CN108499371A - The enhanced amidoxim modified polyacrylonitrile nanofiber membrane preparation method of montmorillonite - Google Patents
The enhanced amidoxim modified polyacrylonitrile nanofiber membrane preparation method of montmorillonite Download PDFInfo
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- CN108499371A CN108499371A CN201810370242.8A CN201810370242A CN108499371A CN 108499371 A CN108499371 A CN 108499371A CN 201810370242 A CN201810370242 A CN 201810370242A CN 108499371 A CN108499371 A CN 108499371A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
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- 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
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
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- 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
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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- 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
- D01F6/44—Monocomponent 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
- D01F6/54—Monocomponent 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
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/007—Addition polymers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/368—Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
Abstract
The invention discloses a kind of enhanced amidoxim modified polyacrylonitrile nanofiber membrane preparation methods of montmorillonite, with N, N ' dimethylformamides are solvent, polymer poly acrylonitrile is basis material, organo montmorillonite as reinforcing material, montmorillonite stripping is distributed to the spinning solution for being configured to various concentration in polymer solution by graft process, nano fibrous membrane is prepared using method of electrostatic spinning；Amidoxime modification is carried out to nano fibrous membrane by hydroxylamine solution, a kind of enhanced polyacrylonitrile nanofiber film with amidoxime group of montmorillonite is made.Raw material sources of the present invention are abundant, nanofiber preparation process is simple controllably, yield is big, nanofiber prepares Lian Xingqiang；Resulting materials porosity height, the sequestering power that mechanical performance is excellent, strong, can be repeated several times utilization at large specific surface area, the ability with efficient absorption metal ion in solution.
Description
Technical field
The present invention relates to nanofiber technical field of membrane, especially a kind of enhanced amidoxim modified polyacrylonitrile of montmorillonite
Nanofiber membrane preparation method.
Background technology
Currently, it is a kind of simple controllable, base material doping letter of technique to prepare micro nanometer fiber film by high-voltage electrostatic spinning method
List can be mass-produced, the high efficiency technical means that raw material sources are abundant, and polymer tunica fibrosa product as obtained by electrostatic spinning has
There are the advantage of high voidage, large specific surface area, structure-controllable, product to be widely used in filtering, absorption, reinforcing material, catalysis, health
The fields such as protection, barrier and dress ornament.
Polyacrylonitrile is a kind of important industrial polymerisation raw material, and in field of textile industry, its usage amount ranking is in synthesis
The 4th in polymer.Acrylic fibers be often used to carbonization prepare high intensity, high-modulus, the carbon fiber on lightweight ground, carbon nanotube/
Line etc., at the same in polyacrylonitrile strand containing a large amount of highly polar cyano functional group have certain chemical reactivity and
The combinations such as stronger hydrogen bond action can be formed with inorganic matter etc., through modified, functional modification frequently as polyacrylonitrile polymer
Active site.By electro-spinning for high voidage, the nanosizing acrylic fiber and composite fibre of large specific surface area, made
It is widely used in filtering, adsorbing separation film field for base material.But Static Spinning acrylon nano fiber has stronger hydrophily, nanometer
Film is in liquid environment for a long time during routine use, is easy that fiber is made to disperse and be broken, be detached from tunica fibrosa, along with
It is adsorbed on the disengaging of the metal ion inside tunica fibrosa and on fiber, while being not easy from liquid environment after tunica fibrosa fracture dispersion
It separates, cause reusing difference and the secondary pollution problems of environment can be caused.
The study found that the montmorillonite after organically-modified belongs to a layer structured calcium silicate minerals, have special stratiform one-dimensional
Nanostructure can remove dispersion lamellar structure by modes such as intercalation, mechanical oscillations.It has stronger thermal stability, absorption
Property, interlayer ion exchangeability, lipophilicity, between organo montmorillonite and polymer have preferable compatibility, be added to polymer
Its mechanical strength and dimensional stability can be significantly improved in the middle.
Contain lone electron pair in amidoxime group its molecule link, can chelate, generate stable with metallic ion coordination
Effect, is commonly used to be combined with metal ion, and the uses such as metal ion and trace test analysis are removed for detaching.Occur at present
Have much using the material for removing metal ion containing amidoxime group, Chinese patent of invention (102329959 B of CN) passes through
The polyacrylonitrile resin polymer with amidoxim is obtained using hydroxylamine hydrochloride processing polyacrylonitrile, for dividing from silver electrolyte
From palladium metal ion, resin specific surface area is small few with the active site of metal ion-chelant, while metal ion and resin connect
Having a sudden inspiration can be seldom, so as to cause palladium metal ion isolation effect unobvious, the separation duration is long the problems such as.Amidoxim have compared with
The ability of good chelated metal ions will be combined and be received if loading to the excellent nanostructured fibers film surface of mechanical performance
The large specific surface area of rice fiber, voidage is high, sequestering activity site is more, metal contact chelating probability height, good stability of the dimension, machine
The advantages such as tool intensity is high, can be used repeatedly, but so far, about using organo montmorillonite enhancing mechanical performance and with together with amine
The preparation research of the polyacrylonitrile nanofiber film of oximido group has not been reported, and so that organo montmorillonite is distributed to polyacrylonitrile and receives
Enhance its mechanical strength in rice fiber, obtain montmorillonite enhancing amidoxim polyacrylonitrile nano fibre using process for modifying surface
Dimension, it is current problem in the urgent need to address that the absorption for metal ion, which removes,.
Invention content
The object of the present invention is to provide a kind of enhanced amidoxim modified polyacrylonitrile nanofiber film preparation sides of montmorillonite
Method, the technical issues of to solve in the prior art, it can be prepared, and large specific surface area, voidage are high, sequestering activity site is more,
Metal contact chelating probability height, good stability of the dimension, high mechanical strength, the efficiently removal metal ion that can be used repeatedly
The enhanced amidoxim modified polyacrylonitrile nano fibrous membrane of montmorillonite.
The present invention provides a kind of enhanced amidoxim modified polyacrylonitrile nanofiber membrane preparation methods of montmorillonite, including
Following steps：
(1) organo montmorillonite is dispersed in N by supersonic oscillations, in N '-dimethyl formamide solution, further to molten
Polymer poly acrylonitrile is added in liquid, removing dispersion montmorillonite by intercalation in the solution obtains organo montmorillonite doping polypropylene
Nitrile nanofibre is molded spinning solution；
(2) high-voltage electrostatic spinning method is used, the obtained organo montmorillonite doping polyacrylonitrile nano of step (1) is fine
Nano fibrous membrane is made by high-voltage electrostatic spinning in dimension molding spinning solution, and drying is received to get to montmorillonite enhanced polyacrylonitrile
Rice tunica fibrosa；
(3) hydroxylamine solution is used to carry out amidoxime to the montmorillonite enhanced polyacrylonitrile nano fibrous membrane obtained in step (2)
Change modification to get the enhanced amidoxim modified polyacrylonitrile nano fibrous membrane of montmorillonite.
A kind of enhanced amidoxim modified polyacrylonitrile nanofiber membrane preparation method of montmorillonite as described above, wherein
Preferably, organo montmorillonite is the modified organic quaternary ammonium salt montmorillonite of octadecyltrimethylammonium chloride in step (1), is surpassed
The frequency of sound wave is 10kHz~50kHz, and duration of oscillation is 1~5 hour, by mass, organo montmorillonite a concentration of 0.1~
2%；By mass, polyacrylonitrile in entire solution a concentration of 5~20%, magnetic agitation 5~10 hours obtains described having
Machine montmorillonite adulterates polyacrylonitrile nanofiber and is molded spinning solution.
A kind of enhanced amidoxim modified polyacrylonitrile nanofiber membrane preparation method of montmorillonite as described above, wherein
Preferably, in step (2) Static Spinning voltage be 15~25kv, fiber receive distance be 5~15cm, spinning speed be 0.2~
1.2ml/h, spinning temperature are 25~45 DEG C, and drying temperature is 60~80 DEG C, and the time is 2~5 hours, obtain the montmorillonite and increase
Strong type polyacrylonitrile nanofiber film.
A kind of enhanced amidoxim modified polyacrylonitrile nanofiber membrane preparation method of montmorillonite as described above, wherein
Preferably, the preparation method of the enhanced amidoxim modified polyacrylonitrile nano fibrous membrane of montmorillonite is in the step (3), will
Hydroxylamine hydrochloride salt and sodium hydroxide in molar ratio 1:1 is dissolved in methanol solution, and filtering removal precipitation is configured to a concentration of 1mol/L
Hydroxylamine solution；By bath raio 1：10~1：50 add the montmorillonite enhanced polyacrylonitrile nano fibrous membrane obtained in step (2)
Enter into hydroxylamine solution, temperature be 60~80 DEG C, magnetic agitation react 2~5 hours, successively use methanol, deionization wash
Reaction product is washed, dries, finally obtains the enhanced amidoxim modified polyacrylonitrile nano fibrous membrane of montmorillonite.
The present invention adsorbed in solution environmental remove heavy metal ion principle be：It will stripping by ultra sonic machinery oscillation
From organo montmorillonite, the highly polar cyano that collaboration polyacrylonitrile carries is combined to form stronger hydrogen with the Si-O in organo montmorillonite
Key reaches intercalation separation montmorillonite effect, makes have the organo montmorillonite of 1-dimention nano lamella evenly dispersed in a polymer solution
The mechanical performance and thermal stability for enhancing polymer, polyacrylonitrile nano is prepared by high-voltage electrostatic spinning by polymer solution
Fiber is to get to montmorillonite enhanced polyacrylonitrile micro-nano fiber film；Passing through hydroxylamine hydrochloride to enhanced polyacrylonitrile micro-nano
Tunica fibrosa surface graft modification makes its surface with to amidoxim of the metal ion with chelation, synergic nano tunica fibrosa
High voidage, bigger serface, which are realized, removes metal with stronger absorption.
Compared with prior art, the enhanced amidoxim modified polyacrylonitrile nano fibrous membrane of montmorillonite that the present invention is obtained
Not only realizing montmorillonite enhancing makes nano fibrous membrane be provided with preferable mechanical strength, dimensional stability and profit can be repeated several times
The property used；And in nano fibrous membrane surface modification amidoxim, large specific surface area, voidage height, sequestering activity is prepared
Site is more, metal contact chelates probability height, good stability of the dimension, high mechanical strength, the nano fibrous membrane that can be used repeatedly,
Gained membrane material of the invention, has the amidoxim of chelation containing metal, cooperates with the nanofiber of high voidage, bigger serface
The characteristic of film realizes the efficient absorption removal to metal ion.
Description of the drawings
Fig. 1 is the preparation method flow chart of the present invention.
Fig. 2 is the montmorillonite enhanced polyacrylonitrile nanofiber scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 provides.
Fig. 3 is the enhanced amidoxim modified polypropene nitrile nanofibre scanning electricity of montmorillonite that the embodiment of the present invention 1 provides
Mirror figure.
Fig. 4 is that the polyacrylonitrile nanofiber film that the embodiment of the present invention 1 provides and the enhanced amidoxim of montmorillonite are modified and gather
Modulus change tendency chart of the acrylonitrile nano fibrous membrane under wet condition.
Fig. 5 is the enhanced amidoxim modified polyacrylonitrile nano fibrous membrane of montmorillonite that provides of the embodiment of the present invention 1 to Cu2 +、Cr3+Saturated extent of adsorption block diagram.
Specific implementation mode
The embodiments described below with reference to the accompanying drawings are exemplary, is only used for explaining the present invention, and cannot be construed to
Limitation of the present invention.
The embodiment provides a kind of enhanced amidoxim modified polyacrylonitrile nanofiber film preparations of montmorillonite
Method includes the following steps：
(1) first, by the modified organic quaternary ammonium salt montmorillonite of octadecyltrimethylammonium chloride in N, N '-dimethyl first
Supersonic oscillations are disperseed in amide solution, and the frequency of ultrasonic wave is 10kHz~50kHz, and duration of oscillation is 1-5 hours, a concentration of
0.1~2%；Be added polymer poly acrylonitrile, by mass, polyacrylonitrile in entire solution a concentration of 5~20%, magnetic force
Stirring 5~10 hours obtains organo montmorillonite doping polyacrylonitrile nanofiber molding spinning solution.
(2) organo montmorillonite doping polyacrylonitrile nanofiber molding spinning solution in step (1) is placed in electrostatic spinning machine
In equipment, Static Spinning voltage is 15~25kv, and it is 5~15cm that fiber, which receives distance, and spinning speed is 0.2~1.2ml/h, spinning
Temperature is 25~45 DEG C, and drying temperature is 60~80 DEG C, and the time is 2~5 hours, obtains montmorillonite enhanced polyacrylonitrile nanometer
Tunica fibrosa.
(3) by hydroxylamine hydrochloride salt and sodium hydroxide in molar ratio 1:1 is dissolved in methanol solution, and compound concentration is 1mol/L's
Hydroxylamine solution；By bath raio 1：10~1：50 the montmorillonite enhanced polyacrylonitrile nano fibrous membrane obtained in step (2) is added
Into hydroxylamine solution, temperature be 60~80 DEG C, magnetic agitation react 2~5 hours, successively use methanol, deionized water wash
Reaction product, drying, obtains the enhanced amidoxim modified polyacrylonitrile nano fibrous membrane of montmorillonite.
Embodiment 1
Referring to attached drawing 1, preparation method flow chart of the invention.Organo montmorillonite is added to N, N '-dimethyl first first
In amide solution, is vibrated its mechanical stripping into the nanometer sheet of single layer by ultra sonic machinery, continue to add poly- third into solution
Alkene nitrile, the highly polar cyano that polyacrylonitrile carries is combined with the Si-O in organo montmorillonite to be formed stronger hydrogen bond and reaches intercalation point
It is acted on from montmorillonite, makes have the organo montmorillonite of 1-dimention nano lamella evenly dispersed in a polymer solution, it is poly- to reach enhancing
The purpose of the mechanical performance and thermal stability of object is closed, then polymer solution is prepared by polyacrylonitrile by high-voltage electrostatic spinning and is received
Rice fiber, obtains montmorillonite enhanced polyacrylonitrile micro-nano fiber film；Passing through hydroxylamine hydrochloride to enhanced polyacrylonitrile micro-nano
Fiber surface graft modification makes its surface with to amidoxim of the metal ion with chelation, it is enhanced to obtain montmorillonite
Amidoxim modified polyacrylonitrile nano fibrous membrane.The method of preparation is as follows：
(1) prepared by organo montmorillonite doping polyacrylonitrile nanofiber molding spinning solution：1g organo montmorillonites are weighed, are added
To 100mLN, in N '-dimethyl formamide solution, the frequency that solution is put into ultrasonic wave in ultrasonic oscillator is 40kHz, acute
Strong oscillation 2 hours makes organo montmorillonite be dispersed into nanometer sheet by supersonic oscillations stripping in N, N '-dimethyl formamide solution
Layer structure；It weighs in the solution after oscillation is added in 7g polyacrylonitrile, magnetic agitation 8 hours, obtains organo montmorillonite doping poly- third
Alkene nitrile nanofibre is molded spinning solution.
(2) the obtained organo montmorillonite doping polyacrylonitrile nanofiber molding spinning solution of step (1) is packed into high pressure
In the mating micro propulsion pump of electrostatic spinning, the syringe needle with electrostatic high-pressure is flowed to by pipeline spinning solution, is band below syringe needle
There are the tunica fibrosa receiver board of aluminium foil, setting Static Spinning voltage 20kv, fiber to receive distance 10cm, spinning speed 1mL/h, temperature 40
DEG C, montmorillonite enhanced polyacrylonitrile nano fibrous membrane is prepared.
(3) hydroxylamine hydrochloride for weighing 6.95g is dissolved in 100mL methanol/deionized water (V:V=4:1) in mixed solution, so
4g sodium hydroxides are added in backward solution, filtering removal precipitation obtains the hydroxylamine solution of a concentration of 1mol/L；By bath raio 1：30,
It weighs the montmorillonite enhanced polyacrylonitrile nano fibrous membrane obtained in 3.3g steps (2) to be added in hydroxylamine solution, in temperature
It is reacted 3 hours for 70 DEG C, magnetic agitation, methanol, deionized water washing reaction product, drying is used to obtain montmorillonite increasing successively
Strong type amidoxim modified polyacrylonitrile nano fibrous membrane.
Referring to attached drawing 2,3, hence it is evident that covered as it can be seen that organo montmorillonite is entrained in polyacrylonitrile solution to be formed by electrostatic spinning
De- soil enhanced polyacrylonitrile nanofiber, fiber surface have rough protrusion and slot, further increase nanofiber
Specific surface area provides more multiple binding sites for the amidoxim modifying and decorating of next step.After being handled by hydroxylamine hydrochloride, obtain
The enhanced amidoxim modified polypropene nitrile nanofibre of montmorillonite, fiber surface protrusion and slot disappear, and have greatly in fiber surface
The block of amount generates, and illustrates that nanofiber surface has loaded a large amount of amidoxime groups, to which montmorillonite has been prepared in verification
Enhanced amidoxim modified polyacrylonitrile nano fibrous membrane.
It is that polyacrylonitrile nanofiber film provided in this embodiment and the enhanced amidoxim of montmorillonite are modified referring to attached drawing 4
The modulus change that polyacrylonitrile nanofiber film uses in water environment.As can be seen that the nanometer after organo montmorillonite adulterates
The mechanical strength of tunica fibrosa improves very much, although by impregnating in water for a long time, the enhanced amidoxim of montmorillonite is modified poly-
The modulus of acrylonitrile nano fibrous membrane is still higher than pure polyacrylonitrile fibre membrane, illustrate nanometer film have preferable water resistance and
Dimensional stability is used repeatedly and can simply be separated from solution after and provide possibility for film cycle.
Attached drawing 5 is participated in, is the enhanced amidoxim modified polypropene nitrile nanofibre of organo montmorillonite provided in this embodiment
Film is to Cu2+、Cr3+Saturated extent of adsorption block diagram.As shown, nano fibrous membrane is to Cu2+、Cr3+Saturated extent of adsorption be respectively
500.12mg/g、554.24mg/g.By high-voltage electrostatic spinning by polymer solution be prepared into polyacrylonitrile nanofiber to get
To montmorillonite enhanced polyacrylonitrile micro-nano fiber film；Enhanced polyacrylonitrile micro-nano fiber surface is connect by hydroxylamine hydrochloride
Branch is modified, makes its surface with to amidoxim of the metal ion with chelation, synergic nano tunica fibrosa high voidage, big ratio
Surface area, which is realized, removes metal with stronger absorption.
Embodiment 2
(1) prepared by organo montmorillonite doping polyacrylonitrile nanofiber molding spinning solution：2g organo montmorillonites are weighed, are added
To 100mLN, in N '-dimethyl formamide solution, the frequency that solution is put into ultrasonic wave in ultrasonic oscillator is 50kHz, acute
Strong oscillation 5 hours makes organo montmorillonite be dispersed into nanometer sheet by supersonic oscillations stripping in N, N '-dimethyl formamide solution
Layer structure；It weighs in the solution after oscillation is added in 10g polyacrylonitrile, magnetic agitation 9 hours, obtains organo montmorillonite doping poly- third
Alkene nitrile nanofibre is molded spinning solution.
(2) the obtained organo montmorillonite doping polyacrylonitrile nanofiber molding spinning solution of step (1) is packed into high pressure
In the mating micro propulsion pump of electrostatic spinning, the syringe needle with electrostatic high-pressure is flowed to by pipeline spinning solution, is band below syringe needle
There are the tunica fibrosa receiver board of aluminium foil, setting Static Spinning voltage 24kv, fiber to receive distance 12cm, spinning speed 1.1mL/h, temperature
44 DEG C, montmorillonite enhanced polyacrylonitrile nano fibrous membrane is prepared.
(3) hydroxylamine hydrochloride for weighing 6.95g is dissolved in 100mL methanol/deionized water (V:V=4:1) in mixture, then
4g sodium hydroxides are added into solution, filtering removal precipitation obtains the hydroxylamine solution of a concentration of 1mol/L；By bath raio 1：40, claim
It takes the montmorillonite enhanced polyacrylonitrile nano fibrous membrane obtained in 2.5g steps (2) to be added in hydroxylamine solution, is in temperature
75 DEG C, magnetic agitation react 4 hours, successively use methanol, deionized water washing reaction product, drying, obtain montmorillonite enhancing
Type amidoxim modified polyacrylonitrile nano fibrous membrane.
Embodiment 3
(1) prepared by organo montmorillonite doping polyacrylonitrile nanofiber molding spinning solution：1.5g organo montmorillonites are weighed, are added
Entering to 100mLN, in N '-dimethyl formamide solution, the frequency that solution is put into ultrasonic wave in ultrasonic oscillator is 48kHz,
Acutely oscillation 3 hours make organic modification montmonrillonite be dispersed by supersonic oscillations stripping in N, N '-dimethyl formamide solution
Nano-lamellar structure；It weighs in the solution after oscillation is added in 12g polyacrylonitrile, magnetic agitation 10 hours obtains organo montmorillonite
It adulterates polyacrylonitrile nanofiber and is molded spinning solution.
(2) the obtained organo montmorillonite doping polyacrylonitrile nanofiber molding spinning solution of step (1) is packed into high pressure
In the mating micro propulsion pump of electrostatic spinning, the syringe needle with electrostatic high-pressure is flowed to by pipeline spinning solution, is band below syringe needle
There are the tunica fibrosa receiver board of aluminium foil, setting Static Spinning voltage 22kv, fiber to receive distance 11cm, spinning speed 0.9mL/h, temperature
32 DEG C, montmorillonite enhanced polyacrylonitrile nano fibrous membrane is prepared.
(3) hydroxylamine hydrochloride for weighing 6.95g is dissolved in 100mL methanol/deionized water (V:V=4:1) in mixture, then
4g sodium hydroxides are added into solution, filtering removal precipitation obtains the hydroxylamine solution of a concentration of 1mol/L；By bath raio 1：20, claim
It takes the montmorillonite enhanced polyacrylonitrile nano fibrous membrane obtained in 5.0g steps (2) to be added in hydroxylamine solution, is in temperature
63 DEG C, magnetic agitation react 4 hours, successively use methanol, deionized water washing reaction product, drying, obtain montmorillonite enhancing
Type amidoxim modified polyacrylonitrile nano fibrous membrane.
The structure, feature and effect of the present invention, the above institute are described in detail based on the embodiments shown in the drawings
Only presently preferred embodiments of the present invention is stated, but the present invention is not to limit practical range, every structure according to the present invention shown in drawing
Change made by thinking, or is revised as the equivalent embodiment of equivalent variations, when not going beyond the spirit of the description and the drawings,
It should all be within the scope of the present invention.
Claims (4)
1. a kind of enhanced amidoxim modified polyacrylonitrile nanofiber membrane preparation method of montmorillonite, which is characterized in that including with
Lower step：
(1) organo montmorillonite is dispersed in N by supersonic oscillations, in N '-dimethyl formamide solution, further into solution
Addition polymer poly acrylonitrile obtains organo montmorillonite doping polyacrylonitrile by intercalation stripping dispersion montmorillonite in the solution and receives
Rice fiberizing spinning solution；
(2) use high-voltage electrostatic spinning method, by step (1) obtained organo montmorillonite doping polyacrylonitrile nanofiber at
Nano fibrous membrane is made by high-voltage electrostatic spinning in type spinning solution, and drying is to get to montmorillonite enhanced polyacrylonitrile Nanowire
Tie up film；
(3) it uses hydroxylamine solution to carry out amidoxime to the montmorillonite enhanced polyacrylonitrile nano fibrous membrane obtained in step (2) to change
Property processing to get the enhanced amidoxim modified polyacrylonitrile nano fibrous membrane of montmorillonite.
2. the enhanced amidoxim modified polyacrylonitrile nanofiber membrane preparation method of montmorillonite according to claim 1,
It is characterized in that：Organo montmorillonite is the modified organic quaternary ammonium salt montmorillonite of octadecyltrimethylammonium chloride in step (1), is surpassed
The frequency of sound wave is 10kHz~50kHz, and duration of oscillation is 1~5 hour, by mass, organo montmorillonite a concentration of 0.1~
2%；By mass, polyacrylonitrile in entire solution a concentration of 5~20%, magnetic agitation 5~10 hours obtains described having
Machine montmorillonite adulterates polyacrylonitrile nanofiber and is molded spinning solution.
3. the enhanced amidoxim modified polyacrylonitrile nanofiber membrane preparation method of montmorillonite according to claim 1,
It is characterized in that：In step (2) Static Spinning voltage be 15~25kv, fiber receive distance be 5~15cm, spinning speed be 0.2~
1.2ml/h, spinning temperature are 25~45 DEG C, and drying temperature is 60~80 DEG C, and the time is 2~5 hours, obtain the montmorillonite and increase
Strong type polyacrylonitrile nanofiber film.
4. the enhanced amidoxim modified polyacrylonitrile nanofiber membrane preparation method of montmorillonite according to claim 1,
It is characterized in that：The preparation method of the enhanced amidoxim modified polyacrylonitrile nano fibrous membrane of montmorillonite is in the step (3), will
Hydroxylamine hydrochloride salt and sodium hydroxide in molar ratio 1:1 is dissolved in methanol solution, and filtering removal precipitation is configured to a concentration of 1mol/L
Hydroxylamine solution；By bath raio 1：10~1：50 add the montmorillonite enhanced polyacrylonitrile nano fibrous membrane obtained in step (2)
Enter into hydroxylamine solution, temperature be 60~80 DEG C, magnetic agitation react 2~5 hours, successively use methanol, deionization wash
Reaction product is washed, dries, finally obtains the enhanced amidoxim modified polyacrylonitrile nano fibrous membrane of montmorillonite.
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