CN106000134A - Temperature-sensitive filtering membrane with small pore size distribution and preparation method thereof - Google Patents
Temperature-sensitive filtering membrane with small pore size distribution and preparation method thereof Download PDFInfo
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- CN106000134A CN106000134A CN201610546688.2A CN201610546688A CN106000134A CN 106000134 A CN106000134 A CN 106000134A CN 201610546688 A CN201610546688 A CN 201610546688A CN 106000134 A CN106000134 A CN 106000134A
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
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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
- B01D67/0002—Organic membrane manufacture
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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
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Abstract
A temperature-sensitive filtering membrane with small pore size distribution is designed and prepared based on the thought of bionics by taking a metal chloride saline solution as a solvent in order to solve the problems that a large number of organic solvents hard to recycle are used in the traditional film preparation process, consequently, environmental pollution is caused, a polymeric membrane material is wide in membrane pore size distribution, and the membrane is in lack of responsiveness and is likely to be contaminated. Firstly, a temperature-sensitive polymer N-isopropylacrylamide is prepared in the metal chloride saline solution in a polymerization mode, and then N-isopropylacrylamide is homogeneously grafted with polyacrylonitrile to obtain a membrane casting solution; then the membrane casting solution is placed in a coagulating bath of water, metal ions and chloridions are gradually dispersed into the water, and a N-isopropylacrylamide grafted polyacrylonitrile polymer is subjected to phase transformation to form the membrane. The metal ions and the chloridions achieve a hole forming function, N-isopropylacrylamide and polyacrylonitrile are subjected to microphase separation, and a hydrophili channel subjected to ion hole forming is formed in the interface of N-isopropylacrylamide and polyacrylonitrile. The filtering membrane is expected to be used for the fields of fine separation, temperature response membrane on-off and the like.
Description
Technical field
The present invention relates to filter membrane of the sensitive narrow pore-size distribution of a kind of temperature and preparation method thereof, belong to macromolecular 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.China exists
Start the nineties in last century to explore Nanofiltration-membrane technique [chemical equipment technology, 2002,23 (8): 14-17], participate in this technology
Research side includes that National Bureau of Oceanography's Hangzhou water treatment centers, Beijing ecology are cyclized center, the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences, Shanghai atom
Core institute, Tianjin University of Technology etc., the research great majority today for NF membrane still rest on laboratory stage, due to by many
The restriction of aspect condition, it is impossible to carry out deeper into research.The only cellulose diacetate rolling of batch production can be accomplished at present
NF membrane and Triafol T hollow fiber nanofiltration membrane two kinds [Treatment of Industrial Water, 2004,24 (3): 5-8].
Polyacrylonitrile has certain development in terms of NF membrane in recent years.Xu Chenyan et al. with polyacrylonitrile as raw material, dimethyl
Sulfoxide is solvent, and polyethylene glycol 200 is that porogen prepares basement membrane.Chitosan is coated in [Shanghai City on polyacrylonitrile basement membrane
Learning chemical science can 2009 annual Annual Conference collection of thesis. Shanghai City chemical association, 2009:2].After glycerine water solution processes,
Taking-up obtains chitosan/polyacrylonitrile composite nanometer filtering film after drying, and have studied it to amino acid whose separating property.
The most be applied at present the traditional membrane material that produces can not the change of response environment, the pore size of its film will not
Change with environmental change, when the multi-component material of different molecular weight is separated, generally require and use different several in aperture
Plant filter membrane and just can obtain required composition through multiple times of filtration, so that separation process complicates, increase production cost, and affect
The modernization separated.Therefore, to have the separation film new varieties of environment-responsive significant in exploitation.Smart membrane is imitative
One of the important technology progress in raw functional membrane field.Smart membrane is exactly that changes in environmental conditions has sensitivity response and oneself adjusts to external world
The functional membrane of joint, as in environment to external world, the change of functional group, ionic strength, pH value, temperature, electric field etc. has sensing and rings
Answer the film of function.Shtanko etc. are irradiated by gamma-rays and PNIPA are grafted to polyethylene terephthalate (PET)
Or on polypropylene (PP) film, make 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 NIPA
(NIPAAm) and the sensitive acrylic acid (AAc) of pH is intellectual material, by a kind of alkali treatment method, PVDF is entered
Row surface modification, PVDF doughnut film surface grafting poly-N-isopropyl acrylamide (P NIPAAm) gel,
Polyacrylic acid (PAAc) gel, prepares the PVDF hollow fiber intelligent having temperature sensitivity sensitive with pH respectively and coagulates
Glue 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.
The generally preparation process of polymeric membrane inevitably uses organic solvent, causes environmental pollution.Macromolecule member material fenestra
Footpath wider distribution, the film lack of responsiveness and easily polluting.The present invention is based on bionic thought, with metal chloride brine solution
For solvent, the filter membrane of the sensitive narrow pore-size distribution of a kind of temperature is prepared in design.First pass through in metal chloride brine solution poly-
Temperature sensing polymer PNIPAM is prepared in conjunction, is then obtained by PNIPAM homogeneous graft polypropylene nitrile
Casting solution, then puts it in the coagulating bath of water, and metal ion and chloride ion are gradually diffused in water, poly-isopropyl acrylamide
Amine graft polypropylene nitrile polymer generation phase in version film forming.Metal ion and chloride ion play the effect of pore, and poly-isopropyl third
Acrylamide and polyacrylonitrile generation microphase-separated, also form the hydrophilic channel of ion pore at its interface.This filter membrane is expected application
In fields such as fine separation, temperature-responsive membrane switch.
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
Becoming environmental pollution, membrane aperture wider distribution, film lacks the problem such as temperature-responsive and easy pollution.
The present invention solves described film-forming process and inevitably uses organic solvent to cause environmental pollution, membrane aperture wider distribution, film
The technical scheme lacking the problem such as temperature-responsive and easy pollution is to design the filter membrane of the sensitive narrow pore-size distribution of a kind of temperature.
The invention provides filter membrane of the sensitive narrow pore-size distribution of a kind of temperature and preparation method thereof, it is characterized in that comprising the following steps:
A) be the metal chloride brine solution of 10%-100% with deionized water is prepared mass percent concentration, weigh account for from
The N-isopropylacrylamide of sub-water quality percentage ratio 1%-30%, is dissolved in metal chloride salt by N-isopropylacrylamide
In aqueous solution, obtain N-isopropylacrylamide metal chloride brine solution, then by N-isopropylacrylamide metal chlorine
Compound saline solution is poured in there-necked flask, logical nitrogen deoxygenation 5-30min, adds and accounts for N-isopropylacrylamide quality hundred
The initiator of proportion by subtraction 0.1%-2% causes polymerization, obtains PNIPAM metal chloride brine solution；
B) in the PNIPAM metal chloride brine solution of step a), the ionized water quality that accounts under agitation is added
The acrylonitrile of percentage ratio 2%-30% and the initiator accounting for acrylonitrile mass percent 0.1%-10%, cause acrylonitrile to gather
Close, reaction temperature 5-90 DEG C, response time 30-240min, by the solution for vacuum deaeration after polymerization, obtain 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, scrape 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 PNIPAM graft polypropylene nitrile film containing part metals chloride salt；By controlling the temperature of coagulating bath
Degree controls the phase in version of PNIPAM graft polypropylene nitrile, thus regulates and controls membrane aperture size and distribution；
E) the PNIPAM graft polypropylene nitrile film pH=1-3 containing part metals chloride salt step d) obtained
Dilute hydrochloric acid rinsing, remove the metal ion in membrane removal, finally repeatedly rinse with deionized water, obtain poly-isopropyl propylene
Acid amide-grafted polyacrylonitrile NF membrane.
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., azo two
Any one or two or more mixture in isopropyl cyanide, sodium sulfite, ferrous sulfate, ferrous chloride.
The filter membrane antipollution of the sensitive narrow pore-size distribution of a kind of temperature prepared by the present invention, has temperature sensitivity, and the aperture of 90% is divided
Cloth is between 0.34-0.44nm, and it 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 5%-30%, and under 0.1MPa, flux is 40-100L/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) it is the solder(ing)acid of 10% with deionized water is prepared mass percent concentration, weighs and account for ionized water percent mass
N-isopropylacrylamide than 1%, is dissolved in N-isopropylacrylamide in solder(ing)acid, obtains isopropyl third
Acrylamide solder(ing)acid, then pours in there-necked flask by N-isopropylacrylamide solder(ing)acid, logical nitrogen
Deoxygenation 30min, adds the Ammonium persulfate .-ferrous sulfate initiation polymerization accounting for N-isopropylacrylamide mass percent 2%,
Obtain PNIPAM solder(ing)acid；
B) in the PNIPAM solder(ing)acid of step a), the ionized water mass percent that accounts under agitation is added
The acrylonitrile of 30% and the tert-butyl hydroperoxide accounting for acrylonitrile mass percent 0.1%, On Polymerization of Acrylonitrile Initiated, reaction
Temperature 90 DEG C, response time 30min, by the solution for vacuum deaeration after polymerization, 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, scrape 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 PNIPAM graft polypropylene nitrile film of partial oxidation zinc；Poly-isopropyl is controlled by the temperature controlling coagulating bath
The phase in version of base acrylamide graft polyacrylonitrile, thus regulate and control membrane aperture size and distribution；
The dilute hydrochloric acid of the PNIPAM graft polypropylene nitrile film pH=1 containing partial oxidation zinc e) step d) obtained
Rinsing, removes the metal ion in membrane removal, finally repeatedly rinses with deionized water, obtains PNIPAM grafting
Polyacrylonitrile NF membrane, the rejection to the dyestuff of 660 molecular weight is 95%, and under 0.1MPa, flux is 70L/m2h。
Embodiment 2.
A) it is the solder(ing)acid of 100% with deionized water is prepared mass percent concentration, weighs and account for ionized water quality hundred
The N-isopropylacrylamide of proportion by subtraction 30%, is dissolved in N-isopropylacrylamide in solder(ing)acid, obtains isopropyl
Acrylamide chlorination zinc aqueous solution, then pours in there-necked flask by N-isopropylacrylamide solder(ing)acid, logical nitrogen
Gas deoxygenation 5min, addition accounts for sodium peroxydisulfate-sodium sulfite of N-isopropylacrylamide mass percent 0.1% and causes poly-
Close, obtain PNIPAM solder(ing)acid；
B) in the PNIPAM solder(ing)acid of step a), the ionized water mass percent that accounts under agitation is added
The acrylonitrile of 2% and the sodium peroxydisulfate-sodium sulfite accounting for acrylonitrile mass percent 0.1%, On Polymerization of Acrylonitrile Initiated,
Reaction temperature 5 DEG C, response time 240min, by the solution for vacuum deaeration after polymerization, 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, scrape 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 PNIPAM graft polypropylene nitrile film of partial oxidation zinc；Poly-isopropyl is controlled by the temperature controlling coagulating bath
The phase in version of base acrylamide graft polyacrylonitrile, thus regulate and control membrane aperture size and distribution；
The dilute hydrochloric acid of the PNIPAM graft polypropylene nitrile film pH=3 containing partial oxidation zinc e) step d) obtained
Rinsing, removes the metal ion in membrane removal, finally repeatedly rinses with deionized water, obtains PNIPAM grafting
Polyacrylonitrile NF membrane, the rejection to the dyestuff of 660 molecular weight is 100%, and under 0.1MPa, flux is 74L/m2h。
Embodiment 3.
A) it is the calcium chloride water of 60% with deionized water is prepared mass percent concentration, weighs and account for ionized water percent mass
N-isopropylacrylamide than 10%, is dissolved in N-isopropylacrylamide in calcium chloride water, obtains isopropyl third
Acrylamide calcium chloride water, then pours in there-necked flask by N-isopropylacrylamide calcium chloride water, logical nitrogen
Deoxygenation 10min, adds the potassium peroxydisulfate initiation polymerization accounting for N-isopropylacrylamide mass percent 1%, obtains poly-different
Propylacrylamide calcium chloride water；
B) in the PNIPAM calcium chloride water of step a), the ionized water mass percent that accounts under agitation is added
The acrylonitrile of 10% and the potassium peroxydisulfate accounting for acrylonitrile mass percent 0.5%, On Polymerization of Acrylonitrile Initiated, reaction temperature
30 DEG C, response time 60min, by the solution for vacuum deaeration after polymerization, 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, scrape 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 gathered
N-isopropylacrylamide graft polypropylene nitrile film；Control PNIPAM by the temperature controlling coagulating bath to be grafted
The phase in version of polyacrylonitrile, thus regulate and control membrane aperture size and distribution；
The dilute hydrochloric acid rinsing of the PNIPAM graft polypropylene nitrile film pH=1 e) obtained by step d), goes in membrane removal
Metal ion, finally repeatedly rinse with deionized water, obtain PNIPAM graft polypropylene nitrile NF membrane,
Rejection to the dyestuff of 660 molecular weight is 96%, and under 0.1MPa, flux is 80L/m2h。
Embodiment 4.
A) it is the calcium chloride water of 50% with deionized water is prepared mass percent concentration, weighs and account for ionized water percent mass
N-isopropylacrylamide than 150%, is dissolved in N-isopropylacrylamide in calcium chloride water, obtains isopropyl
Acrylamide chlorination calcium aqueous solution, then pours in there-necked flask by N-isopropylacrylamide calcium chloride water, logical nitrogen
Gas deoxygenation 20min, adds the Ammonium persulfate. initiation polymerization accounting for N-isopropylacrylamide mass percent 0.8%, is gathered
N-isopropylacrylamide calcium chloride water；
B) in the PNIPAM calcium chloride water of step a), the ionized water mass percent that accounts under agitation is added
The acrylonitrile of 20% and the Ammonium persulfate. accounting for acrylonitrile mass percent 1%, On Polymerization of Acrylonitrile Initiated, reaction temperature
20 DEG C, response time 80min, by the solution for vacuum deaeration after polymerization, obtain casting solution；
C) preparing pH with dilute hydrochloric acid is the aqueous solution of 4, as coagulating bath；
D) casting solution that step b) obtains is poured on the sheet glass of dry cleansing, scrape 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 gathered
N-isopropylacrylamide graft polypropylene nitrile film；Control PNIPAM by the temperature controlling coagulating bath to be grafted
The phase in version of polyacrylonitrile, thus regulate and control membrane aperture size and distribution；
The dilute hydrochloric acid rinsing of the PNIPAM graft polypropylene nitrile film pH=2 e) obtained by step d), goes in membrane removal
Metal ion, finally repeatedly rinse with deionized water, obtain PNIPAM graft polypropylene nitrile NF membrane,
Rejection to the dyestuff of 660 molecular weight is 99%, and under 0.1MPa, flux is 68L/m2h。
Claims (5)
1. a filter membrane for the sensitive narrow pore-size distribution of temperature, is characterized in that, based on bionic thought, first passing through at metal chlorination
In thing saline solution, temperature sensing polymer PNIPAM, the then equal grafted branches of PNIPAM are prepared in polymerization
Polyacrylonitrile obtains casting solution, then puts it in the coagulating bath of water, and metal ion and chloride ion are gradually diffused in water,
PNIPAM graft polypropylene nitrile polymer generation phase in version film forming；Metal ion and chloride ion play the work of pore
With, and PNIPAM and polyacrylonitrile generation microphase-separated, the hydrophilic channel of ion pore is also formed at its interface.
2. a preparation method for the filter membrane of the sensitive narrow pore-size distribution of temperature, is characterized in that comprising the following steps:
A) be the metal chloride brine solution of 10%-100% with deionized water is prepared mass percent concentration, weigh account for from
The N-isopropylacrylamide of sub-water quality percentage ratio 1%-30%, is dissolved in metal chloride salt by N-isopropylacrylamide
In aqueous solution, obtain N-isopropylacrylamide metal chloride brine solution, then by N-isopropylacrylamide metal chlorine
Compound saline solution is poured in there-necked flask, logical nitrogen deoxygenation 5-30min, adds and accounts for N-isopropylacrylamide quality hundred
The initiator of proportion by subtraction 0.1%-2% causes polymerization, obtains PNIPAM metal chloride brine solution；
B) in the PNIPAM metal chloride brine solution of step a), the ionized water quality that accounts under agitation is added
The acrylonitrile of percentage ratio 2%-30% and the initiator accounting for acrylonitrile mass percent 0.1%-10%, cause acrylonitrile to gather
Close, reaction temperature 5-90 DEG C, response time 30-240min, by the solution for vacuum deaeration after polymerization, obtain 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 PNIPAM graft polypropylene nitrile film containing part metals chloride salt；By controlling the temperature of coagulating bath
Degree controls the phase in version of PNIPAM graft polypropylene nitrile, thus regulates and controls membrane aperture size and distribution；
E) the PNIPAM graft polypropylene nitrile film pH=1-3 containing part metals chloride salt step d) obtained
Dilute hydrochloric acid rinsing, remove the metal ion in membrane removal, finally repeatedly rinse with deionized water, obtain poly-isopropyl propylene
Acid amide-grafted polyacrylonitrile NF membrane.
The preparation method of the filter membrane of the sensitive narrow pore-size distribution of a kind of temperature the most as claimed in claim 2, is characterized in that described gold
Genus chloride salt is any one or two or more mixture in zinc chloride, iron chloride, calcium chloride.
The preparation method of the filter membrane of the sensitive narrow pore-size distribution of a kind of temperature the most as claimed in claim 2, is characterized in that described drawing
Send out agent be benzoyl peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate., azodiisobutyronitrile,
Any one or two or more mixture in sodium sulfite, ferrous sulfate, ferrous chloride.
5. a filter membrane for the sensitive narrow pore-size distribution of temperature, is characterized in that the film antipollution of preparation, has temperature sensitivity, 90%
Pore-size distribution is between 0.34-0.44nm, and the dyestuff of molecular weight more than 660 and the rejection of Polyethylene Glycol are by it
90%-100%, is 5%-30% to the dyestuff of molecular weight less than 600 and the rejection of Polyethylene Glycol, and under 0.1MPa, flux is
40-100I/m2h。
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| CN110052177B (en) * | 2019-04-04 | 2021-04-30 | 天津工业大学 | Preparation method of hollow microsphere reinforced high-flux polyacrylonitrile filter membrane |
| 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 |
| CN111007109A (en) * | 2019-12-24 | 2020-04-14 | 华中科技大学 | Gradient microporous filtration gas sensor and preparation method thereof |
| CN111007109B (en) * | 2019-12-24 | 2021-05-18 | 华中科技大学 | Gradient microporous filtration gas sensor and preparation method thereof |
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