CN106000134B - A kind of filter membrane and preparation method thereof of the narrow pore-size distribution of temperature sensitivity - Google Patents
A kind of filter membrane and preparation method thereof of the narrow pore-size distribution of temperature sensitivity Download PDFInfo
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- CN106000134B CN106000134B CN201610546688.2A CN201610546688A CN106000134B CN 106000134 B CN106000134 B CN 106000134B CN 201610546688 A CN201610546688 A CN 201610546688A CN 106000134 B CN106000134 B CN 106000134B
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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
The organic solvent that a large amount of difficult recycling are used for traditional film-forming process causes environmental pollution, macromolecule member material membrane aperture wider distribution, the problems such as film lack of responsiveness and easy pollution, the present invention is based on bionic thoughts, using metal chloride brine solution as solvent, design prepares a kind of filter membrane of the narrow pore-size distribution of temperature sensitivity.First by metal chloride brine solution polymerization prepare temperature sensing polymer polyisopropyl acrylamide, then casting solution is obtained by the homogeneous graft polypropylene nitrile of polyisopropyl acrylamide, then it puts it into the coagulating bath of water, metal ion and chlorion are gradually diffused into water, and phase transition film forming occurs for polyisopropyl acrylamide graft polypropylene nitrile polymer.Metal ion and chlorion play the role of pore, and microphase-separated occurs for polyisopropyl acrylamide and polyacrylonitrile, and the hydrophilic channel of ion pore is also formed at its interface.The filter membrane is expected to be applied to the fields such as fine separation, temperature-responsive membrane switch.
Description
Technical field
The present invention relates to a kind of filter membrane and preparation method thereof of the sensitive narrow pore-size distribution of temperature, belong to high molecular material and
Film field.
Background technology
The advantages that membrane technology is efficient, low energy consumption and cost of investment is small due to it, is widely applied in water process.I
State started to explore Nanofiltration-membrane technique in the nineties in last century【Chemical equipment technology, 2002,23 (8)：14-17】, participate in the technology
Research side include that National Bureau of Oceanography's Hangzhou water treatment centers, Beijing ecology cyclisation center, the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences, Shanghai are former
Daughter nucleus institute, Tianjin Polytechnic University etc., nowadays still rest on laboratory stage for most of research of NF membrane, due to by
The limitation of many-sided condition, can not carry out deeper into research.It can accomplish the only cellulose diacetate of batch production at present
Two kinds of rolling NF membrane and Triafol T hollow fiber nanofiltration membrane【Treatment of Industrial Water, 2004,24 (3)：5-8】.
Polyacrylonitrile has certain development in recent years in terms of NF membrane.Perhaps Chen Yan et al. using polyacrylonitrile as raw material,
Dimethyl sulfoxide (DMSO) is solvent, and polyethylene glycol 200 is that pore-foaming agent prepares basement membrane.By chitosan coated on polyacrylonitrile basement membrane【On
The 2009 year Shanghai City Annual Conference collection of thesis chemical association of sea market chemical association, 2009：2】.It is water-soluble through glycerine
After liquid processing, taking-up obtains chitosan/polyacrylonitrile composite nanometer filtering film after drying, and has studied its separation property to amino acid
Energy.
The variation of environment can not be responded by being applied to the traditional membrane material of production at present, and the aperture of film is big
It is small to change with environmental change, when the multi-component material to different molecular weight detaches, generally require to use aperture
Different several filter membranes can just obtain required ingredient by being filtered for multiple times, and to make separation process complicate, increase is produced into
This, and influence the modernization of separation.Therefore, seperation film new varieties of the exploitation with environment-responsive are of great significance.
Smart membrane is one of the important technology progress in bionic function film field.Smart membrane is exactly to have sensitivity to extraneous changes in environmental conditions
The functional membrane of reaction and self-control, such as have to the variation of functional group, ionic strength, pH value, temperature, electric field in external environment
There is the film of induction and response function.Shtanko etc. is irradiated by gamma-rays is grafted to polyethylene terephthalate by PNIPA
(PET) or on polypropylene (PP) film temperature response type macromolecule composite membrane is made【J.Membr.Sci 2000,179：155~
161】.Wang Wenyu etc. is using Kynoar (PVDF) doughnut as basement membrane, with temperature sensitive n-isopropyl acrylamide
(NIPAAm) and the acrylic acid of pH sensitivities (AAc) is intellectual material, and surface modification is carried out to PVDF by a kind of alkali treatment method,
It is grafted poly-N-isopropyl acrylamide (P NIPAAm) gel, polyacrylic acid (PAAc) gel in PVDF hollow fiber membrane surfaces,
The PVDF hollow fiber intelligent gel compound membranes with temperature sensitivity and pH sensitivities are prepared respectively【J Appl Polym Sci
2006；101(2)：833-837】.But the N-isopropylacrylamide grafting rate that the method for above-mentioned grafting obtains is relatively low, temperature
Quick property is poor.
The preparation process of usual polymeric membrane inevitably uses organic solvent, causes environmental pollution.Macromolecule membrane material
Expect membrane aperture wider distribution, the film lack of responsiveness and easy pollution.The present invention is based on bionic thoughts, with metal chloride salt
Aqueous solution is solvent, and design prepares a kind of filter membrane of the narrow pore-size distribution of temperature sensitivity.First by metal chloride brine
Polymerization prepares temperature sensing polymer polyisopropyl acrylamide in solution, then poly- by the equal grafted branches of polyisopropyl acrylamide
Acrylonitrile obtains casting solution, then puts it into the coagulating bath of water, and metal ion and chlorion are gradually diffused into water, gathers different
Phase transition film forming occurs for propylacrylamide graft polypropylene nitrile polymer.Metal ion and chlorion play the role of pore,
And microphase-separated occurs for polyisopropyl acrylamide and polyacrylonitrile, and the hydrophilic channel of ion pore is also formed at its interface.It should
Filter membrane is expected to be applied to the fields such as fine separation, temperature-responsive membrane switch.
Invention content
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve is film-forming process inevitably using organic
The problems such as solvent causes environmental pollution, membrane aperture wider distribution, and film lacks temperature-responsive and is easy pollution.
The present invention solves the film-forming process and inevitably causes environmental pollution using organic solvent, membrane aperture distribution compared with
The technical solution of the problems such as width, film lacks temperature-responsive and is easy pollution is a kind of mistake of the sensitive narrow pore-size distribution of temperature of design
Filter membrane.
The present invention provides a kind of filter membranes and preparation method thereof of the sensitive narrow pore-size distribution of temperature, it is characterized in that include with
Lower step：
A) it with the metal chloride brine solution that mass percent concentration is 10%-100% is prepared in deionized water, weighs
N-isopropylacrylamide is dissolved in metal chloride by the N-isopropylacrylamide for accounting for ionized water mass percent 1%-30%
In saline solution, N-isopropylacrylamide metal chloride brine solution is obtained, then by N-isopropylacrylamide metal chlorination
Object saline solution pours into three-necked flask, leads to nitrogen deoxygenation 5-30min, and addition accounts for N-isopropylacrylamide mass percent
The initiator of 0.1%-2% causes polymerization, obtains polyisopropyl acrylamide metal chloride brine solution；
B) it is added under stiring into the polyisopropyl acrylamide metal chloride brine solution of step a) and accounts for ion
The acrylonitrile of water quality percentage 2%-30% and the initiator for accounting for acrylonitrile mass percent 0.1%-10% cause acrylonitrile
Solution vacuum defoamation after polymerization is obtained casting solution by polymerization, 5-90 DEG C of reaction temperature, reaction time 30-240min；
C) aqueous solution that pH is 2-5 is prepared with dilute hydrochloric acid, as coagulating bath；
D) the obtained casting solutions of step b) are poured on the sheet glass of dry cleansing, scrapes uniform film with knifing stick, so
Film is dipped into 30-120min in the coagulating bath of step c) together with sheet glass afterwards, the temperature for controlling coagulating bath is 5-90 DEG C,
Obtain the polyisopropyl acrylamide graft polypropylene nitrile film of the chloride salt containing part metals；By the temperature control for controlling coagulating bath
The phase transition of polyisopropyl acrylamide graft polypropylene nitrile processed, to regulate and control membrane aperture size and distribution；
E) the polyisopropyl acrylamide graft polypropylene nitrile film of the obtained chloride salts containing part metals of step d) is used
The dilute hydrochloric acid of pH=1-3 rinses, and removes the metal ion in membrane removal, is finally rinsed repeatedly with deionized water, obtains poly- isopropyl third
Acrylamide graft polypropylene nitrile NF membrane.
Metal chloride salt of the present invention be zinc chloride, iron chloride, in calcium chloride any one or it is two or more
Mixture.The initiator be benzoyl peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate,
Any one in azodiisobutyronitrile, sodium hydrogensulfite, ferrous sulfate, frerrous chloride or two or more mixtures.
A kind of filter membrane antipollution of the sensitive narrow pore-size distribution of temperature prepared by the present invention, has a temperature sensitivity, and 90%
Pore-size distribution between 0.34-0.44nm, the rejection of dyestuff and polyethylene glycol to 660 or more molecular weight is 90%-
100%, it is 5%-30% to the rejection of 600 dyestuff below of molecular weight and polyethylene glycol, flux is 40- under 0.1MPa
100L/m2h。。
Specific implementation mode
Specific embodiments of the present invention are described below, but the present invention should not be limited by the examples.
Embodiment 1.
A) solder(ing)acid for preparing that mass percent concentration is 10% in deionized water, weighing is used to account for deionized water
The N-isopropylacrylamide for measuring percentage 1%, N-isopropylacrylamide is dissolved in solder(ing)acid, isopropyl third is obtained
Then acrylamide solder(ing)acid pours into N-isopropylacrylamide solder(ing)acid in three-necked flask, lead to nitrogen deoxygenation
30min is added the ammonium persulfate-ferrous sulfate initiation polymerization for accounting for N-isopropylacrylamide mass percent 2%, obtains poly- isopropyl
Base acrylamide chlorination zinc aqueous solution；
B) it is added under stiring into the polyisopropyl acrylamide solder(ing)acid of step a) and accounts for ion water quality
The acrylonitrile of percentage 30% and the tert-butyl hydroperoxide for accounting for acrylonitrile mass percent 0.1% cause acrylonitrile polymerization, instead
90 DEG C, reaction time 30min of temperature is answered, by the solution vacuum defoamation after polymerization, obtains casting solution；
C) aqueous solution that pH is 2 is prepared with dilute hydrochloric acid, as coagulating bath；
D) the obtained casting solutions of step b) are poured on the sheet glass of dry cleansing, scrapes uniform film with knifing stick, so
Film is dipped into 120min in the coagulating bath of step c) together with sheet glass afterwards, the temperature for controlling coagulating bath is 5 DEG C, is contained
The polyisopropyl acrylamide graft polypropylene nitrile film of partial oxidation zinc；Temperature by controlling coagulating bath controls poly- isopropyl third
The phase transition of acrylamide graft polypropylene nitrile, to regulate and control membrane aperture size and distribution；
E) by the polyisopropyl acrylamide graft polypropylene nitrile film pH=1's of the obtained zinc containing partial oxidation of step d)
Dilute hydrochloric acid rinses, and removes the metal ion in membrane removal, is finally rinsed repeatedly with deionized water, obtains polyisopropyl acrylamide grafting
Polyacrylonitrile NF membrane, the rejection to the dyestuff of 660 molecular weight are that flux is 70L/m under 95%, 0.1MPa2h。
Embodiment 2.
A) solder(ing)acid for preparing that mass percent concentration is 100% in deionized water, weighing is used to account for ionized water
The N-isopropylacrylamide of mass percent 30%, N-isopropylacrylamide is dissolved in solder(ing)acid, obtains isopropyl
Base acrylamide chlorination zinc aqueous solution, then pours into N-isopropylacrylamide solder(ing)acid in three-necked flask, leads to nitrogen
Deoxygenation 5min is added the sodium peroxydisulfate-sodium hydrogensulfite initiation polymerization for accounting for N-isopropylacrylamide mass percent 0.1%, obtains
To polyisopropyl acrylamide solder(ing)acid；
B) it is added under stiring into the polyisopropyl acrylamide solder(ing)acid of step a) and accounts for ion water quality
It is poly- to cause acrylonitrile for the acrylonitrile of percentage 2% and the sodium peroxydisulfate-sodium hydrogensulfite for accounting for acrylonitrile mass percent 0.1%
It closes, 5 DEG C, reaction time 240min of reaction temperature by the solution vacuum defoamation after polymerization, obtains casting solution；
C) aqueous solution that pH is 5 is prepared with dilute hydrochloric acid, as coagulating bath；
D) the obtained casting solutions of step b) are poured on the sheet glass of dry cleansing, scrapes uniform film with knifing stick, so
Film is dipped into 30min in the coagulating bath of step c) together with sheet glass afterwards, the temperature for controlling coagulating bath is 90 DEG C, is contained
The polyisopropyl acrylamide graft polypropylene nitrile film of partial oxidation zinc；Temperature by controlling coagulating bath controls poly- isopropyl third
The phase transition of acrylamide graft polypropylene nitrile, to regulate and control membrane aperture size and distribution；
E) by the polyisopropyl acrylamide graft polypropylene nitrile film pH=3's of the obtained zinc containing partial oxidation of step d)
Dilute hydrochloric acid rinses, and removes the metal ion in membrane removal, is finally rinsed repeatedly with deionized water, obtains polyisopropyl acrylamide grafting
Polyacrylonitrile NF membrane, the rejection to the dyestuff of 660 molecular weight are that flux is 74L/m under 100%, 0.1MPa2h。
Embodiment 3.
A) calcium chloride water for preparing that mass percent concentration is 60% in deionized water, weighing is used to account for deionized water
The N-isopropylacrylamide for measuring percentage 10%, N-isopropylacrylamide is dissolved in calcium chloride water, isopropyl is obtained
Acrylamide chlorination calcium aqueous solution, then pours into N-isopropylacrylamide calcium chloride water in three-necked flask, leads to nitrogen row
Oxygen 10min is added the potassium peroxydisulfate initiation polymerization for accounting for N-isopropylacrylamide mass percent 1%, obtains poly- isopropyl propylene
Amide calcium chloride water；
B) it is added under stiring into the polyisopropyl acrylamide calcium chloride water of step a) and accounts for ion water quality
The acrylonitrile of percentage 10% and the potassium peroxydisulfate for accounting for acrylonitrile mass percent 0.5% cause acrylonitrile polymerization, reaction temperature
30 DEG C, reaction time 60min, by the solution vacuum defoamation after polymerization, obtain casting solution；
C) aqueous solution that pH is 3 is prepared with dilute hydrochloric acid, as coagulating bath；
D) the obtained casting solutions of step b) are poured on the sheet glass of dry cleansing, scrapes uniform film with knifing stick, so
Film is dipped into 60min in the coagulating bath of step c) together with sheet glass afterwards, the temperature for controlling coagulating bath is 20 DEG C, is gathered
N-isopropylacrylamide graft polypropylene nitrile film；Temperature by controlling coagulating bath controls polyisopropyl acrylamide grafting poly- third
The phase transition of alkene nitrile, to regulate and control membrane aperture size and distribution；
E) dilute hydrochloric acid of the obtained polyisopropyl acrylamide graft polypropylene nitrile film pH=1 of step d) is rinsed, is gone
Metal ion in membrane removal is finally rinsed with deionized water repeatedly, obtains polyisopropyl acrylamide graft polypropylene nitrile nanofiltration
Film, the rejection to the dyestuff of 660 molecular weight are that flux is 80L/m under 96%, 0.1MPa2h。
Embodiment 4.
A) calcium chloride water for preparing that mass percent concentration is 50% in deionized water, weighing is used to account for deionized water
The N-isopropylacrylamide for measuring percentage 150%, N-isopropylacrylamide is dissolved in calcium chloride water, isopropyl is obtained
Acrylamide chlorination calcium aqueous solution, then pours into N-isopropylacrylamide calcium chloride water in three-necked flask, leads to nitrogen row
Oxygen 20min is added the ammonium persulfate initiation polymerization for accounting for N-isopropylacrylamide mass percent 0.8%, obtains poly- isopropyl third
Acrylamide calcium chloride water；
B) it is added under stiring into the polyisopropyl acrylamide calcium chloride water of step a) and accounts for ion water quality
The acrylonitrile of percentage 20% and the ammonium persulfate for accounting for acrylonitrile mass percent 1% cause acrylonitrile polymerization, reaction temperature 20
DEG C, the solution vacuum defoamation after polymerization is obtained casting solution by reaction time 80min；
C) aqueous solution that pH is 4 is prepared with dilute hydrochloric acid, as coagulating bath；
D) the obtained casting solutions of step b) are poured on the sheet glass of dry cleansing, scrapes uniform film with knifing stick, so
Film is dipped into 60min in the coagulating bath of step c) together with sheet glass afterwards, the temperature for controlling coagulating bath is 20 DEG C, is gathered
N-isopropylacrylamide graft polypropylene nitrile film；Temperature by controlling coagulating bath controls polyisopropyl acrylamide grafting poly- third
The phase transition of alkene nitrile, to regulate and control membrane aperture size and distribution；
E) dilute hydrochloric acid of the obtained polyisopropyl acrylamide graft polypropylene nitrile film pH=2 of step d) is rinsed, is gone
Metal ion in membrane removal is finally rinsed with deionized water repeatedly, obtains polyisopropyl acrylamide graft polypropylene nitrile nanofiltration
Film, the rejection to the dyestuff of 660 molecular weight are that flux is 68L/m under 99%, 0.1MPa2h。
Claims (5)
1. the filter membrane of the sensitive narrow pore-size distribution of a kind of temperature, it is characterized in that bionic thought is based on, first by metal
Polymerization prepares temperature sensing polymer polyisopropyl acrylamide in chloride salt aqueous solution, and then polyisopropyl acrylamide is homogeneous
Graft polypropylene nitrile obtains casting solution, then puts it into the coagulating bath of water, and metal ion and chlorion are gradually diffused into water
In, phase transition film forming occurs for polyisopropyl acrylamide graft polypropylene nitrile polymer；Metal ion and chlorion play pore
Effect, and microphase-separated occurs for polyisopropyl acrylamide and polyacrylonitrile, and the hydrophilic of ion pore is also formed at its interface
Channel.
2. the preparation method of the filter membrane of the sensitive narrow pore-size distribution of a kind of temperature, it is characterized in that including the following steps：
A) with the metal chloride brine solution that mass percent concentration is 10%-100% is prepared in deionized water, weighing accounts for
The N-isopropylacrylamide of ionized water mass percent 1%-30%, metal chloride brine is dissolved in by N-isopropylacrylamide
In solution, N-isopropylacrylamide metal chloride brine solution is obtained, then by N-isopropylacrylamide metal chloride salt
Aqueous solution pours into three-necked flask, leads to nitrogen deoxygenation 5-30min, and addition accounts for N-isopropylacrylamide mass percent 0.1%-
2% initiator causes polymerization, obtains polyisopropyl acrylamide metal chloride brine solution；
B) it is added under stiring into the polyisopropyl acrylamide metal chloride brine solution of step a) and accounts for deionized water
The acrylonitrile of amount percentage 2%-30% and the initiator for accounting for acrylonitrile mass percent 0.1%-10%, it is poly- to cause acrylonitrile
It closes, the solution vacuum defoamation after polymerization is obtained casting solution by 5-90 DEG C of reaction temperature, reaction time 30-240min；
C) aqueous solution that pH is 2-5 is prepared with dilute hydrochloric acid, as coagulating bath；
D) the obtained casting solutions of step b) are poured on the sheet glass of dry cleansing, uniform film is scraped with knifing stick, then will
Film is dipped into 30-120min in the coagulating bath of step c) together with sheet glass, and the temperature for controlling coagulating bath is 5-90 DEG C, is obtained
The polyisopropyl acrylamide graft polypropylene nitrile film of the chloride salt containing part metals；It is poly- by the temperature control for controlling coagulating bath
The phase transition of N-isopropylacrylamide graft polypropylene nitrile, to regulate and control membrane aperture size and distribution；
E) by the polyisopropyl acrylamide graft polypropylene nitrile film pH=of the obtained chloride salts containing part metals of step d)
The dilute hydrochloric acid of 1-3 rinses, and removes the metal ion in membrane removal, is finally rinsed repeatedly with deionized water, obtains poly- isopropyl acrylamide
Amine graft polypropylene nitrile NF membrane.
3. the preparation method of the filter membrane of the narrow pore-size distribution of a kind of temperature sensitivity as claimed in claim 2, it is characterized in that described
Metal chloride salt be zinc chloride, iron chloride, any one or two or more mixtures in calcium chloride.
4. the preparation method of the filter membrane of the narrow pore-size distribution of a kind of temperature sensitivity as claimed in claim 2, it is characterized in that described
Initiator be benzoyl peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, two isobutyl of azo
Any one in nitrile, sodium hydrogensulfite, ferrous sulfate, frerrous chloride or two or more mixtures.
5. the preparation method of the filter membrane of the narrow pore-size distribution of a kind of temperature sensitivity as claimed in claim 2, it is characterized in that preparing
Film antipollution, have temperature sensitivity, 90% pore-size distribution is between 0.34-0.44nm, to 660 or more molecular weight
The rejection of dyestuff and polyethylene glycol is 90%-100%, and the rejection to 600 dyestuff below of molecular weight and polyethylene glycol is
Flux is 40-100L/m under 5%-30%, 0.1MPa2h。
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| CN107281943B (en) * | 2016-04-12 | 2020-04-03 | 青岛大学 | Temperature-controllable switch type nanofiltration membrane and preparation method thereof |
| CN109382002B (en) * | 2017-08-02 | 2021-06-04 | 浙江工业大学 | Intelligent switch membrane based on nanogel and preparation method thereof |
| CN108864472B (en) * | 2018-05-22 | 2021-02-23 | 西南大学 | Ultrathin microporous silk fibroin film, preparation method and application |
| CN109433017B (en) * | 2018-10-24 | 2021-05-25 | 北京机械设备研究所 | Microfiltration membrane and modification method |
| 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 |
| CN110052174B (en) * | 2019-04-04 | 2021-04-30 | 天津工业大学 | Preparation method of high-flux bubble-containing polyacrylonitrile-based 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 |
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| CN103091429A (en) * | 2012-12-27 | 2013-05-08 | 天津工业大学 | Preparation method and application of solid phase extraction membrane comprising amphipathicity functional group |
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