CN109174062A - A kind of modified seperation film of heavy metal ion adsorbed type PVDF - Google Patents
A kind of modified seperation film of heavy metal ion adsorbed type PVDF Download PDFInfo
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- CN109174062A CN109174062A CN201811162921.2A CN201811162921A CN109174062A CN 109174062 A CN109174062 A CN 109174062A CN 201811162921 A CN201811162921 A CN 201811162921A CN 109174062 A CN109174062 A CN 109174062A
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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
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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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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- 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
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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
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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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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of modified seperation films of heavy metal ion adsorbed type PVDF, belong to separation technical field of membrane, in particular to a kind of heavy metal ion adsorbed type plate membrane.Present invention be characterized in that the modified seperation film of the PVDF is modified obtained, used PAMAM to PVDF plate membrane by polyamide-amide (PAMAM) and has suction-operated to heavy metal ion.The modified seperation film of PVDF of the present invention increases heavy metal ion adsorbed ability with the increase of PAMAM grafting algebra.The heavy metal ion of the modified seperation film absorption of PVDF of the present invention recycles after being cleaned by cleaning solution, and seperation film can be reused.The modified purer pvdf membrane of separation membrane flux of PVDF of the present invention improves, the stable physical property of seperation film.Present invention production does not need special installation, preparation simply, is easy to implement, and the modified seperation film cost of made PVDF is little.
Description
Technical field
The invention belongs to separate technical field of membrane, in particular to a kind of modified seperation film of heavy metal ion adsorbed type PVDF.
Background technique
In recent years, the waste water row with the development of modernization industry, in industry containing heavy metal ion such as copper, cadmium, nickel, zinc
Pollution caused by putting is got worse, and has resulted in serious problem of environmental pollution, for economic sustainable development and to ecology
The protection of environment, it is extremely urgent to the processing of heavy metal wastewater thereby.
Currently, commonly the method for processing heavy metal ion has chemical precipitation method, membrane separation process, ion-exchange, complexing
Method and absorption method etc..The advantages of wherein membrane separation process is due to easy to operate, and adsorption efficiency is high, can be recycled and obtain extensively
Concern, specifically include ultrafiltration membrane, nanofiltration membrane, electrodialytic membranes and reverse osmosis membrane etc..But it is handled using traditional membrane separation technique
When waste water, membrane material can not carry out selective absorption to heavy metal ion, realize that selective absorption just needs to hand over by ion
It changes, reverse osmosis equal complicated process flow is unfavorable for the popularization and application of wastewater treatment method to increase cost.Therefore, it develops
The membrane material that selective absorption can be carried out to heavy metal ion reduces cost with important to waste water treatment process is simplified
Meaning.
Currently in seperation film field, PVDF seperation film is due to high mechanical strength, good thermal stability, resistance to acid and alkali, corrosion resistant
Corrosion, hydrophobicity, soil resistance, the excellent characteristics such as cheap and the concern that is subject to have been widely applied to chemical industry, electronics, food
The fields such as product, weaving.But pvdf membrane equally exists the problem of can not carrying out selective absorption to heavy metal ion, PVDF is
With-CH2-CF2It is the chain crystalline polymer of structural unit, it is special there is no that can be carried out with heavy metal ion in membrane structure
Property complexing group, therefore can not to heavy metal ion carry out selective absorption.Currently, often can by the introducing in pvdf membrane
Functional group such as amino, carboxyl of complexing etc. occurs with heavy metal ion to improve selection of the pvdf membrane to heavy metal ion
Property absorption.
Polyamide-amide (PAMAM) is rich in characteristic groups such as amino, the characteristic feature with dendritic: high
Geometrical symmetry is spent, controllable molecular structure etc., furthermore PAMAM branches end also has a large amount of primary amine group, and acyl is contained in inside
Amine groups, carbonyl group etc., and radical amount is in exponential increase with the increase of algebra.Energy between heavy metal ion and containing n-donor ligand
Complexing is enough generated, so that PAMAM has high selective adsorption capacity to heavy metal ion.In addition, PAMAM is dendroid
Structure, the cavity being formed in the interior thereof can chelate and wrap up heavy metal ion, in the feelings of energy selective absorption heavy metal ion
Under condition, moreover it is possible to further enhance its adsorption capacity to heavy metal ion.
Currently, related carry out hyperbranched modification to PVDF, for improving film to the report of heavy metal ion adsorbed ability not
It is more, how dissaving polymer to be introduced into membrane material do the trick be still the field a great problem.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the technical issues of present invention intends to solve is to provide a kind of heavy metal ion
((PVDF-g-PAA-Gn PAMAM film), the seperation film is to heavy metals such as copper, zinc, cadmium, nickel for the modified seperation film of absorbent-type PVDF
Ion has efficient absorption effect.
The modified PVDF powder is obtained to be modified by acrylic acid (AA) to Kynoar (PVDF) powder, is denoted as
PVDF-g-PAA powder.The PVDF-g-PAA powder, which can be used for preparing, has height to heavy metal ion such as copper, zinc, cadmium, nickel
Imitate the flat-plate separation film or hollow fiber separating film basement membrane of suction-operated.
The modified seperation film of heavy metal ion adsorbed type PVDF is will to dissipate multistep processes using PVDF-g-PAA film as basement membrane
The polyamide-amide (Gn PAMAM) of the different algebra of preparation is grafted to obtained from film surface.The generation of seperation film grafting GnPAMAM
Several very big to heavy metal ion adsorbed capacity, seperation film adsorbs the ability of heavy metal ion with grafting Gn PAMAM algebra
Increase and significantly increases.
Utilize a kind of putting down for preparation method preparation of the modified seperation film of heavy metal ion adsorbed type PVDF of the present invention
Plate seperation film or hollow fiber separating film can efficient absorption heavy metal ion, and after adsorbing heavy metal ion, cleaning solution can be passed through
The heavy metal ion that cleaning seperation film is adsorbed with high efficiente callback, achievees the effect that reuse.
A kind of heavy metal ion adsorbed type PVDF is modified seperation film (PVDF-g-PAA-Gn PAMAM film), n 1,2,3 or
4) it is film forming matrix that, the modified seperation film, which is PVDF powder is preprocessed, the modified modification PVDF powder being prepared, is led to
It crosses immersion precipitation phase inversion process and striking forms a film to obtain PVDF modification seperation film basement membrane (PVDF-g-PAA film), by the PVDF-
After g-PAA film is activated, by by the GnPAMAM of dispersion multistep processes preparation, (4) n 1,2,3 is grafted to the PVDF-g-
On PAA film, PVDF-g-PAA-GnPAMAM film is prepared;The activation processing condition of the modified seperation film of the PVDF are as follows: will
PVDF-g-PAA film is immersed in activating solution;The activating solution is by 1- ethyl -3- (3- dimethylamine propyl) carbodiimide hydrochloride
Salt (EDCHCl) and N- hydroxysuccinimide (NHS) sequentially add in water, and the final concentration in activating solution is respectively as follows:
EDCHCl:0.05~0.1mol/L, NHS:0.05~0.1mol/L.
Wherein, the PAMAM of different algebra is named as Gn PAMAM (n 1,2,3 or 4), wherein Gn shows the generation of PAMAM
Number, if G1.0 represents first generation PAMAM, other and so on.
Preferably, the activation condition of the PVDF-g-PAA film is, by the PVDF-g-PAA film and activating solution according to matter
Volume ratio 0.01-0.05g:10-50ml mixing is measured, vibrates 1.5-3h at 25~30 DEG C.
Preferably, n is 3 or 4 in the Gn PAMAM.
It is highly preferred that in the Gn PAMAM, n 3.
Preferably, the pre-treatment step of the PVDF powder are as follows: by PVDF powder through strong base solution and dehydrated alcohol alkali
After processing, after agitated, suction filtration, washing, drying obtains PVDF pretreatment powder;The matter of the PVDF powder and dehydrated alcohol
Measure volume ratio are as follows: 20~30g:4~6mL.
Preferably, the strong base solution is one of potassium hydroxide or sodium hydroxide.
It is highly preferred that the pre-treatment step of the PVDF powder are as follows: under the conditions of 60~70 DEG C, PVDF powder is quickly added
Enter into the potassium hydroxide solution of 2.5~3mol/L, while pouring into dehydrated alcohol rapidly, after agitated, suction filtration, washing, drying
It is spare, obtain PVDF pretreatment powder;The mass volume ratio of the PVDF powder, potassium hydroxide solution and dehydrated alcohol are as follows: 20
~30g:150-300mL:4~6mL.
Preferably, the preparation step of the modified PVDF powder are as follows: after pretreatment by PVDF powder, obtain PVDF and locate in advance
Manage powder, by the PVDF pretreatment powder and N-N dimethylformamide (DMF) according to 5~11g:100 of mass volume ratio~
120mL mixing, leads to 5~15min of nitrogen at 60~70 DEG C, after adding acrylic acid (AA) and azodiisobutyronitrile (AIBN),
Logical 15~25min of nitrogen is dried for standby after being filtered, being washed, and obtains the modified PVDF powder;The PVDF pre-processes powder
End and AA the and AIBN mass ratio being added are as follows: 5~11:10~15:0.1~0.3.
Preferably, the PVDF-g-PAA film the preparation method is as follows:
By the modified PVDF powder, polyethylene glycol (PEG) powder and DMF according to 8~10:4 of mass ratio~6:35~45
Mixing, stirs 6~12 hours at 60~70 DEG C, obtains casting solution, be poured on glass pane surface after deaeration after the casting solution,
100-300 μm of film forming thickness of knifing stick striking for being 100-300 μm with specification, glass plate is put into 25~30 DEG C of water and is solidified
Molding, obtains PVDF-G-PAA film;
Preferably, the step of heavy metal ion adsorbed type PVDF is modified seperation film is as follows:
(1) under the conditions of 60~70 DEG C, PVDF powder the pretreatment of PVDF powder: is added rapidly to 2.5~3mol/L
Potassium hydroxide solution in, while pouring into dehydrated alcohol rapidly, it is agitated, filter, after washing, be dried for standby, it is pre- to obtain PVDF
Handle powder;The mass volume ratio of the PVDF powder, potassium hydroxide solution and dehydrated alcohol are as follows: 20~30g:150-300mL:
4~6mL;
The preparation of modified PVDF powder: by PVDF pretreatment powder and N-N dimethylformamide (DMF) according to quality
5~11g:100 of volume ratio~120mL mixing, lead at 60~70 DEG C it is nitrogen gas dissolved, continue after powder dissolution logical nitrogen 5~
15min after adding acrylic acid (AA) and azodiisobutyronitrile (AIBN), leads to 15~25min of nitrogen, after being filtered, being washed, dries
It does spare, obtains modified PVDF powder;AA the and AIBN mass ratio of PVDF the pretreatment powder and addition are as follows: 5~11:10~
15:0.1~0.3.
(2) preparation of PVDF-g-PAA film:
By the modified PVDF powder, polyethylene glycol (PEG) powder and DMF according to 8~10:4 of mass ratio~6:35~45
Mixing, stirs 6~12 hours at 60~70 DEG C, obtains casting solution, be poured on glass pane surface after deaeration after the casting solution,
100-300 μm of film forming thickness of knifing stick striking for being 100-300 μm with specification, glass plate is put into 25~30 DEG C of water and is solidified
Molding, obtains PVDF-g-PAA film;
(3) preparation of Gn PAMAM:
1. preparing the PAMAM dendrimer of G0.5
Ethylenediamine (EDA) is mixed with methanol according to 4~6g:20ml of mass volume ratio, lead in ice-water bath nitrogen 1~
3h obtains EDA mixed liquor 1;Methyl acrylate (MA) is mixed with methanol according to 55~60g:20ml of mass volume ratio, MA is obtained
Mixed liquor;The MA mixed liquor is added drop-wise in the EDA mixed liquor with 1~3 drop/sec of speed, the MA mixed liquor and EDA
1 volume ratio of mixed liquor are as follows: 1-3:1 continues logical 30~50min of nitrogen, stops logical nitrogen later, in room temperature 20- after being added dropwise to complete
It is rotated after reacting 12-24h at 35 DEG C, temperature is 40~50 DEG C, obtains the PAMAM dendrimer of G0.5;
2. preparing G1.0PAMAM dendrimer
EDA is mixed with methanol according to 35~40g:50ml of mass volume ratio, 1~3h of nitrogen deoxidation is led under ice-water bath, is obtained
To EDA mixed liquor 2;G0.5PAMAM is mixed with methanol according to 10~20g:30ml of mass volume ratio, it is mixed to obtain G0.5PAMAM
Close liquid;The G0.5PAMAM mixed liquor is added drop-wise in the EDA mixed liquor 2 with 1~3 drop/sec of speed, it is described
G0.5PAMAM mixed liquor and 2 volume ratio of EDA mixed liquor are 1-3:1;Continue logical 30~60min of nitrogen after being added dropwise, later
Stop logical nitrogen, is rotated, 60~70 DEG C of temperature, finally obtained after being stirred to react 24~48h at 20-35 DEG C of room temperature
G1.0PAMAM。
3. preparing the PAMAM dendrimer of G1.5: using G1.0PAMAM as raw material, 1. preparing G0.5's according to step (3)
The EDA is replaced with the G1.0PAMAM, the PAMAM of G1.5 is finally prepared by the synthesis step of PAMAM.
4. preparing G2.0PAMAM dendrimer: it is raw material according to step (3) 2. step using the PAMAM of the G1.5, it will
The PAMAM of the G0.5 replaces with the PAMAM of the G1.5, and G2.0PAMAM is finally prepared;
5. the preparation of PAMAM, G4.0PAMAM dendrimer of PAMAM, G3.0PAMAM, G3.5 of G2.5 is according to step
(3) iteration synthesis is 1. 2. 3. 4. circuited sequentially, G1.0PAMAM, G2.0PAMAM, G3.0PAMAM are finally prepared respectively,
G4.0PAMAM。
Further, the step (3) is 5. specifically:
According to the synthesis step of step (3) 1. PAMAM of G0.5, the EDA is replaced with into the G2.0PAMAM, finally
The PAMAM of G2.5 is prepared.
According to the synthesis step of step (3) 2. G1.0PAMAM, the PAMAM of the G0.5 is replaced with the G2.5's
G3.0PAMAM is finally prepared in PAMAM.
Prepare the PAMAM dendrimer of G3.5: according to the synthesis step of step (3) 1. PAMAM of G0.5, by the second
Diamines (EDA) replaces with the G3.0PAMAM, and the PAMAM of G3.5 is finally prepared.
Prepare G4.0PAMAM dendrimer: according to the synthesis step of step (3) 2. G1.0PAMAM, by the G0.5's
PAMAM replaces with the PAMAM of the G3.5, and G4.0PAMAM is finally prepared.
(4) preparation of the modified seperation film of PVDF:
1. PVDF-g-PAA film is immersed in activating solution;The activating solution is by 1- ethyl -3- (3- dimethylamine propyl)
Carbodiimide hydrochloride (EDCHCl) and N- hydroxysuccinimide (NHS) sequentially add in water, the end in activating solution
Concentration is respectively as follows: EDCHCl:0.05~0.1mol/L, NHS:0.05~0.1mol/L;
After 2. basement membrane after will be activated is washed, be placed on the Gn PAMAM that quality solubility is 2~4% (n 1,
2,3 or 4) in solution, after vibrating 12-24h at 25~30 DEG C, it is modified that washed drying obtains heavy metal ion adsorbed type PVDF
Seperation film.
Beneficial effects of the present invention
PAMAM dendritic (as shown in Fig. 1) of the present invention, structure branches end have a large amount of primary amine
Group, inside is containing amide group, carbonyl group etc., and radical amount is in exponential increase with the increase of algebra.In addition, PAMAM
For dendritic structure, the cavity being formed in the interior thereof can chelate and wrap up heavy metal ion.Therefore, PAMAM dendrimer
Good absorption heavy metal ion effect can be obtained applied to heavy metal ion-containing waste water process field.
After PVDF seperation film grafting PAMAM of the present invention, film surface contains a large amount of hydrophilic amide groups and primary amine
Group, so that film significantly improves the suction-operated of heavy metal ion.And with grafting PAMAM algebra increase, film surface
Characteristic group number is exponentially increased, so that the effect of absorption heavy metal ion constantly increases.To G3.0PAMAM grafting
PVDF-g-PAA seperation film carries out heavy metal ion adsorbed test, the results showed that, modified caudacoria counterweight metal ion Cu2+、Ni2+、
Cd2+Adsorbance more than 100mg/g, removal of heavy metal ions rate has good suction to heavy metal ion 90% or more
Attached removal effect.
Utilize a kind of putting down for preparation method preparation of the modified seperation film of heavy metal ion adsorbed type PVDF of the present invention
Plate seperation film or hollow fiber separating film can efficient absorption heavy metal ion, and after adsorbing heavy metal ion, cleaning solution can be passed through
The heavy metal ion that cleaning seperation film is adsorbed with high efficiente callback, achievees the effect that reuse.
The purer pvdf membrane of water flux of the modified seperation film of PVDF of the present invention increases, and the hydrophily of film is changed
Kind and seperation film stable physical property.The preparation process of product of the present invention does not need special installation, implements to be easy, in general
Simple process is suitble to industrialization to generate, and increased costs amplitude is little.
In the present invention, EDCHCl and NHS proportion promotes the formation of the carboxyl of PVDF-g-PAA film surface in activating solution, only
Having the ratio of suitable activated solution just can significantly activate more carboxyls, improve the graft site of PAMAM.Utilize this hair
The Modified Membrane of bright preparation obtains unexpected technical effect, Cu2+The desorption of ion is significantly better than with regeneration performance
Compound film properties in the prior art.
Present invention seperation film basement membrane thickness control modified for PVDF keeps film surface bigger at 100-300 μm, can be containing more
More G n PAMAM is conducive to absorption G n PAMAM.
Detailed description of the invention
Fig. 1 is the structure chart of the G3.0PAMAM dendritic macromole in the embodiment of the present invention;
The static contact angle of Fig. 2 difference film;
Fig. 3 is the pure water flux of different films, wherein film -1:PVDF film, film -2:PVDF-g-PAA film, film -3:PVDF-g-
PAA-G1.0PAMAM film, film -4:PVDF-g-PAA-G2.0PAMAM film, film -5:PVDF-g-PAA-G3.0PAMAM film, film -6:
PVDF-g-PAA-G4.0PAMAM film;
Fig. 4 is the adsorbance of different films, wherein film -1:PVDF film, film -2:PVDF-g-PAA film, film -3:PVDF-g-
PAA-G1.0PAMAM film, film -4:PVDF-g-PAA-G2.0PAMAM film, film -5:PVDF-g-PAA-G3.0PAMAM film, film -6:
PVDF-g-PAA-G4.0PAMAM film;
Fig. 5 is different films to Cu2+The desorption and regeneration performance of ion, wherein (a) (b) (c) (d) is respectively indicated
PVDF-g-PAA-G1.0PAMAM film, PVDF-g-PAA-G2.0PAMAM film, PVDF-g-PAA-G3.0PAMAM film, PVDF-g-
PAA-G4.0PAMAM film;
Specific embodiment
The present invention is described below by specific embodiment.Unless stated otherwise, technological means used in the present invention
It is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, it is not intended to limit the present invention
Range, the spirit and scope of the invention are limited only by the claims that follow.To those skilled in the art, without departing substantially from this
Under the premise of invention spirit and scope, to the various changes or change of material component and dosage progress in these embodiments
It belongs to the scope of protection of the present invention.
The preparation of the modified seperation film PVDF-g-PAA-Gn PAMAM film of the heavy metal ion adsorbed type PVDF of embodiment 1
(1) pretreatment of PVDF powder.The potassium hydroxide solution that 25g potassium hydroxide is configured to 2.5mol/L is weighed, 60
Under DEG C water-bath, 20g PVDF powder is added rapidly in potassium hydroxide solution, control PVDF powder, potassium hydroxide solution ratio are
20g:150-300mL, while pouring into 4mL dehydrated alcohol rapidly and being filtered after stirring 10min, and washing 3 with a large amount of deionized waters
More than secondary, the product finally obtained is dried for standby.The PVDF powder 5g after processing is taken to be placed on 100mL N-N dimethyl formyl
In amine (DMF), lead at 60 DEG C nitrogen gas dissolved, continues logical nitrogen 5min after the dissolution of PVDF powder, add 10g acrylic acid
(AA) and 0.1g azodiisobutyronitrile (AIBN) leads to nitrogen 15min afterwards, filters after persistently stirring 12h, multiple using deionized water
Washing, the product finally obtained are dried for standby.
(2) preparation of the modified seperation film basement membrane of PVDF.Take modified PVDF powder 8g, polyethylene glycol (PEG) powder 4g, DMF
Solution 35g is placed in three-necked flask, is stirred 6 hours at 60 DEG C, casting solution is poured on glass pane surface after standing and defoaming, with rule
The knifing stick striking film forming thickness that lattice are 200 μm is 200 μm, and glass plate is put into curing molding in 25 DEG C of water, takes out film and protects
It deposits spare in deionized water.
(3) Gn PAMAM (n=1,2,3,4).1. preparing G0.5PAMAM dendrimer: it is molten to weigh 4g ethylenediamine (EDA)
In 20ml methanol, nitrogen 1h is led in ice-water bath, EDA mixed liquor 1 is obtained, weighs 55g methyl acrylate (MA) and be dissolved in 20ml
Methanol obtains MA mixed liquor, and MA mixed liquor is placed in constant pressure funnel, maintains reaction condition constant, with 1 drop/sec of speed
Degree is added drop-wise in EDA solution, continues logical nitrogen 30min after being added dropwise to complete, and stops logical nitrogen later, after reacting for 24 hours at room temperature
It is rotated, temperature is 40 DEG C, obtains the PAMAM dendrimer of G0.5, the MA mixed liquor and 1 volume ratio of EDA mixed liquor
Are as follows: 1:1.
2. preparing G1.0PAMAM dendrimer: weighing 35gEDA and be dissolved in 50ml methanol, lead to nitrogen deoxidation under ice-water bath
1h obtains EDA mixed liquor 2;Then G0.5PAMAM 10g will be taken to be dissolved in 30ml methanol, and will obtain G0.5PAMAM mixed liquor, sets
It in constant pressure funnel, is added drop-wise in solution with 1 drop/sec of speed, continues logical nitrogen 30min after being added dropwise, later
Stopping logical nitrogen, reaction is stirred at room temperature and is rotated afterwards with Rotary Evaporators for 24 hours, temperature 60 C finally obtains G1.0PAMAM,
The G0.5PAMAM mixed liquor and 2 volume ratio of EDA mixed liquor are 1-2:1.
3. preparing the PAMAM dendrimer of G1.5: using G1.0PAMAM as raw material, 1. preparing G0.5's according to step (3)
The EDA is replaced with the G1.0PAMAM, the PAMAM of G1.5 is finally prepared by the synthesis step of PAMAM.
4. preparing G2.0PAMAM dendrimer: it is raw material according to step (3) 2. step using the PAMAM of the G1.5, it will
The PAMAM of the G0.5 replaces with the PAMAM of the G1.5, and G2.0PAMAM is finally prepared;
5. the preparation of PAMAM, G4.0PAMAM dendrimer of PAMAM, G3.0PAMAM, G3.5 of G2.5 is according to step
(3) iteration synthesis is 1. 2. 3. 4. circuited sequentially, G1.0PAMAM, G2.0PAMAM, G3.0PAMAM are finally prepared respectively,
G4.0PAMAM。
(4) 1. the modified seperation film basement membrane of PVDF is immersed in activating solution;The activating solution is by 1- ethyl -3- (3- bis-
Methylamine propyl) carbodiimide hydrochloride (EDCHCl) and N- hydroxysuccinimide (NHS) sequentially add in water, activating
Final concentration in liquid is respectively as follows: EDCHCl:0.05mol/L, NHS:0.05mol/L, by the PVDF-g-PAA film and activation
Liquid is mixed according to mass volume ratio 0.01g:10ml, 1.5h is vibrated at 25 DEG C, by the ultrapure water repeated flushing of the basement membrane after activation
5-6 times;
After 2. four pieces of basement membranes after will be activated are washed, it is individually positioned in the G1.0PAMAM that quality solubility is 3%,
In G2.0PAMAM, G3.0PAMAM, G4.0PAMAM solution, after vibrating 12h at 25~30 DEG C, after ultrapure water repeated flushing
Drying respectively obtains the modified seperation film PVDF-g-PAA-G1.0PAMAM film of heavy metal ion adsorbed type PVDF, PVDF-g-PAA-
G2.0PAMAM film, PVDF-g-PAA-G3.0PAMAM, PVDF-g-PAA-G4.0PAMAM.
Embodiment 2: the preparation of the modified seperation film PVDF-g-PAA-Gn PAMAM film of heavy metal ion adsorbed type PVDF
(1) pretreatment of PVDF powder.The sodium hydroxide solution that 30g potassium hydroxide is configured to 3mol/L is weighed, at 70 DEG C
Under water-bath, 30g PVDF powder is added rapidly in sodium hydroxide solution, while pouring into 6mL dehydrated alcohol rapidly and stirring
It filters after 20min, and is washed 5 times or more with a large amount of deionized waters, the product finally obtained is dried for standby.It takes after processing
PVDF powder 11g is placed in 120mL N-N dimethylformamide (DMF), lead at 70 DEG C it is nitrogen gas dissolved, it is molten to PVDF powder
Continue logical nitrogen 15min after solution, add 15g acrylic acid (AA) and 0.3g azodiisobutyronitrile (AIBN) and lead to nitrogen 25min afterwards,
It filters, is repeatedly washed using deionized water, the product finally obtained is dried for standby, PVDF powder, hydroxide after persistently stirring 12h
Potassium solution mass volume ratio is 30g:150mL.
(2) preparation of the modified seperation film basement membrane of PVDF.Take modified PVDF powder 10g, polyethylene glycol (PEG) powder 6g, DMF
Solution 45g is placed in three-necked flask, stirs 12 hours at 70 DEG C, casting solution is poured on glass pane surface after standing and defoaming, is used
The knifing stick striking that specification is 150 μm forms a film 150 μm, and glass plate is put into curing molding in 30 DEG C of water, takes out film and is stored in
It is spare in deionized water.
(3) preparation of Gn PAMAM.1. preparing G0.5PAMAM dendrimer: weighing 6g ethylenediamine (EDA) and be dissolved in 20ml
In methanol, nitrogen 3h is led in ice-water bath, EDA mixed liquor 1 is obtained, weighs 60g methyl acrylate (MA) and be dissolved in 20ml methanol, obtain
To MA mixed liquor, after MA mixed liquor is placed in constant pressure funnel, maintain reaction condition constant, be added dropwise with 3 drops/sec of speed
Into EDA solution, continue logical nitrogen 50min after being added dropwise to complete, stops logical nitrogen later, revolved after reacting 13h at room temperature
It steams, temperature is 50 DEG C, the PAMAM dendrimer of G0.5 is obtained, wherein MA mixed liquor and 1 volume ratio of EDA mixed liquor are as follows: 1-2:
1。
2. preparing G1.0PAMAM dendrimer: weighing 40gEDA and be dissolved in 50ml methanol, lead to nitrogen deoxidation under ice-water bath
3h obtains EDA mixed liquor 2, then G0.5PAMAM 20g will be taken to be dissolved in 30ml methanol, obtains G0.5PAMAM mixed liquor, will
G0.5PAMAM mixed liquor is placed in constant pressure funnel, is added drop-wise in solution with 3 drops/sec of speed, is continued after being added dropwise
Logical nitrogen 60min stops logical nitrogen later, is rotated after reaction 48h is stirred at room temperature with Rotary Evaporators, temperature 70 C, most
After obtain G1.0PAMAM, G0.5PAMAM mixed liquor and 2 volume ratio of EDA mixed liquor are 1:1.
Using the G1.0PAMAM of synthesis as raw material, G1.5PAMAM can be made in the synthesis step according to G0.5PAMAM.With synthesis
G1.5PAMAM be raw material, G2.0PAMAM can be made according to the synthetic method of G1.0PAMAM, so repeatedly step, until closing
At G4.0PAMAM.
(4) preparation of the modified seperation film of PVDF
1. the modified seperation film basement membrane of PVDF is immersed in activating solution;The activating solution is by 1- ethyl -3- (3- dimethylamine
Propyl) carbodiimide hydrochloride (EDCHCl) and N- hydroxysuccinimide (NHS) sequentially add in water, in activating solution
Final concentration be respectively as follows: EDCHCl:0.1mol/L, NHS:0.1mol/L, by the PVDF-g-PAA film and activating solution according to
Mass volume ratio 0.05g:50ml is mixed, and 3h is vibrated at 30 DEG C, by the basement membrane after activation with ultrapure water repeated flushing 6 times;
After 2. four pieces of basement membranes after will be activated are washed, it is individually positioned in the G1.0PAMAM that quality solubility is 2%,
In G2.0PAMAM, G3.0PAMAM, G4.0PAMAM solution, after vibrating 13h at 25~30 DEG C, after ultrapure water repeated flushing
Drying respectively obtains the modified seperation film PVDF-g-PAA-G1.0PAMAM film of heavy metal ion adsorbed type PVDF, PVDF-g-PAA-
G2.0PAMAM film, PVDF-g-PAA-G3.0PAMAM, PVDF-g-PAA-G4.0PAMAM.
The preparation of the modified seperation film PVDF-g-PAA-Gn PAMAM film of the heavy metal ion adsorbed type PVDF of embodiment 3
(1) pretreatment of PVDF powder.The potassium hydroxide solution that 28g potassium hydroxide is configured to 2.8mol/L is weighed, 65
Under DEG C water-bath, 25g PVDF powder is added rapidly in potassium hydroxide solution, while pouring into 5mL dehydrated alcohol rapidly and stirring
It filters after 15min, and is washed 4 times or more with a large amount of deionized waters, the product finally obtained is dried for standby.It takes after processing
PVDF powder 8g is placed in 110mL N-N dimethylformamide (DMF), lead at 65 DEG C it is nitrogen gas dissolved, it is molten to PVDF powder
Continue logical nitrogen 10min after solution, add 12g acrylic acid (AA) and 0.2g azodiisobutyronitrile (AIBN) and lead to nitrogen 20min afterwards,
Persistently stir 12h after filter, repeatedly washed using deionized water, the product finally obtained is dried for standby, wherein PVDF powder with
Potassium hydroxide solution mass volume ratio are as follows: 25g:150-300mL.
(2) preparation of the modified seperation film basement membrane of PVDF.Take modified PVDF powder 9g, polyethylene glycol (PEG) powder 5g, DMF
Solution 40g is placed in three-necked flask, is stirred 8 hours at 65 DEG C, casting solution is poured on glass pane surface after standing and defoaming, with rule
The knifing stick striking film forming thickness that lattice are 100 μm is 100 μm, and glass plate is put into curing molding in 28 DEG C of water, takes out film and protects
It deposits spare in deionized water.
(3) preparation of Gn PAMAM.
1. preparing G0.5PAMAM dendrimer: weighing 5g ethylenediamine (EDA) and be dissolved in 20ml methanol, in ice-water bath
Logical nitrogen 2h, obtains EDA mixed liquor 1;It weighs 58g methyl acrylate (MA) and is dissolved in 20ml methanol, obtain MA mixed liquor;It will be described
MA mixed liquor is placed in constant pressure funnel, is maintained reaction condition constant, is added drop-wise in EDA solution with 2 drops/sec of speed, is dripped
Continuing logical nitrogen 40min after adding into, stops logical nitrogen later, react rotated afterwards for 24 hours at room temperature, temperature is 45 DEG C,
Obtain the PAMAM dendrimer of G0.5.
2. preparing G1.0PAMAM dendrimer: weighing 38gEDA and be dissolved in 50ml methanol, lead to nitrogen deoxidation under ice-water bath
2h obtains EDA mixed liquor 2;Then G0.5PAMAM 15g will be taken to be dissolved in 30ml methanol, and will obtain G0.5PAMAM mixed liquor, it will
The G0.5PAMAM mixed liquor is placed in constant pressure funnel, is added drop-wise in solution with 2 drops/sec of speed, after being added dropwise
Continue logical nitrogen 45min, stop logical nitrogen later, is rotated after reaction 36h is stirred at room temperature with Rotary Evaporators, temperature 65
DEG C, finally obtain G1.0PAMAM.
3. preparing the PAMAM dendrimer of G1.5: using G1.0PAMAM as raw material, 1. preparing G0.5's according to step (3)
The EDA is replaced with the G1.0PAMAM, the PAMAM of G1.5 is finally prepared by the synthesis step of PAMAM.
4. preparing G2.0PAMAM dendrimer: it is raw material according to step (3) 2. step using the PAMAM of the G1.5, it will
The PAMAM of the G0.5 replaces with the PAMAM of the G1.5, and G2.0PAMAM is finally prepared;
5. the EDA is replaced with the G2.0PAMAM, most according to the synthesis step of step (3) 1. PAMAM of G0.5
The PAMAM of G2.5 is prepared eventually.
According to the synthesis step of step (3) 2. G1.0PAMAM, the PAMAM of the G0.5 is replaced with the G2.5's
G3.0PAMAM is finally prepared in PAMAM.
Prepare the PAMAM dendrimer of G3.5: according to the synthesis step of step (3) 1. PAMAM of G0.5, by the second
Diamines (EDA) replaces with the G3.0PAMAM, and the PAMAM of G3.5 is finally prepared.
Prepare G4.0PAMAM dendrimer: according to the synthesis step of step (3) 2. G1.0PAMAM, by the G0.5's
PAMAM replaces with the PAMAM of the G3.5, and G4.0PAMAM is finally prepared.
(4) preparation of the modified seperation film of PVDF.
1. the modified seperation film basement membrane of PVDF is immersed in activating solution;The activating solution is by 1- ethyl -3- (3- dimethylamine
Propyl) carbodiimide hydrochloride (EDCHCl) and N- hydroxysuccinimide (NHS) sequentially add in water, in activating solution
Final concentration be respectively as follows: EDCHCl:0.08mol/L, NHS:0.08mol/L, the PVDF-g-PAA film is pressed with activating solution
It is mixed according to mass volume ratio 0.03g:35ml, 2h is vibrated at 25~30 DEG C, by the ultrapure water repeated flushing 5-6 of the basement membrane after activation
Time;
After 2. four pieces of basement membranes after will be activated are washed, be individually positioned in quality solubility be 2~4% it is described
In G1.0PAMAM, G2.0PAMAM, G3.0PAMAM, G4.0PAMAM solution, after vibrating 16h at 25~30 DEG C, ultrapure water is used
Drying respectively obtains the modified seperation film PVDF-g-PAA-G1.0PAMAM film of heavy metal ion adsorbed type PVDF after repeated flushing,
PVDF-g-PAA-G2.0PAMAM film, PVDF-g-PAA-G3.0PAMAM, PVDF-g-PAA-G4.0PAMAM.
The preparation of the modified seperation film PVDF-g-PAA-Gn PAMAM film of the heavy metal ion adsorbed type PVDF of embodiment 4
(1) pretreatment of PVDF powder.The potassium hydroxide solution that 25g potassium hydroxide is configured to 3mol/L is weighed, at 60 DEG C
Under water-bath, 30g PVDF powder is added rapidly in potassium hydroxide solution, while pouring into 4mL dehydrated alcohol rapidly and stirring
It filters after 20min, and is washed 3 times or more with a large amount of deionized waters, the product finally obtained is dried for standby.It takes after processing
PVDF powder 11g is placed in 100mL N-N dimethylformamide (DMF), lead at 70 DEG C it is nitrogen gas dissolved, it is molten to PVDF powder
Continue logical nitrogen 5min after solution, add 15g acrylic acid (AA) and 0.1g azodiisobutyronitrile (AIBN) and lead to nitrogen 25min afterwards,
It filters, is repeatedly washed using deionized water, the product finally obtained is dried for standby, wherein PVDF powder, hydrogen after persistently stirring 12h
Potassium oxide solution mass volume ratio are as follows: 30g:300mL.
(2) preparation of the modified seperation film basement membrane of PVDF.Take modified PVDF powder 8g, polyethylene glycol (PEG) powder 6g, DMF
Solution 35g is placed in three-necked flask, is stirred 6 hours at 70 DEG C, casting solution is poured on glass pane surface after standing and defoaming, with rule
The knifing stick striking film forming thickness that lattice are 250 μm is 250 μm, and glass plate is put into curing molding in 30 DEG C of water, takes out film and protects
It deposits spare in deionized water.
(3) preparation of Gn PAMAM.1. preparing G0.5PAMAM dendrimer: weighing 4g ethylenediamine (EDA) and be dissolved in 20ml
In methanol, leads to nitrogen 3h in ice-water bath and obtains EDA mixed liquor 1, weigh 55g methyl acrylate (MA) and be dissolved in 20ml methanol, it obtains
To MA mixed liquor, the MA mixed liquor is placed in constant pressure funnel, maintains reaction condition constant, is dripped with 3 drops/sec of speed
It is added in EDA solution, continues logical nitrogen 30min after being added dropwise to complete, stop logical nitrogen later, carried out after reacting at room temperature for 12 hours
Revolving, temperature are 50 DEG C, obtain the PAMAM dendrimer of G0.5, wherein the MA mixed liquor and 1 volume ratio of EDA mixed liquor
Are as follows: 1:1.
2. preparing G1.0PAMAM dendrimer: weighing 35gEDA and be dissolved in 50ml methanol, lead to nitrogen deoxidation under ice-water bath
3h obtains EDA mixed liquor 2;Then G0.5PAMAM 10g will be taken to be dissolved in 30ml methanol, and will obtain G0.5PAMAM mixed liquor;It will
The G0.5PAMAM mixed liquor is placed in constant pressure funnel, is added drop-wise in solution with 3 drops/sec of speed, after being added dropwise
Continue logical nitrogen 30min, stop logical nitrogen later, is rotated after reaction 48h is stirred at room temperature with Rotary Evaporators, temperature 60
DEG C, finally obtain G1.0PAMAM, wherein the G0.5PAMAM mixed liquor is 1:1 with 2 volume ratio of EDA mixed liquor
3. preparing the PAMAM dendrimer of G1.5: using G1.0PAMAM as raw material, 1. preparing G0.5's according to step (3)
The EDA is replaced with the G1.0PAMAM, the PAMAM of G1.5 is finally prepared by the synthesis step of PAMAM.
4. preparing G2.0PAMAM dendrimer: it is raw material according to step (3) 2. step using the PAMAM of the G1.5, it will
The PAMAM of the G0.5 replaces with the PAMAM of the G1.5, and G2.0PAMAM is finally prepared;
5. the preparation of PAMAM, G4.0PAMAM dendrimer of PAMAM, G3.0PAMAM, G3.5 of G2.5 is according to step
(3) iteration synthesis is 1. 2. 3. 4. circuited sequentially, G1.0PAMAM, G2.0PAMAM, G3.0PAMAM are finally prepared respectively,
G4.0PAMAM。
(4) preparation of the modified seperation film of PVDF.
1. the modified seperation film basement membrane of PVDF is immersed in activating solution;The activating solution is by 1- ethyl -3- (3- dimethylamine
Propyl) carbodiimide hydrochloride (EDCHCl) and N- hydroxysuccinimide (NHS) sequentially add in water, in activating solution
Final concentration be respectively as follows: EDCHCl:0.1mol/L, NHS:0.05mol/L, by the PVDF-g-PAA film and activating solution according to
Mass volume ratio 0.03g:20ml is mixed, and 2h is vibrated at 30 DEG C, by the basement membrane after activation with ultrapure water repeated flushing 6 times;
After 2. four pieces of basement membranes after will be activated are washed, be individually positioned in quality solubility be 2% it is described
In G1.0PAMAM, G2.0PAMAM, G3.0PAMAM, G4.0PAMAM solution, after vibrating 12h at 30 DEG C, repeatedly with ultrapure water
Drying respectively obtains the modified seperation film PVDF-g-PAA-G1.0PAMAM film of heavy metal ion adsorbed type PVDF, PVDF- after flushing
G-PAA-G2.0PAMAM film, PVDF-g-PAA-G3.0PAMAM, PVDF-g-PAA-G4.0PAMAM.
The preparation of the modified seperation film PVDF-g-PAA-Gn PAMAM film of the heavy metal ion adsorbed type PVDF of embodiment 5
(1) pretreatment of PVDF powder.The potassium hydroxide solution that 30g potassium hydroxide is configured to 2.5mol/L is weighed, 70
Under DEG C water-bath, 20g PVDF powder is added rapidly in potassium hydroxide solution, while pouring into 6mL dehydrated alcohol rapidly and stirring
It filters after 10min, and is washed 5 times or more with a large amount of deionized waters, the product finally obtained is dried for standby.It takes after processing
PVDF powder 5g is placed in 120mL N-N dimethylformamide (DMF), lead at 60 DEG C it is nitrogen gas dissolved, it is molten to PVDF powder
Continue logical nitrogen 15min after solution, add 10g acrylic acid (AA) and 0.3g azodiisobutyronitrile (AIBN) and lead to nitrogen 15min afterwards,
It filters, is repeatedly washed using deionized water, the product finally obtained is dried for standby, wherein PVDF powder, hydrogen after persistently stirring 12h
Potassium oxide solution mass volume ratio are as follows: 30g:150-300mL.
(2) preparation of the modified seperation film basement membrane of PVDF.Take modified PVDF powder 10g, polyethylene glycol (PEG) powder 4g, DMF
Solution 45g is placed in three-necked flask, stirs 12 hours at 60 DEG C, casting solution is poured on glass pane surface after standing and defoaming, is used
300 μm of specification of knifing stick striking film forming thickness is 300 μm, and glass plate is put into curing molding in 25 DEG C of water, takes out film and protects
It deposits spare in deionized water.
(3) preparation of PAMAM.1. preparing G0.5PAMAM dendrimer: weighing 6g ethylenediamine (EDA) and be dissolved in 20ml first
In alcohol, nitrogen 1h is led in ice-water bath, obtains EDA mixed liquor 1;It weighs 60g methyl acrylate (MA) and is dissolved in 20ml methanol, obtain
MA mixed liquor;The MA mixed liquor is placed in constant pressure funnel, maintains reaction condition constant, is added dropwise with 1 drop/sec of speed
Into EDA solution, continue logical nitrogen 50min after being added dropwise to complete, stops logical nitrogen later, react revolved afterwards for 24 hours at room temperature
It steams, temperature is 40 DEG C, the PAMAM dendrimer of G0.5 is obtained, wherein MA mixed liquor and 1 volume ratio of EDA mixed liquor are as follows: 1-2:
1,.
2. preparing G1.0PAMAM dendrimer: weighing 40gEDA and be dissolved in 50ml methanol, lead to nitrogen deoxidation under ice-water bath
1h obtains EDA mixed liquor 2;Then G0.5PAMAM 20g will be taken to be dissolved in 30ml methanol, and will obtain G0.5PAMAM mixed liquor;It will
The G0.5PAMAM mixed liquor is placed in constant pressure funnel, is added drop-wise in solution with 1 drop/sec of speed, after being added dropwise
Continue logical nitrogen 60min, stop logical nitrogen later, reaction is stirred at room temperature and is rotated afterwards with Rotary Evaporators for 24 hours, temperature 70
DEG C, finally obtain G1.0PAMAM, wherein G0.5PAMAM mixed liquor is 1-2:1 with 2 volume ratio of EDA mixed liquor.
3. preparing the PAMAM dendrimer of G1.5: using G1.0PAMAM as raw material, 1. preparing G0.5's according to step (3)
The EDA is replaced with the G1.0PAMAM, the PAMAM of G1.5 is finally prepared by the synthesis step of PAMAM.
4. preparing G2.0PAMAM dendrimer: it is raw material according to step (3) 2. step using the PAMAM of the G1.5, it will
The PAMAM of the G0.5 replaces with the PAMAM of the G1.5, and G2.0PAMAM is finally prepared;
According to the synthesis step of step (3) 1. PAMAM of G0.5, the EDA is replaced with into the G2.0PAMAM, finally
The PAMAM of G2.5 is prepared.
According to the synthesis step of step (3) 2. G1.0PAMAM, the PAMAM of the G0.5 is replaced with the G2.5's
G3.0PAMAM is finally prepared in PAMAM.
Prepare the PAMAM dendrimer of G3.5: according to the synthesis step of step (3) 1. PAMAM of G0.5, by the second
Diamines (EDA) replaces with the G3.0PAMAM, and the PAMAM of G3.5 is finally prepared.
Prepare G4.0PAMAM dendrimer: according to the synthesis step of step (3) 2. G1.0PAMAM, by the G0.5's
PAMAM replaces with the PAMAM of the G3.5, and G4.0PAMAM is finally prepared.(4) preparation of the modified seperation film of PVDF:
The modified seperation film basement membrane of PVDF is immersed in activating solution;The activating solution is by 1- ethyl -3- (3- dimethylamine third
Base) carbodiimide hydrochloride (EDCHCl) and N- hydroxysuccinimide (NHS) sequentially add in water, in activating solution
Final concentration is respectively as follows: EDCHCl:0.05~0.1mol/L, NHS:0.05~0.1mol/L, by the PVDF-g-PAA film with
Activating solution is mixed according to mass volume ratio 0.01-0.05g:10-50ml, vibrates 4h at 25 DEG C;
After four pieces of basement membranes after will be activated are washed, be individually positioned in quality solubility be 2~4% it is described
In G1.0PAMAM, G2.0PAMAM, G3.0PAMAM, G4.0PAMAM solution, after vibrating 12h at 25~30 DEG C, ultrapure water is used
Drying respectively obtains the modified seperation film PVDF-g-PAA-G1.0PAMAM film of heavy metal ion adsorbed type PVDF after repeated flushing,
PVDF-g-PAA-G2.0PAMAM film, PVDF-g-PAA-G3.0PAMAM, PVDF-g-PAA-G4.0PAMAM.
The preparation of the modified seperation film PVDF-g-PAA-Gn PAMAM film of the heavy metal ion adsorbed type PVDF of embodiment 6
(1) pretreatment of PVDF powder.The potassium hydroxide solution that 28g potassium hydroxide is configured to 2.5mol/L is weighed, 60
Under DEG C water-bath, 28.57g PVDF powder is added rapidly in potassium hydroxide solution, while pouring into 5.6mL dehydrated alcohol rapidly
And filtered after stirring 15min, and washed 5 times or more with a large amount of deionized waters, the product finally obtained is dried for standby, wherein PVDF
The mass volume ratio of powder and potassium hydroxide solution are as follows: 28.57g:150-300mL.
It takes the PVDF powder 10g after processing to be placed in 120mL N-N dimethylformamide (DMF), leads at 70 DEG C
It is nitrogen gas dissolved, continue logical nitrogen 15min after the dissolution of PVDF powder, adds two isobutyl of 12g acrylic acid (AA) and 0.2g azo
Nitrile (AIBN) leads to nitrogen 20min afterwards, filters after persistently stirring 12h, is repeatedly washed using deionized water, and the product finally obtained dries
It does spare.
(2) preparation of the modified seperation film basement membrane of PVDF.Take modified PVDF powder 8g, polyethylene glycol (PEG) powder 4g, DMF
Solution 38g is placed in three-necked flask, stirs 12 hours at 60 DEG C, casting solution is poured on glass pane surface after standing and defoaming, is used
The knifing stick striking film forming thickness that specification is 200 μm is 200 μm, and glass plate is put into curing molding in 25 DEG C of water, takes out film
It saves spare in deionized water.
(3) preparation of G1.0PAMAM, G2.0PAMAM, G3.0PAMAM, G4.0PAMAM are the same as embodiment 5
(4) preparation of the modified seperation film of PVDF:
1. the modified seperation film basement membrane of PVDF is immersed in activating solution;The activating solution is by 1- ethyl -3- (3- dimethylamine
Propyl) carbodiimide hydrochloride (EDCHCl) and N- hydroxysuccinimide (NHS) sequentially add in water, in activating solution
Final concentration be respectively as follows: EDCHCl:0.05mol/L, NHS:0.05mol/L, the PVDF-g-PAA film is pressed with activating solution
It is mixed according to mass volume ratio 0.01-0.05g:10-50ml, vibrates 1.5-2h at 25~30 DEG C;By the basement membrane after activation with ultrapure
Water repeated flushing 3 times;
After 2. four pieces of basement membranes after will be activated are washed, be individually positioned in quality solubility be 2~4% it is described
In G1.0PAMAM, G2.0PAMAM, G3.0PAMAM, G4.0PAMAM solution, after vibrating 12-15h at 25~30 DEG C, use is ultrapure
Drying respectively obtains the modified seperation film PVDF-g-PAA-G1.0PAMAM film of heavy metal ion adsorbed type PVDF after water repeated flushing,
PVDF-g-PAA-G2.0PAMAM film, PVDF-g-PAA-G3.0PAMAM, PVDF-g-PAA-G4.0PAMAM.
7 comparative experiments of embodiment
(1) pretreatment of PVDF powder.The potassium hydroxide solution that 70g potassium hydroxide is configured to 2.5mol/L is weighed, 60
Under DEG C water-bath, 70g PVDF powder is added rapidly in potassium hydroxide solution, while pouring into 15mL dehydrated alcohol rapidly and stirring
It filters after mixing 15min, and is washed 3 times or more with a large amount of deionized waters, the product finally obtained is dried for standby.It takes after processing
PVDF powder 10g is placed in 120mL N-N dimethylformamide (DMF), lead at 70 DEG C it is nitrogen gas dissolved, it is molten to PVDF powder
Continue logical nitrogen 15min after solution, add 12g acrylic acid (AA) and 0.2g azodiisobutyronitrile (AIBN) and lead to nitrogen 20min afterwards,
It filters, is repeatedly washed using deionized water, the product finally obtained is dried for standby after persistently stirring 12h.
(2) preparation of the modified seperation film basement membrane of PVDF.Take modified PVDF powder 6g, polyethylene glycol (PEG) powder 3g, DMF
Solution 28.5g is placed in three-necked flask, stirs 12 hours at 60 DEG C, casting solution is poured on glass pane surface after standing and defoaming,
It is formed a film with 300 μm of knifing stick strikings, glass plate is put into curing molding in 25 DEG C of water, taken out film and save in deionized water
It is spare.
(3) preparation of PAMAM.With embodiment 5
(4) preparation of the modified seperation film of PVDF.
The modified seperation film basement membrane of PVDF is immersed in activating solution;The activating solution is by 1- ethyl -3- (3- dimethylamine third
Base) carbodiimide hydrochloride (EDCHCl) and N- hydroxysuccinimide (NHS) sequentially add in water, in activating solution
Final concentration is respectively as follows: EDCHCl:0.002mol/L, NHS:0.005mol/L, and the PVDF-g-PAA film is pressed with activating solution
It is mixed according to mass volume ratio 0.01-0.05g:10-50ml, vibrates 1h at 25 DEG C;
By 4 pieces of basement membrane after activation with after ultrapure water repeated flushing 3 times, being individually positioned in quality solubility is 3%
In G1.0PAMAM, G2.0PAMAM, G3.0PAMAM, G4.0PAMAM solution, after being vibrated for 24 hours at 25 DEG C, repeatedly with ultrapure water
Drying respectively obtains the modified seperation film PVDF-g-PAA-G1.0PAMAM film of heavy metal ion adsorbed type PVDF, PVDF- after flushing
G-PAA-G2.0PAMAM film, PVDF-g-PAA-G3.0PAMAM, PVDF-g-PAA-G4.0PAMAM.It will measure, the above film is to parent
Aqueous, permeability, Cu2+Adsorbance and film are to Cu2+The desorption cycle of ion tests discovery, and wherein average behavior is best is
PVDF-g-PAA-G3.0PAMAM film.
The performance test of embodiment 8PVDF-g-PAA-Gn PAMAM film
PVDF-g-PAA-G1.0PAMAM film as described below, PVDF-g-PAA-G2.0PAMAM film, PVDF-g-PAA-
G3.0PAMAM, PVDF-g-PAA-G4.0PAMAM are prepared by embodiment 6;
PVDF-g-PAA film as described below is the PVDF-g-PAA film that is prepared of 6 step of embodiment (2) (without work
Change);
Pvdf membrane as described below is selection and the method for 6 step of embodiment (2), will be same as Example 6 initial
PVDF powder (not pretreated starting powder), 8g, polyethylene glycol (PEG) powder 4g, DMF solution 38g are placed in three-necked flask
In, it is stirred 12 hours at 60 DEG C, casting solution is poured on glass pane surface after standing and defoaming, the knifing stick for being 200 μm with specification
Striking film forming thickness is 200 μm, and glass plate is put into curing molding in 25 DEG C of water, obtains pvdf membrane.
1, hydrophily is tested
In the hydrophilicity measurement to different films, the pvdf membrane it can be seen from 2 figure of attached drawing, PVDF-g-PAA film,
The contact angle of PVDF-g-PAA-G1.0PAMAM film-PVDF-g-PAA-G4.0PAMAM film is 91.2 ° at the beginning, 84.7 °,
65.9 °, 61.1 °, 36.7 ° and 50.7 °, and after grafting PAMAM, the downward trend of contact angle increases.PVDF-g-PAA-PAMAM
The contact angle of film declines, and is that can quickly make moisture film because the amino and amide groups that PAMAM has are hydrophilic radical.PAMAM
Algebra increases, can make containing amino and amide groups increase so that the PAMAM of high algebra have more hydrophily.But pass through
The hydrophily of PVDF-g-PAA-G3.0 film is optimal known to experiment, this is because there are space steric effects in grafting, makes
The grafting rate of G4.0PAMAM is lower than G3.0PAMAM, so that its hydrophily is lower than G3.0PAMAM.
The static contact angle of the different films of table 1
2, permeability
In it can measure to different permeability of the membranes, attached drawing 2 is pvdf membrane, PVDF-g-PAA film, PVDF-g-PAA-
The pure water flux of G1.0PAMAM film-PVDF-g-PAA-G4.0PAMAM film, is respectively 199L/ (m2h)、361L/(m2h)、
428L/(m2h)、448L/(m2h)、502L/(m2h)、485L/(m2h).Due to hydrophobicity, the flux of pvdf membrane is lower;Grafting
After PAA, for PVDF-g-PAA film due to the hydrophily of AA, flux increases 361L/ (m2h);After being grafted PAMAM, the flux of film
It improves, flux is peak when being grafted G3.0PAMAM.It is since cavity structure has water conservation that grafting PAMAM, which can improve hydrophily,
Property, water energy run through hydrated sheath, then plus its contain a large amount of hydrophilic radical, can be improved hydrophily.Also due to space bit
The influence of resistance, the film permeation flux for being grafted G3.0PAMAM are higher than G4.0PAMAM.
The pure water flux of the different films of table 2
3, cupric ion adsorption
In the performance measurement of the adsorbance to different films, attached drawing 3 is pvdf membrane, PVDF-g-PAA film, PVDF-g-PAA-
The adsorbance of G1.0PAMAM film-PVDF-g-PAA-G4.0PAMAM film, is respectively 3.2mg/g, 25.6mg/g, 70.29mg/
G, 75.7mg/g, 100.98mg/g, 92.62mg/g (quality that mg/g indicates every gram of film absorption copper ion).Pvdf membrane is with electrostatic
Active force etc. is adsorbed between power, hydrogen bond and surface molecular, and adsorbance is lower;PVDF-g-PAA film strips have carboxyl energy and copper ion
Coordinate bond absorption is formed, therefore adsorbance improves;In grafting after PAMAM, adsorbance is significantly improved, and PVDF-g-PAA-G3.0 film reaches
To peak 100.98mg/g.This is because PVDF-g-PAA-PAMAM film surface has amino, it can be with copper ion complex coordination
And internal cavity can chelate copper ion.Also due to the influence of steric hindrance, the film adsorbance for being grafted G3.0PAMAM is higher than
G4.0PAMAM。
The adsorbance of the different films of table 3
4, film is to Cu2+The desorption cycle of ion is tested
In desorption and regeneration performance test of the PVDF-g-PAA-PAMAM film to Cu2+ ion (attached drawing 4), passing through
After crossing five circulations, PVDF-g-PAA-G1.0PAMAM film, film -4:PVDF-g-PAA-G2.0PAMAM film, film -5:PVDF-g-
PAA-G3.0PAMAM film, film -6:PVDF-g-PAA-G4.0PAMAM film to the adsorbance of Cu2+ ion respectively by 71.3mg/g,
76mg/g, 104.69mg/g and 91.84mg/g slightly drop to 55.50mg/g, 59.80mg/g, 80.00mg/g and 72.20mg/
G, and 75% or more of initial adsorption amount is remained at, show after being used for multiple times, Modified Membrane still being capable of effective Adsorption of Cu 2+.
Furthermore PVDF-g-PAA-PAMAM film Adsorption of Cu2+The desorption efficiency of caudacoria is above 90%.The experimental results showed that PVDF-g-PAA-
PAMAM film is to Cu2+With preferable absorption property and higher desorption efficiency.
It should be noted that the PVDF-g-PAA-G1.0PAMAM film that 1-5 of the embodiment of the present invention is prepared, PVDF-g-
PAA-G2.0PAMAM film, PVDF-g-PAA-G3.0PAMAM, PVDF-g-PAA-G4.0PAMAM are likewise supplied with such as above-described embodiment
Similar technical effect in performance test listed by 8.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations;To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement;And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (7)
1. a kind of modified seperation film PVDF-g-PAA-Gn PAMAM of heavy metal ion adsorbed type PVDF, it is characterised in that: described
PVDF-g-PAA-Gn PAMAM film is that PVDF powder is preprocessed, the modified modification PVDF powder being prepared is the base that forms a film
Matter, by immersion precipitation phase inversion process and striking forms a film to obtain PVDF-g-PAA film, by the PVDF-g-PAA film it is activated after,
By by the Gn PAMAM of dispersion multistep processes preparation, (4) n 1,2,3 is grafted on the PVDF-g-PAA film, be prepared
PVDF-g-PAA-Gn PAMAM film, wherein n is 1,2,3 or 4;The activation processing condition of the PVDF-g-PAA film are as follows: will
PVDF-g-PAA film is immersed in activating solution;The activating solution is by 1- ethyl -3- (3- dimethylamine propyl) carbodiimide hydrochloride
Salt (EDCHCl) and N- hydroxysuccinimide (NHS) sequentially add in water, and the final concentration in activating solution is respectively as follows:
EDCHCl:0.05~0.1mol/L, NHS:0.05~0.1mol/L.
2. the modified seperation film of a kind of heavy metal ion adsorbed type PVDF as described in claim 1, it is characterised in that:
The activation condition of the PVDF-g-PAA film is, by the PVDF-g-PAA film and activating solution according to mass volume ratio
0.01-0.05g:10-50ml is mixed, and vibrates 1.5-3h at 25~30 DEG C.
3. the modified seperation film of a kind of heavy metal ion adsorbed type PVDF as described in claim 1, it is characterised in that: the Gn
N is 3 or 4 in PAMAM.
4. the modified seperation film of a kind of heavy metal ion adsorbed type PVDF as described in claim 1, it is characterised in that: the PVDF
The pre-treatment step of powder are as follows: by PVDF powder after strong base solution and dehydrated alcohol alkali process, agitated, suction filtration, washing
Afterwards, it dries, obtains PVDF pretreatment powder;The mass volume ratio of the PVDF powder and dehydrated alcohol are as follows: 20~30g:4~
6mL。
5. the modified seperation film of a kind of heavy metal ion adsorbed type PVDF as described in claim 1, it is characterised in that: the modification
The preparation step of PVDF powder are as follows: after pretreatment by PVDF powder, obtain PVDF pretreatment powder, the PVDF is pre-processed
Powder is mixed with N-N dimethylformamide (DMF) according to 5~11g:100 of mass volume ratio~120mL, is led at 60~70 DEG C
5~15min of nitrogen after adding acrylic acid (AA) and azodiisobutyronitrile (AIBN), leads to 15~25min of nitrogen, is filtered, washed
It after washing, is dried for standby, obtains the modified PVDF powder;AA the and AIBN mass ratio of PVDF the pretreatment powder and addition
Are as follows: 5~11:10~15:0.1~0.3.
6. the modified seperation film of a kind of heavy metal ion adsorbed type PVDF as described in claim 1, it is characterised in that: described
PVDF-g-PAA film the preparation method is as follows:
The modified PVDF powder, polyethylene glycol (PEG) powder are mixed with DMF according to 8~10:4 of mass ratio~6:35~45,
It is stirred 6~12 hours at 60~70 DEG C, obtains casting solution, glass pane surface is poured on after deaeration after the casting solution, with rule
100-300 μm of film forming thickness of the knifing stick striking that lattice are 100-300 μm, glass plate is put into 25~30 DEG C of water and is solidified into
Type obtains PVDF-g-PAA film.
7. the modified seperation film of a kind of heavy metal ion adsorbed type PVDF as described in claim 1, it is characterised in that: the huge sum of money
It is as follows to belong to the step of ion type PVDF is modified seperation film:
(1) under the conditions of 60~70 DEG C, PVDF powder the pretreatment of PVDF powder: is added rapidly to the hydrogen of 2.5~3mol/L
In potassium oxide solution, while dehydrated alcohol is poured into rapidly, after agitated, suction filtration, washing, be dried for standby, obtain PVDF pretreatment
Powder;The mass volume ratio of the PVDF powder, potassium hydroxide solution and dehydrated alcohol are as follows: 20~30g:150-300mL:4~
6mL;
The preparation of modified PVDF powder: by PVDF pretreatment powder and N-N dimethylformamide (DMF) according to quality volume
Than 5~11g:100~120mL mixing, lead at 60~70 DEG C it is nitrogen gas dissolved, continue after powder dissolution logical nitrogen 5~
15min after adding acrylic acid (AA) and azodiisobutyronitrile (AIBN), leads to 15~25min of nitrogen, after being filtered, being washed, dries
It does spare, obtains modified PVDF powder;AA the and AIBN mass ratio of PVDF the pretreatment powder and addition are as follows: 5~11:10~
15:0.1~0.3;
(2) preparation of PVDF-g-PAA film:
The modified PVDF powder, polyethylene glycol (PEG) powder are mixed with DMF according to 8~10:4 of mass ratio~6:35~45,
It is stirred 6~12 hours at 60~70 DEG C, obtains casting solution, glass pane surface is poured on after deaeration after the casting solution, with rule
100-300 μm of film forming thickness of the knifing stick striking that lattice are 100-300 μm, glass plate is put into 25~30 DEG C of water and is solidified into
Type obtains PVDF-g-PAA film;
(3) preparation of Gn PAMAM:
1. preparing the PAMAM dendrimer of G0.5
Ethylenediamine (EDA) is mixed with methanol according to 4~6g:20ml of mass volume ratio, 1~3h of nitrogen is led in ice-water bath, is obtained
To EDA mixed liquor 1;Methyl acrylate (MA) is mixed with methanol according to 55~60g:20ml of mass volume ratio, MA mixing is obtained
Liquid;The MA mixed liquor is added drop-wise in the EDA mixed liquor with 1~3 drop/sec of speed, the MA mixed liquor is mixed with EDA
1 volume ratio of liquid are as follows: 1-3:1 continues logical 30~50min of nitrogen, stops logical nitrogen later, in 20-35 DEG C of room temperature after being added dropwise to complete
It is rotated after lower reaction 12-24h, temperature is 40~50 DEG C, obtains the PAMAM dendrimer of G0.5;
2. preparing G1.0PAMAM dendrimer
EDA is mixed with methanol according to 35~40g:50ml of mass volume ratio, 1~3h of nitrogen deoxidation is led under ice-water bath, obtains EDA
Mixed liquor 2;G0.5PAMAM is mixed with methanol according to 10~20g:30ml of mass volume ratio, G0.5PAMAM mixed liquor is obtained;
The G0.5PAMAM mixed liquor is added drop-wise in the EDA mixed liquor 2 with 1~3 drop/sec of speed, the G0.5PAMAM is mixed
It closes liquid and 2 volume ratio of EDA mixed liquor is 1-3:1;Continue logical 30~60min of nitrogen after being added dropwise, stop logical nitrogen later,
It is rotated after being stirred to react 24~48h at 20-35 DEG C of room temperature, 60~70 DEG C of temperature, finally obtains G1.0PAMAM;
3. preparing the PAMAM dendrimer of G1.5: using G1.0PAMAM as raw material, 1. preparing G0.5's according to step (3)
The EDA is replaced with the G1.0PAMAM, the PAMAM of G1.5 is finally prepared by the synthesis step of PAMAM;
4. preparing G2.0PAMAM dendrimer: it is raw material according to step (3) 2. step using the PAMAM of the G1.5, it will be described
The PAMAM of G0.5 replaces with the PAMAM of the G1.5, and G2.0PAMAM is finally prepared;
5. the preparation of PAMAM, G4.0PAMAM dendrimer of PAMAM, G3.0PAMAM, G3.5 of G2.5 is according to step (3)
2. G1.0PAMAM, G2.0PAMAM, G3.0PAMAM are finally prepared respectively 1. 3. 4. circuiting sequentially iteration synthesis,
G4.0PAMAM;
(4) preparation of the modified seperation film of PVDF:
1. PVDF-g-PAA film is immersed in activating solution;The activating solution is by 1- ethyl -3- (3- dimethylamine propyl) carbon two
Inferior amine salt hydrochlorate (EDCHCl) and N- hydroxysuccinimide (NHS) sequentially add in water, the final concentration in activating solution
It is respectively as follows: EDCHCl:0.05~0.1mol/L, NHS:0.05~0.1mol/L;
After 2. basement membrane after will be activated is washed, be placed on the GnPAMAM that quality solubility is 2~4% (n 1,2,3 or
4) in solution, after vibrating 12-24h at 25~30 DEG C, washed drying obtains the modified separation of heavy metal ion adsorbed type PVDF
Film.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110975650A (en) * | 2019-12-09 | 2020-04-10 | 西安建筑科技大学 | Method for preparing super-hydrophilic PVDF ultrafiltration membrane by one-pot method |
CN113952849A (en) * | 2021-10-13 | 2022-01-21 | 天津工业大学 | Membrane adsorbent for removing heavy metal ions in water and preparation method thereof |
CN113952936A (en) * | 2021-10-13 | 2022-01-21 | 天津工业大学 | Polyamide-amine modified sodium alginate gel ball for removing heavy metal ions in water and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104472771A (en) * | 2014-12-12 | 2015-04-01 | 嘉应学院医学院 | Method for enriching and separating metal elements in camellia nitidissima by using composite nanofiltration membrane |
CN106582335A (en) * | 2016-12-31 | 2017-04-26 | 天津汉晴环保科技有限公司 | Preparation method of modified PVDF for heavy metal ion adsorption type separation films |
CN106582306A (en) * | 2016-12-31 | 2017-04-26 | 天津汉晴环保科技有限公司 | Heavy-metal-ion-adsorbing type hybrid flat sheet separation film and preparation method thereof |
CN108939939A (en) * | 2014-07-08 | 2018-12-07 | 天津工业大学 | A kind of modified PVDF flat-plate separation film of anticoagulation |
-
2018
- 2018-09-30 CN CN201811162921.2A patent/CN109174062A/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108939939A (en) * | 2014-07-08 | 2018-12-07 | 天津工业大学 | A kind of modified PVDF flat-plate separation film of anticoagulation |
CN104472771A (en) * | 2014-12-12 | 2015-04-01 | 嘉应学院医学院 | Method for enriching and separating metal elements in camellia nitidissima by using composite nanofiltration membrane |
CN106582335A (en) * | 2016-12-31 | 2017-04-26 | 天津汉晴环保科技有限公司 | Preparation method of modified PVDF for heavy metal ion adsorption type separation films |
CN106582306A (en) * | 2016-12-31 | 2017-04-26 | 天津汉晴环保科技有限公司 | Heavy-metal-ion-adsorbing type hybrid flat sheet separation film and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
秦颖玺: "超支化PVDF/ATP-PAMA复合膜的制备及其重金属离子吸附性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110975650A (en) * | 2019-12-09 | 2020-04-10 | 西安建筑科技大学 | Method for preparing super-hydrophilic PVDF ultrafiltration membrane by one-pot method |
CN113952849A (en) * | 2021-10-13 | 2022-01-21 | 天津工业大学 | Membrane adsorbent for removing heavy metal ions in water and preparation method thereof |
CN113952936A (en) * | 2021-10-13 | 2022-01-21 | 天津工业大学 | Polyamide-amine modified sodium alginate gel ball for removing heavy metal ions in water and preparation method thereof |
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