CN105854646B - A kind of narrow pore-size distribution hydrophilic filter film of temperature and pH sensitivities and preparation method thereof - Google Patents
A kind of narrow pore-size distribution hydrophilic filter film of temperature and pH sensitivities and preparation method thereof Download PDFInfo
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- CN105854646B CN105854646B CN201610415071.7A CN201610415071A CN105854646B CN 105854646 B CN105854646 B CN 105854646B CN 201610415071 A CN201610415071 A CN 201610415071A CN 105854646 B CN105854646 B CN 105854646B
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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
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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
- B01D71/40—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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Abstract
The organic solvent and pore-foaming agent of a large amount of difficult recycling are used for traditional film-forming process, cause environmental pollution, the problems such as membrane aperture wider distribution and the film lack of responsiveness, the present invention is based on bionic thoughts, using metal chloride brine solution as solvent, design prepares the narrow pore-size distribution hydrophilic filter film of a kind of temperature and pH sensitivities.Casting solution is obtained by the homogeneous graft polypropylene nitrile of fibroin and polyisopropyl acrylamide first, then put it into the coagulating bath of water, metal ion and chlorion are gradually diffused into water, and phase transition film forming occurs for the fibroin for being grafted polyisopropyl acrylamide and polyacrylonitrile.Metal ion and chlorion play the role of pore, and microphase-separated occurs for fibroin, polyisopropyl acrylamide and polyacrylonitrile, and the aquaporin of ion pore is also formed at its interface.Fibroin and polyisopropyl acrylamide assign film pH value and temperature sensitivity respectively.And the pore effect of metal ion and chlorion makes the aperture of film smaller and is distributed very narrow.
Description
Technical field
The present invention relates to narrow pore-size distribution hydrophilic filter films of a kind of temperature and pH sensitivities and preparation method thereof, belong to high score
Sub- material and film field.
Background technology
Membrane technology due to its efficiently, low energy consumption and cost of investment is small the advantages that, be widely applied in water process.Mesh
The preceding traditional membrane material for being applied to production can not respond the variation of environment, and the pore size of film will not be with ring
Border changes and changes, when the multi-component material to different molecular weight separates, generally requires to use different several in aperture
Filter membrane can just obtain required ingredient by multiple times of filtration, so that separation process complicates, increase production cost, and influence to divide
From modernization.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 extraneous changes in environmental conditions
Functional membrane with sensitivity response and self-control, such as to functional group, ionic strength, pH value, temperature, electric field in external environment
Variation with sensing and response function film.Shtanko etc. is irradiated by gamma-rays is grafted to poly terephthalic acid by PNIPA
Temperature response type macromolecule composite membrane is made on glycol ester (PET) or polypropylene (PP) film【J.Membr.Sci, 2000,179：
155~161】.Wang Wenyu etc. is using Kynoar (PVDF) doughnut as basement membrane, with temperature sensitive N- isopropyl acrylamides
Amine (NIPAAm) and the acrylic acid (AAc) of pH sensitivities are intellectual material, and carrying out surface to PVDF by a kind of alkali treatment method changes
Property, it is solidifying to be grafted poly-N-isopropyl acrylamide (PNIPAAm) gel, polyacrylic acid (PAAc) in PVDF hollow fiber membrane surfaces
Glue is prepared respectively with the sensitive PVDF hollow fiber intelligent gel compound membranes with pH sensitivities of temperature【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.
Conventional film filtering material easily causes macromolecular, colloid, electrolyte etc. in film surface due to the hydrophobicity of itself
Or film inside irreversible deposition, the flux that causing fouling membrane makes film constantly decline, so that membrane separating process cannot be normally carried out.Mitigate
One effective ways of fouling membrane are the surface naturies for improving film, such as the hydrophiling of chargedization of film surface or hydrophobic film.
The hydrophily of film is mainly improved by blending and modifying, surface coating and surface graft modification at present, so as to improve the anti-pollution of film
Metachromia energy.But blending and modifying complex process, surface coating easily come off, surface graft modification is difficult to uniformly be modified
Film.Meng et al. improves the hydrophily of film in PVDF micropores film surface three kinds of hydrophily brush polymer chains of introducing
【Appl.Surf.Sci, 2011,257：6282-6290】.Common surface chemical modification method is introduced in film surface in document report
Hydrophilic functional group or hydrophilic polymer chain complex process, it is difficult to realize industrialization, be improved to the hydrophily of film limited.
The preparation process of usual polymeric membrane causes environmental pollution inevitably using organic solvent.Macromolecule membrane material
Expect membrane aperture wider distribution.The present invention is based on bionic thoughts, and using metal chloride brine solution as solvent, design prepares one
The narrow pore-size distribution hydrophilic filter film of kind temperature and pH sensitivities.Pass through the homogeneous graft polypropylene nitrile of fibroin and poly- isopropyl third first
Acrylamide obtains casting solution, then puts it into the coagulating bath of water, and metal ion and chlorion are gradually diffused into water, grafting
Phase transition film forming occurs for the fibroin of polyisopropyl acrylamide and polyacrylonitrile.Metal ion and chlorion play the work of pore
With, and microphase-separated occurs for fibroin, polyisopropyl acrylamide and polyacrylonitrile, the water that ion pore is also formed at its interface leads to
Road.Fibroin and polyisopropyl acrylamide assign film pH value and temperature sensitivity respectively.And the pore of metal ion and chlorion
Effect makes the aperture of film smaller and is distributed very narrow.The filter membrane is expected to be applied to fine separation, temperature and pH value responding to switch film
Deng.
The content of the invention
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, and membrane aperture distribution is wide, the film lack of responsiveness and easily pollution.
The present invention solves the film-forming process and inevitably causes environmental pollution, membrane aperture distribution using organic solvent
The technical solution of the problems such as width, the easily film lack of responsiveness and pollution is the narrow pore-size distribution parent of a kind of temperature of design and pH sensitivities
Water filtration film.The film is using metal chloride brine solution as solvent, passes through the homogeneous graft polypropylene nitrile of fibroin and poly- isopropyl
Acrylamide obtains casting solution, then puts it into the coagulating bath of water, and metal ion and chlorion are gradually diffused into water, are connect
Phase transition film forming occurs for the fibroin of branch polyisopropyl acrylamide and polyacrylonitrile；Metal ion and chlorion play the work of pore
With, and microphase-separated occurs for fibroin, polyisopropyl acrylamide and polyacrylonitrile, the water that ion pore is also formed at its interface leads to
Road, so as to obtain narrow pore-size distribution and hydrophilic film.Using the temperature sensitivity of polyisopropyl acrylamide film is made to obtain temperature
Sensibility is spent, the soda acid ionization using amino acid in fibroin makes film obtain pH sensibility.
The present invention provides narrow pore-size distribution hydrophilic filter film of a kind of temperature and pH sensitivities and preparation method thereof, features
It is to comprise the following steps：
A) the metal chloride brine solution of mass percent concentration 10%-100% is prepared, weighing accounts for water quality percentage
Fibroin is dissolved in metal chloride brine solution by the fibroin of 2%-30%, and fibroin metal chloride brine solution is poured into three
In mouth flask, lead to nitrogen deoxygenation 1-30min, added in into three-necked flask account for ionized water mass percent 2%- under stiring
50% acrylonitrile and the N-isopropylacrylamide for accounting for ionized water mass percent 1%-20%；
B) it is added dropwise under stiring and accounts for drawing for acrylonitrile and N-isopropylacrylamide gross mass percentage 0.1%-10%
Agent is sent out, acrylonitrile and N-isopropylacrylamide is triggered to be graft-polymerized on fibroin, reaction time 20-240min, after polymerization
Solution be cooled to room temperature, vacuum defoamation obtains casting solution；
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, scrape uniform film with knifing stick, so
Film is dipped into 30-120min in the coagulating bath of step c) together with sheet glass afterwards, controls the temperature of coagulating bath as 5-90 DEG C,
Obtain the fibroin grafting polyisopropyl acrylamide and polyacrylonitrile film of the chloride salt containing part metals；Bath temperature is solidified by controlling
The phase transition process of degree control film, so as to regulate and control membrane aperture size and distribution；
E) fibroin of the obtained chloride salts containing part metals of step c) is grafted polyisopropyl acrylamide and polypropylene
Nitrile film is rinsed 3-5 times with the dilute hydrochloric acid of pH=1-3, is removed the metal ion in membrane removal, is finally rinsed 3-5 repeatedly with deionized water
It is secondary, obtain the narrow pore-size distribution hydrophilic filter film of a kind of temperature and pH sensitivities.
Metal chloride salt of the present invention is zinc chloride, iron chloride, in calcium chloride any one or it is two or more
Mixture；The initiator for benzoyl peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate,
Any one in sodium pyrosulfite, sodium hydrogensulfite, ferrous sulfate, frerrous chloride or two or more mixtures；The silk
Protein derives from least one of mulberry silk and tussah silk.The pore-size distribution of film 90% prepared by the present invention is in 0.31-0.46nm
Between, it is 90%-100% to the dyestuff of molecular weight more than 660 and the rejection of polyethylene glycol in 0.1MPa lower films, to molecular weight
Less than 600 dyestuff and the rejection of polyethylene glycol are 10%-30%, and membrane flux is 60-120L/m under 0.1MPa2h。
Specific embodiment
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 of mass percent concentration 10% is prepared, weighs the fibroin for accounting for water quality percentage 2%, it will
Fibroin is dissolved in solder(ing)acid, and fibroin solder(ing)acid is poured into three-necked flask, leads to nitrogen deoxygenation 30min, is stirring
Lower add in into three-necked flask is mixed to account for the acrylonitrile of ionized water mass percent 2% and account for ionized water mass percent 20%
N-isopropylacrylamide；
B) be added dropwise under stiring account for the ammonium persulfate of acrylonitrile and N-isopropylacrylamide gross mass percentage 10%-
Ferrous sulfate triggers acrylonitrile and N-isopropylacrylamide to be graft-polymerized on fibroin, reaction time 20min, after polymerization
Solution be cooled to room temperature, vacuum defoamation 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, scrape 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 of coagulating bath is controlled to be contained for 5 DEG C
The fibroin grafting polyisopropyl acrylamide and polyacrylonitrile film of partial oxidation zinc；By the way that coagulation bath temperature is controlled to control the phase of film
Transition process, so as to regulate and control membrane aperture size and distribution；
E) fibroin of the obtained zinc containing partial oxidation of step c) is grafted polyisopropyl acrylamide and polyacrylonitrile film is used
The dilute hydrochloric acid of pH=1 rinses 3 times, removes the zinc ion in membrane removal, is finally rinsed repeatedly with deionized water 3 times, obtains a kind of temperature
With the narrow pore-size distribution hydrophilic filter film of pH sensitivities.
Embodiment 2.
A) solder(ing)acid of mass percent concentration 100% is prepared, weighs the fibroin for accounting for water quality percentage 30%,
Fibroin is dissolved in solder(ing)acid, fibroin solder(ing)acid is poured into three-necked flask, leads to nitrogen deoxygenation 1min, is stirring
Lower add in into three-necked flask is mixed to account for the acrylonitrile of ionized water mass percent 50% and account for ionized water mass percent 1%
N-isopropylacrylamide；
B) persulfuric acid for accounting for acrylonitrile and N-isopropylacrylamide gross mass percentage 0.1% is added dropwise under stiring
Potassium triggers acrylonitrile and N-isopropylacrylamide to be graft-polymerized on fibroin, reaction time 240min, by the solution after polymerization
It is cooled to room temperature, vacuum defoamation 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, scrape 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 of coagulating bath is controlled to be contained for 90 DEG C
The fibroin grafting polyisopropyl acrylamide and polyacrylonitrile film of partial oxidation zinc；By the way that coagulation bath temperature is controlled to control the phase of film
Transition process, so as to regulate and control membrane aperture size and distribution；
E) fibroin of the obtained zinc containing partial oxidation of step c) is grafted polyisopropyl acrylamide and polyacrylonitrile film is used
The dilute hydrochloric acid of pH=3 rinses 5 times, removes the zinc ion in membrane removal, is finally rinsed repeatedly with deionized water 5 times, obtains a kind of temperature
With the narrow pore-size distribution hydrophilic filter film of pH sensitivities.
Embodiment 3.
A) calcium chloride water of mass percent concentration 60% is prepared, weighs the fibroin for accounting for water quality percentage 10%,
Fibroin is dissolved in calcium chloride water, fibroin calcium chloride water is poured into three-necked flask, leads to nitrogen deoxygenation 10min,
It is added under stirring into three-necked flask and accounts for the acrylonitrile of ionized water mass percent 10% and account for ionized water mass percent
10% N-isopropylacrylamide；
B) be added dropwise under stiring account for the sodium peroxydisulfate of acrylonitrile and N-isopropylacrylamide gross mass percentage 1%-
Sodium hydrogensulfite triggers acrylonitrile and N-isopropylacrylamide to be graft-polymerized on fibroin, and reaction time 60min will polymerize
Solution afterwards is cooled to room temperature, and vacuum defoamation obtains 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, scrape 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 of coagulating bath is controlled to be contained for 20 DEG C
The fibroin grafting polyisopropyl acrylamide and polyacrylonitrile film of partial oxidation calcium；By the way that coagulation bath temperature is controlled to control the phase of film
Transition process, so as to regulate and control membrane aperture size and distribution；
E) fibroin of the obtained calcium containing partial oxidation of step c) is grafted polyisopropyl acrylamide and polyacrylonitrile film is used
The dilute hydrochloric acid of pH=1-3 rinses 4 times, removes the calcium ion in membrane removal, is finally rinsed repeatedly with deionized water 4 times, obtains a kind of temperature
The narrow pore-size distribution hydrophilic filter film of degree and pH sensitivities.
Embodiment 4.
A) calcium chloride water of mass percent concentration 50% is prepared, weighs the fibroin for accounting for water quality percentage 5%, it will
Fibroin is dissolved in calcium chloride water, and fibroin calcium chloride water is poured into three-necked flask, leads to nitrogen deoxygenation 5min, is stirring
Lower added in into three-necked flask accounts for the acrylonitrile of ionized water mass percent 5% and accounts for ionized water mass percent 5%
N-isopropylacrylamide；
B) be added dropwise under stiring account for the potassium peroxydisulfate of acrylonitrile and N-isopropylacrylamide gross mass percentage 5%-
Sodium hydrogensulfite triggers acrylonitrile and N-isopropylacrylamide to be graft-polymerized on fibroin, and reaction time 50min will polymerize
Solution afterwards is cooled to room temperature, and vacuum defoamation 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, scrape uniform film with knifing stick, so
Film is dipped into 40min in the coagulating bath of step c) together with sheet glass afterwards, the temperature of coagulating bath is controlled to be contained for 50 DEG C
The fibroin grafting polyisopropyl acrylamide and polyacrylonitrile film of partial oxidation calcium；By the way that coagulation bath temperature is controlled to control the phase of film
Transition process, so as to regulate and control membrane aperture size and distribution；
E) fibroin of the obtained calcium containing partial oxidation of step c) is grafted polyisopropyl acrylamide and polyacrylonitrile film is used
The dilute hydrochloric acid of pH=2 rinses 4 times, removes the calcium ion in membrane removal, is finally rinsed repeatedly with deionized water 3 times, obtains a kind of temperature
With the narrow pore-size distribution hydrophilic filter film of pH sensitivities.
Claims (7)
1. a kind of narrow pore-size distribution hydrophilic filter film of temperature and pH sensitivities, it is characterized in that using metal chloride brine solution to be molten
Agent obtains casting solution by the homogeneous graft polypropylene nitrile of fibroin and polyisopropyl acrylamide, then puts it into the solidification of water
In bath, metal ion and chlorion are gradually diffused into water, and the fibroin for being grafted polyisopropyl acrylamide and polyacrylonitrile occurs
Phase transition forms a film；Metal ion and chlorion play the role of pore, and fibroin, polyisopropyl acrylamide and polyacrylonitrile are sent out
Raw microphase-separated, also forms the aquaporin of ion pore, so as to obtain narrow pore-size distribution and hydrophilic film at its interface.
2. a kind of narrow pore-size distribution hydrophilic filter film of temperature and pH sensitivities, it is characterized in that the temperature using polyisopropyl acrylamide
Degree sensibility makes film obtain temperature sensitivity, and the soda acid ionization using amino acid in fibroin makes film obtain pH sensibility.
3. a kind of narrow pore-size distribution hydrophilic filter film of temperature and pH sensitivities, it is characterized in that the pore-size distribution of film 90% is in 0.31-
It is 90%-100% to the dyestuff of molecular weight more than 660 and the rejection of polyethylene glycol in 0.1MPa lower films between 0.46nm, it is right
The rejection of dyestuff and polyethylene glycol of the molecular weight below 600 is 10%-30%, and membrane flux is 60-120L/m under 0.1MPa2h。
4. a kind of preparation method of the narrow pore-size distribution hydrophilic filter film of temperature and pH sensitivities, it is characterized in that comprising the following steps：
A) the metal chloride brine solution of mass percent concentration 10%-100% is prepared, weighing accounts for water quality percentage 2%-
Fibroin is dissolved in metal chloride brine solution by 30% fibroin, and fibroin metal chloride brine solution is poured into three mouthfuls of burnings
In bottle, lead to nitrogen deoxygenation 1-30min, added in into three-necked flask account for ionized water mass percent 2%-50%'s under stiring
Acrylonitrile and the N-isopropylacrylamide for accounting for ionized water mass percent 1%-20%；
B) initiator for accounting for acrylonitrile and N-isopropylacrylamide gross mass percentage 0.1%-10% is added dropwise under stiring,
Acrylonitrile and N-isopropylacrylamide is triggered to be graft-polymerized on fibroin, reaction time 20-240min, by the solution after polymerization
It is cooled to room temperature, vacuum defoamation obtains casting solution；
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 of coagulating bath is controlled to be obtained for 5-90 DEG C
The fibroin grafting polyisopropyl acrylamide and polyacrylonitrile film of the chloride salt containing part metals；By controlling coagulation bath temperature control
The phase transition process of film, so as to regulate and control membrane aperture size and distribution；
E) fibroin of the obtained chloride salts containing part metals of step c) is grafted polyisopropyl acrylamide and polyacrylonitrile film
It is rinsed 3-5 times with the dilute hydrochloric acid of pH=1-3, removes the metal ion in membrane removal, finally rinsed 3-5 times, obtained repeatedly with deionized water
To the narrow pore-size distribution hydrophilic filter film of a kind of temperature and pH sensitivities.
5. the narrow pore-size distribution hydrophilic filter film of a kind of temperature as described in claim 1 and pH sensitivities, it is characterized in that described
Metal chloride salt is any one or two or more mixtures in zinc chloride, iron chloride, calcium chloride.
6. the preparation method of the narrow pore-size distribution hydrophilic filter film of a kind of temperature as claimed in claim 4 and pH sensitivities, special
Sign is the metal chloride salt for any one in zinc chloride, iron chloride, calcium chloride or two or more mixtures.
7. the preparation method of the narrow pore-size distribution hydrophilic filter film of a kind of temperature as claimed in claim 4 and pH sensitivities, special
Sign is that the initiator is benzoyl peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, Jiao Ya
Any one in sodium sulphate, sodium hydrogensulfite, ferrous sulfate, frerrous chloride or two or more mixtures.
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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 |
| CN111826764B (en) * | 2020-07-28 | 2021-10-15 | 吴忠德悦纺织科技有限公司 | Preparation method of modified multi-component composite yarn |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101537316A (en) * | 2009-03-20 | 2009-09-23 | 淮阴师范学院 | Preparation method for temperature sensitive response type intelligent ceramic composite membrane and product |
| CN102061049A (en) * | 2010-11-30 | 2011-05-18 | 天津工业大学 | Temperature sensitive polyvinylidene fluoride gel film and preparation method thereof |
| CN103736408A (en) * | 2013-12-31 | 2014-04-23 | 中科院广州化学有限公司 | Polysulfone porous film in response to temperature and acidity, preparation method and application of polysuffone porous film |
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-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101537316A (en) * | 2009-03-20 | 2009-09-23 | 淮阴师范学院 | Preparation method for temperature sensitive response type intelligent ceramic composite membrane and product |
| CN102061049A (en) * | 2010-11-30 | 2011-05-18 | 天津工业大学 | Temperature sensitive polyvinylidene fluoride gel film and preparation method thereof |
| CN103736408A (en) * | 2013-12-31 | 2014-04-23 | 中科院广州化学有限公司 | Polysulfone porous film in response to temperature and acidity, preparation method and application of polysuffone porous film |
Non-Patent Citations (2)
| Title |
|---|
| 丙烯腈-丝朊蛋白接枝共聚反应的研究;李秋莲;《四川大学学报（工程科学版）》;20000528;第32卷(第3期);第116-118页 * |
| 丝素蛋白纤维/聚N-异丙基丙烯酰胺复合水凝胶的性能;刘羿君;《功能高分子学报》;20090331;第22卷(第1期);第55-59页 * |
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