CN108893797A - A kind of amidoxim polyacrylonitrile fibre and its preparation method and application - Google Patents
A kind of amidoxim polyacrylonitrile fibre and its preparation method and application Download PDFInfo
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- CN108893797A CN108893797A CN201810366921.8A CN201810366921A CN108893797A CN 108893797 A CN108893797 A CN 108893797A CN 201810366921 A CN201810366921 A CN 201810366921A CN 108893797 A CN108893797 A CN 108893797A
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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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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Abstract
The present invention provides a kind of preparation methods of amidoxim polyacrylonitrile fibre, including preparation polyacrylonitrile solution and the first organic solution, the first organic matter include the organic matter with hydroxyl and amino；The polyacrylonitrile solution and first organic solution are uniformly mixed, spinning solution is configured to, wherein the mass concentration of polyacrylonitrile described in the spinning solution is 8%-15%；The spinning solution is obtained into amidoxim polyacrylonitrile fibre in 40 DEG C -60 DEG C of at a temperature of progress electrostatic spinning；Or by the spinning solution be more than or equal to 20 DEG C and less than 40 DEG C at a temperature of carry out electrostatic spinning and then in 60 DEG C of -80 DEG C of vacuum drying obtain amidoxim polyacrylonitrile fibre.Preparation method provided by the invention is easy to operate, prepares amidoxim polyacrylonitrile fibre by controlling electrostatic spinning temperature, and amidoxim polyacrylonitrile fibre obtained has excellent adsorbing metal performance and reusability.
Description
Technical field
The present invention relates to polymeric material field, in particular to a kind of amidoxim polyacrylonitrile fibre and preparation method thereof
And application.
Background technique
With industrial development and the extensive use of noble metal, noble metal demand increasingly increases severely, just to the recycling of noble metal
Become particularly important.Meanwhile city domestic sewage and various mining wastewaters contain a large amount of heavy metal ion, pass through food chain
And biological concentration, it constitutes a serious threat to biology and human health.Therefore, it anticipates to the removal of heavy metal ions in sewage and recycling
Justice is great.Absorption method is a kind of metal adsorption method of economical and effective flexible operation simplicity generally acknowledged at present.It is most heavy in absorption method
What is wanted is exactly adsorbent.Wherein, polyacrylonitrile fibre material has minor diameter, bigger serface and high porosity, can be formed
Network of fibers film and prepare the advantages that cheap.Meanwhile with amidoxime group (H2N-C=N-OH) the polyacrylonitrile fibre modified
Material can preferably adsorbing metal, it is considered to be one of preferable adsorbent material.
In current research, amidoxim is carried out after having scholar that fiber is made in polyacrylonitrile by electrostatic spinning process
It is modified to obtain amidoxim polyacrylonitrile fibre；Some scholars first pass through carries out polyacrylonitrile progress amidoximization modification again
Amidoxim polyacrylonitrile fibre is made in spinning technique, but this mode causes modifying polyacrylonitrile after-contraction very serious,
Even brittle failure or powdered, lose the characteristic of fiber；And polyacrylonitrile carries out the viscosity generation of the spinning solution after amidoxim
Great changes influence the preparation of subsequent fiber.Therefore, a kind of above-mentioned preparation process disadvantage and easy to operate together with amine of avoiding is needed
Oximate polyacrylonitrile fibre preparation method.
Summary of the invention
In view of this, the present invention provides a kind of amidoxim polyacrylonitrile fibre preparation method, including prepare polypropylene
Nitrile solution and the first organic solution, the first organic matter includes the organic matter with hydroxyl and amino, and is mixed to form spinning solution,
Amidoxim polyacrylonitrile fibre is obtained in 40 DEG C -60 DEG C of at a temperature of progress electrostatic spinning；Or 20 DEG C will be more than or equal to
And less than 40 DEG C at a temperature of carry out electrostatic spinning and then obtaining amidoxim polyacrylonitrile in 60 DEG C of -80 DEG C of vacuum drying
Fiber.Preparation method provided by the invention is easy to operate, and the polyacrylonitrile fibre of amidoxim modification is directly prepared, and reduces work
Skill process, meanwhile, amidoxim polyacrylonitrile fibre obtained has excellent adsorbing metal and repeat performance.
In a first aspect, the present invention provides a kind of preparation methods of amidoxim polyacrylonitrile fibre, including：
Polyacrylonitrile and the first organic matter are dissolved in organic solvent respectively, are configured to polyacrylonitrile solution and first organic
Object solution, wherein first organic matter includes the organic matter with hydroxyl and amino；
The polyacrylonitrile solution and first organic solution are uniformly mixed, are configured to spinning solution, wherein described
The mass concentration of polyacrylonitrile described in spinning solution is 8%-15%；
The spinning solution is obtained into amidoxim polyacrylonitrile fibre in 40 DEG C -60 DEG C of at a temperature of progress electrostatic spinning；
Or by the spinning solution be more than or equal to 20 DEG C and less than 40 DEG C at a temperature of carry out electrostatic spinning and then in 60 DEG C -80
DEG C vacuum drying obtains amidoxim polyacrylonitrile fibre.
In the present invention, the mass concentration of polyacrylonitrile described in the spinning solution is 8%-15%.It is further alternative,
The mass concentration of polyacrylonitrile described in the spinning solution is 9%-14%.Specifically, polyacrylonitrile described in the spinning solution
Mass concentration can be, but not limited to be 9%, 10%, 11.5% or 13.7%.In the present invention, described in the spinning solution
When the mass concentration of polyacrylonitrile is 8%-15%, it just can guarantee that the viscosity of the spinning solution is appropriate for electrostatic spinning.
In the present invention, by the spinning solution 40 DEG C -60 DEG C at a temperature of carry out electrostatic spinning when, during the spinning process
The preparation of polyacrylonitrile fibre can be carried out, and carries out amidoxim simultaneously, it is poly- that amidoximization directly is made by electrostatic spinning
Dralon；By the spinning solution be more than or equal to 20 DEG C and less than 40 DEG C at a temperature of carry out electrostatic spinning when, need
It is dried in vacuo after electrostatic spinning at 60 DEG C -80 DEG C, can be prepared by amidoxim polyacrylonitrile fibre, at this time in electrostatic spinning
First organic matter blending in the process reacts in polyacrylonitrile fibre, but not with the group in polyacrylonitrile, when being placed in
When 60 DEG C of -80 DEG C of vacuum drying, amidoxim polyacrylonitrile fibre is made in the first organic matter and polyacrylonitrile fibre reaction.
It is further alternative, the spinning solution is carried out to electrostatic spinning at 45 DEG C -58 DEG C and obtains amidoxim polypropylene
Nitrile fiber.Specifically, can be, but not limited to as the spinning solution is carried out electrostatic spinning at 48 DEG C, 50 DEG C, 53 DEG C or 55 DEG C
Obtain amidoxim polyacrylonitrile fibre.
It is further alternative, the spinning solution is carried out to electrostatic spinning at 20 DEG C -33 DEG C and then in 62 DEG C -77 DEG C
Vacuum drying obtains amidoxim polyacrylonitrile fibre.Specifically, can be, but not limited to for by the spinning solution in 20 DEG C, 25
DEG C, carry out electrostatic spinning at 27 DEG C or 33 DEG C and then obtain amidoxim in 62 DEG C, 65 DEG C, 72 DEG C or 77 DEG C vacuum drying
Polyacrylonitrile fibre.
Optionally, the electrostatic spinning includes dry spinning, wet spinning or dry-wet spinning.
In the present invention, first organic matter includes the organic matter with hydroxyl and amino, i.e., described first organic matter
There is hydroxyl and amino simultaneously, that is to say, that first organic matter is that the organic of amidoxim can occur with polyacrylonitrile
Object.Optionally, first organic matter include azanol, hydroxylamine hydrochloride, sulfuric acid hydroxyurea, in 2- amino -3- pyridone at least
It is a kind of.
Optionally, the molar ratio of polyacrylonitrile described in the spinning solution and first organic matter is 1：(1-2).Into one
Step is optional, and the molar ratio of polyacrylonitrile described in the spinning solution and first organic matter is 1：(1-1.75).Specifically,
The molar ratio of polyacrylonitrile described in the spinning solution and first organic matter can be, but not limited to be 1：1,1：1.25,1：
1.5 or 1：1.75.
Optionally, the concentration of the first organic matter described in first organic solution is 10g/L-30g/L.Specifically,
The concentration of first organic matter described in first organic solution can be, but not limited to as 10g/L, 17g/L, 20g/L or 30g/
L。
Optionally, the molecular weight of the polyacrylonitrile is 8.5 × 104-15×104。
Optionally, the organic solvent includes dimethyl sulfoxide, n,N-Dimethylformamide and n,N-dimethylacetamide
At least one of.
Optionally, the process conditions of the electrostatic spinning are anode voltage 12kV-16kV, cathode voltage (- 3) kV- (- 2)
KV, 100 turns/min-120 of roller rotation rate turn/min, sample introduction speed 1mL/h-1.2mL/h, humidity 35%-60%.
Optionally, the spinning solution is greater than 0.35PaS, apparent tensile viscosity in 20 DEG C -60 DEG C of apparent shear viscosity
For greater than 105Pa·S。
Second aspect, the present invention provides amidoxim polypropylene made from a kind of preparation method as described in relation to the first aspect
The oximate rate of nitrile fiber, the amidoxim polyacrylonitrile fibre is greater than 30%.
Optionally, the oximate rate of the amidoxim polyacrylonitrile fibre is greater than 50%.
Wherein, the diameter of the amidoxim polyacrylonitrile fibre is 200nm-300nm, line density 1.01dtex-
1.44dtex, breaking strength 7.3cN/dtex-7.9cN/dtex, break-draw rate are 5%-30%.
Wherein, the amidoxim polyacrylonitrile fibre is in bending.
Wherein, the large amount of adsorption to metallic element of the amidoxim polyacrylonitrile fibre is in 2mol/g.Wherein, described
The adsorbance of the metallic element of amidoxim polyacrylonitrile fibre refers to every gram of amidoxim polyacrylonitrile fibre adsorbing metal member
The molal quantity of element.
The third aspect, the amidoxim polyacrylonitrile fibre that the present invention provides a kind of as described in second aspect is in ADSORPTION OF GOLD
Belong to the application in element.
In the present invention, it is described in adsorbing metal application can be, but not limited to for adsorbing metal compound, metal from
Application in son and/or metal simple-substance.Optionally, the application in adsorbing metal is included in sewage treatment, noble metal returns
The application of receipts.Specifically, can be, but not limited to be applied to for amidoxim polyacrylonitrile fibre to cobalt element, oxidation in solution
The absorption of iron, ferrous oxide, manganese oxide or silver element, cadmium ion and lead ion.
Optionally, the large amount of adsorption to metallic element of the amidoxim polyacrylonitrile fibre is in 2mol/g.
Beneficial effects of the present invention：
(1) preparation method of amidoxim polyacrylonitrile fibre provided by the invention is easy to operate, in electrostatic spinning process
In i.e. prepare polyacrylonitrile fibre, and simultaneously by polyacrylonitrile fibre carry out amidoxim, or again by vacuum drying be made together with
Amidoxime polyacrylonitrile fibre saves preparation cost and time, reproducible；
(2) amidoximization of amidoxim polyacrylonitrile fibre provided by the invention is sufficiently and uniform, has to metallic element
There is excellent absorption property, can reuse, performance is stablized, and is with a wide range of applications in terms of metallic element absorption.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.Specific embodiment described herein is only used to explain this
Invention, is not intended to limit the present invention.
Fig. 1 is that polyacrylonitrile made from amidoxim polyacrylonitrile fibre made from the embodiment of the present invention 1 and comparative example 1 is fine
The infrared spectrogram of dimension；
Fig. 2 is the electron-microscope scanning figure of amidoxim polyacrylonitrile fibre made from the embodiment of the present invention 1；
Fig. 3 is the electron-microscope scanning figure of polyacrylonitrile fibre made from comparative example 1；
Fig. 4 is the energy spectrum analysis figure after amidoxim polyacrylonitrile fibre adsorbing metal made from the embodiment of the present invention 1.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of preparation method of amidoxim polyacrylonitrile fibre, including：
Taking polyacrylonitrile, (molecular weight is 10 × 104) be dissolved in n,N-Dimethylformamide (DMF), 10h is stirred at room temperature,
Obtain transparent polyacrylonitrile solution.Hydroxylamine hydrochloride is dissolved in n,N-Dimethylformamide (DMF), after ultrasonic vibration 5min,
1h is stirred at room temperature, so that hydroxylamine hydrochloride is substantially dissolved in DMF, obtains hydroxylamine hydrochloride solution, wherein the concentration of hydroxylamine hydrochloride
For 10g/L.
Polyacrylonitrile solution and hydroxylamine hydrochloride solution are mixed, 5min is stirred at room temperature, so that two kinds of solution are sufficiently mixed
It is even, and through the bubble in ultrasonic vibration removal solution, obtain spinning solution, wherein the mass concentration of polyacrylonitrile is 10%, poly- third
The molar ratio of alkene nitrile and hydroxylamine hydrochloride is 1:1.
Spinning solution is placed in syringe, and is fixed on spinning machine, electrospinning parameters are set：Anode voltage 12kV,
Cathode voltage -2kV, 100 turns/min of roller rotation rate, sample introduction speed 1mL/h, humidity 35%, 20 DEG C of electrostatic spinning temperature, process is quiet
It is being dried in vacuo after Electrospun, wherein drying temperature is 80 DEG C, obtains amidoxim polyacrylonitrile fibre.Utilize fineness instrument
The line density for measuring amidoxim polyacrylonitrile fibre is 1.2dtex, measures amidoxim polyacrylonitrile fibre using strength tester
Breaking strength be 7.3cN/dtex, break-draw rate be 5%.Meanwhile amidoxim polyacrylonitrile fibre obtained being carried out
IR spectrum scanning and electron-microscope scanning, as a result as depicted in figs. 1 and 2.2245cm as seen from Figure 1-1It is strong to locate absorption band peak type
Strong is sharply the characteristic absorption peak of-CN, 920cm-1The peak that place occurs is the stretching vibration absworption peak of N-O, 1580cm-1Nearby go out
It is the stretching vibration of-C=N- key in amidoxime group (- C=N-OH) that now new absorption peak is corresponding.The appearance at features above peak
Show that amidoxim polyacrylonitrile fibre is made containing-C=N-OH in the fiber of the invention being prepared.It is swept by the Electronic Speculum of Fig. 2
It retouches and carries out analysis and find that the diameter range of amidoxim polyacrylonitrile fibre obtained is 200nm-300nm, fiber is in bending,
And surface smooth even has apparent fibre matting, greatly improves the bonding strength and overall performance of fiber.
Embodiment 2
A kind of preparation method of amidoxim polyacrylonitrile fibre, including：
Taking polyacrylonitrile, (molecular weight is 8 × 104) be dissolved in dimethyl sulfoxide (DMSO), 5h is stirred at room temperature, is obtained saturating
Bright polyacrylonitrile solution.Hydroxylamine hydrochloride is dissolved in dimethyl sulfoxide (DMSO), after ultrasonic vibration 10min, is stirred at room temperature
2h obtains hydroxylamine hydrochloride solution so that hydroxylamine hydrochloride is substantially dissolved in DMSO, and wherein the concentration of hydroxylamine hydrochloride is 30g/L.
Polyacrylonitrile solution and hydroxylamine hydrochloride solution are mixed, 10min is stirred at room temperature, so that two kinds of solution are sufficiently mixed
It is even, and through the bubble in ultrasonic vibration removal solution, obtain spinning solution, wherein the mass concentration of polyacrylonitrile is 8%, poly- third
The molar ratio of alkene nitrile and hydroxylamine hydrochloride is 1:2.
Spinning solution is placed in syringe, and is fixed on spinning machine, electrospinning parameters are set：Anode voltage 16kV,
Cathode voltage -3kV, 120 turns/min of roller rotation rate, sample introduction speed 1.2mL/h, humidity 60%, electrostatic spinning temperature 60 C carry out
Spinning obtains amidoxim polyacrylonitrile fibre.It is using the line density that fineness instrument measures amidoxim polyacrylonitrile fibre
1.3dtex, the breaking strength using strength tester measurement amidoxim polyacrylonitrile fibre is 7.5cN/dtex, and break-draw rate is
10%.
Embodiment 3
Taking polyacrylonitrile, (molecular weight is 15 × 104) be dissolved in n,N-dimethylacetamide, 3h is stirred at room temperature, is obtained saturating
Bright polyacrylonitrile solution.Hydroxylamine hydrochloride is dissolved in n,N-dimethylacetamide, after ultrasonic vibration 5min, is stirred at room temperature
1h obtains hydroxylamine hydrochloride solution, wherein hydroxylamine hydrochloride is dense so that hydroxylamine hydrochloride is substantially dissolved in n,N-dimethylacetamide
Degree is 20g/L.
Polyacrylonitrile solution and hydroxylamine hydrochloride solution are mixed, 15min is stirred at room temperature, so that two kinds of solution are sufficiently mixed
It is even, and through the bubble in ultrasonic vibration removal solution, obtain spinning solution, wherein the mass concentration of polyacrylonitrile is 15%, poly- third
The molar ratio of alkene nitrile and hydroxylamine hydrochloride is 1:1.25.
Spinning solution is placed in syringe, and is fixed on spinning machine, electrospinning parameters are set：Anode voltage 12kV,
Cathode voltage -2kV, 110 turns/min of roller rotation rate, sample introduction speed 1.2mL/h, humidity 45%, are passed through by 30 DEG C of electrostatic spinning temperature
It is being dried in vacuo after electrostatic spinning, wherein drying temperature is 60 DEG C, obtains amidoxim polyacrylonitrile fibre.Utilize fineness
The line density that instrument measures amidoxim polyacrylonitrile fibre is 1.1dtex, fine using strength tester measurement amidoxim polyacrylonitrile
The breaking strength of dimension is 7.8cN/dtex, and break-draw rate is 25%.
Comparative example 1
A kind of preparation method of polyacrylonitrile fibre, including：
Taking polyacrylonitrile, (molecular weight is 10 × 104) be dissolved in n,N-Dimethylformamide (DMF), 10h is stirred at room temperature,
Obtain transparent polyacrylonitrile solution, wherein the mass concentration of polyacrylonitrile is 10%.Polyacrylonitrile solution is placed in syringe
In, and be fixed on spinning machine, electrospinning parameters are set：Anode voltage 12kV, cathode voltage -2kV, 100 turns of roller rotation rate/
Min, sample introduction speed 1mL/h, humidity 35%, carry out spinning, obtain polyacrylonitrile fibre by 20 DEG C of electrostatic spinning temperature.It will be made
Polyacrylonitrile fibre carry out IR spectrum scanning and electron-microscope scanning, as a result as shown in figures 1 and 3.It will be seen from figure 1 that right
It is polyacrylonitrile fibre made from ratio 1, the polyacrylonitrile fibre with amidoxime group modification is made in embodiment 1.From Fig. 3 Electronic Speculum
Scanning result analysis finds that the diameter of polyacrylonitrile fibre prepared by comparative example 1 is 220nm-295nm, and fiber is linearly, does not have
There is bending, and there is no fibre matting.
In order to prove beneficial effects of the present invention, following effect example is carried out：
Effect example 1
Oxidation cobalt nano-particle is placed in aqueous solution, mixing is sufficiently stirred, the amidoxim that embodiment 1 is prepared
Polyacrylonitrile fibre is placed in one, and impregnates 6h, and every the content of cobalt element in 1h sampling and testing solution.By amidoxim after 6h
Change polyacrylonitrile fibre to take out, and using freeze dryer it is dry after, using scanning electron microscope and energy disperse spectroscopy detect it is dry after
The case where amidoxim polyacrylonitrile fibre pattern and fiber surface absorption cobalt element.As shown in figure 4, the cobalt in energy-spectrum scanning
Element detection is to two peaks, and the quality accounting for being detected cobalt element is 71.39%, and the quality accounting of carbon is 2.52%, oxygen
The quality accounting of element is 26.09%, it was demonstrated that there are cobalt ions to be adsorbed in amidoxim polyacrylonitrile fibre in solution,
And oxidation cobalt nano-particle is also adsorbed in amidoxim polyacrylonitrile fibre known to a large amount of oxygen elements detected, is shown
Amidoxim polyacrylonitrile fibre prepared by the present invention in solution cobalt ions and oxidation cobalt nano-particle all have preferably
Adsorption effect.
Effect example 2
Ferric oxide nanometer particle is placed in aqueous solution, mixing is sufficiently stirred, the amidoxim that embodiment 1 is prepared
Polyacrylonitrile fibre is placed in one, and impregnates 6h, and every the content of ferro element in 1h sampling and testing solution.By amidoxim after 6h
Change polyacrylonitrile fibre to take out, and using freeze dryer it is dry after, using scanning electron microscope and energy disperse spectroscopy detect it is dry after
The case where amidoxim polyacrylonitrile fibre pattern and fiber surface absorption ferro element.Fibre is can be found that from energy-spectrum scanning result
Dimension table face almost all is oxidized iron nano-particle and is covered, and has also adsorbed the iron ion of a small amount of dissociation simultaneously, shows this hair
The amidoxim polyacrylonitrile fibre of bright preparation has preferable adsorption effect to iron ion and ferric oxide nanometer particle.
Effect example 3
Ferrous oxide nano particle is placed in aqueous solution, mixing is sufficiently stirred, the amidoxim that embodiment 1 is prepared
Change polyacrylonitrile fibre to be placed in one immersion, and impregnates 6h, and every the content of 1h sampling and testing solution Central Asia ferro element.After 6h
Amidoxim polyacrylonitrile fibre is taken out, and after utilization freeze dryer drying, scanning electron microscope and energy disperse spectroscopy is utilized to detect
The case where amidoxim polyacrylonitrile fibre pattern and fiber surface after drying adsorb ferrous element.From energy-spectrum scanning result
It is covered it can be found that fiber surface almost all is oxidized ferrous iron nanometer particle, and has also adsorbed the ferrous iron of a small amount of dissociation simultaneously
Ion shows that amidoxim polyacrylonitrile fibre prepared by the present invention has preferably ferrous ion and ferrous oxide nano particle
Adsorption effect.
Effect example 4
Manganese oxide nano granule is placed in aqueous solution, mixing is sufficiently stirred, the amidoxim that embodiment 1 is prepared
Polyacrylonitrile fibre is placed in one, and impregnates 6h, and every the content of manganese element in 1h sampling and testing solution.By amidoxim after 6h
Change polyacrylonitrile fibre to take out, and using freeze dryer it is dry after, using scanning electron microscope and energy disperse spectroscopy detect it is dry after
The case where amidoxim polyacrylonitrile fibre pattern and fiber surface absorption manganese element.Fibre is can be found that from energy-spectrum scanning result
Dimension table face almost all is oxidized manganese nano particle and is covered, and has also adsorbed the manganese ion of a small amount of dissociation simultaneously, shows this hair
The amidoxim polyacrylonitrile fibre of bright preparation has preferable adsorption effect to manganese ion and manganese oxide nano granule.
Therefore, the result based on said effect embodiment, it can be seen that amidoxim polyacrylonitrile provided by the invention is fine
Amidoxim polyacrylonitrile fibre made from the preparation method of dimension all has good suction to metal ion and metallic compound
Attached effect.
The above is a preferred embodiment of the present invention, and but it cannot be understood as to the invention patent range
Limitation.It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, also
Several improvements and modifications can be made, these modifications and embellishments are also considered to be within the scope of the present invention.
Claims (10)
1. a kind of preparation method of amidoxim polyacrylonitrile fibre, which is characterized in that including：
Polyacrylonitrile and the first organic matter are dissolved in organic solvent respectively, polyacrylonitrile solution is configured to and the first organic matter is molten
Liquid, first organic matter include the organic matter with hydroxyl and amino；
The polyacrylonitrile solution and first organic solution are uniformly mixed, are configured to spinning solution, in the spinning solution
The mass concentration of the polyacrylonitrile is 8%-15%；
The spinning solution is obtained into amidoxim polyacrylonitrile fibre in 40 DEG C -60 DEG C of at a temperature of progress electrostatic spinning；Or
By the spinning solution be more than or equal to 20 DEG C and less than 40 DEG C at a temperature of carry out electrostatic spinning and then in 60 DEG C -80 DEG C it is true
Sky is dried to obtain amidoxim polyacrylonitrile fibre.
2. the preparation method of amidoxim polyacrylonitrile fibre as described in claim 1, which is characterized in that in the spinning solution
The molar ratio of the polyacrylonitrile and first organic matter is 1：(1-2).
3. the preparation method of amidoxim polyacrylonitrile fibre as described in claim 1, which is characterized in that described first is organic
The concentration of first organic matter described in object solution is 10g/L-30g/L.
4. the preparation method of amidoxim polyacrylonitrile fibre as described in claim 1, which is characterized in that the polyacrylonitrile
Molecular weight be 8.5 × 104-15×104, the organic solvent includes dimethyl sulfoxide, n,N-Dimethylformamide and N, N- bis-
At least one of methylacetamide.
5. the preparation method of amidoxim polyacrylonitrile fibre as described in claim 1, which is characterized in that the electrostatic spinning
Process conditions be anode voltage 12kV-16kV, cathode voltage (- 3) kV- (- 2) kV, 100 turns/min-120 of roller rotation rate turn/
Min, sample introduction speed 1mL/h-1.2mL/h, humidity 35%-60%.
6. the preparation method of amidoxim polyacrylonitrile fibre as described in claim 1, which is characterized in that the spinning solution exists
20 DEG C -60 DEG C of apparent shear viscosity is greater than 0.35PaS, and apparent tensile viscosity is greater than 105Pa·S。
7. a kind of amidoxim polyacrylonitrile fibre, feature as made from preparation method described in any one of claims 1-6
It is, the oximate rate of the amidoxim polyacrylonitrile fibre is greater than 30%.
8. amidoxim polyacrylonitrile fibre as claimed in claim 7, which is characterized in that the amidoxim polyacrylonitrile is fine
The diameter of dimension is 200nm-300nm, line density 1.01dtex-1.44dtex, breaking strength 7.3cN/dtex-7.9cN/
Dtex, break-draw rate are 5%-30%.
9. a kind of such as described in any item amidoxim polyacrylonitrile fibre the answering in adsorbing metal element of claim 7-8
With.
10. application of the amidoxim polyacrylonitrile fibre as claimed in claim 9 in adsorbing metal element, feature exist
In the amidoxim polyacrylonitrile fibre is to the large amount of adsorption of metallic element in 2mol/g.
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| CN111118884A (en) * | 2019-12-27 | 2020-05-08 | 北京化工大学 | Amidoximated polyacrylonitrile fiber and preparation method and application thereof |
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| CN113231038B (en) * | 2021-04-09 | 2022-04-12 | 哈尔滨工程大学 | Braided type adsorption material for extracting uranium from seawater and flexible regulation and control preparation method thereof |
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