CN109157928A - A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof - Google Patents

A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof Download PDF

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Publication number
CN109157928A
CN109157928A CN201810996163.8A CN201810996163A CN109157928A CN 109157928 A CN109157928 A CN 109157928A CN 201810996163 A CN201810996163 A CN 201810996163A CN 109157928 A CN109157928 A CN 109157928A
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China
Prior art keywords
functionalization graphene
filter membrane
functionalization
high polymer
nanometer fiber
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CN201810996163.8A
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Chinese (zh)
Inventor
李晶
李虓
李启龙
张丽萍
郝相龙
朱宏伟
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Fangda Carbon New Materials Technology Co Ltd
Tsinghua University
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Fangda Carbon New Materials Technology Co Ltd
Tsinghua University
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Priority to CN201810996163.8A priority Critical patent/CN109157928A/en
Publication of CN109157928A publication Critical patent/CN109157928A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/54Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
    • B01D46/543Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0001Making filtering elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D46/00Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0027Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
    • B01D46/0036Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions by adsorption or absorption
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/56Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonwoven Fabrics (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof, belongs to air cleaning and membrane material preparation technical field.The filter membrane contains high polymer nanometer fiber and functionalization graphene layer, and functionalization graphene layer inserts in inside high polymer nanometer fiber, and the two is mutually overlapping.Preparation method is: the dispersion liquid and Polymer Solution of the functionalization graphene of various concentration is respectively configured, using electrospinning device, two kinds of dispersion liquids are respectively placed in two syringes and carry out spraying spinning, make to form filter membrane in functionalization graphene layer insertion high polymer nanometer fiber.The filter membrane can effectively adsorb NH3、CO、NO2Equal polluted gas, and smog, pollen, PM in energy high efficiency filter air2.5Etc. tiny particles contents, significantly promote filter efficiency, realize air cleaning;It can also be used for personal protection device (such as mask), be beneficial to health.

Description

A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof
Technical field
The present invention relates to a kind of efficient intercalation formula nanofiber filter membranes, belong to air cleaning and membrane material technology of preparing neck Domain.
Background technique
Due to economic rapid growth and industrialization and the automobile to increase sharply uses and urbanization, and China is just by serious big The influence of pellet (PM) in gas, global air pollution is increasingly severe, and the health of the mankind is on the hazard, weather Deteriorate and the damage of the ecosystem is also on the rise.Efficiently, economic, energy-efficient filter membrane is to solve the problems, such as the ideal hand Section.However the shortcomings that can not overcoming there are many existing fiber filter films, as fibre diameter is relatively thick (micro- from several microns to tens Rice) and synthetic aperture it is larger, filter particulate efficiency it is relatively low, film heaviness etc..Currently, having developed number of ways to prepare Nano fibrous membrane is used for separate fine particles, including mutually separates, templated synthesis, corona treatment and fusion method.But in these sides In method, most of there are still filter efficiency is low and the high problem of energy consumption.Thus developing one kind can simply prepare and high efficiency filter The filter membrane of various pollutants, and be applied to most important in production and living.The technology simple and powerful as one kind, Tunica fibrosa is prepared under nanometer and submicron-scale, electrostatic spinning has been obtained for more and more paying close attention to.
But existing filter membrane function is more single in the market, is only capable of filtering some large particles, is not able to satisfy high efficiency filter Demand.
Summary of the invention
The purpose of the present invention is a kind of improvement to common macromolecular filtering film, imitate the filter membrane with higher filtering Rate does not increase complicated preparation process.
Technology of the invention is as follows:
A kind of nanofiber filter membrane of functionalization graphene intercalation, it is characterised in that: the filter membrane contains high molecular nanometer fibre Peacekeeping functionalization graphene layer, the functionalization graphene layer insert in inside high polymer nanometer fiber, mutually overlapping between the two.
It is using electrostatic that functionalization graphene layer of the present invention, which is inserted in inside high polymer nanometer fiber and mutually overlapped, The synchronous realization of spinning technique.
Preferably, the functionalization graphene layer be by graphene oxide, redox graphene, hydroxylating graphene and One or more of carboxylated graphene material is formed.
Preferably, the high polymer nanometer fiber be by polyacrylonitrile, polypropylene, Polyurethane, polyvinylpyrrolidone, The nanofiber that one or more of bisphenol-a polysulfone, polystyrene and nylon material is formed.
The preparation method of the nanofiber filter membrane of a kind of functionalization graphene intercalation provided by the invention, it is characterised in that should Method includes the following steps:
1) functionalization graphene and high molecular material are added separately in organic solvent, before being configured to functionalization graphene Drive liquid and high molecular material precursor liquid;
2) electrospinning device is used, macromolecule precursor liquid and functionalization graphene precursor liquid are respectively placed in syringe It is interior, and technological parameter is set are as follows: spray head distance between two tips receiver distance is 18-20.5cm, voltage 8-20kV, fltting speed 0.6- 1.0mm/min makes functionalization graphene layer is synchronous with high polymer nanometer fiber forming process to carry out, can make functionalization graphene Layer inserts in inside high polymer nanometer fiber, forms mutually overlapping nanofiber filter membrane.
Preferably, the mass-volume concentration of the functionalization graphene precursor liquid is 0.01-0.5g/mL, high molecular material The mass-volume concentration of precursor liquid is 0.5-2g/10mL.
Preferably, the organic solvent is using n,N-Dimethylformamide, N-Methyl pyrrolidone and dimethyl sulfoxide One or more of mixing.
The present invention has the following advantages that and high-lighting technical effect: the present invention is in conventional nano fiber membrane preparation process In, insertions function graphite alkene layer, so that the functional group abundant using functionalization graphene surface greatly improves fine grained The strainability of object can effectively adsorb NH3、CO、NO2Equal polluted gas, and smog, pollen, PM in energy high efficiency filter air2.5 Etc. tiny particles contents.Preparation method simple process simultaneously, can one-pass molding, preparation efficiency is high, effectively reduces production cost.
Detailed description of the invention
Fig. 1 is the schematic diagram of preparation method of the present invention.
Fig. 2 is the nanofiber filter membrane SEM figure for being a kind of functionalization graphene intercalation provided by the invention.
Specific embodiment
The present invention is further elaborated with reference to the accompanying drawings and examples.
Fig. 1 is the schematic diagram of preparation method of the present invention, which includes the following steps:
1) functionalization graphene and high molecular material are added separately in organic solvent, before being configured to functionalization graphene Drive liquid and high molecular material precursor liquid;The mass-volume concentration of functionalization graphene precursor liquid is preferably 0.01-0.5g/mL, high The mass-volume concentration of molecular material precursor liquid is preferably 0.5-2g/10mL;The organic solvent uses volatile N, N- The mixing of one or more of dimethylformamide, N-Methyl pyrrolidone and dimethyl sulfoxide;The functionalization graphene layer It is by one or more of graphene oxide, redox graphene, hydroxylating graphene and carboxylated graphene material shape At;The high polymer nanometer fiber is gathered by polyacrylonitrile, polypropylene, Polyurethane, polyvinylpyrrolidone, bisphenol A-type The nanofiber that one of sulfone, polystyrene and nylon Hu different materials are formed.
2) electrospinning device is used, macromolecule precursor liquid 1 and functionalization graphene precursor liquid 2 are respectively placed in syringe It is interior, and technological parameter is set are as follows: spray head distance between two tips receiver distance is 18-20.5cm, voltage 8-20kV, fltting speed 0.6- 1.0mm/min making functionalization graphene layer is synchronous with high polymer nanometer fiber forming process to carry out, functionalization graphene can be made Layer inserts in inside high polymer nanometer fiber, forms mutually overlapping nanofiber filter membrane.
Fig. 2 is the nanofiber filter membrane SEM figure for being a kind of functionalization graphene intercalation provided by the invention.The Nanowire Dimension filter membrane contains functionalization graphene layer 4 and high polymer nanometer fiber 3, and functionalization graphene layer inserts in high polymer nanometer fiber Portion, it is mutually overlapping between the two;It is to adopt that the functionalization graphene layer, which is inserted in inside high polymer nanometer fiber and mutually overlapped, With the synchronous realization of electrostatic spinning process.
Embodiment 1:
Step A, graphene oxide, eccentric cleaning drying are prepared using improved Hummer method.
Step B, 10mg graphene oxide and polyacrylonitrile n,N-Dimethylformamide dispersion liquid are prepared respectively, and it is poly- to weigh 1g 10mLN is added in acrylonitrile, and in dinethylformamide, stirring makes precursor liquid be uniformly dispersed, and weighs 10mg graphene oxide and adds Enter in 10mL n,N-Dimethylformamide, stirring ultrasound keeps its evenly dispersed.
Step C, configured two kinds of precursor solutions are placed on electrospinning device with syringe, needle tip distance connects Device 20.5cm, voltage 10kV, fltting speed 0.8mm/min are received, 10mg graphene oxide is inserted into polyacrylonitrile fibre, is formed The nanofiber filter membrane of graphene oxide insertion.
Embodiment 2:
Step A, redox graphene, eccentric cleaning freeze-drying are prepared.
Step B, 15mg redox graphene and bisphenol-a polysulfone ethylene glycol dispersion liquid are prepared, 1.5g bisphenol A-type is weighed Polysulfones is added in 10mL ethylene glycol, and stirring makes precursor liquid be uniformly dispersed, then weigh 15mg redox graphene, and 10mL is added In ethylene glycol, stirring ultrasound makes precursor liquid be uniformly dispersed.
Step C, configured two kinds of precursor solutions are placed on electrospinning device with syringe, needle tip distance connects Device 18cm, voltage 15kV, fltting speed 1mm/min are received, 15mg redox graphene is inserted into bisphenol-a polysulfone fiber, Form the nanofiber filter membrane of redox graphene intercalation.
Embodiment 3:
Step A, hydroxylating graphene, eccentric cleaning drying are prepared.
Step B, 5mg hydroxylating graphene and polyvinylpyrrolidone N-Methyl pyrrolidone dispersion liquid are prepared, 2g is weighed Polyvinyl alcohol is added in 10mL N-Methyl pyrrolidone, and stirring makes precursor liquid be uniformly dispersed, then weigh 5mg hydroxyl graphite Alkene is added in 10mL N-Methyl pyrrolidone, and stirring ultrasound makes precursor liquid be uniformly dispersed.
Step C, configured two kinds of precursor solutions are placed on electrospinning device with syringe, needle tip distance connects Device 20cm, voltage 8kV, fltting speed 0.6mm/min are received, by the polyvinyl pyrrolidone fibers of 5mg hydroxylating graphene intercalation In, form the nanofiber filter membrane of hydroxylating graphene intercalation.

Claims (7)

1. a kind of nanofiber filter membrane of functionalization graphene intercalation, it is characterised in that: the filter membrane contains high polymer nanometer fiber (3) it inserts in inside high polymer nanometer fiber with functionalization graphene layer (4), the functionalization graphene layer, mutually hands between the two It is folded.
2. a kind of nanofiber filter membrane of functionalization graphene intercalation according to claim 1, it is characterised in that: described Functionalization graphene layer, which is inserted in inside high polymer nanometer fiber and mutually overlapped, to be realized using electrostatic spinning process is synchronous.
3. a kind of nanofiber filter membrane of functionalization graphene intercalation as claimed in claim 1 or 2, it is characterised in that: described Functionalization graphene layer is by one in graphene oxide, redox graphene, hydroxylating graphene and carboxylated graphene What kind or different materials were formed.
4. a kind of nanofiber filter membrane of functionalization graphene intercalation as claimed in claim 1 or 2, it is characterised in that: described High polymer nanometer fiber be by polyacrylonitrile, polypropylene, Polyurethane, polyvinylpyrrolidone, bisphenol-a polysulfone, polyphenyl second The nanofiber that one or more of alkene and nylon material are formed.
5. a kind of preparation method of the nanofiber filter membrane of functionalization graphene intercalation as described in claim 1, feature exist In this method comprises the following steps:
1) functionalization graphene and high molecular material are added separately in organic solvent, are configured to functionalization graphene precursor liquid With high molecular material precursor liquid;
2) electrospinning device is used, macromolecule precursor liquid (1) and functionalization graphene precursor liquid (2) are respectively placed in syringe It is interior, and technological parameter is set are as follows: spray head distance between two tips receiver distance is 18-20.5cm, voltage 8-20kV, fltting speed 0.6- 1.0mm/min makes functionalization graphene layer is synchronous with high polymer nanometer fiber forming process to carry out, can make functionalization graphene Layer inserts in inside high polymer nanometer fiber, forms mutually overlapping nanofiber filter membrane.
6. a kind of preparation method of the nanofiber filter membrane of functionalization graphene intercalation as claimed in claim 5, feature exist In: the mass-volume concentration of the functionalization graphene precursor liquid is 0.01-0.5g/mL, the quality of high molecular material precursor liquid Volumetric concentration is 0.5-2g/10mL.
7. such as a kind of preparation method of the nanofiber filter membrane of functionalization graphene intercalation described in claim 5 or 6, feature Be: the organic solvent uses one of N,N-dimethylformamide, N-Methyl pyrrolidone and dimethyl sulfoxide or several The mixing of kind.
CN201810996163.8A 2018-08-29 2018-08-29 A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof Pending CN109157928A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110284263A (en) * 2019-06-13 2019-09-27 上海交通大学 The preparation method of lamination composite nano fiber
CN112619622A (en) * 2020-12-23 2021-04-09 广州大学 Nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and preparation method and application thereof
WO2022183215A1 (en) * 2021-02-26 2022-09-01 Merit Medical Systems, Inc. Fibrous constructs with therapeutic material particles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103147226A (en) * 2013-02-07 2013-06-12 江西师范大学 Method for preparing high dielectric constant polymer-based nano composite material
CN105568401A (en) * 2015-12-12 2016-05-11 大连理工大学 Ultrasonic atomization assisted electrospinning technique
CN106245232A (en) * 2016-07-27 2016-12-21 山东大学 Graphene oxide@high polymer nano fiber multilayer film and its preparation method and application
CN107583377A (en) * 2017-08-24 2018-01-16 清华大学 A kind of air-filtering membrane of functionalization graphene modification and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103147226A (en) * 2013-02-07 2013-06-12 江西师范大学 Method for preparing high dielectric constant polymer-based nano composite material
CN105568401A (en) * 2015-12-12 2016-05-11 大连理工大学 Ultrasonic atomization assisted electrospinning technique
CN106245232A (en) * 2016-07-27 2016-12-21 山东大学 Graphene oxide@high polymer nano fiber multilayer film and its preparation method and application
CN107583377A (en) * 2017-08-24 2018-01-16 清华大学 A kind of air-filtering membrane of functionalization graphene modification and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110284263A (en) * 2019-06-13 2019-09-27 上海交通大学 The preparation method of lamination composite nano fiber
CN110284263B (en) * 2019-06-13 2022-03-08 上海交通大学 Preparation method of laminated composite nanofiber
CN112619622A (en) * 2020-12-23 2021-04-09 广州大学 Nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and preparation method and application thereof
WO2022183215A1 (en) * 2021-02-26 2022-09-01 Merit Medical Systems, Inc. Fibrous constructs with therapeutic material particles

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Application publication date: 20190108