CN109382078B - Poly (m-phenylenediamine)/polyvinyl alcohol film and preparation method and application thereof - Google Patents
Poly (m-phenylenediamine)/polyvinyl alcohol film and preparation method and application thereof Download PDFInfo
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- CN109382078B CN109382078B CN201811530647.XA CN201811530647A CN109382078B CN 109382078 B CN109382078 B CN 109382078B CN 201811530647 A CN201811530647 A CN 201811530647A CN 109382078 B CN109382078 B CN 109382078B
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- 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
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- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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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
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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
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Abstract
The invention discloses a poly (m-phenylenediamine)/polyvinyl alcohol film and a preparation method and application thereof, wherein the poly (m-phenylenediamine)/polyvinyl alcohol film is a poly (m-phenylenediamine)/polyvinyl alcohol film woven by taking poly (m-phenylenediamine) and polyvinyl alcohol as raw materials; wherein the mass ratio of the poly (m-phenylenediamine) to the polyvinyl alcohol is 2:8-4: 6. The film can efficiently adsorb the pollutant chromium (VI) in the water body and can be recycled.
Description
Technical Field
The invention relates to a polymer film, in particular to a poly (m-phenylenediamine)/polyvinyl alcohol film, a preparation method and application thereof.
Background
Heavy metal pollution is considered to be one of the most toxic pollutants in sewage because of the toxicity and carcinogenicity of heavy metals. Chromium (VI) as a heavy metal ion enters the body mainly through the aqueous route and can cause kidney and liver damage, even carcinogenesis. Generally, chromium (VI) comes from industrial production activities such as electroplating, chrome mining, leather manufacturing, fertilizer plants, etc. According to the standard of the world health organization, the concentration of chromium (VI) in surface water is not more than 0.1mg/L, and the drinking water is not more than 0.05 mg/L. Therefore, in order to prevent the chromium (VI) from harming human beings, the problem of chromium (VI) contamination must be solved so that the content of water is lower than the standard value.
At present, methods for removing chromium (VI) in water mainly comprise photocatalytic reduction, film separation, electrochemical degradation, reverse osmosis, adsorption and the like. Among these methods, the adsorption method is the most effective method, and thus, the adsorption method is attracting increasing attention. It has the advantages of low price, simple operation, etc. The common adsorbing materials at present comprise activated carbon, clay minerals, chitosan and the like, but the adsorbing materials have the problems of low efficiency, difficult recovery and the like.
In recent years, poly (m-phenylenediamine) has attracted attention because of its strong reducing ability and chelating ability. The polymetaphenylene diamine consists of basic quinoid imino groups and benzenoid amino groups, and the higher the content of quinoid imino groups, the higher the oxidation state of the polymetaphenylene diamine is, and the poorer the reducibility is. Poly (m-phenylenediamine) has stronger adsorption and reduction capacity of chromium (VI), but poly (m-phenylenediamine) is easy to agglomerate in water, so that the adsorption capacity of poly (m-phenylenediamine) is reduced. And is difficult to recycle due to its minute size, which easily causes secondary pollution. However, the existing recovery methods for absorbing chromium (VI) in water by m-phenylenediamine mainly comprise cross-flow filtration, compounding with magnetic materials, centrifugal separation and the like, but the methods have the problems of extra cost increase, low efficiency, environmental friendliness and the like, so that a novel technology or material which is low in cost, high in efficiency and environment-friendly is urgently needed. The above problem is a key to restrict the use of poly (m-phenylenediamine) for absorbing chromium (VI).
As a good film former, polyvinyl alcohol has many active groups. Because of its low price, non-toxic and good biocompatibility, it has been widely used in pharmacy, biomedicine and other fields. After dissolving in the solvent, the polyvinyl alcohol is present in the solution in the form of polymer chains. Due to a large amount of hydroxyl groups, polyvinyl alcohol can be woven into a dense grid under the action of hydrogen bond crosslinking. The poly-m-phenylenediamine has a large amount of amino groups and imino groups which have strong hydrogen bonding effect as the polyvinyl alcohol, so that the poly-m-phenylenediamine is embedded and bound in the grids. Therefore, the poly (m-phenylenediamine) cannot be agglomerated, and the poly (m-phenylenediamine) is easy to separate from water and recover due to the large size of the membrane. Likewise, the absorption of chromium (VI) by poly (m-phenylenediamine) in water is also promoted due to the extremely strong hydrophilicity of polyvinyl alcohol. At present, the polymer film which can effectively adsorb chromium (VI) and is easy to recycle has not been reported.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a poly (m-phenylenediamine)/polyvinyl alcohol film, a preparation method and application thereof. The poly (m-phenylenediamine)/polyvinyl alcohol film has the advantages of high chromium (VI) adsorption quantity, easy recovery and reutilization.
The invention relates to a poly (m-phenylenediamine)/polyvinyl alcohol film, which is woven by using poly (m-phenylenediamine) and polyvinyl alcohol as raw materials. Wherein the mass ratio of the poly (m-phenylenediamine) to the polyvinyl alcohol is 2:8-4: 6.
Furthermore, the poly-m-phenylenediamine/polyvinyl alcohol film is assembled by cross-linking poly-m-phenylenediamine and polyvinyl alcohol in low oxidation state in an organic solvent through a hydrogen bond.
The low oxidation state poly-m-phenylenediamine is prepared by a method comprising the following steps:
adding m-phenylenediamine and a strong oxidant in a molar weight ratio of 1:1 into water respectively, stirring and dissolving to obtain a m-phenylenediamine solution with the concentration of 0.56mol/L and a strong oxidant solution with the concentration of 1.68mol/L, and preparing an alkaline solution with the concentration of 1-2mol/L simultaneously; adding a strong oxidant solution and an alkaline solution into the m-phenylenediamine solution at the same time according to the mass ratio of 1:1 and at the speed of one drop per second to start polymerization reaction, and continuously stirring and reacting for 5 hours at the temperature of 25 ℃; and (3) washing the polymer obtained after the reaction by ultrapure water, ethanol and ammonia water in sequence to remove inorganic salt, oligomer and other impurities, and drying in vacuum at 50 ℃ for 24 hours to obtain the low oxidation state poly (m-phenylenediamine).
The particle size of the low oxidation state poly-m-phenylenediamine microsphere is 0.5-2 μm.
The strong oxidant is selected from hydrogen peroxide, dichromate or persulfate and the like.
The alkaline solution is selected from sodium carbonate solution, sodium bicarbonate solution, sodium hydroxide solution or potassium hydroxide solution, and the concentration is 1-2 mol/L.
The preparation method of the poly (m-phenylenediamine)/polyvinyl alcohol film comprises the following steps:
adding low oxidation state poly (m-phenylenediamine) and polyvinyl alcohol into an organic solvent, raising the temperature to 85-100 ℃ to dissolve the poly (m-phenylenediamine), stirring and dispersing the mixture uniformly, putting the obtained mixed solution into a vacuum oven, controlling the temperature to be constant at 50 ℃, and weaving the polyvinyl alcohol and the low oxidation state poly (m-phenylenediamine) to form a polymer film through hydrogen bond crosslinking along with the evaporation of the organic solvent.
The thickness of the poly (m-phenylenediamine)/polyvinyl alcohol film is 30-50 mu m.
The organic solvent is selected from dimethyl sulfoxide, N-methyl pyrrolidone and the like.
A large number of hydrogen bonds existing in the polymer chains of the poly (m-phenylenediamine) and the polyvinyl alcohol are woven into a film which is uniformly distributed under the cross-linking action of the hydrogen bonds, and the film has a good adsorption effect on chromium (VI).
The poly (m-phenylenediamine)/polyvinyl alcohol film is applied to removing chromium (VI) pollutants in water by taking the poly (m-phenylenediamine)/polyvinyl alcohol film as an adsorbing material, and has high-efficiency adsorption effect at the temperature of 25-45 ℃ when the pH value is 2.0.
Compared with the prior art, the invention has the beneficial effects that:
1. the poly (m-phenylenediamine)/polyvinyl alcohol film has simple preparation process and raw materials and low price.
2. Compared with the existing poly (m-phenylenediamine) base material, the poly (m-phenylenediamine)/polyvinyl alcohol film disclosed by the invention is not easy to agglomerate, and fully exerts high-efficiency adsorption capacity.
3. The poly (m-phenylenediamine)/polyvinyl alcohol film is used for adsorbing chromium (VI) in water, is simple to operate, high in efficiency, easy to recover, reusable and capable of preventing secondary pollution.
Drawings
FIG. 1 is a schematic diagram of the process for synthesizing poly (m-phenylenediamine)/poly (vinyl alcohol) film and the mechanism of chromium (VI) adsorption of the film.
FIG. 2 is a graph showing the effect of pH on the adsorption of chromium (VI) onto a poly (m-phenylenediamine)/poly (vinyl alcohol) film. As can be seen from fig. 2, the adsorption efficiency of the poly (m-phenylenediamine)/polyvinyl alcohol film to chromium (VI) in water is the highest at pH 2.0, and the adsorption efficiency is drastically decreased at pH > 2.0. Shows that the pH value has important influence on the chromium (VI) adsorption of the poly (m-phenylenediamine)/polyvinyl alcohol film.
FIG. 3 shows the characteristics of chromium (VI) adsorption of poly (m-phenylenediamine)/poly (vinyl alcohol) films with different component ratios. As can be seen from FIG. 3, the higher the proportion of poly (m-phenylenediamine) in the film, the better the adsorption effect of the film on chromium (VI), and the higher the concentration of chromium (VI) in water, the more obvious the advantage is.
FIG. 4 is a graph showing the effect of adsorption time on chromium (VI) adsorption by poly (m-phenylenediamine)/poly (vinyl alcohol) films. As can be seen from fig. 4, the amount of adsorption gradually increased with the lapse of time, and the increase was very rapid within 200 minutes, and gradually decreased after 200 minutes.
FIG. 5 is a graph showing the effect of ambient temperature and initial concentration of chromium (VI) solution on the adsorption of chromium (VI) to a poly (m-phenylenediamine)/poly (vinyl alcohol) film. As can be seen from FIG. 5, the higher the temperature, the better the adsorption effect of the film on chromium (VI), and similarly, the adsorption amount gradually becomes larger as the initial concentration increases, and when the initial concentration is less than 300mg/L, the adsorption amount rapidly increases, and when it exceeds 300mg/L, the increase becomes slow.
FIG. 6 shows the application of poly (m-phenylenediamine)/poly (vinyl alcohol) film in practical environment, and the solution water is taken from a nearby lake. As can be seen from FIG. 6, the chromium (VI) solution becomes gradually lighter with time, indicating that the poly (m-phenylenediamine)/poly (vinyl alcohol) film is also well applied in practical environments.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, which are not intended to be limiting.
Example 1:
1. preparation of low oxidation state poly (m-phenylenediamine)
10.00g of m-phenylenediamine was dissolved in 165ml of ultrapure water, and 20.10g of ammonium persulfate (molar ratio 1:1) was dissolved in 55ml of water, while an alkaline solution was prepared from 11.66g of sodium hydrogencarbonate (2 mol/L). At 25 ℃, ammonium persulfate solution and sodium bicarbonate solution are added dropwise into m-phenylenediamine solution at the same speed (one drop per second) to start polymerization reaction, and the stirring is continued for 5 hours, so that poly-m-phenylenediamine with low oxidation state is generated in the polymerization reaction. And washing the polymer by ultrapure water, ethanol and ammonia water to remove inorganic salt, oligomer and other impurities, and drying the polymer in vacuum at 50 ℃ for 24 hours to obtain the dry low-oxidation-state poly (m-phenylenediamine).
2. Preparation of poly (m-phenylenediamine)/polyvinyl alcohol film
0.4g of polyvinyl alcohol is dissolved in 10ml of dimethyl sulfoxide at a temperature of 95 ℃, stirred thoroughly for half an hour, the temperature is reduced to 75 ℃, 0.1g of poly-m-phenylenediamine is dissolved in the solution, and stirred thoroughly for 0.5 hour. And then, pouring the mixed solution into a clean glass culture dish, putting the glass culture dish into a vacuum drying oven, carrying out vacuum drying for 24 hours, weaving polyvinyl alcohol polymer chains into a dense network structure along with the evaporation of the solvent, and fixing the poly (m-phenylenediamine) in a grid to form a poly (m-phenylenediamine)/polyvinyl alcohol film so that the poly (m-phenylenediamine) is not easy to agglomerate in a water body.
The prepared poly-m-phenylenediamine/polyvinyl alcohol film is used for adsorbing chromium (VI) in a water body. The adsorption performance is shown in fig. 3.
Example 2:
1. preparation of low oxidation state poly (m-phenylenediamine)
The method for preparing metaphenylene diamine in low oxidation state in this example is the same as that of example 1.
2. Preparation of poly (m-phenylenediamine)/polyvinyl alcohol film
0.35g of polyvinyl alcohol was dissolved in 10ml of dimethyl sulfoxide at a temperature of 95 ℃ and stirred thoroughly for half an hour, the temperature was lowered to 75 ℃ and 0.15g of poly-m-phenylenediamine was dissolved in this solution and stirred thoroughly for 0.5 hour. And then, pouring the mixed solution into a clean glass culture dish, putting the glass culture dish into a vacuum drying oven, carrying out vacuum drying for 24 hours, weaving polyvinyl alcohol polymer chains into a dense network structure along with the evaporation of the solvent, and fixing the poly (m-phenylenediamine) in a grid to form a poly (m-phenylenediamine)/polyvinyl alcohol film so that the poly (m-phenylenediamine) is not easy to agglomerate in a water body.
The prepared poly-m-phenylenediamine/polyvinyl alcohol film is used for adsorbing chromium (VI) in a water body. The adsorption performance is shown in fig. 3.
Example 3:
1. preparation of low oxidation state poly (m-phenylenediamine)
The method for preparing the carbon dots in this example was the same as in example 1.
2. Preparation of poly (m-phenylenediamine)/polyvinyl alcohol film
0.30g of polyvinyl alcohol was dissolved in 10ml of dimethyl sulfoxide at a temperature of 95 ℃ and stirred thoroughly for half an hour, the temperature was lowered to 75 ℃ and 0.20g of poly-m-phenylenediamine was dissolved in the solution and stirred thoroughly for 0.5 hour. And then, pouring the mixed solution into a clean glass culture dish, putting the glass culture dish into a vacuum drying oven, carrying out vacuum drying for 24 hours, weaving polyvinyl alcohol polymer chains into a dense network structure along with the evaporation of the solvent, and fixing the poly (m-phenylenediamine) in a grid to form a poly (m-phenylenediamine)/polyvinyl alcohol film so that the poly (m-phenylenediamine) is not easy to agglomerate in a water body.
The prepared poly-m-phenylenediamine/polyvinyl alcohol film is used for adsorbing chromium (VI) in a water body. The adsorption performance is shown in fig. 3.
Claims (7)
1. A preparation method of poly (m-phenylenediamine)/polyvinyl alcohol film is characterized by comprising the following steps:
adding low oxidation state poly (m-phenylenediamine) and polyvinyl alcohol into an organic solvent, raising the temperature to 85-100 ℃ to dissolve the poly (m-phenylenediamine), stirring and dispersing the mixture uniformly, putting the obtained mixed solution into a vacuum oven, controlling the temperature to be constant at 50 ℃, and weaving the polyvinyl alcohol and the low oxidation state poly (m-phenylenediamine) to form a polymer film through hydrogen bond crosslinking along with the evaporation of the organic solvent; wherein the mass ratio of the poly (m-phenylenediamine) to the polyvinyl alcohol is 2:8-4: 6;
the low oxidation state poly-m-phenylenediamine is prepared by a method comprising the following steps:
adding m-phenylenediamine and a strong oxidant in a molar weight ratio of 1:1 into water respectively, and stirring and dissolving to obtain a m-phenylenediamine solution and a strong oxidant solution respectively; adding a strong oxidant solution and an alkaline solution into the m-phenylenediamine solution at the same time according to the mass ratio of 1:1 and at the speed of one drop per second to start polymerization reaction, and continuously stirring and reacting for 5 hours at the temperature of 25 ℃; and (3) washing the polymer obtained after the reaction by ultrapure water, ethanol and ammonia water in sequence to remove inorganic salt, oligomer and other impurities, and drying in vacuum at 50 ℃ to obtain the low oxidation state poly (m-phenylenediamine).
2. The method of claim 1, wherein:
the concentration of the m-phenylenediamine solution is 0.56mol/L, and the concentration of the strong oxidant solution is 1.68 mol/L.
3. The method of claim 1, wherein:
the strong oxidizing agent is selected from hydrogen peroxide, dichromate or persulfate.
4. The method of claim 1, wherein:
the alkaline solution is selected from sodium carbonate solution, sodium bicarbonate solution, sodium hydroxide solution or potassium hydroxide solution, and the concentration is 1-2 mol/L.
5. The method of claim 1, wherein:
the thickness of the poly (m-phenylenediamine)/polyvinyl alcohol film is 30-50 mu m.
6. Use of a poly (m-phenylenediamine)/poly (vinyl alcohol) film obtained according to any of the production methods of claims 1 to 5, wherein:
the poly (m-phenylenediamine) and polyvinyl alcohol film is used as an adsorbing material to remove the pollutant chromium VI in the water body.
7. Use according to claim 6, characterized in that:
when the poly (m-phenylenediamine)/polyvinyl alcohol film is used as an adsorbing material to remove the pollutant chromium VI in the water body, the pH value of the system is controlled to be 2.0, and the temperature is controlled to be 25-45 ℃.
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