CN106256839B - A kind of method that surface thermal polymerization prepares ion blotting composite membrane - Google Patents
A kind of method that surface thermal polymerization prepares ion blotting composite membrane Download PDFInfo
- Publication number
- CN106256839B CN106256839B CN201510342113.4A CN201510342113A CN106256839B CN 106256839 B CN106256839 B CN 106256839B CN 201510342113 A CN201510342113 A CN 201510342113A CN 106256839 B CN106256839 B CN 106256839B
- Authority
- CN
- China
- Prior art keywords
- ion
- composite membrane
- membrane
- initiator
- template
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of methods that surface thermal polymerization prepares ion blotting composite membrane, it is characterized in that, using polymer microporous filtering film as support membrane, cause function monomer and crosslinking agent by heating and modifies polymerization in membrane surface, using ionic imprinting technique, the ion blotting composite membrane that there is Selective Separation effect to template ion is prepared.Preparation process of the invention specifically includes four-stage: (1) membrane surface coats initiator；(2) preparation of metal ion trace composite membrane；(3) elution of template ion；(4) Performance of composite membrane.Preparation process is not required to complicated and special installation, and simple process is easily operated, mild condition, and production cost is low.Ion blotting composite membrane prepared by the present invention can remove the metal ion in water body by membrane process, have the characteristics that easy to operate, high-efficient, at low cost, selectivity is strong, have broad application prospects in the field of waste water treatment containing heavy metal ion.
Description
Technical field
The present invention relates to a kind of methods for preparing ion blotting composite membrane, relate more specifically to a kind of surface thermal polymerization preparation
The method of heavy metal ion Selective Separation composite membrane, the invention belongs to technical field of membrane separation.
Background technique
The presence of heavy metal is possible to cause serious injury to people's health in water, and heavy metal is primarily referred to as biology in water
The significant lead of toxicity, mercury, cadmium, chromium, arsenic etc. further include having the pollutants such as virose heavy metal zinc, copper, cobalt, nickel, tin, vanadium.
Lead is the heavy metal that a kind of pair of human body has serious harm, can be generated obviously to nervous system, kidney, hemopoietic system etc.
Damage.Lead ion is not biodegradable, is easy to be enriched with and expand in environment or biological chain, long-term drinking is containing lead doping
Water will lead to pregnant woman's miscarriage, fetus deformity, shorten the service life of people.
Mercury and mercuric compounds are very big to warm-blooded animal toxicity, will be promptly absorbed by the mercury that alimentary canal enters human body and with
Blood is transferred to each organ of whole body and tissue, and then causes systemic poisoning, seriously endangers human health.
Cadmium is hypertoxic element, if long period edible food, the water etc. severely exceeded containing cadmium ion, will cause digestion
Road cancer, cancer of the esophagus, liver kidney etc., or even death can be caused.
Chromium compound has the effect of whole body intoxicating to people and animals' body, also has carcinogenic and mutagenesis, is priority control
Water pollutant.
Edible water or food containing arsenic ion can induce kinds cancer, arsenic ion can be entered by alimentary canal blood throughout
Whole body, the osmotic pressure by changing cell enter into the cell, promote protein coagulating and cause death.
The method of heavy metal ion chlorination in water can not remove, because chlorine is for heavy metal ion in water
Oxidation, decomposition it is very weak, or even do not work at all.Mainly there is absorption for the processing method of heavy metal in water at present
Method, flocculent precipitation, bioanalysis, organic material method and membrane separation technique etc..Traditional chemistry such as absorption, flocculation sedimentation, physics
With biological separation method due to there are severe reaction conditions, operating cost it is high or the disadvantages of be also easy to produce secondary pollution, make it using valence
Value is restricted significantly.Using membrane separation process carry out heavy metal ion separation, have it is high-efficient, without phase-change, energy conservation and environmental protection, set
The advantages that standby simple, easy to operate, make it that there is comparable technical advantage in water treatment field, it has also become Industrial Wastewater Treatment is not
One of the technology that can lack.The major way that the technology is taken have electroosmose process, liquid-film method, nano filtering process, ultra-low-pressure reverse osmosis film,
Micelle enhanced ultrafiltration method and water-soluble polymer complexing ultrafiltration etc., but these conventional polymer films are similar to structure, volume phase
The separation of close heavy metal ion lacks selectivity, although in polymeric membrane area load liquid film or bonded energy and heavy metal ion
The functional group for generating complexing, can assign film to the selectivity of special metal ion, but supported liquid membrane stability is poor, and
The selective effect of surface-functionalized modified membrane is not satisfactory.
The ionic imprinting technique to grow up on the basis of molecular imprinting technology, by specific ion blotting in polyphosphazene polymer
It closes in object, forms specific trace hole after elution.Distribution inside the ion imprinted polymer as made from ionic imprinting technique
There are the trace hole of a large amount of template ions, these holes and template ion in size, space structure, binding site distribution etc.
Aspect matched, thus there is special recognition capability to template ion.Using metal ion as the ion blotting of template ion
Its trace hole of polymer energy efficient identification metal ion, thus polymeric membrane is modified using ionic imprinting technique, it can
Recognition site is introduced on the surface of film, on the basis of retaining polymeric membrane separation advantage, it is assigned and target metal ions is selected
The ability of selecting property separation, removal of the prepared ion blotting film for heavy metal ion in water, is the membrane technology having a extensive future
Method, and go the ion blotting composite membrane of removing heavy metals to be rarely reported before this by surface thermal polymerization preparation.
Summary of the invention
In order to overcome the shortcomings in the prior art, the present invention combines ionic imprinting technique and membrane technology, with commercially available
Commodity plate or hollow fiber polymeric miillpore filter are basement membrane, using surface thermal polymerization method to microporous membrane surface carry out from
Sub- trace provides a kind of preparation method of the stable metal ion trace composite membrane of simple process, performance.
Technology of the invention be using commercially available commodity plate or hollow fiber polymeric miillpore filter as basement membrane, heavy metal from
Son is template ion, causes function monomer and crosslinking agent by heating and carries out ion blotting modification, preparation in membrane surface polymerization
Ion blotting composite membrane is obtained, including membrane surface coating initiator, the preparation of metal ion trace composite membrane, template ion
Elution, composite membrane the processes such as Performance.
Technical solution of the present invention specifically includes the following steps:
1, membrane surface coats initiator: using commercially available commodity plate or hollow fiber polymeric miillpore filter as basement membrane,
It is molten that polymer microporous filtering film is immersed into the ethyl alcohol containing initiator, methanol, acetonitrile, N,N-dimethylformamide or dimethyl sulfoxide
In liquid, naturally dry is taken out after a period of time, the film surface after drying, which just applies, has been covered with a thin layer initiator to get solid to surface
Surely there is the polymer microporous filtering film of initiator.
2, the preparation of metal ion trace composite membrane: using heavy metal ion as template ion, first and a certain amount of function list
Body mixing adds crosslinking agent, solvent and initiator and is uniformly mixed, obtains reaction solution, wherein template ion is with its metal
The form of salt is added into above-mentioned solution, and template ion metal salt, function monomer and crosslinking agent are 1:(2~8 in molar ratio): (2
~50) ratio weighs respectively, then ultrasonic degassing, then the polymer microporous filtering film immersion that surface is fixed with initiator is above-mentioned
In reaction solution, be passed through 5~10min of nitrogen, under nitrogen protection in 45~65 DEG C insulation reaction 10~50 hours, do not taken off
The metal ion trace composite membrane of removing template ion.
3, the elution of template ion: it is 5~20% that metal ion trace composite membrane obtained above, which is immersed in volumetric concentration,
Acetic acid, hydrochloric acid, in sulfuric acid or EDTA solution, oscillation treatment 4~12 hours, eluted template ion at room temperature, then spend from
Son is washed to neutrality, is dried under vacuum to constant weight up to metal ion trace composite membrane.
On the basis of above scheme, the commercially available commodity plate or hollow fiber polymeric miillpore filter are that polysulfones is micro-
Hole filter membrane, polyethersulfone millipore filter, polyvinylidene fluoride microporous filtering film, polypropylene microporous filter membrane or polyacrylonitrile miillpore filter.
On the basis of above scheme, the initiator is azodiisobutyronitrile, azobisisoheptonitrile, two isobutyric acid of azo
Any one in dimethyl ester, in step 1 selected initiator in step 2 selected by initiator identical be advisable.
On the basis of above scheme, the solution concentration containing initiator is 0.005~0.1g/ml.
On the basis of above scheme, polymer microporous filtering film described in step 1 the ethyl alcohol of initiator, methanol, acetonitrile,
The time impregnated in N,N-dimethylformamide or dimethyl sulphoxide solution is 1~4 hour.
On the basis of above scheme, the template ion be Pb (II), Cd (II), Ni (II), Hg (II), Cu (II),
Any one in Zn (II), the template ion metal salt is chloride, sulfate, acetate, any one in nitrate
Kind.
On the basis of above scheme, the function monomer is both one of following or any mixture: acrylic acid, first
Base acrylic acid, methyl methacrylate, acrylamide, 1- vinyl imidazole, 2- vinylpyridine, 4-vinylpridine.
On the basis of above scheme, the crosslinking agent is both one of following or any mixture: glycol dinitrate
Base acrylate, trimethoxypropane gave trimethyl acrylic ester, N, N'- methylene diacrylamine, divinylbenzene.
On the basis of above scheme, the dosage of initiator described in step 2 (is rubbed for the 0.1%~5% of function monomer amount
That percentage).
On the basis of above scheme, solvent described in step 2 be ethyl alcohol, methanol, acetonitrile, n,N-Dimethylformamide or
Any one in dimethyl sulfoxide, the solvent usage are as follows: 15~20ml solvent is added in 1mmol template ion metal salt.
Metal ion blotting membrane of the present invention is that function monomer and template ion pass through polymerization methods formation ion print
Mark high molecular polymer elutes inside post-consumer polymer according to the coordination of metal ion and other compounds in polymerization process
The opening structure and chemical bonding effect complementary with template ion space structure can be left, to realize to the special of target heavy metal
The identification of one property.Preparation process of the present invention is easy, and easy to operate, reproducible, prepared membrane stability is strong, long service life.
The beneficial effects are mainly reflected as follows: the present invention provides a kind of for removing heavy metal ions in sewage
The preparation method of film after initiator is added in the reaction system, achieves that the ion blotting of membrane surface is modified by heating,
The film preparation process is relatively easy, and obtained metal ion blotting membrane has specific recognition ability, the selection to heavy metal ion
Property it is good, reusable after regeneration, film process process is easy, and preparation process is not necessarily to special and complex device, and production cost is low, easily
Operation, treatment effeciency are high.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention., the people that is skilled in technique in the field
Member can make some nonessential modifications and adaptations according to the content of aforementioned present invention.If not specified, it is adopted in embodiment
Raw material is commercially available.
It is below specific embodiment.By metal ion blotting membrane prepared by the method for the invention, permeance property is surveyed
Pinged following steps progress:
(1) aquarium, that is, supply pool and acceptance pool for making two identical connections by oneself, are fixed on two for the film of preparation
Among a aquarium, the H-type of composition bottom connection seals osmotic device, guarantees that two ponds do not leak；
(2) be added in supply pool metal ion solution (template ion a and non-template ion b), be added in acceptance pool go from
Sub- water seals two ponds, the timing sampling under electromagnetic agitation, dense with the ion in atomic absorption spectrophotometer measurement acceptance pool
Degree.Wherein, the initial molar concentration of two metal ion species is 50.0mmol/L in metal ion solution described in supply pool.?
In same time, if ion blotting composite membrane prepared by the present invention to the permeance property of template ion be higher than other non-templates from
Son illustrates that ion blotting composite membrane prepared by the present invention has good ion selectivity to template ion.
Ion blotting composite membrane permeates selective factor B α to the permeance property of template ion to investigate, and permeates selective factor B α
Calculation formula are as follows:
Wherein Qa、QbRespectively infiltration capacity (μm ol/ of the ion blotting composite membrane to template ion a and non-template ion b
cm2)。
Embodiment 1
(1) using Kynoar microwell plate filter membrane as basement membrane, it is by Kynoar microwell plate filter membrane immersion concentration
In the acetonitrile solution of the initiator azodiisobutyronitrile of 0.03g/ml, naturally dry is taken out after 1 hour, is obtained film surface and is covered with
The polymer microporous filtering film of initiator.
(2) with heavy metal ion Pb (II) for template ion, take the plumbi nitras of 1.0mmol, 2.0mmol acrylic acid sufficiently mixed
It closes, adds 50.0mmol ethylene glycol dimethacrylate and 0.06mmol azodiisobutyronitrile, mixed with 20ml acetonitrile
It is even, homogeneous phase solution system, ultrasonic degassing is made, then the Kynoar microwell plate filter membrane that surface is covered with initiator is immersed
In the solution system, it is passed through nitrogen 8min, is heated to 55 DEG C of insulation reactions under nitrogen protection 24 hours, is not removed template
The metal ion trace composite membrane of ion.
(3) metal ion trace composite membrane made from above-mentioned steps is immersed in the acetum of 10% (v/v) volumetric concentration
In, oscillation treatment 10 hours, are then washed with deionized water to neutrality, eluted template Pb (II) is dried under vacuum to constant weight at room temperature
Up to Pb (II) ion blotting composite membrane.
(4) aquarium, that is, supply pool and acceptance pool for making two identical connections by oneself, by Pb (II) ion of preparation
Trace composite membrane is fixed among two aquariums, and the H-type of composition bottom connection seals osmotic device, guarantees that two ponds are not seeped
Leakage.The mixed ion solutions that Pb (II) and Zn (II) ion concentration is 50.0mmol/L are added in supply pool, add in acceptance pool
Enter deionized water, two ponds are sealed, the timing sampling under electromagnetic agitation, is measured when balance and received with atomic absorption spectrophotometer
Pb (II) and Zn (II) ion concentration in pond calculate infiltration selective factor B α(Pb/Zn)=3.39.
Embodiment 2
(1) using polypropylene microporous hollow fiber filter membrane as basement membrane, it is by polypropylene microporous hollow fiber filter membrane immersion concentration
In the ethanol solution of the initiator azo-bis-iso-dimethyl of 0.01g/ml, naturally dry is taken out after 4 hours, obtains film surface
It is covered with the polymer microporous filtering film of initiator.
(2) caddy of 1.0mmol, 4.0mmol methacrylic acid is taken to fill for template ion with heavy metal ion Cd (II)
Divide mixing, add 20.0mmol trimethoxypropane gave trimethyl acrylic ester and 0.04mmol azo-bis-iso-dimethyl,
It is uniformly mixed with 18ml ethyl alcohol, is made homogeneous phase solution system, ultrasonic degassing, then surface is covered with to the polypropylene microporous of initiator
Hollow fiber filter membrane immerses in the solution system, is passed through nitrogen 10min, and it is small to be heated to 50 DEG C of insulation reactions 36 under nitrogen protection
When, the metal ion trace composite membrane of template ion is not removed.
(3) metal ion trace composite membrane made from above-mentioned steps is immersed in the salt that concentration is 10% (v/v) volumetric concentration
In acid solution, oscillation treatment 12 hours, are then washed with deionized water to neutrality, eluted template Cd (II), vacuum drying at room temperature
To constant weight up to Cd (II) ion blotting composite membrane.
(4) aquarium, that is, supply pool and acceptance pool for making two identical connections by oneself, by Cd (II) ion of preparation
Trace composite membrane is fixed among two aquariums, and the H-type of composition bottom connection seals osmotic device, guarantees that two ponds are not seeped
Leakage.The mixed ion solutions that Cd (II) and Cu (II) ion concentration is 50.0mmol/L are added in supply pool, add in acceptance pool
Enter deionized water, two ponds are sealed, the timing sampling under electromagnetic agitation, is measured when balance and received with atomic absorption spectrophotometer
Cd (II) and Cu (II) ion concentration in pond calculate infiltration selective factor B α(Cd/Cu)=10.39.
Embodiment 3
(1) using polyacrylonitrile microporous hollow fiber filter membrane as basement membrane, polyacrylonitrile microporous hollow fiber filter membrane is immersed dense
Degree is that naturally dry is taken out after 2 hours in the methanol solution of the initiator azobisisoheptonitrile of 0.005g/ml, obtains film surface
It is covered with the polymer microporous filtering film of initiator.
(2) nickel sulfate, the 8.0mmol methyl methacrylate of 1.0mmol are taken for template ion with heavy metal ion Ni (II)
The ethylene glycol dimethacrylate of ester, 20.0mmol trimethoxypropane gave trimethyl acrylic ester and 10mmol is sufficiently mixed,
0.008mmol azobisisoheptonitrile is added, is uniformly mixed with 16ml methanol, homogeneous phase solution system, ultrasonic degassing is made, then incite somebody to action
The polyacrylonitrile microporous hollow fiber filter membrane that surface is covered with initiator immerses in the solution system, nitrogen 5min is passed through, in nitrogen
It is heated to 45 DEG C of insulation reactions under gas shielded 50 hours, is not removed the metal ion trace composite membrane of template ion.
(3) metal ion trace composite membrane made from above-mentioned steps is immersed in the sulfuric acid that concentration is 5% (v/v) volumetric concentration
In solution, oscillation treatment 8 hours, are then washed with deionized water to neutrality, eluted template Ni (II) is dried under vacuum to perseverance at room temperature
Weight is up to Ni (II) ion blotting composite membrane.
(4) aquarium, that is, supply pool and acceptance pool for making two identical connections by oneself, by Ni (II) ion of preparation
Trace composite membrane is fixed among two aquariums, and the H-type of composition bottom connection seals osmotic device, guarantees that two ponds are not seeped
Leakage.It is added in Ni (II), the Cu (II) and Zn (II) ternary mixed ion solutions that ion concentration is 50mmol/L, connects in supply pool
By deionized water is added in pond, two ponds are sealed, the timing sampling under electromagnetic agitation, atomic absorption spectrophotometer when balance
The ion concentration of Ni (II), Cu (II) and Zn (II) in measurement acceptance pool calculate infiltration selective factor B and are respectively as follows: α(Ni/Cu)=
7.56 α(Ni/Zn)=5.82.
Embodiment 4
(1) using polysulfones microwell plate filter membrane as basement membrane, polysulfones microwell plate filter membrane is immersed into the initiation that concentration is 0.1g/ml
In the dimethyl sulphoxide solution of agent azo-bis-iso-dimethyl, naturally dry is taken out after 4 hours, is obtained film surface and is covered with and draws
Send out the polymer microporous filtering film of agent.
(2) with heavy metal ion Hg (II) for template ion, take the mercuric acetate of 1.0mmol, 3.0mmol acrylamide,
10.0mmol trimethoxypropane gave trimethyl acrylic ester is sufficiently mixed, and adds 0.15mmol azo-bis-iso-dimethyl,
It is uniformly mixed with 18ml dimethyl sulfoxide, is made homogeneous phase solution system, ultrasonic degassing, then surface is covered with to the polysulfones of initiator
Microwell plate filter membrane immerses in the solution system, is passed through nitrogen 10min, and it is small to be heated to 65 DEG C of insulation reactions 10 under nitrogen protection
When, the metal ion trace composite membrane of template ion is not removed.
(3) metal ion trace composite membrane made from above-mentioned steps is immersed in the vinegar that concentration is 10% (v/v) volumetric concentration
In acid solution, oscillation treatment 10 hours, are then washed with deionized water to neutrality, eluted template Hg (II), vacuum drying at room temperature
To constant weight up to Hg (II) ion blotting composite membrane.
(4) aquarium, that is, supply pool and acceptance pool for making two identical connections by oneself, by Hg (II) ion of preparation
Trace composite membrane is fixed among two aquariums, and the H-type of composition bottom connection seals osmotic device, guarantees that two ponds are not seeped
Leakage.The Hg (II) and Cu (II) mixed ion solutions that ion concentration is 50mmol/L are added in supply pool, is added and goes in acceptance pool
Ionized water seals two ponds, the timing sampling under electromagnetic agitation, in atomic absorption spectrophotometer measurement acceptance pool when balance
Hg (II) and Cu (II) ion concentration, calculate infiltration selective factor B α(Hg/Cu)=8.71.
Embodiment 5
(1) using polysulfones microporous hollow fiber filter membrane as basement membrane, it is by polysulfones microporous hollow fiber filter membrane immersion concentration
In the n,N-Dimethylformamide solution of the initiator azodiisobutyronitrile of 0.01g/ml, naturally dry is taken out after 2 hours, is obtained
Film surface is covered with the polymer microporous filtering film of initiator.
(2) with metal ion Cu (II) for template ion, take the copper chloride of 1.0mmol, 2.0mmol 1- vinyl imidazole,
2.0mmol divinylbenzene is sufficiently mixed, and adds 0.04mmol azodiisobutyronitrile, and with 15mlN, dinethylformamide is mixed
It closes uniformly, homogeneous phase solution system, ultrasonic degassing is made, then the polysulfones microporous hollow fiber filter membrane that surface is covered with initiator is soaked
Enter in the solution system, be passed through nitrogen 5min, be heated to 60 DEG C of insulation reactions under nitrogen protection 20 hours, is not removed mould
The metal ion trace composite membrane of plate ion.
(3) metal ion trace composite membrane made from above-mentioned steps is immersed into solution in the EDTA solution that concentration is 20%
In, oscillation treatment 12 hours, are then washed with deionized water to neutrality, eluted template Cu (II) is dried under vacuum to constant weight at room temperature
Up to Cu (II) ion blotting composite membrane.
(4) aquarium, that is, supply pool and acceptance pool for making two identical connections by oneself, by Cu (II) ion of preparation
Trace composite membrane is fixed among two aquariums, and the H-type of composition bottom connection seals osmotic device, guarantees that two ponds are not seeped
Leakage.Cu (II) is added in supply pool and Pd (II) ion concentration is the mixed ion solutions of 50.0mmol/L, adds in acceptance pool
Enter deionized water, two ponds are sealed, the timing sampling under electromagnetic agitation, is measured when balance and received with atomic absorption spectrophotometer
Cu (II) and Pb (II) ion concentration in pond calculate infiltration selective factor B α(Cd/Cu)=6.93.
Embodiment 6
(1) using polyether sulfone microwell plate filter membrane as basement membrane, it is 0.05g/ml that polyether sulfone microwell plate filter membrane, which is immersed concentration,
Initiator azo-bis-iso-dimethyl ethanol solution in, take out naturally dry after 1 hour, obtain film surface and be covered with and draws
Send out the polymer microporous filtering film of agent.
(2) zinc chloride, the 2.0mmol 2- vinylpyridine, 3.0mmol of 1.0mmol are taken for template ion with Zn (II)
4-vinylpridine, 30mmol trimethoxypropane gave trimethyl acrylic ester are sufficiently mixed, and add two isobutyl of 0.1mmol azo
Nitrile is uniformly mixed with 20ml ethyl alcohol, is made homogeneous phase solution system, ultrasonic degassing, then surface is covered with to the polyether sulfone of initiator
Microwell plate filter membrane immerses in the solution system, is passed through nitrogen 6min, and it is small to be heated to 55 DEG C of insulation reactions 24 under nitrogen protection
When, the metal ion trace composite membrane of template ion is not removed.
(3) metal ion trace composite membrane made from above-mentioned steps is immersed in the salt that concentration is 10% (v/v) volumetric concentration
In acid solution, oscillation treatment 4 hours, are then washed with deionized water to neutrality, eluted template Zn (II) is dried under vacuum at room temperature
Constant weight is up to Zn (II) ion blotting composite membrane.
(4) aquarium, that is, supply pool and acceptance pool for making two identical connections by oneself, by Cd (II) ion of preparation
Trace composite membrane is fixed among two aquariums, and the H-type of composition bottom connection seals osmotic device, guarantees that two ponds are not seeped
Leakage.The mixed ion solutions that Zn (II) and Ni (II) ion concentration is 50.0mmol/L are added in supply pool, add in acceptance pool
Enter deionized water, two ponds are sealed, the timing sampling under electromagnetic agitation, is measured when balance and received with atomic absorption spectrophotometer
Cd (II) and Cu (II) ion concentration in pond calculate infiltration selective factor B α(Zn/Ni)=4.39.
Comparative example 1
(1) preparation of nonionic blotting membrane
Method is same as Example 2, is only added without Cd (II) ion during the preparation process.
(2) film properties test
Method is identical as above-described embodiment 2.Measured when balance with atomic absorption spectrophotometer and calculate infiltration selection because
Sub- α(Cd/Cu)=1.25.
Comparative example 2
(1) preparation of nonionic blotting membrane
Method is same as Example 6, is only added without Zn (II) ion during the preparation process.
(2) film properties test
Method is same as Example 6.It is measured when balance with atomic absorption spectrophotometer and calculates infiltration selective factor B
α(Zn/Ni)=0.86.
As can be seen from the above embodiments the present invention prepared by ion blotting composite membrane in the same time to template from
The infiltration capacity of son is higher than other non-template ions, illustrates that ion blotting composite membrane has good ion selectivity, this is because
Possess in the polymeric layer of ion blotting composite film surface largely and template ion is in size, space structure, binding site
It is distributed the trace hole being mutually matched, substantially increases composite membrane to the compatibility of the template ion, which can preferentially inhale
Attached template ion, then by dissociation, diffusion, in conjunction with, again dissociate, the cyclic process spread again is permeated so that template
Ion can pass through ion blotting composite membrane with faster speed.
The content being not described in detail in this specification belongs to the prior art well known to professional and technical personnel in the field.
Claims (6)
1. a kind of method that surface thermal polymerization prepares ion blotting composite membrane, it is characterised in that the following steps are included:
(1) membrane surface coats initiator: using commercially available commodity plate or hollow fiber polymeric miillpore filter as basement membrane, will gather
It closes object miillpore filter and immerses the ethyl alcohol containing initiator, methanol, acetonitrile, n,N-Dimethylformamide or dimethyl sulphoxide solution
In, naturally dry is taken out after a period of time, the film surface after drying, which just applies, to be covered with a thin layer initiator and fix to get to surface
There is the polymer microporous filtering film of initiator；
(2) preparation of metal ion trace composite membrane: first mixed with a certain amount of function monomer using heavy metal ion as template ion
It closes, adds crosslinking agent, solvent and initiator and be uniformly mixed, obtain reaction solution, wherein template ion is with its metal salt
Form is added into above-mentioned solution, and template ion metal salt, function monomer and crosslinking agent are 1:(2~8 in molar ratio): (2~
50) ratio weighs respectively, then ultrasonic degassing, then the polymer microporous filtering film immersion that surface is fixed with initiator is above-mentioned anti-
Answer in solution, be passed through 5~10min of nitrogen, under nitrogen protection in 45~65 DEG C insulation reaction 10~50 hours, do not removed
The metal ion trace composite membrane of template ion；
(3) metal ion trace composite membrane obtained above the elution of template ion: is immersed in the vinegar that volumetric concentration is 5~20%
In acid, hydrochloric acid, sulfuric acid or EDTA solution, at room temperature then oscillation treatment 4~12 hours, eluted template ion use deionized water
It is washed till neutrality, is dried under vacuum to constant weight up to metal ion trace composite membrane；
Initiator described in step (2) is identical as the initiator selected in step (1), and initiator amount is function monomer dosage
Molar percentage 0.1%~5%；
Initiator described in step (1) is azodiisobutyronitrile, azobisisoheptonitrile, any in azo-bis-iso-dimethyl
It is a kind of；
The solution concentration of initiator described in step (1) is 0.005~0.1g/mL；
Function monomer described in step (2) is both one of following or any mixture: acrylic acid, methacrylic acid, methyl
Methyl acrylate, acrylamide, 1- vinyl imidazole, 2- vinylpyridine, 4-vinylpridine.
2. the method that surface thermal polymerization as described in claim 1 prepares ion blotting composite membrane, it is characterised in that: step (1)
Described in commercially available commodity plate or hollow fiber polymeric miillpore filter be plate or doughnut polysulfone millipore filtering membrane, polyethers
Sulfone miillpore filter, polyvinylidene fluoride microporous filtering film, polypropylene microporous filter membrane or polyacrylonitrile miillpore filter.
3. the method that surface thermal polymerization as described in claim 1 prepares ion blotting composite membrane, it is characterised in that: step (1)
Described in polymer microporous filtering film in the ethyl alcohol of initiator, methanol, acetonitrile, n,N-Dimethylformamide or dimethyl sulphoxide solution
The time of middle immersion is 1~4 hour.
4. the method that surface thermal polymerization as described in claim 1 prepares ion blotting composite membrane, it is characterised in that: step (2)
Described in template ion be Pb (II), Cd (II), Ni (II), Hg (II), Cu (II), any one in Zn (II), the mould
Plate ionic metal salt is chloride, sulfate, acetate, any one in nitrate.
5. the method that surface thermal polymerization as described in claim 1 prepares ion blotting composite membrane, it is characterised in that: step (2)
Described in crosslinking agent be both one of following or any mixture: ethylene glycol dimethacrylate, trimethoxypropane gave three
Methacrylate, N, N'- methylene diacrylamine, divinylbenzene.
6. the method that surface thermal polymerization as described in claim 1 prepares ion blotting composite membrane, it is characterised in that: step (2)
Described in solvent be ethyl alcohol, methanol, acetonitrile, n,N-Dimethylformamide or dimethyl sulfoxide in any one, the solvent
Dosage are as follows: 15~20mL solvent is added in 1mmol template ion metal salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510342113.4A CN106256839B (en) | 2015-06-18 | 2015-06-18 | A kind of method that surface thermal polymerization prepares ion blotting composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510342113.4A CN106256839B (en) | 2015-06-18 | 2015-06-18 | A kind of method that surface thermal polymerization prepares ion blotting composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106256839A CN106256839A (en) | 2016-12-28 |
| CN106256839B true CN106256839B (en) | 2019-02-19 |
Family
ID=57713483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510342113.4A Active CN106256839B (en) | 2015-06-18 | 2015-06-18 | A kind of method that surface thermal polymerization prepares ion blotting composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106256839B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107174962A (en) * | 2017-06-07 | 2017-09-19 | 江苏大学 | A kind of preparation method and use of lithium ion blotting membrane |
| CN107529450B (en) * | 2017-06-16 | 2019-10-01 | 江苏大学 | A kind of Preparation method and use of Janus bilayer ion blotting composite membrane |
| CN108722201A (en) * | 2018-06-11 | 2018-11-02 | 贵州省材料产业技术研究院 | The method of modifying of PVDF hollow-fibre membranes |
| CN109438598B (en) * | 2018-09-28 | 2020-09-25 | 昆明理工大学 | Preparation method and application of hexavalent chromium ion imprinted composite membrane with 2-mercaptopropionic acid as functional monomer |
| CN109438619A (en) * | 2018-09-28 | 2019-03-08 | 昆明理工大学 | It is a kind of using α-methacrylic acid as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer |
| CN109351347A (en) * | 2018-09-28 | 2019-02-19 | 昆明理工大学 | It is a kind of using acrylamide as the preparation method and application of the hexavalent chromium trace composite membrane of function monomer |
| CN109589799B (en) * | 2018-12-03 | 2021-10-22 | 昆明理工大学 | Preparation method of cadmium (II) ion imprinting composite membrane |
| CN109647232B (en) * | 2018-12-03 | 2021-12-31 | 昆明理工大学 | Method for preparing cobalt (II) ion imprinting composite membrane by using N-methylpyrrolidine acrylamide |
| CN109663581B (en) * | 2018-12-03 | 2022-01-14 | 昆明理工大学 | Method for preparing cobalt (II) ion imprinting composite membrane by using N-pyrrolidinylacrylamide |
| CN109589943B (en) * | 2018-12-03 | 2021-11-12 | 昆明理工大学 | Method for preparing cadmium (II) ion imprinting composite membrane |
| CN110256726B (en) * | 2019-07-02 | 2021-11-12 | 昆明理工大学 | Preparation method and application of lead (II) ion imprinting composite membrane |
| CN110339729A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | A kind of preparation method and application of trivalent chromic ion trace composite membrane |
| CN110339727B (en) * | 2019-07-02 | 2021-10-22 | 昆明理工大学 | Preparation method and application of divalent lead ion imprinting composite membrane |
| CN110339728B (en) * | 2019-07-02 | 2021-10-22 | 昆明理工大学 | Preparation method and application of lead (II) ion imprinting composite membrane based on new functional monomer |
| CN110538584B (en) * | 2019-07-26 | 2021-07-20 | 湖南科技大学 | Preparation method of palladium ion imprinted copolymer membrane and application of palladium ion imprinted copolymer membrane |
| CN115739041B (en) * | 2022-11-02 | 2024-03-29 | 徐州医科大学 | Preparation method and application of molecular imprinting membrane for simultaneously enriching and separating 2 antiepileptic drugs and metabolites thereof in blood plasma |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102507515A (en) * | 2011-09-27 | 2012-06-20 | 浙江工业大学 | Fluorescent ion imprint sensor for detection of cadmium ions and preparation method thereof |
| CN102688696A (en) * | 2012-05-25 | 2012-09-26 | 西安理工大学 | Method for preparing modified supported liquid membrane |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0822374B2 (en) * | 1986-05-01 | 1996-03-06 | 旭化成工業株式会社 | Method for producing graft membrane |
| CN100337729C (en) * | 2005-10-22 | 2007-09-19 | 燕山大学 | Chemical modification technique for microfiltering separation film of polyvinylidene fluoride |
| US8939294B2 (en) * | 2010-03-31 | 2015-01-27 | General Electric Company | Block copolymer membranes and associated methods for making the same |
| CN103223308B (en) * | 2013-04-22 | 2015-01-07 | 北京工业大学 | Composite nanofiltration membrane prepared based on aliphatic sulfonate condensation product |
-
2015
- 2015-06-18 CN CN201510342113.4A patent/CN106256839B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102507515A (en) * | 2011-09-27 | 2012-06-20 | 浙江工业大学 | Fluorescent ion imprint sensor for detection of cadmium ions and preparation method thereof |
| CN102688696A (en) * | 2012-05-25 | 2012-09-26 | 西安理工大学 | Method for preparing modified supported liquid membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106256839A (en) | 2016-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106256839B (en) | A kind of method that surface thermal polymerization prepares ion blotting composite membrane | |
| Qiu et al. | Synthesis of high flux forward osmosis membranes by chemically crosslinked layer-by-layer polyelectrolytes | |
| CN105771701B (en) | The preparation method of one metal ion species trace composite membrane | |
| CN103055714B (en) | Method for preparing hydrophilic electrical charge separation film by using one-step method as well as product and application thereof | |
| CN103861472B (en) | A kind of preparation method of amino modified graphene oxide compound forward osmosis membrane | |
| CN109621739B (en) | Hydrophilic modification method for high-flux PVDF porous membrane | |
| CN111004411B (en) | Preparation method of biomass-based molecularly imprinted composite membrane for selectively separating tetracycline | |
| CN104147943A (en) | Preparation method and application of high-molecular forward osmosis membrane | |
| CN101862604A (en) | Method for preparing hydrophilic porous membrane | |
| CN105948159B (en) | A kind of preparation method of heavy metal adsorption filter core | |
| CN105327627B (en) | A kind of block sulfonated polyether aromatic phosphine blending/polyamide of polysulfones is combined the preparation method of forward osmosis membrane | |
| CN104815608A (en) | Preparation method of multifunctional oil-water separation material based on graphene oxide nanobelt | |
| US11826705B2 (en) | Apparatus and process for separation of water from dissolved solutes by forward osmosis | |
| CN108939933A (en) | A kind of preparation method of the amphipathic three block copolymer modified ultrafiltration membrane with pH responsiveness | |
| CN103537200A (en) | Cellulose acetate forward osmotic membrane and preparation method thereof | |
| CN108484900B (en) | A kind of poly ion liquid gel and method with nanometer hole | |
| CN106256414B (en) | A kind of preparation method of the hollow fiber film assembly of Selective Separation metal ion | |
| Kozlowski | Facilitated transport of metal ions through composite and polymer inclusion membranes | |
| CN105817146A (en) | Preparation method of CNT-modified nanofiltration membrane | |
| CN109092083A (en) | A kind of preparation and application of ferroso-ferric oxide/regenerated cellulose magnetism forward osmosis membrane | |
| Mondal et al. | Recovery of H2SO4 from wastewater in the presence of NaCl and KHCO3 through pH responsive polysulfone membrane: Optimization approach | |
| CN101352659B (en) | Polypiperazine-amide nanofiltration membrane and preparation method thereof | |
| JP2006305411A (en) | Eutrophic artificial seawater, and method for producing the same | |
| CN105670021A (en) | Method for wrapping semipermeable membrane on surface of solvent-impregnated resin | |
| Ye et al. | Tubular membrane used in continuous and semi-continuous diffusion dialysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |