentrated nitric acid volume ratio and is in 1: 1 the mixture, refluxed 0.5-4 hour, after the separation, with washed with de-ionized water to pH=7, the carbon nanotube that obtains purifying.
Advantage of the present invention and beneficial effect:
1. the carbon source material that synthesizing carbon nanotubes of the present invention adopted can be a polyolefine, and the recovery polyolefine of composition complexity, even can be that polyolefine is reclaimed disadvantageous polyvinyl chloride, these cost of material are cheap, the source is abundant, only need regulate component content, not need to isolate polyvinyl chloride, directly utilize and decompose the hydrogenchloride that discharges, promote the polyolefine cracking to form carbon nanotube, really simplify the recovery of waste or used plastics, improved the efficient of catalyzer, obtained the carbon nanotube of high added value.
2. the present invention is if use not silica containing blend polymer, the compound of one-tenth such as Organohalogen compounds or metal halide charcoal promotor and iron, cobalt, nickel becomes the reacted product of charcoal or for gas or for dissolving in the metal or the metal halide of nitric acid at Pintsch process so, it is residual not have silicon-dioxide, complete like this can be without hydrofluoric acid, not only reduce the cost, and can reduce environmental pollution.
3. if the present invention adopts the secluding air Pintsch process, not only can make full use of carbon source, improve catalytic efficiency, improve the output of carbon nanotube, and the halogen of this process mainly discharges with gas with the form of hydrogen halide, absorbs through water to obtain useful byproducts: hydrochloric acid, Hydrogen bromide etc.The more important thing is turns waste into wealth, and not only can obtain carbon nanotube, and can obtain a large amount of hydrogen-rich gases, and as " hydrogen source ", the present invention has great importance.
Embodiment
Embodiment 1
The ethylene-vinyl chloride copolymer of chloride 10% weight ratio and nano-cobalt powder are extruded the preparation blend polymer by weight ratio melting mixing in single screw extrusion machine of 90: 10; Wherein to account for the blend polymer weight ratio be 9% to chlorine, and it is 10% that cobalt accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams and be put in 15 milliliters of crucibles, and add and be placed on the crucible.With combustion gas lamp flame envelope heating crucible bottom.After several seconds, blend takes fire, treat not reignition after, take off crucible, be put in shady and cool place and be cooled to room temperature, black solid thing carbon nanotube.
Adding volume ratio in thick product is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxes after 1 hour, takes out and carries out centrifugation, cleaning, obtains carbon nanotube 1.3 grams of purifying.
Embodiment 2
The vinylbenzene-vinyl chloride copolymer of chloride 10% weight ratio and ferric oxide weight ratio melting mixing in Banbury mixer by 90: 10, the preparation blend polymer; Wherein to account for the blend polymer weight ratio be 9% to chlorine, and it is 7% that iron accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams,, get carbon nanotube 0.8 gram with method preparation, the purification of embodiment 1.
Embodiment 3
The ethylene-chlorotrifluoro-ethylene copolymer of halogen-containing 20% weight ratio, green nickel oxide by weight 50: 50 melting mixing in twin screw extruder, are prepared blend polymer; Wherein to account for the blend polymer ratio be 10% to the total weight of chlorine and fluorine, and it is 40% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams,, get carbon nanotube 0.9 gram with method preparation, the purification of embodiment 1.
Embodiment 4
Propylene-the metachloroethylene copolymer of chloride 10% weight ratio and nano-nickel powder are prepared blend polymer by weight the method for 99.95: 0.05 usefulness embodiment 2; Wherein to account for the blend polymer weight ratio be 10% to chlorine, and it is 0.05% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams and be put in 15 milliliters of crucibles, and add and be placed on the crucible.With combustion gas lamp flame envelope heating crucible bottom.After several seconds, blend takes fire, treat not reignition after, take off crucible, be put in shady and cool place and be cooled to room temperature, black solid thing carbon nanotube.
Adding volume ratio in carbon nanotube product is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxes after 4 hours, takes out and carries out centrifugation, cleaning.Obtain carbon nanotube 1.7 grams of purifying this moment.
Embodiment 5
The chlorinated butyl rubber of chloride 5% weight ratio and cobaltous hydroxide added in the mill by 95: 5 weight ratios mix the preparation blend polymer; Wherein chlorine accounts for blend polymer weight ratio 4.75%, and cobalt accounts for blend polymer weight ratio 3.55%.
Get above-mentioned blend 3 grams,, get carbon nanotube 0.9 gram with method preparation, the purification of embodiment 4.
Embodiment 6
The basic nickel carbonate of the Chlorinated Polypropylene III of the chlorinatedpolyethylene of chloride 10% weight ratio of powdery, chloride 10% weight ratio of powdery, porphyrize was mixed the preparation blend polymer in homogenizer by weight 45: 45: 10; Wherein chlorine accounts for blend polymer weight ratio 9%, and nickel accounts for blend polymer weight ratio 5.5%.
Get above-mentioned blend 3 grams,, get carbon nanotube 1.1 grams with method preparation, the purification of embodiment 1.
Embodiment 7
The chlorinatedpolyethylene of chloride 10% weight ratio, Diaquaoxalato cobalt weight ratio, prepare blend polymer with the method for embodiment 6 by 80: 20; Wherein to account for the blend polymer weight ratio be 0.83% to bromine, and it is 3% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams,, get carbon nanotube 0.8 gram with method preparation, the purification of embodiment 4.
Embodiment 8
The brominated Polystyrenes of brominated 10% weight ratio of 9 grams are dissolved in 100 milliliters the methylene dichloride, add the 1g nanometer iron powder again and stir, volatilization is desolvated and is obtained blend polymer; Wherein to account for the blend polymer weight ratio be 9% to bromine, and it is 10% that iron accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams,, get carbon nanotube 0.7 gram with method preparation, the purification of embodiment 1.
Embodiment 9
Eight bromo ether, polypropylene, polyethylene, nickel content be the nickel Al bimetal oxyhydroxide of 45% weight ratio by 5: 45: 45: 5 weight ratio prepares blend polymer with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 3.35% to bromine, and it is 4.25% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, prepare carbon nanotube product with the method for embodiment 1.
Adding volume ratio then in carbon nanotube product is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxes after 0.5 hour, takes out and carries out centrifugation, cleaning.Obtain carbon nanotube 1.0 grams of purifying this moment.
Embodiment 10
Tribromophenol, polypropylene, maleic anhydride inoculated polypropylene, four water cobaltous acetates by 1: 70: 9: 20 weight ratio prepares blend polymer with the method for embodiment 3; Wherein to account for the blend polymer weight ratio be 3.35% to bromine, and it is 4.25% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, prepare carbon nanotube product with the method for embodiment 1.
Adding volume ratio then in carbon nanotube product is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxes after 3 hours, takes out and carries out centrifugation, cleaning.Obtain carbon nanotube 1.0 grams of purifying this moment.
Embodiment 11
Clorafin, polyethylene, terpolymer EP rubber, nickel weight ratio be 10% the molecular sieve carried nickel formate of ZSM-5 by 10: 30: 55: 5 weight ratios prepare blend polymer with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 7% to chlorine, and it is 0.5% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, prepare carbon nanotube product with the method for embodiment 1.
With mass concentration is that 10% hydrofluoric acid adds in the carbon nanotube product that makes, placed 30 hours, and separated obtaining black carbon powder, adding volume ratio then is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, reflux after 0.5 hour, take out and carry out centrifugation, cleaning.Obtain carbon nanotube 1.0 grams of purifying this moment.
Embodiment 12
Being ammonium chloride, polypropylene, nickel weight ratio 30% the molecular sieve carried nickel oxide of ZSM-5 prepares blend polymer by 10: 85: 5 weight ratios with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 6.6% to chlorine, and it is 1.6% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, prepare carbon nanotube product with the method for embodiment 1.
With mass concentration is that 30% hydrofluoric acid adds in the carbon nanotube product that makes, and places 20 hours, separates obtaining black carbon powder, and adding volume ratio then is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxes after 2 hours, and centrifugation, cleaning are carried out in taking-up.Obtain carbon nanotube 0.7 gram of purifying this moment.
Embodiment 13
Being ammonium iodide, polypropylene, nickel weight ratio 30% the molecular sieve carried nickel oxide of ZSM-5 prepares blend polymer by weight the method for 10: 85: 5 usefulness embodiment 2; Wherein to account for the blend polymer weight ratio be 8.76% to iodine, and it is 1.6% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, prepare carbon nanotube product with the method for embodiment 1.
With mass concentration is that 20% hydrofluoric acid adds in the carbon nanotube product that makes, and places 25 hours, separates obtaining black carbon powder, and adding volume ratio then is 1: 1 the vitriol oil and the mixture of concentrated nitric acid,, reflux after 4 hours, centrifugation, cleaning are carried out in taking-up.Obtain carbon nanotube 0.4 gram of purifying this moment.
Embodiment 14
Decabromodiphenyl oxide, Chlorinated Polypropylene III, polypropylene, nickel content be the alumina load nickel oxide of 30% weight ratio by weight 0.1: 80: 80: the method for 9.9 usefulness embodiment 3 prepares blend polymer; Wherein chlorine account for bromine blend polymer weight ratio be 0.38%, it is 3% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 1.1 with the preparation of embodiment 10 and method of purification and restrain.
Embodiment 15
DCRP, ethylene-vinyl acetate copolymer, two oxalic acid hydrate iron are prepared blend polymer by 0.1: 90: 9.9 weight ratio with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.065% to chlorine, and it is 3% that iron accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 0.7 with the preparation of embodiment 4 and method of purification and restrain.
Embodiment 16
Aluminum Chloride Hexahydrate, polypropylene, black nickel oxide are prepared blend polymer by 1: 94: 5 weight ratio with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.43% to chlorine, and it is 3.5% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 1.3 with the preparation of embodiment 9 and method of purification and restrain.
Embodiment 17
Iron trichloride hexahydrate, polypropylene, black nickel oxide are prepared blend polymer by 1: 94: 5 weight ratio with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.39% to chlorine, and it is 3.5% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 6 and restrain 950 ℃ of heating in the inert atmosphere that is put in silica tube, collect 6 liters of decomposition gases (room temperature normal pressure), wherein 5 liters of hydrogen (room temperature normal pressure).Silica tube is cooled to room temperature, gets the black carbon nanotube product, carbon nanotube 2.7 grams after purifying with the method for embodiment 1.
Embodiment 18
Cuprous chloride, polypropylene, black nickel oxide are prepared blend polymer by 1: 94: 5 weight ratio with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.35% to chlorine, and it is 3.5% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 6 and restrain 750 ℃ of heating in the inert atmosphere that is put in silica tube, collect 6.1 liters of decomposition gases (room temperature normal pressure), wherein 5.05 liters of hydrogen (room temperature normal pressure).Silica tube is cooled to room temperature, gets the black carbon nanotube product, gets carbon nanotube 2.5 grams after purifying with the method for embodiment 1.
Embodiment 19
Copper dichloride dihydrate, polypropylene, black nickel oxide are prepared blend polymer by 1: 94: 5 weight ratio with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.4% to chlorine, and it is 3.5% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 6 and restrain 600 ℃ of heating in the inert atmosphere that is put in silica tube, collect 5.5 liters of decomposition gases (room temperature normal pressure), wherein 4.75 liters of hydrogen (room temperature normal pressure).Silica tube is cooled to room temperature, gets the black carbon nanotube product, gets carbon nanotube 2.0 grams after purifying with the method for embodiment 1.
Embodiment 20
Cupric bromide, polypropylene, black nickel oxide are prepared blend polymer by 1: 94: 5 weight ratio with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.7% to bromine, and it is 3.5% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 1.4 grams after purifying with the method preparation of embodiment 10.
Embodiment 21
Chromium chloride hexahydrate, polypropylene, black nickel oxide are prepared blend polymer by 1: 94: 5 weight ratio with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.4% to chlorine, and it is 3.5% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 1.4 grams after purifying with the method preparation of embodiment 1.
Embodiment 22
Six water nickelous chlorides, polypropylene, black nickel oxide are prepared blend polymer by 1: 94: 5 weight ratio with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.29% to chlorine, and it is 3.5% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 1.5 grams after purifying with the method preparation of embodiment 4.
Embodiment 23
Polyvinyl chloride, ethylene-octene copolymer, polypropylene, nickel cobalt contents are 20% weight ratio
Molecular sieve carried nickel cobalt was by 1: 19: 70: 10 weight ratio prepares blend polymer with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.57% to chlorine, and it is 4% that nickel and cobalt account for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 1.2 grams after purifying with the method preparation of embodiment 11.
Embodiment 24
Fluorinated ethylene propylene, ethene-hexene copolymer, polypropylene, iron level be the montmorillonite load iron of 9% weight ratio by 1: 19: 70: 10 weight ratio prepares blend polymer with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.4% to fluorine, and it is 0.9% that iron accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 0.7 gram after purifying with the method preparation of embodiment 11.
Embodiment 25
Brominated Polystyrene, styrene-butadiene-styrene multipolymer, poly-1, nickel content be the tripolite loading nickel of 5% weight ratio by 1: 75: 23: 1 weight ratio prepares blend polymer with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.67% to bromine, and it is 0.05% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 0.7 gram after purifying with the method preparation of embodiment 13.
Embodiment 26
Voltalef, ethylene-propylene copolymer, polypropylene, two oxalic acid hydrate nickel by 0.1: 5: 90: 4.9 weight ratio prepares blend polymer with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.08% to bromine, and it is 1.5% that nickel accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 0.8 gram after purifying with the method preparation of embodiment 1.
Embodiment 27
Chlorinated polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, white carbon black, nickel content be the silicon dioxide carried nickel oxide of 50% weight ratio by 1: 39: 50: 10 weight ratio prepares blend polymer with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.7% to chlorine, and it is 5% that nickel accounts for the blend polymer weight ratio, and it is 50% that white carbon black accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 0.5 gram after purifying with the method preparation of embodiment 11.
Embodiment 28
Polymerize aluminum chloride, polyhutadiene, polypropylene, cobalt contents be the montmorillonite supported cobalt of 10% weight ratio by 0.05: 60: 35: 4.95 weight ratio prepares blend polymer with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.01% to chlorine, and it is 0.495% that cobalt accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 0.6 gram after purifying with the method preparation of embodiment 11.
Embodiment 29
Chloride be 20% weight ratio chlorinated natural rubber, chloride be Chlorinated Polypropylene III, natural rubber, the nickel content of 20% weight ratio be the montmorillonite load nickel oxide of 9% weight ratio by 5: 45: 45: 5 weight ratio prepares blend polymer with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 10% to chlorine, and it is 0.45% that nickel accounts for the blend polymer weight ratio).
Get above-mentioned blend 3 grams, get carbon nanotube 0.8 gram after purifying with the method preparation of embodiment 12.
Embodiment 30
Brominated be that polyoxygenated dibromobenzene, polystyrene, maleic anhydride graft polystyrene, organic modification montmonrillonite, the iron nickel content of 64% weight ratio is 5% the molecular sieve carried iron nickel of ZSM-5 by 1: 70: 10: 9: 10 weight ratio prepares blend polymer with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.64% to bromine, and it is 1% that iron and nickel account for the blend polymer weight ratio, and it is 9% that organic modification montmonrillonite accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 1.0 grams after purifying with the method preparation of embodiment 13.
Embodiment 31
Perchloropentacyclodecane, polypropylene, isoprene-isobutylene rubber, white oil, nickel content be the carbon nanotube loaded nickel oxide of 50% weight ratio by 0.1: 30: 50: 10: 9.9 weight ratio prepares blend polymer with the method for embodiment 2; Wherein to account for the blend polymer weight ratio be 0.078% to chlorine, and it is 5% that nickel accounts for the blend polymer weight ratio, and it is 10% that white oil accounts for the blend polymer weight ratio.
Get above-mentioned blend 3 grams, get carbon nanotube 1.2 grams after purifying with the method preparation of embodiment 1.
Embodiment 32
The alumina load iron cobalt that politef, butadiene-styrene copolymer, iron cobalt contents is 15% weight ratio prepares blend polymer by 0.1: 89.9: 10 weight ratio with the method for embodiment 5; Wherein to account for the blend polymer weight ratio be 0.085% to chlorine, and it is 3% that nickel accounts for the blend polymer weight ratio).
Get above-mentioned blend 3 grams, get carbon nanotube 1.6 grams after purifying with the method preparation of embodiment 1.
Claims (13)
1. method of synthesizing nanometer carbon pipe by cracking polymer is characterised in that step and condition are as follows:
I. at least a promotor, at least a alkene main polymer and at least a char forming catalyst are mixed, prepare halogen-containing and blend polymer char forming catalyst;
Described promotor is:
Polyvinyl chloride, sovprene, fluorinated ethylene propylene, polyvinylidene chloride, chlorinatedpolyethylene, brominated Polystyrene, chlorinated butyl rubber, chlorinated natural rubber, vinyl chloride-ethylene copolymer, vinyl chloride-ethylene-vinyl acetate copolymer, chlorinated polyvinyl chloride, acrylonitrile-chlorianted polyethylene-styrene terpolymer, ethylene-vinyl chloride copolymer, VCP, vinylbenzene-brominated styrene multipolymer, vinylbenzene-Benzene Chloride ethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer, vinylbenzene-trieline multipolymer, propylene-metachloroethylene copolymer, the polyoxygenated dibromobenzene, brominated epoxy resin, politef, voltalef or brominated polyphenylether eight bromo ether; Or
Decabromodiphenyl oxide, ten tetrabromos, two phenoxy group benzene, decabromodiphenyl, DCRP, the special acid in sea, extra large special acid anhydrides, hexachlorocyclopentadiene, tetrachlorophthalic tetrachlorophthalic anhydrid, perchloropentacyclodecane, tribromo-benzene, tribromophenol, TDE, tetrabromo-bisphenol diglycidylether, clorafin or tetrachlorobisphenol A; Or
The crystalline hydrate of aluminum chloride, iron(ic) chloride, iron protochloride, cupric chloride, cuprous chloride, nickelous chloride, cobalt chloride, zinc chloride, gallium chloride, antimony chloride, tin chloride, zirconium chloride, chromium chloride, Manganous chloride tetrahydrate, cupric bromide, polymerize aluminum chloride, aluminium iron polychloride, ammonium chloride, brometo de amonio, ammonium iodide or above compound;
The alkene main polymer:
Be to be the homopolymer or the multipolymer of principal monomer with ethene, alpha-olefin, iso-butylene, cycloolefin and diolefine, or the chemical modification of polymer of these homopolymer and multipolymer, have:
(1) olefin polymer has: polyethylene, polypropylene, ethylene-octene copolymer, ethylene-butene copolymer, ethene-hexene copolymer, ethylene-propylene rubber(EPR), terpolymer EP rubber, polystyrene, polyisobutene, polyhutadiene, natural rubber, styrene-butadiene rubber(SBR) or styrene-butadiene-styrene block copolymer; Or
(2) ethene, alpha-olefin, iso-butylene, cycloolefin and diolefine and other monomeric multipolymers have: acrylonitrile-butadiene-styrene copolymer, acrylonitrile ethylene styrene copolymer, ethylene-vinyl acetate copolymer or perbutan; Or
(3) olefin polymer by the chemical modification of polymer that grafting, replacement, crosslinking reaction obtain is: polypropylene/Ethylene Propylene Terpolymer thermoplastic elastomer that chlorinated polyethylene is rare, Chlorinated Polypropylene III, brominated Polystyrene, chlorinated butyl rubber, maleic anhydride inoculated polypropylene, maleic anhydride graft polystyrene, methyl methacrylate-grafted terpolymer EP rubber, maleic anhydride graft polystyrene or dynamic vulcanization obtain;
Char forming catalyst is the catalyzer of active site with iron, cobalt or nickel, and it is:
(1) iron, cobalt or the nickel with 0 valency is the catalyzer of main active site, and it is nano level iron, cobalt or nickel and loads on iron, cobalt or nickel catalyzator on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or the carbon nanotube; Or
(2) oxide compound of iron, cobalt or nickel and the oxide compound that loads on iron, cobalt or nickel on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or the carbon nanotube; Or
(3) oxyhydroxide of iron, cobalt or nickel, subcarbonate, oxalate or formate and these compound loaded loaded catalysts that on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or carbon nanotube, forms; Or iron, cobalt, nickel is a kind of or any two or three houghite that forms with aluminium element;
Blend polymer, raw-material proportioning is:
The weight ratio that the weight of halogen accounts for blend polymer is 0.01%-10%; Playing the weight ratio that metallic element weight into the charcoal katalysis accounts for blend polymer is 0.05%-40%;
Obtain blend polymer, the hybrid mode of employing is: mechanical stirring blend, solution blending or melt blending;
II. the preparation of carbon nanotube
Above-mentioned blend polymer is burnt in air, treat that naked light extinguishes the back and collects carbon residue, be carbon nanotube product.
2. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1, it is characterized in that among the described step I, be that at least a Halogen organic polymer promotor and at least a char forming catalyst are mixed, prepare halogen-containing and blend polymer char forming catalyst;
Described Halogen organic polymer promotor is: (1) vinylchlorid, vinylidene chloride, trifluorochloroethylene, chloro-styrene, trieline and bromstyrol and ethene, propylene, cinnamic multipolymer, and it is ethylene-vinyl chloride copolymer, VCP, vinylbenzene-brominated styrene multipolymer, vinylbenzene-Benzene Chloride ethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer, vinylbenzene-trieline multipolymer or propylene-metachloroethylene copolymer; Or the homopolymer or the multipolymer of (2) ethene, iso-butylene, alpha-olefin, diolefine introduce the halogen containing polymers that halogen obtains by high molecular weight reactive on molecular chain, and it is that chlorinated polyethylene is rare, Chlorinated Polypropylene III, brominated Polystyrene, chlorinated natural glue or chlorinated butyl rubber.
3. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1 is characterized in that, in the raw-material proportioning of the blend polymer that described step I obtains, the weight ratio that the weight of halogen accounts for blend polymer is 0.1-8%.
4. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1 is characterized in that, in the raw-material proportioning of the blend polymer that described step I obtains, the weight ratio that the weight of halogen accounts for blend polymer is 0.5-5%.
5. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1, it is characterized in that, in the raw-material proportioning of the blend polymer that described step I obtains, playing the weight ratio that metallic element weight into the charcoal katalysis accounts for blend polymer is 0.1%-25%.
6. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1, it is characterized in that, in the raw-material proportioning of the blend polymer that described step I obtains, playing the weight ratio that metallic element weight into the charcoal katalysis accounts for blend polymer is 1%-10%.
7. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1 is characterized in that among the described step I, described blend polymer, and the hybrid mode of employing is: solution blending or melt blending.
8. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1 is characterized in that among the described step I, the described blend polymer that obtains, and the hybrid mode of employing is: melt blending.
9. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1, it is characterized in that in the Step II of preparation of carbon nanotube, described be with blend at secluding air, 600 ℃ of-950 ℃ of decomposition, the carbon residue of collection is carbon nanotube product.
10. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1, it is characterized in that among the step I of preparation of described carbon nanotube, the described blend polymer that obtains by proportioning adds with at least a inert material in potter's clay, talcum powder, titanium dioxide, carbon black, white carbon black, mica powder and the glass fibre and mixes, and/or with mineral oil and paraffin at least a petroleum product add and mix, be used as the raw material for preparing carbon nanotube; Wherein the inert material addition is no more than blend polymer gross weight 50%, and petroleum product is no more than blend polymer gross weight 10%.
11. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1, it is characterized in that in the Step II of preparation of described carbon nanotube, described char forming catalyst is the catalyzer of active site with iron, cobalt or nickel, and it is: the oxide compound of iron, cobalt or nickel and the oxide compound that loads on iron, cobalt or nickel on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or the carbon nanotube.
12. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1, it is characterized in that in the Step II of preparation of described carbon nanotube, described char forming catalyst is the catalyzer of active site with iron, cobalt, nickel, it is: the oxyhydroxide of iron, cobalt or nickel, subcarbonate, oxalate or formate, and these compound loaded loaded catalysts that form on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or carbon nanotube; Or iron, cobalt or nickel are a kind of or any two or three houghite that forms with aluminium element.
13. the method for a kind of synthesizing nanometer carbon pipe by cracking polymer according to claim 1, after the preparation process of carbon nanotube of Step II that it is characterized in that the preparation of described carbon nanotube is finished, also in steps:
III. the purification of carbon nanotube
The method of purification of siliceous system is: with mass concentration is that the hydrofluoric acid of 10-30% joins in the carbon nanotube product that Step II makes, and places 20-30 hour, separates obtaining black carbon powder; Adding volume ratio again is 1: 1 the vitriol oil and the mixture of concentrated nitric acid, refluxed 0.5-4 hour, after the separation, with washed with de-ionized water to pH=7, the carbon nanotube that obtains purifying; Or the method for purification of not siliceous system is: directly carbon nanotube product is joined the vitriol oil and concentrated nitric acid volume ratio and is in 1: 1 the mixture, refluxed 0.5-4 hour, after the separation, with washed with de-ionized water to pH=7, the carbon nanotube that obtains purifying.
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| CN101531363B (en) * | 2009-04-17 | 2011-04-27 | 北京化工大学 | Method for preparing carbon nano tube by using houghite to catalyze polymer to decompose |
| CN102491308A (en) * | 2011-11-25 | 2012-06-13 | 卓心康 | Method for synthesis of carbon nanostructure material by using organic material |
| CN105836727B (en) * | 2016-03-21 | 2018-10-23 | 陕西师范大学 | A kind of method that low cost prepares multi-walled carbon nanotube |
| CN105858635A (en) * | 2016-03-29 | 2016-08-17 | 北京化工大学 | Preparation method for diameter-controllable carbon nanotube |
| CN108298517B (en) * | 2017-01-12 | 2020-01-31 | 中国科学院化学研究所 | method for preparing porous carbon material by using halogenated polyolefin polymer as precursor and product thereof |
| CN106904597B (en) * | 2017-04-13 | 2018-10-19 | 合肥工业大学 | A method of preparing carbon nanotube to be orientated Freeze Drying Technique |
| SG11202002828YA (en) | 2017-09-27 | 2020-04-29 | Agency Science Tech & Res | Processes for production of carbon nanotubes from natural rubber |
| CN108529701A (en) * | 2018-04-23 | 2018-09-14 | 杭州鼎好新材料有限公司 | A kind of use in waste water treatment polyethylene ball and preparation method thereof |
| GB2578517B (en) * | 2018-05-22 | 2020-11-04 | Univ Northeastern | Method and equipment for extracting carbon materials from plastics |
| CN114634174A (en) * | 2020-12-16 | 2022-06-17 | 东北林业大学 | Method for synthesizing carbon nano tube by using starch or cellulose biomass as carbon source |
| CN112938938B (en) * | 2021-03-28 | 2022-08-23 | 中北大学 | Preparation method of multi-wall fluorescent carbon nano tube |
| CN114538415B (en) * | 2022-02-25 | 2024-03-26 | 暨南大学 | Method for preparing carbon nano tube by taking wax as carbon source |
| CN115304055B (en) * | 2022-08-24 | 2023-11-24 | 广东能源集团科学技术研究院有限公司 | Method for recycling polyethylene waste plastics and carbon nano tube prepared by method |
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