CN105854646A - Narrow pore size distributed hydrophilic filtering membrane sensitive to temperature and pH and preparation method thereof - Google Patents
Narrow pore size distributed hydrophilic filtering membrane sensitive to temperature and pH and preparation method thereof Download PDFInfo
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- CN105854646A CN105854646A CN201610415071.7A CN201610415071A CN105854646A CN 105854646 A CN105854646 A CN 105854646A CN 201610415071 A CN201610415071 A CN 201610415071A CN 105854646 A CN105854646 A CN 105854646A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
For the problems that a large quantity of organic solvents and pore-foaming agents which are difficult to recycle are used in the traditional membrane preparing process, environmental contamination is caused, the pore size distribution of membranes is wide, and the membranes lack of responsiveness, the invention provides a narrow pore size distributed hydrophilic filtering membrane sensitive to temperature and pH on the basis of the idea of bionics by taking a metal chloride saline solution as the solvent. A preparation method of the membrane comprises the steps that fibroin is grafted with polyacrylonitrile and poly(N-isopropylacrylamide) in a homogeneous mode, and a membrane casting solution is obtained; the membrane casting solution is put into a water coagulating bath, metal ions and chloride ions are gradually scattered in water, an the fibroin grafted with poly(N-isopropylacrylamide) and polyacrylonitrile is subjected to phase transformation to form the membrane. The metal ions and the chloride ions play the role of hole forming, the fibroin, poly(N-isopropylacrylamide) and polyacrylonitrile are subjected to microphase separation, and water channels subjected to ion hole forming are formed in the interface. By means of the fibroin and poly(N-isopropylacrylamide), the pH value sensitivity and temperature sensitivity of the membrane are achieved. By means of the hole forming effect of the metal ions and the chloride ions, the hole size of the membrane is smaller, and the hole size distribution is narrow.
Description
Technical field
The present invention relates to narrow pore-size distribution hydrophilic filter film of a kind of temperature and pH sensitivity and preparation method thereof, belong to macromolecule material
Material and film field.
Background technology
Membrane technology, due to advantages such as it are efficient, energy consumption is low and cost of investment is little, is widely applied in water processes.The most
Be applied to the traditional membrane material that produces can not the change of response environment, the pore size of its film will not be with environmental change
And change, when the multi-component material of different molecular weight is separated, generally require several filter membrane warps using aperture different
Cross multiple times of filtration and just can obtain required composition, so that separation process complicates, increase production cost, and affect the modern times of separation
Change process.Therefore, to have the separation film new varieties of environment-responsive significant in exploitation.
Smart membrane is one of the important technology progress in bionic function film field.Smart membrane be exactly to external world changes in environmental conditions have quick
Sense reaction and the functional membrane of self regulation, such as the change of functional group, ionic strength, pH value, temperature, electric field etc. in environment to external world
Change and there is sensing and the film of response function.Shtanko etc. are irradiated by gamma-rays and PNIPA are grafted to poly terephthalic acid second
Make on diol ester (PET) or polypropylene (PP) film temperature response type macromolecule composite membrane [J.Membr.Sci, 2000,179:
155～161].Wang Wenyu etc. with Kynoar (PVDF) doughnut as basement membrane, with temperature sensitive N-isopropyl third
The acrylic acid (AAc) of acrylamide (NIPAAm) and pH sensitivity is intellectual material, by a kind of alkali treatment method to PVDF
Carry out surface modification, PVDF doughnut film surface grafting poly-N-isopropyl acrylamide (PNIPAAm) gel,
Polyacrylic acid (PAAc) gel, prepares respectively and has the PVDF hollow fiber intelligent gel that temperature is sensitive and pH is sensitive
Composite membrane [J.Appl.Polym.Sci, 2006,101 (2): 833-837].But the method for above-mentioned grafting obtains
N-isopropylacrylamide percent grafting is relatively low, and Thermo-sensitive is poor.
Conventional film filtering material easily causes macromole, colloid, electrolyte etc. in film surface or film due to the hydrophobicity of itself
Irreversible deposition, causes fouling membrane to make the flux of film constantly decline, so that membrane separating process can not be normally carried out.Alleviate fouling membrane
Effective ways be the surface nature improving film, such as chargedization or the hydrophiling etc. of hydrophobic film on film surface.Currently mainly
Improved the hydrophilic of film by blending and modifying, surface-coated and surface graft modification, thus improve the antifouling property of film.But
Being blending and modifying complex process, surface-coated easily comes off, and surface graft modification is difficult to obtain uniform Modified Membrane.Meng et al.
Introduce on PVDF microporous membrane surface three kinds of hydrophilic brush polymer chains improve film hydrophilic [Appl.Surf.Sci, 2011,
257:6282-6290].Surface chemical modification method common in document report introduces hydrophilic functional group on film surface or hydrophilic gathers
Compound chain complex process, it is difficult to realize industrialization, improves limited to the hydrophilic of film.
The generally preparation process of polymeric membrane inevitably uses organic solvent, causes environmental pollution.Macromolecule member material fenestra
Footpath wider distribution.The present invention is based on bionic thought, with metal chloride brine solution as solvent, and a kind of temperature of design preparation
The narrow pore-size distribution hydrophilic filter film sensitive with pH.First pass through fibroin homogeneous graft polypropylene nitrile and PNIPAM
Obtaining casting solution, then put it in the coagulating bath of water, metal ion and chloride ion are gradually diffused in water, are grafted poly-isopropyl
The fibroin generation phase in version film forming of base acrylamide and polyacrylonitrile.Metal ion and chloride ion play the effect of pore, and fibroin,
PNIPAM and polyacrylonitrile generation microphase-separated, also form the aquaporin of ion pore at its interface.Fibroin is with poly-
N-isopropylacrylamide gives film pH value and temperature sensitivity respectively.And the pore effect of metal ion and chloride ion makes the hole of film
Footpath is less and distribution is the narrowest.This filter membrane is expected to be applied to fine separation, temperature and pH value responding to switch film etc..
Summary of the invention
For the deficiencies in the prior art, what the present invention intended to solve technical problem is that film-forming process inevitably uses organic solvent to make
Become the problems such as environmental pollution, membrane aperture distribution width, the film lack of responsiveness and easily pollution.
The present invention solves described film-forming process and inevitably uses organic solvent to cause environmental pollution, and membrane aperture distribution width, film lacks
The technical scheme of the problems such as weary response and easily pollution is to design a kind of temperature and the narrow pore-size distribution hydrophilic filter film of pH sensitivity.
This film is with metal chloride brine solution as solvent, is obtained by fibroin homogeneous graft polypropylene nitrile and PNIPAM
Casting solution, then puts it in the coagulating bath of water, and metal ion and chloride ion are gradually diffused in water, is grafted poly-isopropyl third
The fibroin generation phase in version film forming of acrylamide and polyacrylonitrile；Metal ion and chloride ion play the effect of pore, and fibroin, poly-
N-isopropylacrylamide and polyacrylonitrile generation microphase-separated, also form the aquaporin of ion pore, thus obtain narrow at its interface
Pore-size distribution and hydrophilic film.The temperature sensitivity utilizing PNIPAM makes film obtain temperature sensitivity, utilizes silk
In protein, the ionization of amino acid whose soda acid makes film obtain pH sensitivity.
The invention provides narrow pore-size distribution hydrophilic filter film of a kind of temperature and pH sensitivity and preparation method thereof, it is characterized in that bag
Include following steps:
A) prepare the metal chloride brine solution of mass percent concentration 10%-100%, weigh and account for water quality percentage ratio
The fibroin of 2%-30%, is dissolved in metal chloride brine solution by fibroin, is fallen by fibroin metal chloride brine solution
Enter in there-necked flask, logical nitrogen deoxygenation 1-30min, in there-necked flask, under agitation add the ionized water quality hundred that accounts for
The acrylonitrile of proportion by subtraction 2%-50% and the N-isopropylacrylamide of ionized water mass percent 1%-20% that accounts for；
B) under agitation it is added dropwise over accounting for acrylonitrile and the initiator of N-isopropylacrylamide gross mass percentage ratio 0.1%-10%, draws
Sending out acrylonitrile and N-isopropylacrylamide glycerol polymerization on fibroin, the response time is 20-240min, after polymerization
Solution is cooled to room temperature, vacuum defoamation, obtains casting solution；
C) preparing pH with dilute hydrochloric acid is the aqueous solution of 2-5, as coagulating bath；
D) casting solution that step b) obtains is poured on the sheet glass of dry cleansing, scrapes uniform film with knifing rod, then by film
Being dipped into 30-120min in the coagulating bath of step c) together with sheet glass, the temperature controlling coagulating bath is 5-90 DEG C,
Obtain the fibroin grafting PNIPAM containing part metals chloride salt and polyacrylonitrile film；Solidified by control
Bath temperature controls the phase in version process of film, thus regulates and controls membrane aperture size and distribution；
E) the grafting PNIPAM of the fibroin containing part metals chloride salt obtained by step c) and polyacrylonitrile film are used
The dilute hydrochloric acid of pH=1-3 rinses 3-5 time, removes the metal ion in membrane removal, finally repeatedly rinses 3-5 time with deionized water,
Obtain a kind of temperature and the narrow pore-size distribution hydrophilic filter film of pH sensitivity.
Metal chloride salt of the present invention is any one or two or more mixture in zinc chloride, iron chloride, calcium chloride；
Described initiator is benzoyl peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate., burnt sulfurous
Any one or two or more mixture in acid sodium, sodium sulfite, ferrous sulfate, ferrous chloride；Described fibroin source
At least one in mulberry silk and tussah silk.The pore-size distribution of film 90% prepared by the present invention between 0.31-0.46nm,
Under 0.1MPa, film is 90%-100% to the dyestuff of molecular weight more than 660 and the rejection of Polyethylene Glycol, to molecular weight less than 600
Dyestuff and the rejection of Polyethylene Glycol be 10%-30%, under 0.1MPa, membrane flux is 60-120L/m2h。
Detailed description of the invention
The specific embodiment of the present invention is described below, but the present invention should not be limited by the examples.
Embodiment 1.
A) prepare the solder(ing)acid of mass percent concentration 10%, weigh the fibroin accounting for water quality percentage ratio 2%, by fibroin
It is dissolved in solder(ing)acid, fibroin solder(ing)acid is poured in there-necked flask, logical nitrogen deoxygenation 30min,
In there-necked flask, the acrylonitrile of the ionized water mass percent 2% that accounts for and the ionized water percent mass that accounts for is added under stirring
N-isopropylacrylamide than 20%；
B) Ammonium persulfate .-sulphuric acid being under agitation added dropwise over accounting for acrylonitrile and N-isopropylacrylamide gross mass percentage ratio 10% is sub-
Ferrum, causes acrylonitrile and N-isopropylacrylamide glycerol polymerization on fibroin, and the response time is 20min, after being polymerized
Solution be cooled to room temperature, vacuum defoamation, obtain casting solution；
C) preparing pH with dilute hydrochloric acid is the aqueous solution of 2, as coagulating bath；
D) casting solution that step b) obtains is poured on the sheet glass of dry cleansing, scrapes uniform film with knifing rod, then by film
Being dipped into 120min in the coagulating bath of step c) together with sheet glass, the temperature controlling coagulating bath is 5 DEG C, is contained
The fibroin grafting PNIPAM of partial oxidation zinc and polyacrylonitrile film；Film is controlled by controlling coagulation bath temperature
Phase in version process, thus regulate and control membrane aperture size and distribution；
E) fibroin containing partial oxidation zinc grafting PNIPAM step c) obtained and polyacrylonitrile film pH=1
Dilute hydrochloric acid rinses 3 times, removes the zinc ion in membrane removal, finally repeatedly rinses with deionized water 3 times, obtains a kind of temperature
The narrow pore-size distribution hydrophilic filter film sensitive with pH.
Embodiment 2.
A) prepare the solder(ing)acid of mass percent concentration 100%, weigh the fibroin accounting for water quality percentage ratio 30%, by silk
Protein is dissolved in solder(ing)acid, pours in there-necked flask by fibroin solder(ing)acid, logical nitrogen deoxygenation 1min,
In there-necked flask, under agitation add the acrylonitrile of the ionized water mass percent 50% that accounts for and the ionized water quality that accounts for
The N-isopropylacrylamide of percentage ratio 1%；
B) under agitation it is added dropwise over accounting for acrylonitrile and the potassium peroxydisulfate of N-isopropylacrylamide gross mass percentage ratio 0.1%, causes
The glycerol polymerization on fibroin of acrylonitrile and N-isopropylacrylamide, the response time is 240min, by the solution after polymerization
It is cooled to room temperature, vacuum defoamation, obtains casting solution；
C) preparing pH with dilute hydrochloric acid is the aqueous solution of 5, as coagulating bath；
D) casting solution that step b) obtains is poured on the sheet glass of dry cleansing, scrapes uniform film with knifing rod, then by film
Being dipped into 30min in the coagulating bath of step c) together with sheet glass, the temperature controlling coagulating bath is 90 DEG C, is contained
The fibroin grafting PNIPAM of partial oxidation zinc and polyacrylonitrile film；Film is controlled by controlling coagulation bath temperature
Phase in version process, thus regulate and control membrane aperture size and distribution；
E) fibroin containing partial oxidation zinc grafting PNIPAM step c) obtained and polyacrylonitrile film pH=3
Dilute hydrochloric acid rinses 5 times, removes the zinc ion in membrane removal, finally repeatedly rinses with deionized water 5 times, obtains a kind of temperature
The narrow pore-size distribution hydrophilic filter film sensitive with pH.
Embodiment 3.
A) prepare the calcium chloride water of mass percent concentration 60%, weigh the fibroin accounting for water quality percentage ratio 10%, by fibroin
It is dissolved in calcium chloride water, fibroin calcium chloride water is poured in there-necked flask, logical nitrogen deoxygenation 10min,
In there-necked flask, the acrylonitrile of the ionized water mass percent 10% that accounts for and the ionized water quality hundred that accounts for is added under stirring
The N-isopropylacrylamide of proportion by subtraction 10%；
B) under agitation it is added dropwise over accounting for acrylonitrile and the sodium peroxydisulfate-sulfurous acid of N-isopropylacrylamide gross mass percentage ratio 1%
Hydrogen sodium, causes acrylonitrile and N-isopropylacrylamide glycerol polymerization on fibroin, and the response time is 60min, will polymerization
After solution be cooled to room temperature, vacuum defoamation, obtain casting solution；
C) preparing pH with dilute hydrochloric acid is the aqueous solution of 3, as coagulating bath；
D) casting solution that step b) obtains is poured on the sheet glass of dry cleansing, scrapes uniform film with knifing rod, then by film
Being dipped into 60min in the coagulating bath of step c) together with sheet glass, the temperature controlling coagulating bath is 20 DEG C, is contained
The fibroin grafting PNIPAM of partial oxidation calcium and polyacrylonitrile film；Film is controlled by controlling coagulation bath temperature
Phase in version process, thus regulate and control membrane aperture size and distribution；
E) the grafting PNIPAM of the fibroin containing partial oxidation calcium step c) obtained and polyacrylonitrile film pH=1-3
Dilute hydrochloric acid rinse 4 times, remove the calcium ion in membrane removal, finally repeatedly rinse with deionized water 4 times, obtain a kind of temperature
Degree and the narrow pore-size distribution hydrophilic filter film of pH sensitivity.
Embodiment 4.
A) prepare the calcium chloride water of mass percent concentration 50%, weigh the fibroin accounting for water quality percentage ratio 5%, by fibroin
It is dissolved in calcium chloride water, fibroin calcium chloride water is poured in there-necked flask, logical nitrogen deoxygenation 5min,
In there-necked flask, the acrylonitrile of the ionized water mass percent 5% that accounts for and the ionized water percent mass that accounts for is added under stirring
N-isopropylacrylamide than 5%；
B) under agitation it is added dropwise over accounting for acrylonitrile and the potassium peroxydisulfate-sulfurous acid of N-isopropylacrylamide gross mass percentage ratio 5%
Hydrogen sodium, causes acrylonitrile and N-isopropylacrylamide glycerol polymerization on fibroin, and the response time is 50min, will polymerization
After solution be cooled to room temperature, vacuum defoamation, obtain casting solution；
C) preparing pH with dilute hydrochloric acid is the aqueous solution of 5, as coagulating bath；
D) casting solution that step b) obtains is poured on the sheet glass of dry cleansing, scrapes uniform film with knifing rod, then by film
Being dipped into 40min in the coagulating bath of step c) together with sheet glass, the temperature controlling coagulating bath is 50 DEG C, is contained
The fibroin grafting PNIPAM of partial oxidation calcium and polyacrylonitrile film；Film is controlled by controlling coagulation bath temperature
Phase in version process, thus regulate and control membrane aperture size and distribution；
E) fibroin containing partial oxidation calcium grafting PNIPAM step c) obtained and polyacrylonitrile film pH=2
Dilute hydrochloric acid rinses 4 times, removes the calcium ion in membrane removal, finally repeatedly rinses with deionized water 3 times, obtains a kind of temperature
The narrow pore-size distribution hydrophilic filter film sensitive with pH.
Claims (7)
1. temperature and a narrow pore-size distribution hydrophilic filter film for pH sensitivity, is characterized in that with metal chloride brine solution as solvent,
Obtain casting solution by fibroin homogeneous graft polypropylene nitrile and PNIPAM, then put it into the coagulating bath of water
In, metal ion and chloride ion are gradually diffused in water, grafting PNIPAM and the fibroin generation phase of polyacrylonitrile
Change film forming；Metal ion and chloride ion play the effect of pore, and fibroin, PNIPAM and polyacrylonitrile are sent out
Raw microphase-separated, also forms the aquaporin of ion pore, thus obtains narrow pore-size distribution and hydrophilic film at its interface.
2. temperature and a narrow pore-size distribution hydrophilic filter film for pH sensitivity, is characterized in that the temperature utilizing PNIPAM is quick
Perception makes film obtain temperature sensitivity, utilizes amino acid whose soda acid ionization in fibroin to make film obtain pH sensitivity.
3. temperature and a narrow pore-size distribution hydrophilic filter film for pH sensitivity, is characterized in that the pore-size distribution of film 90% is at 0.31-0.46nm
Between, under 0.1MPa, film is 90%-100% to the dyestuff of molecular weight more than 660 and the rejection of Polyethylene Glycol, to dividing
The dyestuff of son amount less than 600 and the rejection of Polyethylene Glycol are 10%-30%, and under 0.1MPa, membrane flux is 60-120L/m2h。
4. a preparation method for the narrow pore-size distribution hydrophilic filter film of temperature and pH sensitivity, is characterized in that comprising the following steps:
A) prepare the metal chloride brine solution of mass percent concentration 10%-100%, weigh and account for water quality percentage ratio
The fibroin of 2%-30%, is dissolved in metal chloride brine solution by fibroin, is fallen by fibroin metal chloride brine solution
Enter in there-necked flask, logical nitrogen deoxygenation 1-30min, in there-necked flask, under agitation add the ionized water quality hundred that accounts for
The acrylonitrile of proportion by subtraction 2%-50% and the N-isopropylacrylamide of ionized water mass percent 1%-20% that accounts for；
B) under agitation it is added dropwise over accounting for acrylonitrile and the initiator of N-isopropylacrylamide gross mass percentage ratio 0.1%-10%, draws
Sending out acrylonitrile and N-isopropylacrylamide glycerol polymerization on fibroin, the response time is 20-240min, after polymerization
Solution is cooled to room temperature, vacuum defoamation, obtains casting solution；
C) preparing pH with dilute hydrochloric acid is the aqueous solution of 2-5, as coagulating bath；
D) casting solution that step b) obtains is poured on the sheet glass of dry cleansing, scrapes uniform film with knifing rod, then by film
Being dipped into 30-120min in the coagulating bath of step c) together with sheet glass, the temperature controlling coagulating bath is 5-90 DEG C,
Obtain the fibroin grafting PNIPAM containing part metals chloride salt and polyacrylonitrile film；Solidified by control
Bath temperature controls the phase in version process of film, thus regulates and controls membrane aperture size and distribution；
E) the grafting PNIPAM of the fibroin containing part metals chloride salt obtained by step c) and polyacrylonitrile film are used
The dilute hydrochloric acid of pH=1-3 rinses 3-5 time, removes the metal ion in membrane removal, finally repeatedly rinses 3-5 time with deionized water,
Obtain a kind of temperature and the narrow pore-size distribution hydrophilic filter film of pH sensitivity.
5. a kind of temperature as described in claim Isosorbide-5-Nitrae and the preparation method of the sensitive narrow pore-size distribution hydrophilic filter film of pH, it is special
Levy be described metal chloride salt be any one or the two or more mixture in zinc chloride, iron chloride, calcium chloride.
The preparation method of the narrow pore-size distribution hydrophilic filter film of a kind of temperature the most as claimed in claim 4 and pH sensitivity, is characterized in that
Described initiator is benzoyl peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate., Jiao Ya
Any one or two or more mixture in sodium sulfate, sodium sulfite, ferrous sulfate, ferrous chloride.
7. such as claim 1, a kind of temperature described in 2,4 and the narrow pore-size distribution hydrophilic filter film of pH sensitivity, it is characterized in that described
Fibroin derive from least one in mulberry silk and tussah silk.
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| CN112023723A (en) * | 2019-07-01 | 2020-12-04 | 江苏久吾高科技股份有限公司 | Hollow fiber membrane and manufacturing method thereof |
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