CN106731894B - The carboxyl modified MOF film and preparation method thereof that heavy metal ion high definition is removed in a kind of pair of blood - Google Patents
The carboxyl modified MOF film and preparation method thereof that heavy metal ion high definition is removed in a kind of pair of blood Download PDFInfo
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Abstract
The present invention provides the carboxyl modified MOF film and preparation method thereof that heavy metal ion high definition in a kind of pair of blood is removed, and belongs to MOF technical field of membrane.Carboxyl modified MOF membrane structure formula is as shown in formula I.The present invention also provides the preparation method for the carboxyl modified MOF film that heavy metal ion high definition in a kind of pair of blood is removed, this method first prepares the carboxyl modified MOF material of bromine substitution；The carboxyl in carboxyl modified MOF material replaced to bromine is protected, and the MOF of carboxy protective is obtained；Then the MOF of carboxy protective and grignard reagent are reacted, obtains the MOF material with double bond；The MOF material with double bond is finally grafted on polymer-based end material surface by pre-irradiated or mutual radiation method, obtains carboxyl modified MOF film.MOF film of the invention is in blood to Cr6+、Mn2+、Ni2+、Cu2+、Zn2+、Cd2+、Hg2+、Pb2+、As3+Etc. heavy metal ion have the characteristics that high cleaning performance and in situ capture.
Description
Technical field
The invention belongs to MOF technical field of membrane, and in particular to the carboxyl that heavy metal ion high definition is removed in a kind of pair of blood is repaired
Adorn MOF film and preparation method thereof.
Background technique
The heavy metal pollution situation of China is very severe.According to " the national soil pollution situation tune of publication in 2014
Look into bulletin " it shows, national soil environment situation totally allows of no optimist, and some areas soil pollution is heavier.Pollution type is with inorganic
Based on type, organic type takes second place, and compound pollution specific gravity is smaller, and exceeded digit of inorganic pollution accounts for whole exceeded points
82.8%.Wherein, 4 kinds of cadmium, mercury, arsenic, lead level of inorganic contaminants distributions are presented from northwest to the southeast, from northeast to southwestward
The situation gradually risen.These harmful substances can penetrate into soil, then reached in human body by food chain, cause to endanger to human body
Evil.Data from Chinese Ministry of Environmental Protection show, heavy metal pollution event in 2009 causes that 4035 people's blood leads are exceeded, 182 people's cadmiums are exceeded, draw
Send out 32 Mass disturbances；14 heavy metal pollution events occur altogether within 2010, wherein 9 are blood lead events；2011 are only 1-8
9 blood lead events just have occurred in the moon.
Currently, the conventional therapy for heavy metal poisoning generally has emetic, gastric lavage, diuresis, catharsis etc., activity also may be selected
Charcoal adsorbing therapy；It is removed using metal chelating agent drug, such as Beracilline, anti-lewisite (BAL), dimercaptosuccinic acid
(DMSA), natrii demercaptopancsulfonas (DMPS), EDTA, Prussian blue etc.；And the methods of hemodialysis, blood perfusion.But these
All there is the disadvantages of poor selectivity, side effect is big in method.And metal chelating agent can generate precipitating in human body, it is difficult to be discharged.
In comparison, absorption method has a clear superiority, and does not have deposition, causes secondary pollution.But traditional adsorbent is (main
Having diatomite, coke, active carbon, cellulose, resin and zeolite etc.) generally existing adsorption capacity is lower, non-selectivity or again
The problems such as raw difficult.
Metal-organic framework materials (metal-organic frameworks, MOFs) are a kind of porous materials of novel nano
Material, has many advantages, such as specific diversity, structure designability and Modulatory character, high-specific surface area and good thermal stability,
As current chemistry, a research hotspot of material subject, potential application prospect is shown in multiple fields, is especially being divided
From aspect.
Summary of the invention
The purpose of the present invention is to solve it is existing remove blood heavy metal ion method adsorption capacity it is lower, without choosing
Selecting property is difficult to be discharged or regenerate difficult problem, and provides the carboxyl modified MOF that heavy metal ion high definition is removed in a kind of pair of blood
Film and preparation method thereof.
Present invention firstly provides the carboxyl modified MOF film that heavy metal ion high definition in a kind of pair of blood is removed, structural formula such as formulas I
It is shown:
In formula I, R is Zr or Fe,Represent polymer-based bottom material.
The present invention also provides the preparation methods for the carboxyl modified MOF film that heavy metal ion high definition in a kind of pair of blood is removed, should
Method includes:
Step 1: the carboxyl modified MOF material of bromine substitution is prepared；
Step 2: the carboxyl in carboxyl modified MOF material replaced to the bromine that step 1 obtains is protected, and carboxyl is obtained
The MOF of protection；
Step 3: MOF and the grignard reagent reaction for the carboxy protective that step 2 is obtained obtain the MOF material with double bond；
Step 4: the MOF material with double bond that step 3 is obtained is grafted on high score by pre-irradiated or mutual radiation method
Sub- substrate material surface obtains carboxyl modified MOF film.
Preferably, the step one prepares the carboxyl modified MOF MATERIALS METHODS of bromine substitution are as follows: by RClxWith 2- carboxylic
Base -5- bromo terephthalic acid is dissolved in a solvent, is added in reaction kettle after mixing, is reacted 18-26h at 100-125 DEG C,
The carboxyl modified MOF material of bromine substitution is obtained, the R is Zr or Fe, and x is 3 or 4.
Preferably, the RClxIt is (1-3) with 2- carboxyl -5- bromo terephthalic acid's weight fraction ratio: 1.
Preferably, the grignard reagent is vinylimidazolium chloride magnesium, allylmgcl or 3- butylene magnesium chloride.
Preferably, the pre-irradiation method specifically:
(1), polymer-based bottom material is put into radiation source, pre-irradiation is carried out to polymer-based bottom material；
(2), the MOF material with double bond is made into MOF colloid；
(3), polymer-based bottom material and MOF colloid after pre-irradiation are added in the reaction vessel, is passed through nitrogen, then will
Reactant moves into water-bath, reacts 5-7h at 50-60 DEG C, obtains carboxyl modified MOF film.
Preferably, the mutual radiation method specifically:
(1), the MOF material with double bond is made into MOF colloid；
(2), MOF colloid is coated in macromolecule matrix material surface, be put into radiation source, to macromolecule matrix material table
Face is irradiated, and carboxyl modified MOF film is obtained.
Preferably, the dose of radiation is 5-100kGy, radiation dose rate 0.8-1.5kGy/h.
Preferably, the mass fraction of MOF is 10-30% in MOF colloid.
Preferably, the macromolecule matrix material is polypropylene screen, polyethylene film or polyethylene terephthalate
Ester film.
Beneficial effects of the present invention
Present invention firstly provides the carboxyl modified MOF film that heavy metal ion high definition in a kind of pair of blood is removed, structural formula such as formulas I
Shown, the MOF film is in blood to Cr6+、Mn2+、Ni2+、Cu2+、Zn2+、Cd2+、Hg2+、Pb2+、As3+Etc. heavy metal ion have
High cleaning performance and the characteristics of capturing in situ.
The present invention also provides the preparation methods for the carboxyl modified MOF film that heavy metal ion high definition in a kind of pair of blood is removed, should
Method first prepares the carboxyl modified MOF material of bromine substitution；The carboxyl in carboxyl modified MOF material replaced to bromine is protected,
Obtain the MOF of carboxy protective；
Then the MOF of carboxy protective and grignard reagent are reacted, obtains the MOF material with double bond；It finally will be with double bond
MOF material is grafted on polymer-based end material surface by pre-irradiated or mutual radiation method, obtains carboxyl modified MOF film.This hair
Bright preparation method is simple, and the MOF material of particular functional group is had by synthesizing, and is fixed in polymer surface,
Obtain the high-performance MOF film that adsorption capacity is high, selectivity is strong and captures in situ.
Specific embodiment
Present invention firstly provides the carboxyl modified MOF film that heavy metal ion high definition in a kind of pair of blood is removed, structural formula such as formulas I
It is shown:
In formula I, R is Zr or Fe,Represent polymer-based bottom material, preferably polypropylene
Film, polyethylene film or polyethylene terephthalate film.
The present invention also provides the preparation methods for the carboxyl modified MOF film that heavy metal ion high definition in a kind of pair of blood is removed, should
Method includes:
Step 1: the carboxyl modified MOF material of bromine substitution is prepared；
Step 2: the carboxyl in carboxyl modified MOF material replaced to the bromine that step 1 obtains is protected, and carboxyl is obtained
The MOF of protection；
Step 3: MOF and the grignard reagent reaction for the carboxy protective that step 2 is obtained obtain the MOF material with double bond；
Step 4: the MOF material with double bond that step 3 is obtained is grafted on high score by pre-irradiated or mutual radiation method
Sub- substrate material surface obtains carboxyl modified MOF film.
According to the present invention, the carboxyl modified MOF MATERIALS METHODS for preparing bromine substitution are as follows: by RClxWith 2- carboxyl -5-
Bromo terephthalic acid is dissolved in deionized water, is added in reaction kettle after mixing, is reacted 18-26h at 100-125 DEG C,
The post-treated carboxyl modified MOF material for obtaining bromine substitution of obtained product, the R are Zr or Fe, and x is 3 or 4.Described
Post-processing is, by product deionized water repeated flushing, product powder impregnates reflow treatment 16 hours in deionized water, product
Powder uses deionized water repeated flushing after filtering, last room temperature in vacuo is dry.The RClxWith 2- carboxyl -5- bromine terephthaldehyde
Sour weight fraction ratio is preferably (1-3): 1.
According to the present invention, the carboxyl in carboxyl modified MOF material that bromine obtained above replaces is protected, carboxylic is obtained
The MOF of base protection；The guard method is not particularly limited, and according to guard method well known in the art, the present invention is logical
It crosses organic procedures to be protected, it is preferred that when R is Zr, the carboxyl modified MOF material that bromine is replaced is in 0 DEG C of addition methanol
And sulfuric acid, kept for 5 DEG C react 18 hours after stirring 1 hour, it is dry after successively being cleaned with methanol and distilled water；The bromine replaces
Carboxyl modified MOF material, methanol and sulfuric acid weight fraction ratio be preferably 1:2:1；When R is Fe, carboxyl that bromine is replaced
It modifies MOF material and bromoethane and 1 is added, 11 carbon -7- alkene (DBU) of 8- diazabicylo reacts 4 hours for 25 DEG C in acetonitrile,
Dry, carboxyl modified MOF material, the bromoethane and 1 that the bromine replaces, 8- diazabicylo ten after distilled water, ethyl alcohol cleaning
The weight fraction ratio of one carbon -7- alkene is preferably 2:5:1.
According to the present invention, the MOF of the above-mentioned carboxy protective being prepared is dissolved in solvent, the solvent is preferably dry
Dry tetrahydrofuran, then in a solvent by grignard reagent dissolution, the solvent is preferably dry tetrahydrofuran, preferably at 0 DEG C
Under be slowly dropped into MOF solution, be warming up to room temperature reaction, the reaction time is preferably 1-2h, after then carrying out product
Processing, obtains the MOF material with double bond；The post-processing preferably by after product saturated ammonium chloride quenching reaction, carries out
Centrifuge separation is successively used deionized water and ethyl alcohol repeated flushing, is dried in vacuo at room temperature.The grignard reagent is preferably ethylene
Base magnesium chloride, allylmgcl or 3- butylene magnesium chloride, the parts by weight of carboxyl modified MOF material and grignard reagent that bromine replaces
Number is than being preferably 1:3.
According to the present invention, the MOF material obtained above with double bond is grafted on height by pre-irradiated or mutual radiation method
Molecule substrate material surface obtains carboxyl modified MOF film.The method of the pre-irradiation, preferably includes:
(1), polymer-based bottom material is put into radiation source, pre-irradiation is carried out to polymer-based bottom material；
(2), the MOF material with double bond is made into MOF colloid；
(3), polymer-based bottom material and MOF colloid after pre-irradiation are added in the reaction vessel, is passed through nitrogen, then will
Reactant moves into water-bath, reacts 5-7h at 50-60 DEG C, obtains carboxyl modified MOF film.
According to the present invention, before the polymer-based bottom material carries out pre-irradiation again, is preferably first cleaned and gone forward side by side with acetone
Row drying, the macromolecule matrix material are preferably polypropylene screen, polyethylene film or polyethylene terephthalate film, institute
That states is not particularly limited the form of polymer-based bottom material, preferably plate, particle, film or threadiness.
According to the present invention, the radiation source is not particularly limited, and is radiation source commonly used in the art, preferably cobalt
60 sources or electron accelerator, dose of radiation different, preferably 5-100kGy according to the difference of polymer-based bottom material, radiation
Dosage rate is preferably 0.8-1.5kGy/h, and the radiation field temperature is preferably 20-25 DEG C.
According to the present invention, it is that the MOF material with double bond is dissolved in solvent that the MOF material with double bond, which is made into MOF colloid,
It is made into MOF colloid after excusing from death uniformly, the solvent is preferably tetrahydrofuran (THF), and the mass fraction of MOF is excellent in MOF colloid
It is selected as 10-30%.
According to the present invention, polymer-based bottom material and MOF colloid after pre-irradiation are added in the reaction vessel, is passed through nitrogen
Gas, reaction vessel is closed, nitrogen atmosphere is kept, then reactant is moved into water-bath, reacts 5-7h at 50-60 DEG C, to
Temperature is cooled to room temperature, and is washed to product, obtains carboxyl modified MOF film after dry.The polymer-based bottom material and
The weight fraction ratio of MOF material with double bond is preferably 20:1.
According to the present invention, the method for the mutual radiation is preferably included:
(1), the MOF material with double bond is made into MOF colloid；
(2), MOF colloid is coated in macromolecule matrix material surface, be put into radiation source, to macromolecule matrix material table
Face is irradiated, and carboxyl modified MOF film is obtained.
According to the present invention, it is that the MOF material with double bond is dissolved in solvent that the MOF material with double bond, which is made into MOF colloid,
It is made into MOF colloid after excusing from death uniformly, the solvent is preferably tetrahydrofuran (THF), and the mass fraction of MOF is excellent in MOF colloid
It is selected as 10-30%.
According to the present invention, MOF colloid is coated in macromolecule matrix material surface, the polymer-based bottom material is preferred
It is first cleaned and is dried with acetone, the macromolecule matrix material is preferably polypropylene screen, polyethylene film or poly- to benzene two
Formic acid glycol ester film, the form to polymer-based bottom material are not particularly limited, preferably plate, particle, film
Or threadiness.
According to the present invention, the polymer-based bottom material for being coated with MOF colloid is put into radiation source, to macromolecule matrix material
Material surface is irradiated, and after carrying out washing drying to product, obtains carboxyl modified MOF film.The radiation source does not have special limit
System is radiation source commonly used in the art, preferably cobalt 60 source or electron accelerator, and dose of radiation is according to polymer-based ground
The difference of material and different, preferably 5-100kGy, radiation dose rate are preferably 0.8-1.5kGy/h, the radiation field temperature is excellent
It is selected as 20-25 DEG C.
Further detailed description is done to the present invention combined with specific embodiments below.
Embodiment 1
1) in deionized water by 1 part of zirconium chloride and 1 part of 2- carboxyl -5- bromo terephthalic acid dissolution, 100 DEG C of back flow reactions
24 hours, crude product used deionized water repeated flushing after filtering, and product powder impregnates reflow treatment 16 hours in deionized water,
Product powder uses deionized water repeated flushing after filtering, last room temperature in vacuo is dry, obtains the carboxyl modified MOF material of bromine substitution
Material；
2) it keeps 5 DEG C to react after 0 DEG C of addition methanol and sulfuric acid, stirring 1 hour 18 hours, successively uses methanol and distilled water
It is dry after cleaning, obtain the MOF of carboxy protective；
3) MOF of the carboxy protective of 1 part of above-mentioned preparation is suspended in dry tetrahydrofuran (THF), by 3 parts of allyl chlorides
Change magnesium (grignard reagent), which is dissolved in dry THF, to be slowly dropped into wherein for 0 DEG C, is warming up to and is reacted 1 hour at room temperature, with saturation chlorination
Crude product is centrifugated after ammonium quenching reaction, is successively used deionized water and ethyl alcohol repeated flushing, is dried in vacuo at room temperature, obtains band
The MOF material of double bond；
4) the MOF material with double bond is dissolved in tetrahydrofuran (THF), is made into MOF colloid (mass fraction after excusing from death uniformly
20%), polypropylene (PP) to be cleaned and being dried with acetone, MOF colloid is then coated in polypropylene (PP) film surface,
The polypropylene screen for being coated with MOF colloid is put into cobalt 60 source, dose of radiation 5kGy, radiation dose rate 1kGy/h, radiation
Field temperature is 22 DEG C, lithium iodide and pyridine is added in obtained product, back flow reaction 3 hours, ethyl alcohol was dry after rinsing, acquisition carboxylic
Base modifies MOF film.
The carboxyl modified MOF film that embodiment 1 is obtained carries out adsorption test, and the heavy metal ion initial concentration of configuration is about
10ppm, adsorption time 10 minutes, by ICP-OES test ion concentration, experimental data was as shown in table 1.
Embodiment 2
1) 3 parts of iron chloride and 1 part dissolve in deionized water 2- carboxyl -5- bromo terephthalic acid, 100 DEG C of reflux are anti-
It answers 24 hours, crude product uses deionized water repeated flushing after filtering, it is small that product powder impregnates reflow treatment 16 in deionized water
When, product powder uses deionized water repeated flushing after filtering, last room temperature in vacuo is dry, obtains the carboxyl modified MOF of bromine substitution
Material；
2) bromoethane and 1 is added, 11 carbon -7- alkene (DBU) of 8- diazabicylo reacts for 25 DEG C in acetonitrile, distilled water,
It is dry after ethyl alcohol cleaning, obtain the MOF of carboxy protective；
3) MOF of the carboxy protective of 1 part of above-mentioned preparation is suspended in dry tetrahydrofuran, by 3 parts of vinylimidazolium chloride magnesium
(grignard reagent) is dissolved in dry THF and is slowly dropped into wherein for 0 DEG C, is warming up to and reacts 1 hour at room temperature, is quenched with saturated ammonium chloride
Crude product after reacting of going out is centrifugated, and is successively used deionized water and ethyl alcohol repeated flushing, is dried in vacuo at room temperature, and band double bond is obtained
MOF material；
4) polyethylene terephthalate (PET) film is cleaned and is dried with acetone, be then placed in cobalt 60 source,
Dose of radiation is 80kGy, and radiation dose rate 1kGy/h, radiation field temperature is 22 DEG C, the poly terephthalic acid after being irradiated
Glycol ester film；MOF material with double bond is dissolved in tetrahydrofuran (THF), MOF colloid (quality point is made into after excusing from death uniformly
Number in the three-necked flask for being connected with agitating paddle, leads to for 20%), the PET after irradiation is added in the colloid equipped with MOF material
Enter nitrogen, stops logical nitrogen after 15 minutes, three-necked flask is closed, nitrogen atmosphere is kept, then reactant is moved into water-bath, is beaten
Stirring is opened, 6h is reacted at 55 DEG C, is cooled to room temperature to three-necked flask, trim,ethylchlorosilane and sodium iodide is added in product,
Back flow reaction 8 hours in acetonitrile, distilled water and ethyl alcohol are dry after rinsing, and obtain carboxyl modified MOF film.
The carboxyl modified MOF film that embodiment 2 is obtained carries out adsorption test, and the heavy metal ion initial concentration of configuration is about
10ppm, adsorption time 10 minutes, by ICP-OES test ion concentration, experimental data was as shown in table 1.
Embodiment 3
1) in deionized water by 1 part of zirconium chloride and 1 part of 2- carboxyl -5- bromo terephthalic acid dissolution, 125 DEG C of back flow reactions
22 hours, crude product used deionized water repeated flushing after filtering, and product powder impregnates reflow treatment 16 hours in deionized water,
Product powder uses deionized water repeated flushing after filtering, last room temperature in vacuo is dry, obtains the carboxyl modified MOF material of bromine substitution
Material；
2) it keeps 5 DEG C to react after 0 DEG C of addition methanol and sulfuric acid, stirring 1 hour 18 hours, successively uses methanol and distilled water
It is dry after cleaning, obtain the MOF of carboxy protective；
3) MOF of the carboxy protective of 1 part of above-mentioned preparation is suspended in dry tetrahydrofuran (THF), by 3 parts of 3- butylene chlorine
Change magnesium, which is dissolved in dry THF, to be slowly dropped into wherein for 0 DEG C, is warming up to and is reacted 1 hour at room temperature, with saturated ammonium chloride quenching reaction
Crude product is centrifugated afterwards, is successively used deionized water and ethyl alcohol repeated flushing, is dried in vacuo at room temperature, obtains the MOF with double bond
Material；
4) the MOF material with double bond is dissolved in tetrahydrofuran (THF), is made into MOF colloid (mass fraction after excusing from death uniformly
10%), polyethylene (PE) to be cleaned and being dried with acetone, MOF colloid is then coated in polyethylene (PE) film surface,
The polyethylene film for being coated with MOF colloid is put into electron accelerator, dose of radiation 30kGy, radiation dose rate 1.5kGy/
H, radiation field temperature are 25 DEG C, and lithium iodide and pyridine is added in obtained product, and back flow reaction 3 hours, ethyl alcohol was dry after rinsing,
Obtain carboxyl modified MOF film.
The carboxyl modified MOF film that embodiment 3 is obtained carries out adsorption test, and the heavy metal ion initial concentration of configuration is about
10ppm, adsorption time 10 minutes, by ICP-OES test ion concentration, experimental data was as shown in table 1.
Embodiment 4
1) 3 parts of iron chloride and 1 part dissolve in deionized water 2- carboxyl -5- bromo terephthalic acid, 105 DEG C of reflux are anti-
It answers 18 hours, crude product uses deionized water repeated flushing after filtering, it is small that product powder impregnates reflow treatment 16 in deionized water
When, product powder uses deionized water repeated flushing after filtering, last room temperature in vacuo is dry, obtains the carboxyl modified MOF of bromine substitution
Material；
2) bromoethane and 1 is added, 11 carbon -7- alkene (DBU) of 8- diazabicylo reacts for 25 DEG C in acetonitrile, distilled water,
It is dry after ethyl alcohol cleaning, obtain the MOF of carboxy protective；
3) MOF of the carboxy protective of 1 part of above-mentioned preparation is suspended in dry tetrahydrofuran, by 3 parts of vinylimidazolium chloride magnesium
(grignard reagent) is dissolved in dry THF and is slowly dropped into wherein for 0 DEG C, is warming up to and reacts 1 hour at room temperature, is quenched with saturated ammonium chloride
Crude product after reacting of going out is centrifugated, and is successively used deionized water and ethyl alcohol repeated flushing, is dried in vacuo at room temperature, and band double bond is obtained
MOF material；
4) polyethylene terephthalate (PET) film is cleaned and is dried with acetone, be then placed in cobalt 60 source,
Dose of radiation is 100kGy, and radiation dose rate 0.8kGy/h, radiation field temperature is 20 DEG C, the poly- terephthaldehyde after being irradiated
Sour glycol ester film；MOF material with double bond is dissolved in tetrahydrofuran (THF), is made into MOF colloid (quality after excusing from death uniformly
Score is that 30%), the PET after irradiation is added in the colloid equipped with MOF material, in the three-necked flask for being connected with agitating paddle,
It is passed through nitrogen, stops logical nitrogen after 15 minutes, three-necked flask is closed, nitrogen atmosphere is kept, then moves into reactant in water-bath,
Stirring is opened, 6h is reacted at 55 DEG C, is cooled to room temperature to three-necked flask, trim,ethylchlorosilane and sodium iodide is added in product,
Back flow reaction 8 hours in acetonitrile, distilled water and ethyl alcohol are dry after rinsing, and obtain carboxyl modified MOF film.
The carboxyl modified MOF film that embodiment 4 is obtained carries out adsorption test, and the heavy metal ion initial concentration of configuration is about
10ppm, adsorption time 10 minutes, by ICP-OES test ion concentration, experimental data was as shown in table 1.
Table 1
Claims (9)
1. the carboxyl modified MOF film that heavy metal ion high definition is removed in a kind of pair of blood, which is characterized in that structural formula is as shown in formula I:
In formula I, R is Zr or Fe,Represent polymer-based bottom material；
The preparation method for the carboxyl modified MOF film that heavy metal ion high definition is removed in a kind of pair of blood, this method comprises:
Step 1: the carboxyl modified MOF material of bromine substitution is prepared；
Step 2: the carboxyl in carboxyl modified MOF material replaced to the bromine that step 1 obtains is protected, and carboxy protective is obtained
MOF；
Step 3: MOF and the grignard reagent reaction for the carboxy protective that step 2 is obtained obtain the MOF material with double bond；
Step 4: the MOF material with double bond that step 3 obtains is grafted on by pre-irradiated or mutual radiation method polymer-based
Bottom material surface obtains carboxyl modified MOF film.
2. the carboxyl modified MOF film that heavy metal ion high definition is removed in a kind of pair of blood according to claim 1, feature exist
In the step one prepares the carboxyl modified MOF MATERIALS METHODS of bromine substitution are as follows: by RClxWith 2- carboxyl -5- bromine terephthaldehyde
Acid dissolution in a solvent, is added in reaction kettle after mixing, reacts 18-26h at 100-125 DEG C, obtains the carboxylic of bromine substitution
Base modifies MOF material, and the R is Zr or Fe, and x is 3 or 4.
3. the carboxyl modified MOF film that heavy metal ion high definition is removed in a kind of pair of blood according to claim 2, feature exist
In the RClxIt is (1-3) with 2- carboxyl -5- bromo terephthalic acid's weight fraction ratio: 1.
4. the carboxyl modified MOF film that heavy metal ion high definition is removed in a kind of pair of blood according to claim 1, feature exist
In the grignard reagent is vinylimidazolium chloride magnesium, allylmgcl or 3- butylene magnesium chloride.
5. the carboxyl modified MOF film that heavy metal ion high definition is removed in a kind of pair of blood according to claim 1, feature exist
In the pre-irradiation method specifically:
(1), polymer-based bottom material is put into radiation source, pre-irradiation is carried out to polymer-based bottom material；
(2), the MOF material with double bond is made into MOF colloid；
(3), polymer-based bottom material and MOF colloid after pre-irradiation are added in the reaction vessel, is passed through nitrogen, it then will reaction
Object moves into water-bath, reacts 5-7h at 50-60 DEG C, obtains carboxyl modified MOF film.
6. the carboxyl modified MOF film that heavy metal ion high definition is removed in a kind of pair of blood according to claim 1, feature exist
In the mutual radiation method specifically:
(1), the MOF material with double bond is made into MOF colloid；
(2), by MOF colloid be coated in macromolecule matrix material surface, be put into radiation source, to macromolecule matrix material surface into
Row irradiation, obtains carboxyl modified MOF film.
7. the carboxyl modified MOF film that heavy metal ion high definition is removed in a kind of pair of blood according to claim 5 or 6, special
Sign is that the dose of radiation is 5-100kGy, radiation dose rate 0.8-1.5kGy/h.
8. the carboxyl modified MOF film that heavy metal ion high definition is removed in a kind of pair of blood according to claim 5 or 6, special
Sign is that the mass fraction of MOF is 10-30% in MOF colloid.
9. the carboxyl modified MOF film that heavy metal ion high definition is removed in a kind of pair of blood according to claim 1, feature exist
In the macromolecule matrix material is polypropylene screen, polyethylene film or polyethylene terephthalate film.
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