CN101696005B - Method for preparing acrylonitrile polymer based mesoporous carbon - Google Patents
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Abstract
The invention discloses a method for preparing acrylonitrile polymer based mesoporous carbon, which comprises the following steps: (1) adjusting the pH value of nano silicon oxide hydrosol to 9 to 12 by using ammonia water, and adding 2, 2'-azo (2-amidinopropane) dihydrochloride into the hydrosol to obtain modified nano silicon oxide hydrosol; (2) adding the modified nano silicon oxide hydrosol, acrylonitrile or mixture of acrylonitrile and second monomer, and nonionic emulsifying agent into a reactor, and heating the mixture to perform emulsion polymerization to obtain acrylonitrile polymer/nano silicon oxide compound; (3) carbonizing the acrylonitrile polymer/nano silicon oxide compound at high temperature to obtain carbon/nano silicon oxide compound; and (4) etching and removing the nano silicon oxide in the carbon/nano silicon oxide compound by using hydrofluoric acid to obtain the mesoporous carbon. The mesoporous carbon prepared by adopting the method has the advantages of high mesoporous rate, even aperture distribution, large specific surface area and the like, and has good application prospect in the fields of new energy, environmental protection, industrial catalysis and the like.
Description
Technical field
The present invention relates to technical field of chemical engineering, relate in particular to a kind of preparation method of acrylonitrile polymer based mesopore charcoal.
Background technology
Porous carbon material is widely used in many fields such as environment protection, medical science, new forms of energy.International Union of Pure and Applied Chemistry(IUPAC) (IUPAC) is divided into porous charcoal according to the aperture size of porous charcoal: micropore charcoal (aperture size is less than 2nm), mesopore charcoal (2～50nm) and macropore carbon (＞50nm).The porous charcoal of suitability for industrialized production and application is based on the micropore charcoal at present.Because the aperture of micropore charcoal is little, can not be used for the fractionation by adsorption of larger-size pollutent (as biological and synthetic macromolecule material); During as electrode material for super capacitor, be unfavorable for electrolytic solution rapid permeability and freely come in and go out, had a strong impact on the power characteristic of ultracapacitor.The mesopore charcoal belongs to novel porous raw material of wood-charcoal material, have that the aperture is big, specific surface area is big and characteristics such as pore volume height, can be used as the electrode materials etc. of adsorption separating agent, support of the catalyst, transmitter, fuel cell and the ultracapacitor of organic macromolecule in the waste water (as dyestuff, biomass and polymkeric substance etc.), have broad application prospects in fields such as environmental protection, Industrial Catalysis and new forms of energy.
But the mesopore charcoal can adopt method preparations such as catalytic activation, organogel charing, cleavable polymer/charing poyblend charing and template charing, but adopts the pore size distribution broad of the mesopore charcoal of first three methods preparation.The template charring is the mesopore charcoal novel preparation method that grows up the nineties in 20th century, this method is template usually with the inorganic nano-particle, make the mesopore charcoal through step such as, charing compound with carbon precursor and template elimination, the mesopore charcoal for preparing has advantages such as narrow, the middle porosity height of pore size distribution and specific surface area are big.Adopt the template charring to prepare the mesopore charcoal, except that will selecting suitable presoma and template, the homodisperse of template in carbon precursor also is the key of the high-quality mesopore charcoal of preparation.
Can be a lot of as the material of carbon precursor, comprise coal, pitch, sucrose, natural polymer (as plant shell, stalk etc.) and synthesized polymer material etc.The mesopore raw material of wood-charcoal material that with the synthesized polymer material is the carbon precursor preparation has the purity advantages of higher, and because the macromolecular material forming process is convenient, can obtain the porous carbon material of different shapes (as film, fibrous etc.) as required.The synthesized polymer material that is used for the preparation of mesopore raw material of wood-charcoal material has acrylonitrile polymer, vinylidene chloride polymer, resol, crosslinked polystyrene etc., and is wherein commonly used with acrylonitrile polymer again.In order to improve the cyclisation charring rate of acrylonitrile polymer, usually adopt and contain a small amount of second monomeric acrylonitrile copolymer as carbon precursor, second monomer commonly used has vinylformic acid, methacrylic acid, methylene-succinic acid and ester class or amide derivatives, vinylsulfonate etc.
Template adopts nano silicon oxide, silica sol and silicon oxide molecular sieve more.Nano silicon oxide is reunited easily, with the carbon precursor recombination process in as can not realize the homodisperse of primary particle yardstick, then actual rapping plate effect be the big nano silicon oxide coacervate of size, cause the formation of the inner macropore of raw material of wood-charcoal material, porosity and pore specific surface area reduce in making.Directly adopt silicon sol, the reunion of template particles is lighter, but in order to prepare the mesopore charcoal of even aperture distribution, still need prevent the reunion in template and the carbon precursor recombination process, can adopt the method for nano oxidized silica sol particle being carried out surface modification.With the si molecular sieves is template, can prepare the mesopore charcoal of (duct) structure in order, but the preparation difficulty of si molecular sieves is very big, and price is higher.
Be that template, polymkeric substance are carbon precursor with nano silicon oxide or silica sol, the template charring prepares mesopore charcoal aspect, more existing frontier nature researchs.(Chem.Commun. such as Han, 1999,1955～1956) be that template, resol are that carbon precursor prepares porous charcoal with nano oxidized silicon sol, find to adopt unmodified nano oxidized silicon sol, actual rapping plate effect be the nanoparticle coacervate, the pore size distribution of the raw material of wood-charcoal material that obtains is wide by (10～100nm); And adopt cetyl trimethylammonium bromide surface modified nano silicon oxide colloidal sol is template, and nanoparticle is uniformly dispersed, and the aperture of the raw material of wood-charcoal material that makes concentrates on about 12nm.(Chem.Commun. such as Jang, 2005,4214～4216) in nano oxidized silicon sol, add the modification of chloro dimethyl vinyl silanes earlier, drying obtains the light nano silica powder of reuniting, adopt the vapor deposition polymerization method to prepare polyacrylonitrile/nano oxidized silicon composite then, polyacrylonitrile/nano oxidized silicon composite is removed the nano silicon oxide template particles through charing, hf etching, and obtains the uniform mesopore charcoal in aperture.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, the preparation method of the acrylonitrile polymer based mesopore charcoal that a kind of pore size distribution is narrow, pore volume is big is provided.
The preparation method of acrylonitrile polymer based mesopore charcoal comprises the steps:
(1) with ammoniacal liquor the 100 pH values that restrain the nano silicon oxide water-sols is adjusted to 9～12, add 0.10～1.0 gram 2,2 '-azo (2-amidine propane) dihydrochloride initiator stirs, obtain surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride;
(2) with 100 gram surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride, 20～60 gram vinyl cyanide or vinyl cyanide and the second monomeric mixture, 1.0～5.0 gram nonionic emulsifier add in the reactor, stir, be warmed up to 50～70 ℃ and carried out emulsion polymerization 3～12 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound, and the vinyl cyanide and the second monomeric ratio of mixture are: 95: 5～70: 30;
(3) with acrylonitrile polymer/nano oxidized silicon compound under inert gas atmosphere, be warmed up to 600～1200 ℃ and carry out charing, obtain charcoal/nano oxidized silicon compound;
(4) charcoal/nano oxidized silicon compound is soaked 1～24h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.
The particle diameter of described nano silicon oxide is 5～50nm.Described second monomer is vinylformic acid, methacrylic acid, methylene-succinic acid, methyl acrylate, ethyl propenoate, methyl methacrylate or Jia Jibingxisuanyizhi.Described nonionic surfactant is one or both in polyoxyethylene carboxylicesters, polyol carboxylate, polyoxyethylene polyol carboxylate, the polyethylene oxide alkyl ethers.Described rare gas element is nitrogen or argon gas.
The present invention adopts emulsion polymerization prepared acrylonitrile polymer/nano oxidized silicon compound, mainly by 2 of absorption, 2 '-azo (2-amidine propane) dihydrochloride initiated polymerization.In order to improve the stability of emulsion polymerization systems, do not destroy simultaneously the dispersiveness of nano silicon oxide again, the present invention adopts the method that adds polyoxyethylene carboxylicesters, polyol carboxylate, polyoxyethylene polyol carboxylate, polyethylene oxide alkyl ethers nonionogenic tenside in polymerization system, and above non-ionic emulsifier can independent or two or more compound uses.Letex polymerization 50～70 ℃, carry out under stirring, polymerization time is 3～12 hours.
The acrylonitrile polymer that polymerization obtains/nano oxidized silicon compound heats between 600～1200 ℃ under rare gas element (nitrogen or argon gas) atmosphere, and acrylonitrile polymer generation thermolysis forms charcoal, and cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound that charing is obtained soaks in hydrofluoric acid, silicon oxide and hydrogen fluoride reaction generate volatility silicon fluoride and water, promptly can etching remove the nano silicon oxide particle in the mixture,, can obtain the mesopore charcoal carbide separation, washing, drying.
The mesopore charcoal for preparing can adopt N
2Absorption (BET) method is measured its mean pore size and parameters such as pore size distribution, pore volume, middle porosity and specific surface area.
Adopt the advantage of the inventive method to be: main by being adsorbed onto 2 of nano silicon oxide particle surface, 2 '-azo (2-amidine propane) dihydrochloride initiated polymerization, can realize the good coating of acrylonitrile polymer at the nano silicon oxide particle surface, the nano silicon oxide particle is uniformly dispersed in mixture, can guarantee to form behind charing, the hf etching narrow, the middle porosity height of pore size distribution, mesopore raw material of wood-charcoal material that specific surface area is big.
Embodiment
Embodiment 1
With ammoniacal liquor the pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide mass percent is 10%, median size is 25nm are adjusted to 9, add 0.1g 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride.
The above modified nano silicon oxide water-sol, 20 gram vinyl cyanide, 2 gram polyoxyethylene sorbitan monostearates are joined in the reactor, stir, be warmed up to 60 ℃ of beginning polymerizations, react and finished polymerization in 12 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 800 ℃ and carry out charing under nitrogen atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 24h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 15.2nm, and middle porosity is 91%.
Embodiment 2
With ammoniacal liquor the pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide mass percent is 10%, median size is 25nm are adjusted to 10, add 0.3 gram 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface adsorption 2, the nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride modification.
The above modified nano silicon oxide water-sol, 19 gram vinyl cyanide, 1 gram vinylformic acid, 1 gram polyoxyethylene sorbitan mono-laurate are joined in the reactor, be warmed up to 70 ℃ of beginning polymerizations under the room temperature after the dispersed with stirring, react and finished polymerization in 6 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 800 ℃ and carry out charing under nitrogen atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 24h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 15.5nm, and middle porosity is 91.3% mesopore charcoal.
Embodiment 3
With ammoniacal liquor the pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide mass percent is 10%, median size is 25nm are adjusted to 11, add 0.5 gram 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface adsorption 2, the nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride modification.
The above modified nano silicon oxide water-sol, 18 gram vinyl cyanide, 2 gram methacrylic acids, 2 gram polyoxyethylene sorbitan monooleates are joined in the reactor, be warmed up to 60 ℃ of beginning polymerizations under the room temperature after the dispersed with stirring, react and finished polymerization in 8 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 800 ℃ and carry out charing under nitrogen atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 24h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 16.2nm, and middle porosity is 91.8%.
Embodiment 4
With ammoniacal liquor the pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide mass percent is 10%, median size is 25nm are adjusted to 12, add 1.0 grams 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride.
The above modified nano silicon oxide water-sol, 18 gram vinyl cyanide, 2 gram methyl acrylates, 2 gram sorbitan monooleates are joined in the reactor, be warmed up to 65 ℃ of beginning polymerizations under the room temperature after the dispersed with stirring, react and finished polymerization in 3 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 800 ℃ and carry out charing under nitrogen atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 24h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 15.7nm, and middle porosity is 92.1%.
Embodiment 5
With ammoniacal liquor the pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide mass percent is 10%, median size is 25nm are adjusted to 11, add 0.5 gram 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface adsorption gram 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride.
The above modified nano silicon oxide water-sol, 32 gram vinyl cyanide, 4 gram Jia Jibingxisuanyizhis, 3 gram anhydrous sorbitol monopalmitates are joined in the reactor, be warmed up to 60 ℃ of beginning polymerizations under the room temperature after the dispersed with stirring, react and finished polymerization in 6 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 600 ℃ and carry out charing under nitrogen atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 12h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 13.2nm, and middle porosity is 87%.
Embodiment 6
With ammoniacal liquor the pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide mass percent is 5%, median size is 25nm are adjusted to 10, add 0.25 gram 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride.
The above modified nano silicon oxide water-sol, 45 gram vinyl cyanide, 5 gram methyl methacrylates, 3 gram lauryl alcohol polyoxyethylene ethers are joined in the reactor, be warmed up to 60 ℃ of beginning polymerizations under the room temperature after the dispersed with stirring, react and finished polymerization in 12 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 900 ℃ and carry out charing under nitrogen atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 6h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 6.33nm, and middle porosity is 72%.
Embodiment 7
With ammoniacal liquor the pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide mass percent is 10%, median size is 25nm are adjusted to 10, add 0.25 gram 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride.
The above modified nano silicon oxide water-sol, 42 gram vinyl cyanide, 18 gram methyl methacrylates, 5 gram alkylphenol polyoxyethylene ethers are joined in the reactor, be warmed up to 65 ℃ of beginning polymerizations under the room temperature after the dispersed with stirring, react and finished polymerization in 12 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 800 ℃ and carry out charing under nitrogen atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 1h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 11.2nm, and middle porosity is 86%.
Embodiment 8
With ammoniacal liquor the pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide mass percent is 10%, median size is 15nm are adjusted to 10, add 0.25 gram 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride.
The above modified nano silicon oxide water-sol, 18 gram vinyl cyanide, 2 gram ethyl propenoates, 2 gram Zerols are joined in the reactor, be warmed up to 50 ℃ of beginning polymerizations under the room temperature after the dispersed with stirring, react and finished polymerization in 12 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 800 ℃ and carry out charing under nitrogen atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 12h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 10.2nm, and middle porosity is 89%.
Embodiment 9
With ammoniacal liquor the pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide mass percent is 10%, median size is 35nm are adjusted to 10, add 0.25 gram 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride.
The above modified nano silicon oxide water-sol, 19 gram vinyl cyanide, 1 gram Jia Jibingxisuanyizhi, 2 gram Diethylene Glycol mono-laurates are joined in the reactor, be warmed up to 60 ℃ of beginning polymerizations under the room temperature after the dispersed with stirring, react and finished polymerization in 8 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 800 ℃ and carry out charing under nitrogen atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 24h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 25.1nm, and middle porosity is 92.3%.
Embodiment 10
With ammoniacal liquor the pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide mass percent is 10%, median size is 10nm are adjusted to 10, add 0.25 gram 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride.
The above modified nano silicon oxide water-sol, 16 gram vinyl cyanide, 4 gram methyl methacrylates, 1 gram polyoxyethylene sorbitan monostearate and 1 gram anhydrous sorbitol tristearate are joined in the reactor, be warmed up to 60 ℃ of beginning polymerizations under the room temperature after the dispersed with stirring, react and finished polymerization in 8 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 800 ℃ and carry out charing under nitrogen atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 24h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 8.3nm, and middle porosity is 87%.
Embodiment 11
With ammoniacal liquor the pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide mass percent is 10%, median size is 50nm are adjusted to 10, add 0.25 gram 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride.
The above modified nano silicon oxide water-sol, 16 gram vinyl cyanide, 4 gram methyl methacrylates, 1 gram polyoxyethylene sorbitan monooleate and 1 gram sorbitan monooleate are joined in the reactor, be warmed up to 60 ℃ of beginning polymerizations under the room temperature after the dispersed with stirring, react and finished polymerization in 8 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 800 ℃ and carry out charing under nitrogen atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 24h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 43.6nm, and middle porosity is 94.1%.
Embodiment 12
The pH values of the 100 gram nano silicon oxide water-sols that the nano silicon oxide massfraction is 10%, median size is 5nm are adjusted to 10, add 0.25 gram 2,2 '-azo (2-amidine propane) dihydrochloride, stir, obtain surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride.
The above modified nano silicon oxide water-sol, 16 gram vinyl cyanide, 4 gram methyl methacrylates, 2 gram polyoxyethylene sorbitan monooleates are joined in the reactor, be warmed up to 60 ℃ of beginning polymerizations under the room temperature after the dispersed with stirring, react and finished polymerization in 8 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound.
Acrylonitrile polymer/nano oxidized silicon compound is placed retort furnace, be warmed up to 800 ℃ and carry out charing under argon gas atmosphere, cooling obtains charcoal/nano oxidized silicon compound.
Charcoal/nano oxidized silicon compound is soaked 12h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying.The mean pore size that adopts BET to record the mesopore charcoal is 4.02nm, and middle porosity is 76%.
Claims (3)
1. the preparation method of an acrylonitrile polymer based mesopore charcoal is characterized in that comprising the steps:
(1) with ammoniacal liquor the 100 pH values that restrain the nano silicon oxide water-sols is adjusted to 9～12, add 0.10～1.0 gram 2,2 '-azo (2-amidine propane) dihydrochloride initiator stirs, obtain surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride;
(2) with 100 gram surface adsorption 2, the modified nano silicon oxide water-sol of 2 '-azo (2-amidine propane) dihydrochloride, 20～60 gram vinyl cyanide or vinyl cyanide and the second monomeric mixture, 1.0～5.0 gram nonionic emulsifier add in the reactor, stir, be warmed up to 50～70 ℃ and carried out emulsion polymerization 3～12 hours, drying obtains acrylonitrile polymer/nano oxidized silicon compound, and the vinyl cyanide and the second monomeric ratio of mixture are: 95: 5～70: 30;
(3) with acrylonitrile polymer/nano oxidized silicon compound under inert gas atmosphere, be warmed up to 600～1200 ℃ and carry out charing, obtain charcoal/nano oxidized silicon compound;
(4) charcoal/nano oxidized silicon compound is soaked 1～24h in hydrofluoric acid, be etched away the nano silicon oxide in the mixture,, obtain the mesopore charcoal carbide separation, washing, drying;
Described second monomer is vinylformic acid, methacrylic acid, methylene-succinic acid, methyl acrylate, ethyl propenoate, methyl methacrylate or Jia Jibingxisuanyizhi, and described nonionic emulsifier is a kind of in polyoxyethylene carboxylicesters, polyol carboxylate, polyoxyethylene polyol carboxylate, lauryl alcohol polyoxyethylene ether, the alkylphenol polyoxyethylene ether.
2. the preparation method of a kind of acrylonitrile polymer based mesopore charcoal according to claim 1, the particle diameter that it is characterized in that described nano silicon oxide is 5～50nm.
3. the preparation method of a kind of acrylonitrile polymer based mesopore charcoal according to claim 1 is characterized in that described rare gas element is nitrogen or argon gas.
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| CN102351168B (en) * | 2011-07-07 | 2013-04-17 | 浙江大学 | Preparation method of vinylidene chloride polymer base mesopore-micropore composite porous charcoal |
| CN102502588A (en) * | 2011-11-09 | 2012-06-20 | 上海理工大学 | Method for preparing mesoporous carbon with controllable aperture distribution |
| CN105129771B (en) * | 2015-09-09 | 2017-03-15 | 上海大学 | A kind of preparation method of the mesoporous carbon of aperture controllable |
| CN105126758A (en) * | 2015-09-11 | 2015-12-09 | 华东理工大学 | Preparation method of spherical mesoporous carbon for blood purification |
| CN107311144B (en) * | 2017-08-03 | 2019-12-03 | 安徽大学 | A kind of preparation method of nitrogen-doped nanometer Porous hollow carbon ball |
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