CN106283247B - Poly ion liquid nano-fiber material and preparation method thereof for carbon dioxide adsorption - Google Patents

Poly ion liquid nano-fiber material and preparation method thereof for carbon dioxide adsorption Download PDF

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CN106283247B
CN106283247B CN201610664105.6A CN201610664105A CN106283247B CN 106283247 B CN106283247 B CN 106283247B CN 201610664105 A CN201610664105 A CN 201610664105A CN 106283247 B CN106283247 B CN 106283247B
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ion liquid
poly ion
poly
carbon dioxide
fiber material
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CN106283247A (en
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王先锋
窦绿叶
丁彬
俞建勇
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Donghua University
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/26—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from other polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Abstract

The present invention provides a kind of preparation methods of poly ion liquid nano-fiber material for carbon dioxide adsorption, it is characterised by comprising: poly ion liquid containing alkenyl is made step 1: the polymerizable ionic liquid monomer containing alkenyl structures to be carried out to Controlled Living Radical Polymerization under the action of initiator and chain-transferring agent and is reacted；Step 2: at room temperature, by the stirring and dissolving of poly ion liquid containing alkenyl made from the first step in solvent, obtaining the electrospinning raw material that mass fraction is 5~30%；Step 3: the electrospinning raw material that second step obtains is added in electrostatic spinning apparatus, electrostatic spinning is carried out, nano-fiber material is obtained.Poly ion liquid nano-fiber material carbon dioxide adsorption ability, excellent recycling performance and anti-grinded hardness index with higher prepared by the present invention, preparation method is simple, has huge application potential in carbon capture field.

Description

Poly ion liquid nano-fiber material and preparation method thereof for carbon dioxide adsorption
Technical field
The poly ion liquid nano-fiber material and preparation method thereof that the present invention relates to a kind of for carbon dioxide adsorption belongs to In carbon dioxide adsorption technical field.
Background technique
In recent years, the environmental problems such as global warming, glacial ablation caused by greenhouse effects, sea-level rise are increasingly convex It is aobvious, greenhouse gases CO2Adsorbing separation caused global concern, therefore adsorbing separation CO2It is brought to greenhouse effects are reduced Weather harm have great importance.CO2Trapping and sealing up for safekeeping is one of the important technology for controlling greenhouse gas emission, the U.S., The developed countries and regions such as European Union, Canada have formulated the relevant technologies developing direction and route.The energy resource structure in China is with coal Based on, CO2Discharge amount, which will be chronically at, to be risen situation or remains high-order, and CO is developed2Trapping technique will be long-term greenhouse gas in China The important technology approach of body emission reduction.
Ionic liquid has it instead of tradition due to the characteristics such as vapour pressure is extremely low, thermal stability is good, recycling is good Machine amine aqueous solution is applied to CO2Absorption aspect presents wide application prospect.Ionic liquid by its structure can be divided into it is conventional from Sub- liquid and functionalized ion liquid.Conventional ionic liquid is to CO2With preferable selective absorption effect, but due to ionic liquid Body and CO2Between only general physical action, adsorbance is limited；Have by that can be prepared to ionic liquid progress amino modified CO2The functionalized ion liquid of adsorption function, CO under normal temperature and pressure2Adsorbance is up to 0.17mmol/g, but due in adsorption process Viscosity of il is significantly increased, and leads to adsorption process very slowly (be adsorbed to equilibration time~for 24 hours), limits its and practical answers With.
Poly ion liquid has both ionic liquid and high molecular property, is expected to become a kind of novel CO2Adsorbing separation is used High molecular material.Poly ion liquid is combined with electrostatic spinning technique, preparing poly ion liquid nanofiber has continuously Property it is good, porosity is high, cellular structure is abundant the advantages that, can effectively overcome conventional porous granular materials because structure is discontinuous, easily collapses The applied defects such as easy dusting in bring use process are fallen into, in CO2Adsorbing separation field shows huge application potential.
Summary of the invention
The object of the present invention is to provide a kind of carbon dioxide adsorption preparation method of poly ion liquid nano-fiber material, To solve the problems, such as easy dusting in the generally existing use process of conventional particles shape porous material.
In order to achieve the above object, the present invention provides a kind of poly ion liquid nanofibers for carbon dioxide adsorption The preparation method of material characterized by comprising
Step 1: by the polymerizable ionic liquid monomer containing alkenyl structures under the action of initiator and chain-transferring agent into Row Controlled Living Radical Polymerization, which reacts, is made poly ion liquid containing alkenyl；
Step 2: at room temperature, by the stirring and dissolving of poly ion liquid containing alkenyl made from the first step in solvent, obtaining matter Measure the electrospinning raw material that score is 5~30%；
Step 3: the electrospinning raw material that second step obtains is added in electrostatic spinning apparatus, electrostatic spinning is carried out, is received Rice fibrous material.
Preferably, the Controlled Living Radical Polymerization reaction process in the first step includes chain initiation, chain growth, chain Termination and chain tra nsfer；Polymerization be iniferter agent (iniferter) method, stable free radical polymerization (SFRP) method, One of atom transfer radical polymerization (ATRP) method and reversible addition-fracture transfer (RAFT) method.
Preferably, the mass fraction of the polymerizable ionic liquid monomer containing alkenyl structures in the first step is 70%~90%, the mass fraction of initiator is 5%~15%, and the mass fraction of chain-transferring agent is 5%~15%.
Preferably, the revolving speed in the second step is 100~2500r/min.
Preferably, the electrospinning conditions in the third step are as follows: electrostatic pressure is 10~40kV, and injection flow rate pump is 1 ~4mL/h, spinning head are 10~20cm away from receiving screen distance.
Preferably, the polymerizable ionic liquid monomer containing alkenyl structures be ion liquid of quaternaries monomer, Imidazole salt ionic liquid monomer, pyridine salt ionic liquid monomer or quaternary phosphonium salt ionic liquid monomer.
Preferably, the polymerizable ionic liquid monomer containing alkenyl structures passes through quaternized and ion-exchange reactions It is made.
Preferably, the initiator is azo-initiator, organic peroxy class initiator or inorganic peroxy class initiator.
It is highly preferred that the azo-initiator is at least one in two isobutyl heptonitrile of azodiisobutyronitrile and azo Kind；The organic peroxy class initiator is isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, dibenzoyl peroxide, peroxide Change lauroyl, cumyl peroxide, di-t-butyl peroxide, peroxidized t-butyl perbenzoate, the peroxidating trimethylacetic acid tert-butyl ester, At least one of di-cyclohexylperoxy di-carbonate and dicetyl peroxydicarbonate isopropyl ester；The inorganic peroxy class initiator For at least one of potassium peroxydisulfate and ammonium persulfate.
Preferably, the chain-transferring agent is dithioesters, methanol, n-butyl mercaptan, tert-butyl mercaptan, n-octyl mercaptan, positive 12 Mercaptan, aliphatic mercaptan, lauryl mercaptan, carbon tetrachloride, iodoform, isopropanol, sodium hydrogensulfite, sodium hypophosphite, sodium formate, At least one of the chloro- 1- iodine alkane of 1-, thioacetic acid, mercaptopropionic acid, mercaptoethanol and mercaprol.
Preferably, the poly ion liquid containing alkenyl be quaternary ammonium salt poly ion liquid, imidazole salt poly ion liquid, At least one of pyridiniujm class poly ion liquid and quaternary alkylphosphonium salt class poly ion liquid.
It is highly preferred that the quaternary ammonium salt poly ion liquid is poly- [2- (methacryloxypropyl) ethyl-trimethyl quaternary ammonium Tetrafluoroborate], poly- [(4- ethylene benzyl) triethyl quaternary amine tetrafluoroborate], poly- [(4- ethylene benzyl) tributyl quaternary ammonium six Fluorophosphate], poly- [(4- ethylene benzyl) trimethyl quaternary ammonium benzoic sulfimide salt], poly- [(4- ethylene benzyl) trimethyl season Ammonium trimethyl fluoride sulfonyl amine salt] and poly- [1,2- bis- (4- ethylene benzyl dimethyl quaternary ammonium) ethane tetrafluoroborates] at least It is a kind of；The imidazole salt poly ion liquid is poly- [1- (4- ethylene benzyl) -3- butyl imidazole tetrafluoroborate], poly- [1- (4- ethylene benzyl) -3- butyl imidazole hexafluorophosphate], poly- [1- (4- ethylene benzyl) -3- butyl imidazole benzoic sulfimide Salt], poly- [1- (4- ethylene benzyl) 3- butyl imidazole trimethyl fluoride sulfonyl amine salt], poly- [1- (2- methylacryoyloxyethyl) -3- At least one of butyl imidazole tetrafluoroborate] and poly- [1- (4- ethylene benzyl) 3- methylimidazole hexafluorophosphate]；Institute The pyridiniujm class poly ion liquid stated is poly- [1- (2- methylacryoyloxyethyl) -3- butyl-pyridinium thiocyanate salt], poly- [1- (2- methylacryoyloxyethyl) -3- butyl-pyridinium tetrafluoroborate salt], poly- [1- (2- methylacryoyloxyethyl) -3- butyl At least one of pyridine hexafluorophosphate] and poly- [4- vinyl benzyl pyridinium tetrafluoroborate salt]；The quaternary phosphonium salt Poly ion liquid is poly- [(4- ethylene benzyl) 3 ethyl quaternary phosphonium tetrafluoroborate], poly- [(4- ethylene benzyl) -3- ethyl quaternary phosphonium six At least one of fluorophosphate] and poly- [(4- ethylene benzyl) -3- ethyl quaternary phosphonium trimethyl fluoride sulfonyl amine salt].
Preferably, the solvent in the second step is acetone, n,N-Dimethylformamide, methylene chloride, dimethyl Asia Sulfone, acetonitrile, ether, tetrahydrofuran, n,N-dimethylacetamide, hexane, ethyl alcohol, formic acid, acetic acid, chloroform, benzene, carbon tetrachloride, 1,2- dichloroethanes, trichloroethanes, 1,1,2- trichloro ethylene, 1,2- dimethoxy-ethane, 1,2,3,4-tetrahydro-naphthalene, ring fourth Sulfone, pyrimidine, formamide, n-hexane, chlorobenzene, dioxane, ethylene glycol, toluene, hexahydrotoluene, 1,2- dichloro Ethylene, dimethylbenzene, hexamethylene, N-Methyl pyrrolidone, pentane, methyl phenyl ethers anisole, butyl acetate, three fourth Methyl ethers, isopropyl acetate The mixture of one or more of ester, methyltetrahydrofuran, petroleum ether, trichloroacetic acid, trifluoroacetic acid and pyridine.
The present invention also provides the poly ion liquid Nanowires that carbon dioxide adsorption is used for prepared by above-mentioned preparation method Tie up material.
Compared with prior art, the beneficial effects of the present invention are:
Present invention process is simple, prepares the controllable polyion liquid of molecular weight by using Controlled Living Radical Polymerization method Body, and combine electrostatic spinning technique that poly ion liquid is carried out nanofiber, it is inhaled to obtain high performance carbon dioxide Fufen is from poly ion liquid flexible nano fibrous material.Large specific surface area that nanofiber has, the advantages that porosity is high tax Give the higher adsorbance of the adsorbent material and the rate of adsorption.In addition, fibrous material also has enough mechanical strengths, in gas source height Flow velocity impacts under big, shock conditions with preferable sorption cycle stability.Poly ion liquid nanofiber material prepared by the present invention Expect carbon dioxide adsorption ability, excellent recycling performance and anti-grinded hardness index with higher, preparation method is simple, Carbon capture field has huge application potential.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Ionic liquid monomer in following embodiment is commercial product.
Embodiment 1
A kind of preparation method of the poly ion liquid nano-fiber material for carbon dioxide adsorption, specific steps are as follows:
(1) the ionic liquid monomer 1- by polymerizable containing alkenyl structures (4- ethylene benzyl) -3- butyl imidazole tetrafluoro boron Hydrochlorate 0.45g is added in reaction kettle, accesses condenser pipe, is passed through nitrogen 15min, carries out nitrogen displacement to device, then protect in nitrogen Shield is lower to be added initiator azobisisoheptonitrile 0.025g and chain-transferring agent dithioesters 0.025g, it is closed after in 60 DEG C of oil bath heating items Poly- [1- (4- the ethylene benzyl) -3- fourth of poly ion liquid containing alkenyl is made by iniferter agent (iniferter) method under part Base tetrafluoroborate] 0.5g；
(2) under room temperature, in a stirring kettle by resulting poly- [1- (4- the ethylene benzyl) -3- butyl imidazole tetrafluoro of 0.5g Borate] with revolving speed 100rpm stirring and dissolving in 9.5g acetone, obtain mass fraction be 5% poly- [1- (4- ethylene benzyl)- 3- butyl imidazole tetrafluoroborate] solution is as electrospinning raw material.
(3) resulting electrospinning raw material is added in electrostatic spinning apparatus, is 10kV in electrostatic pressure, injects flow rate pump 0.5mL/h, spinning head obtain having carbon dioxide adsorption function away from electrostatic spinning is carried out under conditions of receiving screen distance 10cm Poly- [1- (4- ethylene benzyl) -3- butyl imidazole tetrafluoroborate] nano-fiber material.
Embodiment 2
A kind of preparation method of the poly ion liquid nano-fiber material for carbon dioxide adsorption, specific steps are as follows:
(1) the ionic liquid monomer 1- by polymerizable containing alkenyl structures (4- ethylene benzyl) -3- butyl imidazole tetrafluoro boron Hydrochlorate 1.35g is added in reaction kettle, accesses condenser pipe, is passed through nitrogen 15min, carries out nitrogen displacement to device, then protect in nitrogen Shield is lower to be added initiator azobisisoheptonitrile 0.075g and chain-transferring agent n-butyl mercaptan 0.075g, it is closed after in 60 DEG C of oil bath heatings Under the conditions of by iniferter agent (iniferter) method be made poly- [1- (4- the ethylene benzyl) -3- of poly ion liquid containing alkenyl Butyl imidazole tetrafluoroborate] 1.5g；
(2) under room temperature, in a stirring kettle by 1.5g poly- [1- (4- ethylene benzyl) -3- butyl imidazole tetrafluoroborate] With revolving speed 200rpm stirring and dissolving in 8.5gN, dinethylformamide, poly- [1- (the 4- ethylene that mass fraction is 15% is obtained Benzyl) -3- butyl imidazole tetrafluoroborate] solution is as electrospinning raw material.
(3) obtained electrospinning raw material is added in electrostatic spinning apparatus, is 20kV in electrostatic pressure, injects flow rate pump 0.5mL/h, spinning head obtain having carbon dioxide adsorption function away from electrostatic spinning is carried out under conditions of receiving screen distance 20cm Poly- [1- (4- ethylene benzyl) -3- butyl imidazole tetrafluoroborate] nano-fiber material.
Embodiment 3
A kind of preparation method of the poly ion liquid nano-fiber material for carbon dioxide adsorption, specific steps are as follows:
(1) the ionic liquid monomer 1- by polymerizable containing alkenyl structures (4- ethylene benzyl) 3- methylimidazole hexafluorophosphoric acid Salt 2.7g is added in reaction kettle, accesses condenser pipe, is passed through nitrogen 15min, carries out nitrogen displacement to device, then under nitrogen protection Be added initiator azodiisobutyronitrile 0.15g and chain-transferring agent tert-butyl mercaptan 0.15, it is closed after under the conditions of 60 DEG C of oil bath heatings Poly- [1- (4- ethylene benzyl) the 3- methylimidazole hexafluoro of poly ion liquid containing alkenyl is made by stable free radical polymerization (SFRT) method Phosphate] 3g；
(2) under room temperature, in a stirring kettle by 3g poly- [1- (4- ethylene benzyl) 3- methylimidazole hexafluorophosphate] with Revolving speed 500rpm stirring and dissolving obtains poly- [1- (4- ethylene benzyl) 3- methyl that mass fraction is 30% in 7g methylene chloride Limidazolium hexafluorophosphate] solution is as electrospinning raw material.
(3) obtained electrospinning raw material is added in electrostatic spinning apparatus, is 15kV in electrostatic pressure, injects flow rate pump 2mL/ H, spinning head obtain the poly- [1- with carbon dioxide adsorption function away from electrostatic spinning is carried out under conditions of receiving screen distance 20cm (4- ethylene benzyl) 3- methylimidazole hexafluorophosphate].
Embodiment 4
A kind of preparation method of the poly ion liquid nano-fiber material for carbon dioxide adsorption, specific steps are as follows:
(2) the ionic liquid monomer 1- by polymerizable containing alkenyl structures (4- ethylene benzyl) 3- methylimidazole hexafluorophosphoric acid Salt 1.8g is added in reaction kettle, accesses condenser pipe, is passed through nitrogen 15min, carries out nitrogen displacement to device, then under nitrogen protection Initiator azodiisobutyronitrile 0.1g and chain-transferring agent tert-butyl mercaptan 0.1g is added, leads under the conditions of 60 DEG C of oil bath heatings after closed It crosses stable free radical polymerization (SFRT) method and poly- [1- (4- ethylene benzyl) the 3- methylimidazole hexafluoro phosphorus of poly ion liquid containing alkenyl is made Hydrochlorate] 2g；
(2) under room temperature, in a stirring kettle by 2g poly- [1- (4- ethylene benzyl) 3- methylimidazole hexafluorophosphate] with Revolving speed 800rpm stirring and dissolving obtains poly- [1- (4- ethylene benzyl) 3- methyl that mass fraction is 20% in 8g methylene chloride Limidazolium hexafluorophosphate] solution is as electrospinning raw material.
(3) obtained electrospinning raw material is added in electrostatic spinning apparatus, is 15kV in electrostatic pressure, injects flow rate pump 1.5mL/h, spinning head obtain having carbon dioxide adsorption function away from electrostatic spinning is carried out under conditions of receiving screen distance 20cm Poly- [1- (4- ethylene benzyl) 3- methylimidazole hexafluorophosphate].
Embodiment 5
A kind of preparation method of the poly ion liquid nano-fiber material for carbon dioxide adsorption, specific steps are as follows:
(1) ionic liquid monomer 2- (methacryloxypropyl) the ethyl-trimethyl quaternary ammonium four by polymerizable containing alkenyl structures Borofluoride 0.9g is added in reaction kettle, accesses condenser pipe, is passed through nitrogen 15min, carries out nitrogen displacement to device, then in nitrogen Protection is lower to be added initiator tert-butyl hydroperoxide 0.05g and chain-transferring agent n-octyl mercaptan 0.05g, it is closed after under the conditions of 25 DEG C It carries out Controlled Living Radical Polymerization and reacts obtained poly- [2- (methacryloxypropyl) the ethyl-trimethyl season of poly ion liquid containing alkenyl Ammonium tetrafluoroborate] 1g；
(2) under room temperature, in a stirring kettle by poly- [2- (methacryloxypropyl) the ethyl-trimethyl quaternary ammonium tetrafluoro boric acid of 1g Salt] with revolving speed 500rpm stirring and dissolving in 9g dimethyl sulfoxide, obtain mass fraction be 10% poly- [2- (methacryl Oxygen) ethyl-trimethyl quaternary ammonium tetrafluoroborate] solution is as electrospinning raw material.
(3) obtained electrospinning raw material is added in electrostatic spinning apparatus, is 20kV in electrostatic pressure, injects flow rate pump 1mL/ H, spinning head obtain the poly- [2- with carbon dioxide adsorption function away from electrostatic spinning is carried out under conditions of receiving screen distance 15cm (methacryloxypropyl) ethyl-trimethyl quaternary ammonium tetrafluoroborate] nano-fiber material.
Embodiment 6
A kind of preparation method of the poly ion liquid nano-fiber material for carbon dioxide adsorption, specific steps are as follows:
(1) ionic liquid monomer 2- (methacryloxypropyl) the ethyl-trimethyl quaternary ammonium four by polymerizable containing alkenyl structures Borofluoride 2.7g is added in reaction kettle, accesses condenser pipe, is passed through nitrogen 15min, carries out nitrogen displacement to device, then in nitrogen Protection is lower to be added initiator tert-butyl hydroperoxide 0.15g and chain-transferring agent n-octyl mercaptan 0.15g, it is closed after under the conditions of 25 DEG C It carries out Controlled Living Radical Polymerization and reacts obtained poly- [2- (methacryloxypropyl) the ethyl-trimethyl season of poly ion liquid containing alkenyl Ammonium tetrafluoroborate] 3g；
(2) under room temperature, in a stirring kettle by poly- [2- (methacryloxypropyl) the ethyl-trimethyl quaternary ammonium tetrafluoro boric acid of 3g Salt] with revolving speed 1000rpm stirring and dissolving in 7g dimethyl sulfoxide, obtain mass fraction be 30% poly- [2- (methacryl Oxygen) ethyl-trimethyl quaternary ammonium tetrafluoroborate] solution is as electrospinning raw material.
(3) obtained electrospinning raw material is added in electrostatic spinning apparatus, is 20kV in electrostatic pressure, injects flow rate pump 2mL/ H, spinning head obtain the poly- [2- with carbon dioxide adsorption function away from electrostatic spinning is carried out under conditions of receiving screen distance 15cm (methacryloxypropyl) ethyl-trimethyl quaternary ammonium tetrafluoroborate] nano-fiber material.
Embodiment 7
A kind of preparation method of the poly ion liquid nano-fiber material for carbon dioxide adsorption, specific steps are as follows:
(1) ionic liquid monomer by polymerizable containing alkenyl structures (4- ethylene benzyl) trimethyl quaternary ammonium trifluoromethyl sulphur Amidic-salt 1.8g is added in reaction kettle, accesses condenser pipe, is passed through nitrogen 15min, carries out nitrogen displacement to device, then protect in nitrogen Shield is lower to be added initiator azobisisoheptonitrile 0.1g and chain-transferring agent isopropanol 0.1g, it is closed after under the conditions of 60 DEG C of oil bath heatings Poly- [(4- ethylene benzyl) trimethyl quaternary ammonium three of poly ion liquid containing alkenyl is made by atom transfer radical polymerization (ATRP) method Methyl fluoride sulfonamide] 2g；
(2) under room temperature, in a stirring kettle by poly- [(4- ethylene benzyl) the trimethyl quaternary ammonium trimethyl fluoride sulfonyl amine of 2g Salt] with revolving speed 1200rpm stirring and dissolving in 8g acetonitrile, obtain mass fraction be 20% poly- [(4- ethylene benzyl) trimethyl Quaternary ammonium trimethyl fluoride sulfonyl amine salt] solution is as electrospinning raw material.
(3) obtained electrospinning raw material is added in electrostatic spinning apparatus, is 15kV in electrostatic pressure, injects flow rate pump 1mL/ H, spinning head obtain the poly- [(4- with carbon dioxide adsorption function away from electrostatic spinning is carried out under conditions of receiving screen distance 20cm Ethylene benzyl) trimethyl quaternary ammonium trimethyl fluoride sulfonyl amine salt] nano-fiber material.
Embodiment 8
A kind of preparation method of the poly ion liquid nano-fiber material for carbon dioxide adsorption, specific steps are as follows:
(1) ionic liquid monomer by polymerizable containing alkenyl structures (4- ethylene benzyl) trimethyl quaternary ammonium trifluoromethyl sulphur Amidic-salt is added in reaction kettle in initiator 1.35g, accesses condenser pipe, is passed through nitrogen 15min, carries out nitrogen displacement to device, Be added azobisisoheptonitrile 0.75g and chain-transferring agent isopropanol 0.75g under nitrogen protection again, it is closed after in 60 DEG C of oil bath heatings Under the conditions of pass through reversible addition-fracture and shift (RAFT) method poly- [(4- ethylene benzyl) trimethyl of poly ion liquid containing alkenyl is made Quaternary ammonium trimethyl fluoride sulfonyl amine salt] 1.5g；
(2) under room temperature, in a stirring kettle by poly- [(4- ethylene benzyl) the trimethyl quaternary ammonium trimethyl fluoride sulfonyl amine of 1.5g Salt] with revolving speed 2500rpm stirring and dissolving in 8.5g acetonitrile, obtain mass fraction be 15% poly- [(4- ethylene benzyl) front three Base quaternary ammonium trimethyl fluoride sulfonyl amine salt] solution is as electrospinning raw material.
(3) obtained electrospinning raw material is added in electrostatic spinning apparatus, is 40kV in electrostatic pressure, injects flow rate pump 2mL/ H, spinning head obtain the poly- [(4- with carbon dioxide adsorption function away from electrostatic spinning is carried out under conditions of receiving screen distance 20cm Ethylene benzyl) trimethyl quaternary ammonium trimethyl fluoride sulfonyl amine salt] nano-fiber material.
Embodiment 9
A kind of preparation method of the poly ion liquid nano-fiber material for carbon dioxide adsorption, specific steps are as follows:
(1) the ionic liquid monomer 1- by polymerizable containing alkenyl structures (2- methylacryoyloxyethyl) -3- butyl pyrrole Pyridine tetrafluoroborate salt 0.9g is added in reaction kettle, accesses condenser pipe, is passed through nitrogen 15min, carries out nitrogen displacement to device, then Be added initiator potassium persulfate 0.05g and chain-transferring agent lauryl mercaptan 0.05g under nitrogen protection, it is closed after in 25 DEG C of items Controlled Living Radical Polymerization is carried out under part reacts the obtained poly- [1- (2- methylacryoyloxyethyl)-of poly ion liquid containing alkenyl 3- butyl-pyridinium tetrafluoroborate salt] 1g；
(2) under room temperature, in a stirring kettle by poly- [1- (2- the methylacryoyloxyethyl) -3- butyl-pyridinium tetrafluoro of 1g Borate salt] with revolving speed 1000rpm stirring and dissolving in 9g methylene chloride, obtain mass fraction be 10% poly- [1- (2- methyl Acrylyl oxy-ethyl) -3- butyl-pyridinium tetrafluoroborate salt] solution is as electrospinning raw material.
(3) obtained electrospinning raw material is added in electrostatic spinning apparatus, is 40kV in electrostatic pressure, injects flow rate pump 3mL/ H, spinning head obtain the poly- [1- with carbon dioxide adsorption function away from electrostatic spinning is carried out under conditions of receiving screen distance 10cm (2- methylacryoyloxyethyl) -3- butyl-pyridinium tetrafluoroborate salt] nano-fiber material.
Embodiment 10
A kind of preparation method of the poly ion liquid nano-fiber material for carbon dioxide adsorption, specific steps are as follows:
(1) the ionic liquid monomer 1- by polymerizable containing alkenyl structures (2- methylacryoyloxyethyl) -3- butyl pyrrole Pyridine tetrafluoroborate salt 2.7g is added in reaction kettle, accesses condenser pipe, is passed through nitrogen 15min, carries out nitrogen displacement to device, then Be added initiator potassium persulfate 0.15g and chain-transferring agent lauryl mercaptan 0.15g under nitrogen protection, it is closed after in 25 DEG C of items Controlled Living Radical Polymerization is carried out under part reacts the obtained poly- [1- (2- methylacryoyloxyethyl)-of poly ion liquid containing alkenyl 3- butyl-pyridinium tetrafluoroborate salt] 3g；
(2) under room temperature, in a stirring kettle by poly- [1- (2- the methylacryoyloxyethyl) -3- butyl-pyridinium tetrafluoro of 3g Borate salt] with revolving speed 1500rpm stirring and dissolving in 7g methylene chloride, obtain mass fraction be 30% poly- [1- (2- methyl Acrylyl oxy-ethyl) -3- butyl-pyridinium tetrafluoroborate salt] solution is as electrospinning raw material.
(3) obtained electrospinning raw material is added in electrostatic spinning apparatus, is 40kV in electrostatic pressure, injects flow rate pump 4mL/ H, spinning head obtain the poly- [1- with carbon dioxide adsorption function away from electrostatic spinning is carried out under conditions of receiving screen distance 20cm (2- methylacryoyloxyethyl) -3- butyl-pyridinium tetrafluoroborate salt] nano-fiber material.
Embodiment 11
The carbon dioxide adsorption of above-mentioned preparation is evaluated with poly ion liquid nano-fiber material:
1, titanium dioxide prepared by Examples 1 to 10 is measured respectively using synchronous thermogravimetric analyzer (TA-Q600TGA/DSC) CO of the carbon adsorption with poly ion liquid nano-fiber material at 40 DEG C2Adsorbance.Experimental result see the table below:
Conclusion: as can be seen from the above table, the carbon dioxide adsorption that the method according to Examples 1 to 10 is prepared is used Poly ion liquid nano-fiber material is to CO2Adsorbance increase with the increase of poly ion liquid mass fraction, to CO2's Adsorbance is superior to the absorption property of commercial active carbon, and maximum can reach the adsorbance of 4.7mmol/g.Therefore real according to the present invention Applying a carbon dioxide adsorption for method preparation has good CO with poly ion liquid nano-fiber material2Absorption property.

Claims (8)

1. a kind of preparation method of the poly ion liquid nano-fiber material for carbon dioxide adsorption characterized by comprising
Step 1: the polymerizable ionic liquid monomer containing alkenyl structures is carried out under the action of initiator and chain-transferring agent can It controls living free radical polymerization and poly ion liquid containing alkenyl is made；The polymerizable ionic liquid list containing alkenyl structures The mass fraction of body is 70% ~ 90%, and the mass fraction of initiator is 5% ~ 15%, and the mass fraction of chain-transferring agent is 5% ~ 15%；Institute The polymerizable ionic liquid monomer containing alkenyl structures stated is ion liquid of quaternaries monomer, imidazole salt ionic liquid list Body, pyridine salt ionic liquid monomer or quaternary phosphonium salt ionic liquid monomer；
Step 2: at room temperature, by the stirring and dissolving of poly ion liquid containing alkenyl made from the first step in solvent, obtaining quality point The electrospinning raw material that number is 5 ~ 30%；
Step 3: the electrospinning raw material that second step obtains is added in electrostatic spinning apparatus, electrostatic spinning is carried out, Nanowire is obtained Tie up material；The electrospinning conditions are as follows: electrostatic pressure is 10 ~ 40kV, and injection flow rate pump is 1 ~ 4mL/h, and spinning head is away from reception Screen distance is 10 ~ 20cm.
2. the preparation method for the poly ion liquid nano-fiber material of carbon dioxide adsorption as described in claim 1, It is characterized in that, the revolving speed in the second step is 100 ~ 2500r/min.
3. the preparation method for the poly ion liquid nano-fiber material of carbon dioxide adsorption as described in claim 1, It is characterized in that, the initiator is azo-initiator, organic peroxy class initiator or inorganic peroxy class initiator.
4. the preparation method for the poly ion liquid nano-fiber material of carbon dioxide adsorption as described in claim 1, It is characterized in that, the chain-transferring agent is dithioesters, methanol, aliphatic mercaptan, carbon tetrachloride, iodoform, isopropanol, bisulfite At least one of sodium, sodium hypophosphite, sodium formate, thioacetic acid, mercaptopropionic acid, mercaptoethanol and mercaprol.
5. the preparation method for the poly ion liquid nano-fiber material of carbon dioxide adsorption as claimed in claim 4, It is characterized in that, the aliphatic mercaptan is positive in butanethiol, tert-butyl mercaptan, n-octyl mercaptan and lauryl mercaptan at least It is a kind of.
6. the preparation method for the poly ion liquid nano-fiber material of carbon dioxide adsorption as described in claim 1, It is characterized in that, the poly ion liquid containing alkenyl is quaternary ammonium salt poly ion liquid, imidazole salt poly ion liquid, pyridiniujm At least one of class poly ion liquid and quaternary alkylphosphonium salt class poly ion liquid.
7. the preparation method for the poly ion liquid nano-fiber material of carbon dioxide adsorption as described in claim 1, It is characterized in that, the solvent in the second step is acetone, n,N-Dimethylformamide, methylene chloride, dimethyl sulfoxide, second Nitrile, ether, tetrahydrofuran, DMAC N,N' dimethyl acetamide, hexane, ethyl alcohol, formic acid, acetic acid, chloroform, benzene, carbon tetrachloride, 1,2- bis- Chloroethanes, trichloroethanes, 1,1,2- trichloro ethylene, 1,2- dimethoxy-ethane, 1,2,3,4-tetralin, sulfolane, pyrimidine, Formamide, chlorobenzene, dioxane, ethylene glycol, toluene, hexahydrotoluene, 1,2- dichloroethylene, dimethylbenzene, ring Hexane, N-Methyl pyrrolidone, pentane, methyl phenyl ethers anisole, butyl acetate, three fourth Methyl ethers, isopropyl acetate, methyl tetrahydro furan It mutters, the mixture of one or more of petroleum ether, trichloroacetic acid, trifluoroacetic acid and pyridine.
8. the preparation described in any one of claim 1 ~ 7 for the poly ion liquid nano-fiber material of carbon dioxide adsorption The poly ion liquid nano-fiber material of carbon dioxide adsorption is used for prepared by method.
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