CN110496652A - A kind of ion exchange resin and its preparation method and application - Google Patents
A kind of ion exchange resin and its preparation method and application Download PDFInfo
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- CN110496652A CN110496652A CN201910791510.8A CN201910791510A CN110496652A CN 110496652 A CN110496652 A CN 110496652A CN 201910791510 A CN201910791510 A CN 201910791510A CN 110496652 A CN110496652 A CN 110496652A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
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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
- D01D5/0015—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
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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
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/42—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising cyclic compounds containing one carbon-to-carbon double bond in the side chain as major constituent
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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
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
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- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
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Abstract
The present invention provides a kind of ion exchange resin and its preparation method and application, the ion exchange resin includes the electrostatic spinning fiber film with ion-exchange group, and the fibre diameter of the electrostatic spinning fiber film is 150-250nm；The electrostatic spinning fiber film is copolymer spinning film.The present invention controls the fibre diameter of ion exchange resin within the above range, the aperture of energy Effective Regulation ion exchange resin and specific surface area, and then promotes its ion-exchanging efficiency.Preparation method of the present invention uses copolymer spinning fluid, and spinning process is smooth easy, in conjunction with the spinning technology parameter of optimization, can continuously spin the superfine fibre that diameter is 150-250nm.
Description
Technical field
The invention belongs to separation membrane technical fields, and in particular to a kind of ion exchange resin and preparation method thereof and answer
With.
Background technique
Ion exchange resin is the high-molecular compound of a kind of reticular structure with functional group, it is by insoluble three
Exchangeable ion three of opposite charges are had on dimension space mesh skeleton, the functional group and functional group being connected on skeleton
Divide and constitutes.
Ion exchange resin is largely used to the removal of water intermediate ion, the preparation of deionized water is used in industry, at present tradition
Ion exchange resin use the method that is modified to polystyrene or polyacrylate particle to prepare, resulting ion
Exchanger resin, which is generally graininess, partial size and dimensional homogeneity, has a great impact to operation operation.The size one of resin particle
As within the scope of 0.3-1.2mm, it is most of between 0.4-0.6mm.
CN106243265A uses homogeneous wet chemistry method to synthesize partial size on the surface of inertia nucleus as 100-150 μm of crosslinking
Polystyrene Archon skeleton；Chloromethyl ether is added as benzene second original in chloromethylation reagents, with the crosslinked polystyrene Archon
Phenyl ring in alkene is reacted, and intermediate product A is obtained；The intermediate product A and the tertiary amine progress amination containing Long carbon chain is anti-
It answers, generates the strong-base anion-exchange resin that partial size is 180-280 μm.CN102641754A is prepared for using a step combined polymerization
A kind of weak-base anion-exchange resin of novel acrylic ester skeleton, steps are as follows: 1) preparation by deionized water, dispersing agent,
NaCl or CaCl2, water phase polymerization inhibitor methine orchid composition water phase；2) it prepares by function monomer, crosslinking agent and fat-soluble tune
Simultaneously initiator is added in the oil phase of section agent mixing composition；3) stirring, heating are reacted during the oil phase is added to the aqueous phase；4) it filters, wash
Wash, extract, dry after can be prepared by gel-type or macroporous type anion exchange resin.Simple process, acid, the variation of alkali conversion volume
It is smaller, and operate and be easy, is with short production cycle.
But the partial size of ion exchange resin obtained influences ion-exchange speed very big in above-mentioned two patent documents,
When granularity is big, running resistance is small, but specific surface area is small simultaneously, and ion-exchange speed is slack-off；Granularity is too small, large specific surface area,
Although ion-exchange speed becomes faster, running resistance is larger, and energy consumption is big.
Therefore, a kind of novel ion exchanger resin is developed, gets rid of ion exchange resin bead diameter and dimensional homogeneity to ion
The influence of exchange efficiency realizes that efficiently promoting the purpose of velocity of ion exchange is to face huge challenge at present.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of ion exchange resin and preparation method thereof and
It is copolymer spinning film using, the ion exchange resin, and a diameter of 150-250nm, by the electrostatic spinning membrane fiber
Diameter control effectively improves the specific surface area of static spinning membrane in above range, and then improves its ion-exchanging efficiency,
In, cation exchange resin is to Na+、K+、Ca2+Permoselectivity highest can achieve respectively 94% or more, 91% or more and
88% or more, anion exchange resin is to Cl-、NO3 -、SO4 2-Permoselectivity highest respectively be up to 92% or more, 88% with
It goes up and 85% or more.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of ion exchange resin, the ion exchange resin includes having ion exchange
The electrostatic spinning fiber film of group, the fibre diameter of the electrostatic spinning fiber film are 150-250nm, preferably 150-210nm, described
Electrostatic spinning fiber film is copolymer spinning film.
The fibre diameter of the electrostatic spinning fiber film be 150-250nm, such as can be 150nm, 160nm, 170nm,
180nm, 190nm, 200nm, 210nm, 220nm, 230nm, 240nm or 250nm etc..
Ion exchange resin of the present invention is copolymer spinning film, and its fibre diameter is thinner, is 150-250nm, when
The aperture of static spinning membrane is certain, and fibre diameter is thinner, then the porosity of the tunica fibrosa obtained is bigger, and specific surface area is bigger, because
This can effectively promote the ratio of static spinning membrane when present invention controls the static spinning membrane fibre diameter in thinner range
Its velocity of ion exchange is substantially improved in surface area.
Preferably, the first comonomer of the copolymer is styrene and/or acrylate；The second of the copolymer
Comonomer is the compound containing at least two double bonds.
Copolymer of the present invention is polymerize to obtain by the first comonomer and the second comonomer, second comonomer
For the compound containing at least two double bonds, this is in order to guarantee after the completion of above-mentioned polymerization reaction, on copolymer molecule chain still
It is subsequent tunica fibrosa after electrostatic spinning to be crosslinked there are double bond, improve the mechanical property and machine of copolymer spinning film
Tool intensity.
Preferably, second comonomer is in 1,3-butadiene, Isosorbide-5-Nitrae-pentadiene, hexadiene or divinylbenzene
Any one or at least two combination.
Preferably, second comonomer is the 5-10% of the first comonomer quality, such as can be 5%,
6%, 7%, 8%, 9% or 10% etc..
The present invention optimizes the mass ratio of first comonomer and the second comonomer, is to control copolymer spinning
Double bond quantity in film, that is, control the degree of cross linking of subsequent cross-linking reaction, and the copolymer spinning film guaranteed had both had certain
Mechanical strength can also be unlikely to excessively to cause amberplex excessively fine and close due to being crosslinked and influence its ion-exchanging efficiency.
Preferably, the average pore size of the electrostatic spinning fiber film be 10-300nm, such as can be 10nm, 20nm, 30nm,
40nm、50nm、60nm、70nm、80nm、90nm、100nm、110nm、120nm、130nm、140nm、150nm、160nm、
170nm、180nm、190nm、200nm、210nm、220nm、230nm、240nm、250nm、260nm、270nm、280nm、290nm
Or 300nm etc., preferably 50-250nm.
Preferably, the specific surface area of the electrostatic spinning fiber film is 10-200m2/ g, such as can be 10m2/g、20m2/g、
30m2/g、40m2/g、50m2/g、60m2/g、70m2/g、80m2/g、90m2/g、100m2/g、110m2/g、120m2/g、130m2/g、
140m2/g、150m2/g、160m2/g、170m2/g、180m2/g、190m2/ g or 200m2/ g etc., preferably 80-200m2/g。
The aperture of electrostatic spinning fiber film provided by the invention is moderate, both will not it is too small due to aperture and cause fluid resistance compared with
Greatly, specific surface area will not be caused too small since aperture is excessive and influences ion-exchanging efficiency, when preferably aperture of the invention is 50-
250nm, specific surface area 80-200m2When/g, while electrostatic spinning fiber film of the invention velocity of ion exchange with higher
Fluid resistance is smaller.
Second aspect, it is described the present invention provides a kind of preparation method of ion exchange resin as described in relation to the first aspect
Then preparation method is crosslinked, at functionalization the following steps are included: by the spinning solution progress electrostatic spinning comprising copolymer
Reason, obtains the ion exchange resin.
Spinning solution of the present invention uses copolymer spinning fluid, does not contain ionic group, spinning process is smooth easy to control, can
To spin diameter continuously as the superfine fibre of 150-250nm；Obtained superfine fibre is crosslinked again, reinforcing fiber film it is strong
Degree, is finally functionalized processing, makes film surface with cation or anionic group, has ion-exchange capacity, and function
The process of change can form hole in the fibre, also can further increase the specific surface area of tunica fibrosa, and ion-exchanging efficiency obtains
Further promoted.
It should be noted that, although the fibre of different-diameter can be obtained by adjusting electrospinning parameters in the prior art
Dimension, but due to influence factors such as polymer molecular weight, viscosity, spinning equipments, diameter is obtained in 150nm fiber below
It is difficult.
Preferably, the preparation method of the copolymer includes in bulk polymerization, polymerisation in solution, emulsion polymerization or suspension polymerisation
One kind or at least two combination.
It preferably, further include crosslinking initiator used in the spinning solution.
Preferably, the initiator is any in benzophenone, diphenylethan, alpha-hydroxyalkyl benzophenone or Michler's keton
It is a kind of or at least two combination.
Preferably, the initiator be copolymer quality 1-5wt%, such as can be 1wt%, 2wt%, 3wt%,
4wt% or 5wt% etc..
Preferably, the solid content of the spinning solution be 1-30wt%, such as can be 1wt%, 2wt%, 3wt%,
5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 25wt%, 29wt% or 30wt% etc..
Preferably, solvent used in the spinning solution is selected from acetone, butanone, n,N-Dimethylformamide (DMF), N, N- bis-
In methylacetamide (DMAc), chloroform, dimethylbenzene, toluene, carbon tetrachloride or isopropyl alkane any one or at least two group
It closes.
Preferably, the voltage of the electrostatic spinning be 10-50kV, such as can be 10kV, 15kV, 20kV, 25kV,
30kV, 36kV, 40kV, 42kV or 50kV etc..
Spray head and to receive the distance between object be 5-25cm, for example, can be 5cm, 8cm, 10cm, 11cm, 15cm, 18cm,
20cm, 22cm or 25cm etc..
The fltting speed of spinning solution be 0.5-5mL/h, such as can be 0.5mL/h, 1mL/h, 1.5mL/h, 2mL/h,
2.5mL/h, 3mL/h, 3.5mL/h, 3.8mL/h, 4mL/h, 4.5mL/h or 5mL/h etc..
The temperature of spinning is 15-60 DEG C, such as can be 15 DEG C, 18 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45
DEG C, 50 DEG C, 55 DEG C or 60 DEG C etc..
The relative humidity of spinning is 30-80%, for example, can be 30%, 32%, 35%, 40%, 46%, 50%, 60%,
70%, 75% or 80% etc..
Preferably, the mode of the crosslinking is using ultraviolet light.
Preferably, the reaction time of the crosslinking be 1-20min, such as can be 1min, 3min, 5min, 7min,
10min, 11min, 15min, 18min or 20min etc..
Preferably, the functionalization processing includes acidification or tertiary-aminated.
Preferably, the acidification is to be handled using the concentrated sulfuric acid, chlorosulfonic acid or concentrated nitric acid.
Preferably, it is described it is tertiary-aminated before, first by after crosslinking electrostatic spinning fiber film carry out chloromethyl ether processing.
Preferably, the preparation method comprises the following steps:
(1) copolymer and benzophenone of styrene and butadiene are added in solvent, stir 5h, obtains spinning solution；
(2) spinning solution for obtaining step (1) carries out electrostatic spinning, obtains electrostatic spinning fiber film, wherein electrostatic spinning
Voltage is 20kV, and the distance between spray head and reception object are 20cm, and the fltting speed of spinning solution is 1mL/h, and the temperature of spinning is
23 DEG C, the relative humidity of spinning is 40%；
(3) electrostatic spinning fiber film that step (2) obtains is irradiated under ultraviolet light after 10min and concentrated sulfuric acid progress sulfonation is added
Reaction, obtains cation exchange resin；
Or (3') step (3) is replaced with into step: the electrostatic spinning fiber film that step (2) obtains is irradiated under ultraviolet light
10min is added after chloromethyl ether is reacted and carries out tertiary-aminated reaction again, obtains anion exchange resin.
The third aspect, the present invention provides a kind of ion exchange resin as described in relation to the first aspect is net in Water warfare, air
Application in change or smoke filtration field.
Compared with the existing technology, the invention has the following advantages:
(1) ion exchange resin of the present invention is copolymer spinning film, and a diameter of 150-250nm will be described quiet
The fibre diameter of electrospun membrane is controlled in above range, can effectively promote the specific surface area of static spinning membrane, and then improve it
Ion-exchanging efficiency；
(2) preparation method of the present invention uses copolymer spinning fluid, does not contain ionic group, and spinning process is smooth easily-controllable
System can continuously spin the superfine fibre that diameter is 150-250nm in conjunction with the spinning technology parameter of optimization；The present invention will obtain
Electrospinning fibre is crosslinked, and enhances fiber film strength, the tensile strength of the ion exchange resin can reach 3.4MPa with
On, processing is then functionalized to it again, makes film surface with cation or anionic group, has ion-exchange capacity,
And functionalized process can form hole in the fibre, also can further increase the specific surface area of tunica fibrosa, ion exchange effect
Rate is further promoted；
(3) ion exchange resin of the present invention is obviously improved the efficiency of ion exchange, wherein cation exchange resin
To Na+、K+、Ca2+Permoselectivity highest can achieve 94% or more, 91% or more and 88% or more respectively, anion is handed over
Resin is changed to Cl-、NO3 -、SO4 2-Permoselectivity highest respectively be up to 92% or more, 88% or more and 85% or more.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
Present embodiments provide a kind of cation exchange resin and preparation method thereof
Wherein, the average fibre diameter of the cation exchange resin is 200nm.
The present embodiment ion exchange resin the preparation method is as follows:
(1) styrene and butadiene copolymer are obtained into copolymer, wherein butadiene is the 5wt% of styrene quality；By institute
It states copolymer and benzophenone is added in DMAc, stir 5h, be configured to the spinning solution that mass fraction is 10wt%, wherein hexichol
Ketone is the 2wt% of copolymer quality；
(2) spinning solution for obtaining step (1) carries out electrostatic spinning, obtains electrostatic spinning fiber film, wherein electrostatic spinning electricity
20kV, spinning distance 20cm, spinning fltting speed 1mL/h are pressed, 23 DEG C of spinning temperature, it is fine to obtain Static Spinning for relative humidity 40%
Tie up film；
(3) electrostatic spinning fiber film that step (2) obtains is irradiated into 10min under ultraviolet light, is then carried out using the concentrated sulfuric acid
Sulfonation processing, obtains cation exchange resin.
Embodiment 2
Present embodiments provide a kind of cation exchange resin and preparation method thereof
Wherein, the average fibre diameter of the cation exchange resin is 180nm.
The present embodiment ion exchange resin the preparation method is as follows:
(1) styrene and butadiene copolymer are obtained into copolymer, wherein butadiene is the 7wt% of styrene quality；By institute
It states copolymer and benzophenone is added in butanone, stir 6h, be configured to the spinning solution that mass fraction is 12wt%, wherein hexichol
Ketone is the 2wt% of copolymer quality；
(2) spinning solution for obtaining step (1) carries out electrostatic spinning, obtains electrostatic spinning fiber film, wherein electrostatic spinning electricity
15kV, spinning distance 23cm, spinning fltting speed 1.5mL/h are pressed, 25 DEG C of spinning temperature, relative humidity 45% obtains Static Spinning
Tunica fibrosa；
(3) electrostatic spinning fiber film that step (2) obtains is irradiated into 15min under ultraviolet light, is then carried out using chlorosulfonic acid
Sulfonation processing, obtains cation exchange resin.
Embodiment 3
Present embodiments provide a kind of anion exchange resin and preparation method thereof
Wherein, the average fibre diameter of the anion exchange resin is 230nm.
The present embodiment ion exchange resin the preparation method is as follows:
(1) styrene and butadiene copolymer are obtained into copolymer, wherein butadiene is the 8wt% of styrene quality；By institute
It states copolymer and benzophenone is added in butanone, stir 8h, be configured to the spinning solution that mass fraction is 15wt%, wherein hexichol
Ketone is the 2wt% of copolymer quality；
(2) spinning solution for obtaining step (1) carries out electrostatic spinning, obtains electrostatic spinning fiber film, wherein electrostatic spinning electricity
22kV, spinning distance 17cm, spinning fltting speed 2mL/h are pressed, 40 DEG C of spinning temperature, it is fine to obtain Static Spinning for relative humidity 37%
Tie up film；
(3) electrostatic spinning fiber film that step (2) obtains is irradiated into 12min under ultraviolet light, is then handled using chloromethyl ether
(Friedel-crafts reaction), is handled after processing with tertiary amine, obtains anion exchange resin.
Embodiment 4
Present embodiments provide a kind of anion exchange resin and preparation method thereof
Wherein, the average fibre diameter of the anion exchange resin is 170nm.
The present embodiment ion exchange resin the preparation method is as follows:
(1) styrene and butadiene copolymer are obtained into copolymer, wherein butadiene is the 6wt% of styrene quality；By institute
It states copolymer and benzophenone is added in chloroform, stir 7h, be configured to the spinning solution that mass fraction is 16wt%, wherein hexichol
Ketone is the 2wt% of copolymer quality；
(2) spinning solution for obtaining step (1) carries out electrostatic spinning, obtains electrostatic spinning fiber film, wherein electrostatic spinning electricity
25kV, spinning distance 25cm, spinning fltting speed 3mL/h are pressed, 50 DEG C of spinning temperature, it is fine to obtain Static Spinning for relative humidity 35%
Tie up film；
(3) electrostatic spinning fiber film that step (2) obtains is irradiated into 14min under ultraviolet light, is then handled using chloromethyl ether
(Friedel-crafts reaction), is handled after processing with tertiary amine, obtains anion exchange resin.
Embodiment 5
Present embodiments provide a kind of cation exchange resin and preparation method thereof
Wherein, the average fibre diameter of the cation exchange resin is 150nm.
The present embodiment ion exchange resin the preparation method is as follows:
(1) methyl acrylate and butadiene copolymer are obtained into copolymer, wherein butadiene is methyl acrylate quality
5wt%；The copolymer and benzophenone are added in DMAc, 6h is stirred, is configured to the spinning solution that mass fraction is 8wt%,
Wherein, benzophenone is the 2wt% of copolymer quality；
(2) spinning solution for obtaining step (1) carries out electrostatic spinning, obtains electrostatic spinning fiber film, wherein electrostatic spinning electricity
24kV, spinning distance 25cm, spinning fltting speed 2mL/h are pressed, 33 DEG C of spinning temperature, it is fine to obtain Static Spinning for relative humidity 45%
Tie up film；
(3) electrostatic spinning fiber film that step (2) obtains is irradiated into 12min under ultraviolet light, is then carried out using the concentrated sulfuric acid
Sulfonation processing, obtains cation exchange resin.
Embodiment 6
Present embodiments provide a kind of anion exchange resin and preparation method thereof
Wherein, the average fibre diameter of the anion exchange resin is 250nm.
The present embodiment ion exchange resin the preparation method is as follows:
(1) ethyl acrylate and butadiene copolymer are obtained into copolymer, wherein butadiene is ethyl acrylate quality
6wt%；The copolymer and benzophenone are added in chloroform, 6h is stirred, is configured to the spinning solution that mass fraction is 15wt%,
Wherein, benzophenone is the 2wt% of copolymer quality；
(2) spinning solution for obtaining step (1) carries out electrostatic spinning, obtains electrostatic spinning fiber film, wherein electrostatic spinning electricity
35kV, spinning distance 16cm, spinning fltting speed 5mL/h are pressed, 60 DEG C of spinning temperature, it is fine to obtain Static Spinning for relative humidity 70%
Tie up film；
(3) electrostatic spinning fiber film that step (2) obtains is irradiated into 18min under ultraviolet light, is then handled using chloromethyl ether
(Friedel-crafts reaction), is handled after processing with tertiary amine, obtains anion exchange resin.
Embodiment 7
Present embodiments provide a kind of anion exchange resin and preparation method thereof
Wherein, the average fibre diameter of the anion exchange resin is 210nm.
The present embodiment ion exchange resin the preparation method is as follows:
(1) styrene, ethyl acrylate and butadiene copolymer are obtained into copolymer, wherein butadiene is styrene and propylene
The 7wt% of acetoacetic ester gross mass；The copolymer and benzophenone are added in chloroform, stir 5h, being configured to mass fraction is
The spinning solution of 14wt%, wherein benzophenone is the 2wt% of copolymer quality；
(2) spinning solution for obtaining step (1) carries out electrostatic spinning, obtains electrostatic spinning fiber film, wherein electrostatic spinning electricity
33kV, spinning distance 22cm, spinning fltting speed 5mL/h are pressed, 50 DEG C of spinning temperature, it is fine to obtain Static Spinning for relative humidity 60%
Tie up film；
(3) electrostatic spinning fiber film that step (2) obtains is irradiated into 16min under ultraviolet light, is then handled using chloromethyl ether
(Friedel-crafts reaction), is handled after processing with tertiary amine, obtains anion exchange resin.
Embodiment 8
The difference from embodiment 1 is that keeping the second comonomer first total by the dosage for changing the second comonomer
10%, 3% (embodiment 9), 13% (embodiment 10) of polycondensation monomer quality.
Comparative example 1
This comparative example ion exchange resin is the cation exchange resin of commercial particulate shape Polystyrene, particle ruler
It is very little in 0.4-0.6mm.
Comparative example 2
This comparative example provides a kind of cation exchange resin and preparation method thereof, the difference from embodiment 1 is that, pass through
Modifying spinning distance is 12cm, and electrostatic spinning voltage is 15kV, cation exchange resin is prepared, average fibre diameter is
300nm。
Performance test
(1) tensile strength
Tensile strength is measured with tensile testing machine, the standard shape of test sample is dumbbell shape, and length 25mm stretches speed
Degree is 3mm/min；It takes 10 sample films to be tested, then takes its arithmetic mean of instantaneous value.
(2) permoselectivity
Cation exchange resin: when the temperature of solution is 25 DEG C in ion exchange resin two sides, in cation-exchange membrane
Two sides are injected separately into the same solution of various concentration, since concentration difference showing for zwitterion surplus occurs in film two sides respectively
As forming film potential in film two sides；Select NaCl, KCl, CaCl2It prepares after various concentration solution measures film potential and uses public affairs
Formula calculates Na+、K+、Ca2+Permoselectivity (P)；
Anion exchange resin: when the temperature of solution is 25 DEG C in ion exchange resin two sides, KCl, KNO are selected3、K2SO4
It prepares formula after various concentration solution measures film potential and calculates Cl-、NO3 -、SO4 2-Permoselectivity (P).
The results are shown in Table 1 for above-mentioned performance test:
Table 1
From embodiment and the result of performance test it is found that embodiment 1-10 obtained fibre diameter 150-250nm from
Sub-exchange resin, and its tensile strength can reach 3.4MPa or more.In addition, the cation exchange resin of embodiment 1,2 and 5
To Na+Permoselectivity can achieve 92% or more, to K+Permoselectivity can achieve 88% or more, to Ca2+Choosing
Selecting permeability can achieve 87% or more；The anion exchange resin of embodiment 3-4,6-7 is to Cl-Permoselectivity be also up to
88% or more, to NO3 -Permoselectivity be up to 84% or more, to SO4 2-Permoselectivity can also reach 81% or more.This
Illustrate that ion exchange resin of the present invention also has macroion permoselectivity while mechanical strength with higher.
Comparative example 1 and embodiment 9, when the content of the second comonomer is lower than the 5% of the first comonomer quality,
The tensile strength for the amberplex being prepared is substantially reduced, simultaneously because the first co-monomer content accordingly increases, In
It is subsequent it is functionalized during, the cation group quantity for introducing amberplex is increase accordingly, so that the ion that makes is handed over
Resin is changed for Na+、K+、Ca2+Permoselectivity have a degree of promotion.
Similarly, comparative example 1 and embodiment 10, when the content of the second comonomer is higher than the first comonomer quality
When 10%, the tensile strength for the amberplex being prepared is significantly improved, simultaneously because the first co-monomer content is corresponding
It reduces, during subsequent functionalized, the cation group quantity for introducing amberplex is accordingly reduced, hence for Na+、
K+、Ca2+Permoselectivity have a degree of decline.
Comparing embodiment 1 and comparative example 1 it is found that amberplex of the present invention to Na+、K+、Ca2+Selection percent of pass
Significantly larger than granular ion exchange resin, this illustrates that the ion-exchanging efficiency of amberplex of the present invention obtains substantially
Promotion.This is because the ion exchange resin large specific surface area that fiber is membranaceous, the solion contact area penetrated with selection
Increase, can be carried out sufficient ion exchange, efficiency improves.
Comparing embodiment 1 and comparative example 2 are as can be seen that the fibre diameter when ion exchange resin of the present invention is greater than
When 250nm, to Na+、K+、Ca2+Permoselectivity be decreased obviously.This is because when fibre diameter is more than 250nm, ion tree
The specific surface area of rouge declines, and ion exchange is insufficient, permoselectivity decline.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of ion exchange resin, which is characterized in that the ion exchange resin includes the electrostatic with ion-exchange group
Spinning fiber film, the fibre diameter of the electrostatic spinning fiber film are 150-250nm；
The electrostatic spinning fiber film is copolymer spinning film.
2. ion exchange resin according to claim 1, which is characterized in that the first comonomer of the copolymer is benzene
Ethylene and/or acrylate；Second comonomer of the copolymer is the compound containing at least two double bonds；
Preferably, second comonomer is any in 1,3-butadiene, Isosorbide-5-Nitrae-pentadiene, hexadiene or divinylbenzene
It is a kind of or at least two combination；
Preferably, second comonomer is the 5-10% of the first comonomer quality.
3. ion exchange resin according to claim 1 or 2, which is characterized in that the average hole of the electrostatic spinning fiber film
Diameter is 10-300nm, preferably 50-250nm.
4. ion exchange resin according to claim 1-3, which is characterized in that the ratio of the electrostatic spinning fiber film
Surface area is 10-200m2/ g, preferably 80-200m2/g。
5. a kind of preparation method of ion exchange resin according to claim 1-4, which is characterized in that the system
Then Preparation Method is crosslinked, functionalization processing the following steps are included: by the spinning solution progress electrostatic spinning comprising copolymer,
Obtain the ion exchange resin.
6. preparation method according to claim 5, which is characterized in that the preparation method of the copolymer includes that ontology is poly-
In conjunction, polymerisation in solution, emulsion polymerization or suspension polymerisation any one or at least two combination；
It preferably, further include crosslinking initiator used in the spinning solution；
Preferably, any one of the initiator in benzophenone, diphenylethan, alpha-hydroxyalkyl benzophenone or Michler's keton
Or at least two combination；
Preferably, the initiator is the 1-5wt% of the copolymer quality；
Preferably, the solid content of the spinning solution is 1-30wt%；
Preferably, solvent used in the spinning solution is selected from acetone, butanone, n,N-Dimethylformamide, N, N- dimethylacetamide
In amine, chloroform, dimethylbenzene, toluene, carbon tetrachloride or isopropyl alkane any one or at least two combination.
7. preparation method according to claim 5 or 6, which is characterized in that the voltage of the electrostatic spinning is 10-50kV,
The distance between spray head and reception object are 5-25cm, and the fltting speed of spinning solution is 0.5-5mL/h, and the temperature of spinning is 15-60
DEG C, the relative humidity of spinning is 30-80%.
8. according to the described in any item preparation methods of claim 5-7, which is characterized in that the mode of the crosslinking is using ultraviolet
Light irradiation；
Preferably, the reaction time of the crosslinking is 1-20min；
Preferably, the functionalization processing includes acidification or tertiary-aminated；
Preferably, the acidification is to be handled using the concentrated sulfuric acid, chlorosulfonic acid or concentrated nitric acid；
Preferably, it is described it is tertiary-aminated before, first the electrostatic spinning fiber film after crosslinking is handled using chloromethyl ether.
9. according to the described in any item preparation methods of claim 5-8, which is characterized in that the preparation method includes following step
It is rapid:
(1) copolymer and benzophenone of styrene and butadiene are added in solvent, stir 5h, obtains spinning solution；
(2) spinning solution for obtaining step (1) carries out electrostatic spinning, obtains electrostatic spinning fiber film, wherein the voltage of electrostatic spinning
For 20kV, the distance between spray head and reception object are 20cm, and the fltting speed of spinning solution is 1mL/h, and the temperature of spinning is 23 DEG C,
The relative humidity of spinning is 40%；
(3) addition concentrated sulfuric acid progress sulfonation is anti-after the electrostatic spinning fiber film that step (2) obtains being irradiated 10min under ultraviolet light
It answers, obtains cation exchange resin；
Or (3') step (3) is replaced with into step: the electrostatic spinning fiber film that step (2) obtains is irradiated into 10min under ultraviolet light,
It is added after chloromethyl ether is reacted and carries out tertiary-aminated reaction again, obtain anion exchange resin.
10. ion exchange resin according to claim 1-4 is in Water warfare, air cleaning or smoke filtration field
In application.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB797191A (en) * | 1954-10-07 | 1958-06-25 | Asahi Chemical Industry Compan | Matrix for ion exchange resins |
| JPH06329815A (en) * | 1993-05-17 | 1994-11-29 | Tokuyama Soda Co Ltd | Production of ion exchange membrane |
| WO2013092862A1 (en) * | 2011-12-22 | 2013-06-27 | Philipps-Universität Marburg | Chemically functionalized electrospun dispersion fibres for layer-by-layer coatings |
| US20140277572A1 (en) * | 2013-03-13 | 2014-09-18 | Tepha, Inc. | Ultrafine Electrospun Fibers of Poly-4-Hydroxybutyrate and Copolymers Thereof |
| CN104593895A (en) * | 2013-11-01 | 2015-05-06 | 林晓 | A functional fiber base material and a preparing method thereof |
| US20150328631A1 (en) * | 2014-05-13 | 2015-11-19 | Taiwan Textile Research Institute | Electrospinning Solution, Polyvinyl Alcohol Nanofibers and Ion-Exchange Membrane |
| CN105297287A (en) * | 2015-09-18 | 2016-02-03 | 东南大学 | Method for preparing cation exchange film through high-voltage static spinning |
| CN107287770A (en) * | 2017-06-08 | 2017-10-24 | 山东大学 | The method that method of electrostatic spinning prepares polyacid/polymer hybridisation nano fibrous membrane |
-
2019
- 2019-08-26 CN CN201910791510.8A patent/CN110496652A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB797191A (en) * | 1954-10-07 | 1958-06-25 | Asahi Chemical Industry Compan | Matrix for ion exchange resins |
| JPH06329815A (en) * | 1993-05-17 | 1994-11-29 | Tokuyama Soda Co Ltd | Production of ion exchange membrane |
| WO2013092862A1 (en) * | 2011-12-22 | 2013-06-27 | Philipps-Universität Marburg | Chemically functionalized electrospun dispersion fibres for layer-by-layer coatings |
| US20140277572A1 (en) * | 2013-03-13 | 2014-09-18 | Tepha, Inc. | Ultrafine Electrospun Fibers of Poly-4-Hydroxybutyrate and Copolymers Thereof |
| CN104593895A (en) * | 2013-11-01 | 2015-05-06 | 林晓 | A functional fiber base material and a preparing method thereof |
| US20150328631A1 (en) * | 2014-05-13 | 2015-11-19 | Taiwan Textile Research Institute | Electrospinning Solution, Polyvinyl Alcohol Nanofibers and Ion-Exchange Membrane |
| CN105297287A (en) * | 2015-09-18 | 2016-02-03 | 东南大学 | Method for preparing cation exchange film through high-voltage static spinning |
| CN107287770A (en) * | 2017-06-08 | 2017-10-24 | 山东大学 | The method that method of electrostatic spinning prepares polyacid/polymer hybridisation nano fibrous membrane |
Non-Patent Citations (3)
| Title |
|---|
| 李旭清等: "紫外光固化FEVE丙烯酸酯电纺超细纤维的制备研究", 《塑料工业》 * |
| 梅雪峰等: "丙烯酸酯压敏胶粘剂的紫外光交联技术研究", 《粘接》 * |
| 甄洪鹏等: "壳聚糖/聚乙烯醇共混超细纤维的制备及紫外光交联研究", 《高分子学报》 * |
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