CN108530566A - A kind of water solubility amidoxim polyacrylonitrile solution and preparation method thereof - Google Patents
A kind of water solubility amidoxim polyacrylonitrile solution and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of water-soluble amidoxim polyacrylonitrile solutions and preparation method thereof, include the following steps：Amidoxim polyacrylonitrile organic solution will be obtained after polyacrylonitrile in organic solvent amidoxim modification；Certain density amidoxim polyacrylonitrile organic solution is dissolved with certain density strong alkali aqueous solution under condition of heating and stirring, the amidoxim polyacrylonitrile of script water-insoluble can be converted into water-soluble amidoxim polyacrylonitrile, obtained homogeneous mixed solution can be diluted to required concentration with water with arbitrary proportion.Using a kind of water-soluble modified method of amidoxim polyacrylonitrile provided by the present invention, mild condition, process are easy, and obtained water solubility amidoxim polyacrylonitrile can easily co-blended prepares corresponding composite material in aqueous solution with the hydrophilies such as hydrogel or water-soluble substances.The invention is greatly expanded synthesis and processing method and the application range of amidoxim polyacrylonitrile.
Description
Technical field
Field more particularly to a kind of water-soluble amidoxim polyacrylonitrile are prepared and are modified the present invention relates to high molecular material
Solution and preparation method thereof.
Background technology
Amidoxime compound with its chelating ability outstanding to metal ion make its heavy metal ion extraction recycling and
The fields such as the purified treatment containing heavy metal containing sewage have obtained good application, have many document report amidoxime compounds at present
Application in this respect, especially the application of extraction uranium is more extensive in the seawater.It is by the nitrogen in amidoxim functional group
It is coordinated to form complex compound with oxygen groups and uranyl radical ion, to make uranyl ion from high salinity and in the seawater containing complicated ingredient
Directly extraction is separated.Amidoxime group can be linked into different bases as a functional group by different chemical methodes
Ideal adsorption and separation material is obtained in matter.According to the difference of matrix, which can be roughly divided into two types：Monomer and polymer.Together with amine
The processing method of oxime material：1. polyacrylonitrile fibre (acrylic fibers) directly amidoxime is modified to obtain；2. containing propylene nitrile functionality
Amidoxime modification, which is done, on the material of (or polyacrylonitrile segment) obtains the functional material containing amidoxime group；3. using poly- third
Alkene nitrile raw material in organic solvent (such as DMF, DMSO, DMAC etc.) with azanol reaction carry out amidoxim processing, to obtain together with
Amidoxime polyacrylonitrile organic solution is further processed, and such as spinning obtains amidoxim polyacrylonitrile material.But by
In polyacrylonitrile and amidoxim polyacrylonitrile itself be water-insoluble macromolecule, so its solution is modified and is processed all only
It can carry out in organic solvent, and to expand the application of the high molecular material, such as amidoxime group hydrogel, if there is method energy
So that amidoxim polyacrylonitrile is fully dissolved in aqueous solution, and exist at homogeneous stability, then will greatly extend amidoxim
The preparation of polyacrylonitrile composite material and processing method and technique, especially amidoxim polyacrylonitrile and hydrogel compound system
Preparation and process.
Invention content
In view of this, the present invention provides a kind of water-soluble modified preparation method for amidoxim polyacrylonitrile, solution
Amidoxim polyacrylonitrile problem not soluble in water in existing research and the technology of having determined；Solves amidoxim in existing research and technology
Polyacrylonitrile is difficult to and the uniform compound problem of hydrogel material；Amidoxim polyacrylonitrile is greatly expanded in aqueous environment
Under preparations and the manufacturing method and technique such as modification, compound, molding, it is poly- that the method for the present invention obtains a kind of water-soluble amidoximization
Acrylonitrile solution.
The technical proposal of the invention is realized in this way：
A kind of preparation method of water solubility amidoxim polyacrylonitrile solution, includes the following steps：
(1) by the processing of polyacrylonitrile amidoximization, amidoxim polyacrylonitrile organic solution is obtained；
(2) amidoxim polyacrylonitrile organic solution and strong alkali aqueous solution heating stirring are obtained water-soluble to dissolving
Amidoxim polyacrylonitrile solution.
Further：It in the step (1), calculates by weight, 15~45 parts of hydroxylamine hydrochlorides is added to containing 100 parts
In n,N-Dimethylformamide or dimethyl sulfoxide (DMSO) or the container of n,N-dimethylacetamide, stir to being completely dissolved, then
5~30 parts of alkali solid powder are added, room temperature is vigorously stirred, and 10~50 parts of polyacrylonitrile raw material powders is then added, after sealing
It is reacted under 60~90 DEG C of constant temperatures, high speed centrifugation after cooling collects supernatant, it is organic to obtain amidoxim polyacrylonitrile afterwards
Solution.
Further：In the step (1), alkali solid powder is sodium hydroxide, sodium carbonate, potassium hydroxide or bicarbonate
Sodium.
Further：In the step (1), reacted 6~48 hours under 60~90 DEG C of constant temperatures after sealing.
Further：In the step (1), with rotating speed 10000~30000r/min high speed centrifugations after cooling.
Further：In the step (2), by isometric amidoxim polyacrylonitrile organic solution and strong alkali aqueous solution
For heating stirring to dissolving, the mass concentration of amidoxim polyacrylonitrile organic solution is≤10%；Strong alkali aqueous solution it is mole dense
Degree is 10~1000mM.
Further：In the step (2), the highly basic used is sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethyl hydrogen
One in amine-oxides, tetraethyl ammonium hydroxide, methyl triethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide
Kind is several.
Further：In the step (2), heating temperature range is 50~100 DEG C.
Further：In the step (2), mixing time is 0.5~30 minute.
The present invention also proposes a kind of water-soluble amidoxim polyacrylonitrile solution, and amidoxim polypropylene is used for according to above-mentioned
The water-soluble modified preparation method of nitrile is prepared.
Compared with prior art, the beneficial effects of the invention are as follows：
The script amidoxim polyacrylonitrile immiscible with water is converted into water-soluble amidoxim polyacrylonitrile solution,
Obtained amidoxim polyacrylonitrile is organic-and water mixed solution can be diluted to required concentration using water with arbitrary proportion, and can
To be mixed with arbitrary proportion with other water-soluble Polymer Solutions (such as hydrogel precursor), amidoxim function is further prepared
Change the composite materials such as hydrogel.
Description of the drawings
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, the accompanying drawings in the following description is only the preferred embodiment of the present invention, for
For those of ordinary skill in the art, without having to pay creative labor, it can also be obtained according to these attached drawings
His attached drawing.
Fig. 1 is obtained the photo of product by embodiment 1.From photo it is found that solution is in homogeneous, limpid pellucidity, explanation
Polymer is dissolved completely in mixed solution.
Fig. 2 is obtained the photo of product by embodiment 2.From photo it is found that solution is in homogeneous, limpid pellucidity, explanation
Polymer is dissolved completely in mixed solution.
Fig. 3 is obtained the sodium alginate aqueous solution mixed production in equal volume of product and 2.5% mass concentration by embodiment 2
Object photo.From photo it is found that solution is in homogeneous, limpid pellucidity, illustrate that polymer is dissolved completely in mixed solution.
Fig. 4 is obtained the photo of product by embodiment 3.From photo it is found that solution is in homogeneous, limpid pellucidity, explanation
Polymer is dissolved completely in mixed solution.
Fig. 5 obtains product by embodiment 3 and water dilutes the photo of product after 10 times.From photo it is found that solution in it is homogeneous,
Limpid pellucidity illustrates that polymer is dissolved completely in mixed solution.
Fig. 6 is obtained the photo of product by comparative example 1.From photo it is found that solution is in heterogeneous, cloudy state, illustrate poly-
Closing object can not be dissolved in mixed solution and be precipitated.
Fig. 7 is obtained the photo of product by comparative example 2.From photo it is found that solution is in heterogeneous, cloudy state, illustrate poly-
Closing object can not be dissolved in mixed solution and be precipitated.
Fig. 8 is obtained the photo of product by comparative example 3.From photo it is found that solution is in heterogeneous, cloudy state, illustrate poly-
Closing object can not be dissolved in mixed solution and be precipitated.
Fig. 9 is obtained the photo of product by comparative example 4.From photo it is found that solution is in heterogeneous, cloudy state, illustrate poly-
Closing object can not be dissolved in mixed solution and be precipitated.
Specific implementation mode
In order to be best understood from the technology of the present invention content, be provided below specific embodiment, and in conjunction with attached drawing to the present invention do into
The explanation of one step.
A kind of preparation method of water solubility amidoxim polyacrylonitrile solution, it is characterised in that：Include the following steps：(1)
By the processing of polyacrylonitrile amidoximization, amidoxim polyacrylonitrile organic solution is obtained；(2) amidoxim polyacrylonitrile is organic
Solution to dissolving, that is, obtains water-soluble amidoxim polyacrylonitrile with strong alkali aqueous solution heating stirring.
Specifically, in the step (1), calculate by weight, 15~45 parts of hydroxylamine hydrochlorides be added to containing 100 parts of N,
In dinethylformamide or dimethyl sulfoxide (DMSO) or the container of n,N-dimethylacetamide, stirs to being completely dissolved, then add
Enter 5~30 parts of alkali solid powder, preferably room temperature is vigorously stirred 0.5~2 hour, and 10~50 parts of polyacrylonitrile raw materials are then added
Powder reacts after sealing under 60~90 DEG C of constant temperatures, and high speed centrifugation after cooling collects supernatant, obtains amidoxim afterwards
Polyacrylonitrile organic solution.In the step (2), by amidoxim polyacrylonitrile organic solution and strong alkali aqueous solution heating stirring
To dissolving, preferably, amidoxim polyacrylonitrile organic solution is equal with strong alkali aqueous solution volume, and amidoxim polyacrylonitrile has
The mass concentration of machine solution is≤10%；The molar concentration of strong alkali aqueous solution is 10~1000mM, and heating temperature range is preferably
50~100 DEG C, mixing time is preferably 0.5~30 minute.
Embodiment 1
A kind of water-soluble amidoxim polyacrylonitrile solution, preparation method includes the following steps：
(1) by the processing of polyacrylonitrile amidoximization, amidoxim polyacrylonitrile organic solution is obtained；
It is embodied as, 15g hydroxylamine hydrochlorides is added in the container of dimethyl sulfoxide (DMSO) containing 100g (DMSO), magnetic agitation
To being completely dissolved, 5g sodium hydroxides are then added, room temperature is vigorously stirred 0.5 hour, and 10g polyacrylonitrile raw material powder is then added
End is reacted 6 hours after sealing under 60 DEG C of constant temperatures, it is cooling after with rotating speed 10000r/min high speed centrifugations 3 times, it is rear to collect
Clear liquid obtains amidoxim polyacrylonitrile organic solution.
(2) isometric amidoxim polyacrylonitrile organic solution and sodium hydrate aqueous solution heating stirring are extremely dissolved；
It is embodied as, heating temperature is 50 DEG C, and mixing time is 0.5 minute, amidoxim polyacrylonitrile organic solution
Mass concentration be 0.5%；The molar concentration of sodium hydrate aqueous solution is 10mM, that is, obtains water-soluble amidoxim polypropylene
Nitrile solution.The results are shown in Figure 1, it may be clearly seen that, amidoxim polyacrylonitrile mixes molten in alkaline DMSO/ water from photo
It is in limpid transparent, homogeneous dissolved state in liquid.Illustrate that amidoxim polyacrylonitrile has been completely transformed into water-soluble polymer.
Herein it should be noted that mass concentration refers to that the quality of solute accounts for the percentage of complete soln quality.Mole
Concentration refers to the molal quantity of contained solute in 1 liter of solution.
Embodiment 2
A kind of water-soluble amidoxim polyacrylonitrile solution, preparation method includes the following steps：
(1) by the processing of polyacrylonitrile amidoximization, amidoxim polyacrylonitrile organic solution is obtained；
It is embodied as, 30g hydroxylamine hydrochlorides is added in the container of n,N-Dimethylformamide containing 100g (DMF), magnetic
Power is stirred to being completely dissolved, and 15g sodium hydroxides are then added, and room temperature is vigorously stirred 1 hour, and it is former that 30g polyacrylonitrile is then added
Feed powder end, react 24 hours after sealing under 80 DEG C of constant temperatures, with rotating speed 20000r/min high speed centrifugations 2 times after cooling down, after
Supernatant is collected, amidoxim polyacrylonitrile organic solution is obtained.
(2) isometric amidoxim polyacrylonitrile organic solution and sodium hydrate aqueous solution heating stirring are extremely dissolved,
Wherein, heating temperature is 100 DEG C, and mixing time is 30 minutes.The mass concentration of amidoxim polyacrylonitrile organic solution is
5%；The molar concentration of sodium hydrate aqueous solution is 500mM, that is, obtains water-soluble amidoxim polyacrylonitrile solution.As a result such as
Shown in Fig. 2, it may be clearly seen that, amidoxim polyacrylonitrile is in alkaline DMF/ water mixed solutions in limpid from photo
Bright, homogeneous dissolved state.Illustrate that amidoxim polyacrylonitrile has been completely transformed into water-soluble polymer.
(3) the DMF/ water mixed solutions of the amidoxim polyacrylonitrile by this after water-soluble modified (contain 2.5% mass concentration
Amidoxim polyacrylonitrile) mixed in equal volume with the sodium alginate aqueous solution of 2.5% mass concentration, the results are shown in Figure 3, from
It may be clearly seen that, mixed solution is in limpid transparent, homogeneous dissolved state in photo.Illustrate in solution at this time polymer (together with
Amidoxime polyacrylonitrile and sodium alginate) still keep fabulous water solubility.Experiment it has also been found that, it is water-soluble modified after amidoxim
Polyacrylonitrile solution can be miscible with the sodium alginate soln of arbitrary proportion and any concentration and keeps homogeneous dissolved state.
Embodiment 3
A kind of water-soluble amidoxim polyacrylonitrile solution, preparation method includes the following steps：
(1) by the processing of polyacrylonitrile amidoximization, amidoxim polyacrylonitrile organic solution is obtained；
It is embodied as, 45g hydroxylamine hydrochlorides is added in the container of n,N-dimethylacetamide containing 100g (DMAC),
Then 30g powdered sodium carbonates are added to being completely dissolved in magnetic agitation, room temperature is vigorously stirred 2 hours, and 50g polypropylene is then added
Nitrile raw material powder reacts 48 hours after sealing under 90 DEG C of constant temperatures, with rotating speed 30000r/min high speed centrifugations 1 after cooling
It is secondary, supernatant is collected afterwards, obtains amidoxim polyacrylonitrile organic solution.
(2) isometric amidoxim polyacrylonitrile organic solution and potassium hydroxide aqueous solution heating stirring are extremely dissolved,
Wherein, heating temperature is 80 DEG C, and mixing time is 15 minutes.The mass concentration of amidoxim polyacrylonitrile organic solution is
10%；The molar concentration of potassium hydroxide aqueous solution is 1000mM, that is, obtains water-soluble amidoxim polyacrylonitrile.As a result as schemed
Shown in 4, from photo it may be clearly seen that, even if amidoxim polyacrylonitrile is in alkaline DMAC/ water mixed solutions at this time
Mass concentration has reached 5%, which is in still limpid transparent, homogeneous dissolved state.Illustrate that amidoximization is poly- at this time
Acrylonitrile has been completely transformed into water-soluble polymer.
(3) the DMAC/ water mixed solutions of the 5% amidoxim polyacrylonitrile by this after water-soluble modified dilute 10 with pure water
Times, the results are shown in Figure 5, and mixed solution is in still limpid transparent, homogeneous dissolved state.Illustrate amidoxim polyacrylonitrile at this time
Still maintain extraordinary water solubility.Experiment it has also been found that, amidoxim polyacrylonitrile solution after this is water-soluble modified can be
It is diluted with arbitrary proportion in aqueous solution, without polymer Precipitation phenomenon occurs.
In above-described embodiment, in the step (2), the highly basic that uses can be sodium hydroxide, potassium hydroxide, sodium carbonate,
Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, methyl triethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide
One or more of ammonium.
Comparative example 1
For intuitively comparative illustration the content of present invention, following comparative example is done, difference lies in steps with embodiment 1
(2) in, isometric amidoxim polyacrylonitrile organic solution is sufficiently mixed with pure water solution under condition of heating and stirring；Tool
Body is embodied as, and heating temperature is 50 DEG C, and mixing time is 0.5 minute.The mass concentration of amidoxim polyacrylonitrile organic solution
It is 0.5%.Remaining step is same as Example 1.The results are shown in Figure 6, it may be clearly seen that, due to amidoximization poly- third at this time
The non-aqueous property of alkene nitrile, even if in the case of concentration very low (0.25%), polymer is precipitated at floccule in the solution.It should
Comparative example illustrates that sodium hydrate aqueous solution is most important to the present invention in the step of embodiment 1 (2), which ensure that amidoximization is poly-
The water-soluble modified success of acrylonitrile.
Comparative example 2
For intuitively comparative illustration the content of present invention, following comparative example is done, the difference from example 2 is that, step
(2) in, isometric amidoxim polyacrylonitrile organic solution is sufficiently mixed with pure water solution under condition of heating and stirring；Tool
Body is embodied as, and heating temperature is 100 DEG C, and mixing time is 30 minutes.The mass concentration of amidoxim polyacrylonitrile organic solution
It is 5%.Remaining step is same as Example 2.The results are shown in Figure 7, it may be clearly seen that, due to amidoxim polypropylene at this time
The non-aqueous property of nitrile, polymer are precipitated at floccule in the solution.The comparative example illustrates hydrogen-oxygen in the step of embodiment 2 (2)
It is most important to the present invention to change sodium water solution, which ensure that the water-soluble modified success of amidoxim polyacrylonitrile.
Comparative example 3
For intuitively comparative illustration the content of present invention, following comparative example is done, difference lies in steps with embodiment 3
(2) in, isometric amidoxim polyacrylonitrile organic solution is sufficiently mixed with pure water solution under condition of heating and stirring；Tool
Body is embodied as, and heating temperature is 80 DEG C, and mixing time is 15 minutes.The mass concentration of amidoxim polyacrylonitrile organic solution is
10%.Remaining step is same as Example 3.The results are shown in Figure 8, it may be clearly seen that, due to amidoxim polyacrylonitrile
Non-aqueous property, polymer are precipitated at floccule in the solution, and since the mass concentration of amidoxim polyacrylonitrile is higher
(5%), there is solid block Precipitation.The comparative example illustrates that potassium hydroxide aqueous solution is to this in the step of embodiment 3 (2)
Invent it is most important, even if which ensure that amidoxim polyacrylonitrile under relatively high concentration (5%), still can be by this hair
Bright method progress is water-soluble modified, and is successfully converted into water-soluble polymer.
Comparative example 4
For intuitively comparative illustration the content of present invention, following comparative example is done, the difference from example 2 is that：Step
(1) in, amidoxim modification is not carried out to polyacrylonitrile, but the DMF for only preparing the polyacrylonitrile of 1% mass concentration is molten
Liquid.It is in step (2), isometric polyacrylonitrile organic solution and sodium hydroxide solution is fully mixed under condition of heating and stirring
It closes；It is embodied as, heating temperature is 100 DEG C, and mixing time is 30 minutes.The mass concentration of polyacrylonitrile organic solution is
1%, the molar concentration of sodium hydrate aqueous solution is 500mM.The results are shown in Figure 9, it may be clearly seen that, due to polypropylene at this time
The non-aqueous property of nitrile, even if under low concentration and highly basic processing, polymer is precipitated at floccule in the solution, and due to
The color of the corrosiveness of highly basic, polyacrylonitrile flocculent deposit becomes orange-yellow.The comparative example illustrates the hot alkali treatment of the present invention
Method of modifying just for amidoxim polyacrylonitrile it is water-soluble modified effectively, and polyacrylonitrile cannot be made to become water-soluble poly
Close object.
Comparative example 5
A kind of water-soluble amidoxim polyacrylonitrile, preparation method and embodiment 1 difference lies in：In step (2),
The mass concentration of amidoxim polyacrylonitrile organic solution is 0.1%；The molar concentration of sodium hydrate aqueous solution is 10mM.Remaining
Step is same as Example 1.
Comparative example 6
A kind of water-soluble amidoxim polyacrylonitrile, preparation method and embodiment 1 difference lies in：In step (2),
The mass concentration of amidoxim polyacrylonitrile organic solution is 0.5%；The molar concentration of sodium hydrate aqueous solution is 5mM.Remaining
Step is same as Example 1.
Comparative example 7
A kind of water-soluble amidoxim polyacrylonitrile, preparation method and embodiment 1 difference lies in：In step (2),
The mass concentration of amidoxim polyacrylonitrile organic solution is 0.5%；The molar concentration of sodium hydrate aqueous solution is 1200mM.Its
Remaining step is same as Example 1.
Comparative example 8
A kind of water-soluble amidoxim polyacrylonitrile, preparation method and embodiment 3 difference lies in：In step (2),
The mass concentration of amidoxim polyacrylonitrile organic solution is 10%；The molar concentration of potassium hydroxide aqueous solution is 1200mM.Its
Remaining step is same as Example 3.
Comparative example 9
A kind of water-soluble amidoxim polyacrylonitrile, preparation method and embodiment 3 difference lies in：In step (2),
The mass concentration of amidoxim polyacrylonitrile organic solution is 10%；The molar concentration of potassium hydroxide aqueous solution is 5mM.Remaining step
It is rapid same as Example 3.
Comparative example 10
A kind of water-soluble amidoxim polyacrylonitrile, preparation method and embodiment 3 difference lies in：In step (2),
The mass concentration of amidoxim polyacrylonitrile organic solution is 12%；The molar concentration of potassium hydroxide aqueous solution is 1200mM.Its
Remaining step is same as Example 3.
Comparative example 11
A kind of water-soluble amidoxim polyacrylonitrile, preparation method and embodiment 3 difference lies in：In step (2),
The mass concentration of amidoxim polyacrylonitrile organic solution is 12%；The molar concentration of potassium hydroxide aqueous solution is 5mM.Remaining step
It is rapid same as Example 3.
The product that embodiment 1 to 3 is obtained carries out different proportion dilution with water.Experimental result is as shown in table 1：
Table 1
The water-soluble phenomenon for the product that comparative example 1 to 9 obtains.Experimental result is as shown in table 2：
Table 2
| Sample | Water-soluble phenomenon |
| Comparative example 1 | Water is insoluble, floccule is precipitated |
| Comparative example 2 | Water is insoluble, floccule is precipitated |
| Comparative example 3 | Water is insoluble, floccule is precipitated |
| Comparative example 4 | Water is insoluble, floccule is precipitated |
| Comparative example 5 | It is completely dissolved |
| Comparative example 6 | Part is precipitated |
| Comparative example 7 | It is completely dissolved, but macromolecular chain is destroyed |
| Comparative example 8 | It is completely dissolved, but macromolecular chain is destroyed |
| Comparative example 9 | Significantly it is precipitated |
| Comparative example 10 | Part is precipitated |
| Comparative example 11 | Significantly it is precipitated |
Product and the sodium alginate aqueous solution (2.5% mass concentration) that embodiment 1 to 3 obtains according to different proportion it is miscible after
Dissolubility phenomenon.Experimental result is as shown in table 3：
Table 3
In conclusion water-insoluble amidoxim polyacrylonitrile originally can be converted into water using preparation method of the present invention
Dissolubility amidoxim polyacrylonitrile solution, obtained amidoxim polyacrylonitrile is organic-and water mixed solution can be using water to appoint
Dilution proportion of anticipating, and can be with other water-soluble Polymer Solutions (such as hydrogel precursor) with arbitrary proportion to required concentration
Mixing, further prepares the composite materials such as amidoxim functionalization hydrogel.Using provided by the present invention a kind of water-soluble together with amine
The preparation method of oximate polyacrylonitrile solution, mild condition, process are easy, of low cost, breach amidoxim polyacrylonitrile
The limitation that can only be carried out in organic solvent with process, institute are used caused by water-insoluble chemical property and the property
Obtained water-soluble amidoxim polyacrylonitrile solution can be easily with the hydrophilies such as hydrogel or water-soluble substances in water
Co-blended prepares corresponding composite material in solution.The invention is greatly expanded synthesis and the processing side of amidoxim polyacrylonitrile
Method and application range.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (10)
1. a kind of preparation method of water solubility amidoxim polyacrylonitrile solution, it is characterised in that：Include the following steps：
(1) by the processing of polyacrylonitrile amidoximization, amidoxim polyacrylonitrile organic solution is obtained；
(2) by amidoxim polyacrylonitrile organic solution and strong alkali aqueous solution heating stirring to dissolving, that is, obtain it is water-soluble together with
Amidoxime polyacrylonitrile solution.
2. a kind of preparation method of water-soluble amidoxim polyacrylonitrile solution according to claim 1, it is characterised in that：
It in the step (1), calculates by weight, 15~45 parts of hydroxylamine hydrochlorides is added to containing 100 parts of n,N-Dimethylformamide,
Or in dimethyl sulfoxide (DMSO) or the container of n,N-dimethylacetamide, stir to being completely dissolved, it is solid that 5~30 parts of alkalinity are then added
Body powder, room temperature are vigorously stirred, and 10~50 parts of polyacrylonitrile raw material powders are then added, in 60~90 DEG C of constant temperatures after sealing
Lower reaction, high speed centrifugation after cooling, collects supernatant, obtains amidoxim polyacrylonitrile organic solution afterwards.
3. a kind of preparation method of water-soluble amidoxim polyacrylonitrile solution according to claim 1, it is characterised in that：
In the step (1), alkali solid powder is sodium hydroxide, sodium carbonate, potassium hydroxide or sodium bicarbonate.
4. a kind of preparation method of water-soluble amidoxim polyacrylonitrile solution according to claim 1, it is characterised in that：
In the step (1), reacted 6~48 hours under 60~90 DEG C of constant temperatures after sealing.
5. a kind of preparation method of water-soluble amidoxim polyacrylonitrile solution according to claim 1, it is characterised in that：
In the step (1), with rotating speed 10000~30000r/min high speed centrifugations after cooling.
6. a kind of preparation method of water-soluble amidoxim polyacrylonitrile solution according to claim 1, it is characterised in that：
In the step (2), isometric amidoxim polyacrylonitrile organic solution and strong alkali aqueous solution heating stirring are extremely dissolved, together with
Mass concentration≤10% of amidoxime polyacrylonitrile organic solution；The molar concentration of strong alkali aqueous solution is 10~1000mM.
7. a kind of preparation method of water-soluble amidoxim polyacrylonitrile solution according to claim 1, it is characterised in that：
In the step (2), the highly basic used is sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, tetraethyl hydrogen-oxygen
Change one or more of ammonium, methyl triethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide.
8. a kind of preparation method of water-soluble amidoxim polyacrylonitrile solution according to claim 1, it is characterised in that：
In the step (2), heating temperature range is 50~100 DEG C.
9. a kind of preparation method of water-soluble amidoxim polyacrylonitrile solution according to claim 8, it is characterised in that：
In the step (2), mixing time is 0.5~30 minute.
10. a kind of water solubility amidoxim polyacrylonitrile solution, according to a kind of water solubility of claim 1 to 9 any one of them
The preparation method of amidoxim polyacrylonitrile is prepared.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734832A (en) * | 2019-01-09 | 2019-05-10 | 海南大学 | A kind of water solubility amidoxime group polymer and its preparation method and application |
| CN109954483A (en) * | 2019-04-04 | 2019-07-02 | 哈尔滨工程大学 | Modified polyacrylonitrile porous foam uranium absorption material and preparation method containing amidoxime group |
| CN110698574A (en) * | 2019-10-15 | 2020-01-17 | 江苏科技大学 | Morphology inducer of super-capacitor active substance and preparation method and application thereof |
| CN111848987A (en) * | 2020-08-12 | 2020-10-30 | 香港中文大学（深圳） | Recoverable organic gel, preparation method, recovery method and application thereof |
| CN113718424A (en) * | 2021-09-06 | 2021-11-30 | 核工业北京化工冶金研究院 | Modified polyacrylonitrile-nylon 66 composite fiber membrane and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734832A (en) * | 2019-01-09 | 2019-05-10 | 海南大学 | A kind of water solubility amidoxime group polymer and its preparation method and application |
| CN109734832B (en) * | 2019-01-09 | 2021-08-03 | 海南大学 | Water-soluble amidoxime group polymer and preparation method and application thereof |
| CN109954483A (en) * | 2019-04-04 | 2019-07-02 | 哈尔滨工程大学 | Modified polyacrylonitrile porous foam uranium absorption material and preparation method containing amidoxime group |
| CN109954483B (en) * | 2019-04-04 | 2022-04-12 | 哈尔滨工程大学 | Amidoxime group-containing modified polyacrylonitrile porous foamed uranium adsorption material and preparation method thereof |
| CN110698574A (en) * | 2019-10-15 | 2020-01-17 | 江苏科技大学 | Morphology inducer of super-capacitor active substance and preparation method and application thereof |
| CN111848987A (en) * | 2020-08-12 | 2020-10-30 | 香港中文大学（深圳） | Recoverable organic gel, preparation method, recovery method and application thereof |
| CN113718424A (en) * | 2021-09-06 | 2021-11-30 | 核工业北京化工冶金研究院 | Modified polyacrylonitrile-nylon 66 composite fiber membrane and preparation method and application thereof |
| CN113718424B (en) * | 2021-09-06 | 2023-06-20 | 核工业北京化工冶金研究院 | Modified polyacrylonitrile-nylon 66 composite fiber membrane and preparation method and application thereof |
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