CN110066415A - A kind of preparation method of the perforated membrane of functionalized surface - Google Patents
A kind of preparation method of the perforated membrane of functionalized surface Download PDFInfo
- Publication number
- CN110066415A CN110066415A CN201910326736.0A CN201910326736A CN110066415A CN 110066415 A CN110066415 A CN 110066415A CN 201910326736 A CN201910326736 A CN 201910326736A CN 110066415 A CN110066415 A CN 110066415A
- Authority
- CN
- China
- Prior art keywords
- perforated membrane
- chlorotrifluoroethylene
- vinylidene
- acid
- porous film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
Abstract
The present invention relates to a kind of method for preparing porous film of functionalized surface, use chain element structure feature for Vinylidene-chlorotrifluoroethylene that wherein m:n is 95:5-80:20 is reacted using the cl radical having in copolymer molecule structure with aminated compounds as basement membrane, prepares vinylidene-chlorotrifluoroethylene perforated membrane of surface lotus positive electricity.Then amido is recycled to be reacted with the molecule with groups such as epoxy group, carboxyl, hydroxyls, upper required functionalization functional group is grafted on vinylidene-chlorotrifluoroethylene strand, for improving vinylidene-chlorotrifluoroethylene perforated membrane resistance tocrocking, oil resistivity, Selective adsorption etc..
Description
Technical field
The invention belongs to UF membrane fields, are related to the modification technology of perforated membrane, especially a kind of preparation of organic porous films
Method.
Background technique
Membrane separating process usually carries out at normal temperature, does not generate secondary pollution, is a kind of energy-efficient isolation of purified skill
Art has been widely used for numerous industry such as feed separation and the purifying of Water warfare and sewage recycling processing, chemical industry and medicine
The people's livelihood field such as field and Water warfare, air cleaning.It is novel as one kind by the membrane separation technique of representative of organic separation membrane
Chemical industry fluid separation element operating technology, achieves the great development to attract people's attention over 30 years, in environmental protection, traditional work
Industry production technology promoted etc. various aspects, based on common technology play an important role, membrane material is then UF membrane
The core of technology.
Perforated membrane refers to a kind of separation membrane for the through hole for having tens nanometer to hundreds of nanometers on membranous wall, porous
Film is applied not only to permeable air-locked separation process such as ultrafiltration, micro-filtration, dialysis, is also used to film absorption, membrane distillation, film aeration, film
The separation process of the permeable watertights such as degassing, membrane crystallization, meanwhile, perforated membrane or reverse osmosis, positive infiltration, nanofiltration, infiltration vapour
The basement membrane of the composite membranes such as change, gas separation.
Currently used Porous-Organic membrane material has: Kynoar, polyvinyl chloride, polysulfones, polyether sulfone, acetate fiber
Element, nylon, polytetrafluoroethylene (PTFE), polyethylene, polypropylene etc., wherein polyvinylidene fluoride material is most widely used with excellent performance.
But there are still alkali resistances that poor, surface is not easy the disadvantages of carrying out grafting modification for PVDF membrane material.
Having been reported is to carry out amination hydrophilic modification to polyvinylidene fluoride material, is using in Kynoar strand
Fluorine atom reacted with aminated compounds, be on the one hand not easy on the strand that amido is introduced to polymer, while can be right
The mechanical property of polyvinylidene fluoride material generates very big negative effect.
Summary of the invention
The alkali resistance that the present invention is directed to PVDF membrane material is poor, surface is not easy the disadvantages of carrying out grafting modification,
It is proposed the basement membrane to the preparation of vinylidene-chlorotrifluoroethylene resin, using the cl radical being had in its molecular structure,
Reacted with diamine compounds, prepare a kind of lotus electropositive perforated membrane, then again with carboxyl, epoxy group etc. react, shape
At various functional groups, the perforated membrane of bear electricity and electroneutral is prepared, and prepares and has adsorption function and pH, temperature etc.
The perforated membrane of response function.UF membrane aperture is 0.01-1.0 microns.
Can be under conditions of unobvious loss film-strength, functional groups required for being introduced in film surface, accordingly
Prepare vinylidene-chlorotrifluoroethylene perforated membrane of lotus positive electricity, antipollution perforated membrane, the polyvinyl alcohol of bear electricity
Class or polyethylene glycols electroneutral antipollution perforated membrane, intelligent response film, have selection absorption function at the perforated membrane of resistance to oily pollution
The functionalized surfaces perforated membranes such as the perforated membrane of energy.
Vinylidene-chlorotrifluoroethylene, chain element following structural features:
Existing vinylidene-chlorotrifluoroethylene, there are two main classes: one kind is to be with chlorotrifluoroethylene molecule segment
Main material, it is 1:9's that as in above-mentioned chain element structural formula, m:n, which is 1:4,；Another kind of is with vinylidene strand
Duan Weizhu's, if m:n is 95:5-80:20.
Vinylidene-chlorotrifluoroethylene resin based on vinylidene molecule segment, is chiefly used in cable at present,
It is the performance using its high resiliency, high-elongation and resistance to cold shock.The present invention uses inclined based on vinylidene molecule segment
Vinyl fluoride-chlorotrifluoroethylene is used for the basement membrane preparation of perforated membrane.Chain element structure feature: m:n 95:5
, it is 90:10,85:15,80:20, wherein vinylidene-chlorotrifluoroethylene that preferred m:n is 85:15 is used
It is prepared in perforated membrane basement membrane of the invention.
Vinylidene used in the present invention-chlorotrifluoroethylene perforated membrane basement membrane, can be using conventional thermotropic phase
The methods of separation, fusion drawn can also also may be used using conventional phase separation method and low temperature thermally induced phase separation
To carry out subsequent stretching and sizing to vinylidene-chlorotrifluoroethylene of nascent forming is hollow or plate.Aperture
Range: 0.01-1.0 microns.
Vinylidene used in the present invention-chlorotrifluoroethylene perforated membrane basement membrane structure type can be internal pressure
The various conventional porous membranes such as formula hollow-fibre membrane, external pressing type hollow fibrous membrane, plate membrane, rolled film, folded membrane, tubular membrane
Form.
The present invention be by diamine compounds directly with the chlorine in vinylidene-chlorotrifluoroethylene molecule segment into
Row substitution reaction is easier the amido of reaction, then again on vinylidene-chlorotrifluoroethylene strand in grafting
It is reacted using amido with the molecule with epoxy group, carboxyl, hydroxyl etc., in vinylidene-chlorotrifluoroethylene point
Upper required functionalization functional group is grafted in subchain, it is anti-for improving vinylidene-chlorotrifluoroethylene perforated membrane
Pollution, oil resistivity, Selective adsorption etc..
Vinylidene of the invention-chlorotrifluoroethylene method for preparing porous film is by vinylidene-three above-mentioned
Fluorine vinyl chloride copolymer perforated membrane basement membrane, the second under the conditions of temperature range of room temperature to 90 DEG C, with 0.1-3.0mol/L concentration
The binary amine aqueous solution such as diamines, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, piperazine, hexamethylene diamine is reacted, reaction
Time 2-48 hour prepares vinylidene-chlorotrifluoroethylene perforated membrane of lotus positive electricity first.It is subsequent again respectively with
Compound containing carboxyl or epoxy group is reacted again, obtain the antipollution perforated membrane of bear electricity, polyvinyl alcohol or
Polyethylene glycols electroneutral antipollution perforated membrane, the perforated membrane of resistance to oily pollution, intelligent response film, with selection adsorption function
The functionalized surfaces perforated membrane such as perforated membrane.It is preferred that: diethylenetriamine, triethylene tetramine
Vinylidene of the invention-chlorotrifluoroethylene method for preparing porous film is by vinylidene-three above-mentioned
Fluorine vinyl chloride copolymer perforated membrane basement membrane, the second under the conditions of temperature range of room temperature to 90 DEG C, with 0.1-3.0mol/L concentration
The aqueous solutions such as hydramine, diethanol amine are reacted, and reaction time 2-48 hour directly obtains the perforated membrane of surface hydrophilicity.
The vinylidene of the lotus positive electricity of amination-chlorotrifluoroethylene perforated membrane, can be with the change containing carboxylic group
Object is closed, such as oxalic acid, malic acid, citric acid, itaconic acid, maleic anhydride, fumaric acid, glue acid anhydrides, low-molecular-weight polypropylene acid
(below 5000 dalton of molecular weight) is reacted again, prepares bear electrical property antipollution perforated membrane and has selection adsorption function
The functionalized surfaces perforated membrane such as perforated membrane.It is then possible to continue to react with polyvinyl alcohol or polyethylene glycols, preparation electricity
Neutral antipollution perforated membrane and with selection adsorption function perforated membrane.
The vinylidene of the lotus positive electricity of amination-chlorotrifluoroethylene perforated membrane, can react, grape with hydracrylic acid
Saccharic acid prepares electroneutral film, and reactant molecule amount is small, will not block fenestra, reduces membrane flux.
It can use vinylidene-chlorotrifluoroethylene porous film surface work wave amido of the lotus positive electricity of amination,
Continue to react with the compound containing epoxy group, such as with the bisphenol A type resin of liquid low-molecular, bisphenol-f type tree
Rouge, bisphenol S type resin, alicyclic diepoxide, glycidyl ester type epoxy resin, hydantoin epoxy etc. are reacted, and are obtained
The perforated membrane of surface hydrophilic.Later, it can also continue to react using the epoxy group continuation introduced with aminated compounds, make
Standby lotus electropositive or the perforated membrane for selecting adsorption function.It can also continue to continue and carboxyl chemical combination using the epoxy group introduced
Object reaction, preparation bear is electrical or selects the perforated membrane of adsorption function.
The advantages and positive effects of the present invention are:
The present invention is to utilize chlorine bigger than Fluorine atom activity in vinylidene-chlorotrifluoroethylene strand
Atom directly carries out substitution reaction with primary amine, the secondary amine in polyamines based compound, the bigger amido grafting of activity is introduced inclined
In vinyl fluoride-chlorotrifluoroethylene strand, the elimination reaction of hydrogen fluoride in polymer molecular chain is reduced to membrane material
The negative effect of mechanical property.It can be functional required for being introduced in film surface under conditions of unobvious loss film-strength
Group, accordingly prepare vinylidene-chlorotrifluoroethylene perforated membrane of lotus positive electricity, the antipollution perforated membrane of bear electricity,
Polyvinyl alcohol or polyethylene glycols electroneutral antipollution perforated membrane, intelligent response film, have choosing at the perforated membrane of resistance to oily pollution
Select the functionalized surfaces perforated membrane such as perforated membrane of adsorption function.
Detailed description of the invention
Fig. 1 is color change figure of the PVDF and PVDF-CTFE after amination treatment；
Fig. 2 is Strength Changes figure of the PVDF and PVDF-CTFE after 1.5mol/L amination treatment.
Specific embodiment
The invention will be further described with reference to the accompanying drawing and by specific embodiment, and following embodiment is descriptive
, it is not restrictive, this does not limit the scope of protection of the present invention.
Embodiment 1
PVDF-CTFE copolymer diaphragm is taken, immerses the 0 of 80 DEG C, the diethylenetriamine water of 0.30,1.0,1.5mol/L respectively
In solution, react 6 hours.With 50% (v/v) ethanol water sufficiently rinses, pure water embathes, dries after reaction.It is modified
Diaphragm is respectively designated as CF2-CTFE original film, CF2-CTFE-0.3, CF2-CTFE-1.0 and CF2-CTFE-1.5.It prepares
CF2- CTFE copolymer Positively charged membrane.
Comparative example 1
PVDF homopolymer diaphragm is taken, immerses the 0 of 80 DEG C, the diethylenetriamine aqueous solution of 0.30,1.0,1.5mol/L respectively
In, it reacts 6 hours.With 50% (v/v) ethanol water sufficiently rinses, pure water embathes, dries after reaction.Modified diaphragm
It is respectively designated as CF2 original film, CF2-0.3, CF2-1.0 and CF2-1.5.
From figure 1 it will be seen that the diethylenetriamine aqueous solution by same concentrations is handled, the face of PVDF-CTFE copolymer
Color is obviously shallower than PVDF.
In terms of Fig. 2, after 1.5mol/L amination treatment, the breaking strength of pvdf membrane is reduced to by 1.432MPa
The breaking strength of 0.39MPa, PVDF-CTFE film rises to 1.172MPa by the 0.964MPa before handling instead.
The chemical composition of film surface of table 1 CF2-CTFE and PVDF after alkali
As can be seen from Table 1, the presence of C-Cl key increases aminating reaction degree in copolymer, especially anti-in low concentration
Under the conditions of answering, in CF2The nitrogen element content of-CTFE film surface obviously increases.
Embodiment 2
PVDF-CTFE copolymer hollow-fibre membrane is taken, is immersed in the triethylene tetramine aqueous solution of 60 DEG C of 1.0mol/L, instead
It answers 4 hours.It embathed, dried with pure water after reaction.Prepare CF2- CTFE copolymer Positively charged membrane.
Embodiment 3
By Modified Membrane CF obtained in embodiment 12- CTFE-1.0 is immersed into the toluene containing 10g/100ml maleic anhydride
In solution, reacted 6 hours at 30 DEG C.Diaphragm is sufficiently washed with dehydrated alcohol after reaction to remove residual toluene solvent, so
It is complete with pure water rinsing afterwards, it is put into thermostatic drying chamber dry complete.It is by the grafting rate that weight method measures maleic anhydride
0.532 μmol/cm2.Prepare CF2- CTFE copolymer bear electrolemma.
Embodiment 4
By Modified Membrane CF obtained in embodiment 12- CTFE-1.0 is immersed into the aqueous solution containing 10g/100ml itaconic acid
In, it is reacted 12 hours at 80 DEG C.Diaphragm is sufficiently washed with pure water after reaction, is put into thermostatic drying chamber dry complete.It is logical
Crossing weight method and measuring the grafting rate of itaconic acid is 0.45 μm of ol/cm2.Prepare CF2- CTFE copolymer bear electrolemma.
Embodiment 5
By Modified Membrane CF obtained in embodiment 12- CTFE-1.0 is immersed into is containing 10g/100ml average molecular weight
In the polyacrylic acid aqueous solution of 5000 dalton, reacted 12 hours at 80 DEG C.Film is sufficiently washed with dehydrated alcohol after reaction
Piece is then complete with pure water rinsing to remove remained unreacted object, is put into thermostatic drying chamber dry complete.Pass through weight method
The grafting rate for measuring polyacrylic acid is 1.35 μm of ol/cm2.Prepare CF2- CTFE copolymer bear electrolemma.
Embodiment 6
PVDF-CTFE copolymer diaphragm is taken, is immersed in the triethylene tetramine aqueous solution of 80 DEG C of 1.0mol/L, reaction 6 is small
When.With 50% (v/v) ethanol water sufficiently rinses, pure water embathes, dries after reaction.Prepare CF2- CTFE copolymer lotus
Positively charged membrane.
Embodiment 7
The modification PVDF-CTFE copolymer diaphragm that embodiment 6 is obtained, is immersed into containing 10g/100ml average molecular weight
To be reacted 12 hours at 80 DEG C in the polyacrylic acid aqueous solution of 5000 dalton.It is sufficiently washed with dehydrated alcohol after reaction
Diaphragm is then complete with pure water rinsing to remove remained unreacted object, is put into thermostatic drying chamber dry complete.Pass through weighing
The grafting rate that method measures polyacrylic acid is 1.35 μm of ol/cm2.Prepare CF2- CTFE copolymer bear electrolemma, the film is to water body
In heavy metal ion have Selective adsorption.
Embodiment 8
The modification PVDF-CTFE copolymer hollow-fibre membrane that embodiment 2 is obtained, is immersed into hydantoin epoxy XB-0.54,
It is reacted 2 hours at 80 DEG C.It is sufficiently washed after reaction with dehydrated alcohol to remove remained unreacted object, then uses pure water rinsing
Completely, it is put into thermostatic drying chamber dry complete.It is 3.1 μm of ol/cm by the grafting rate that weight method measures hydantoin epoxy2.System
The CF of standby surface electroneutrality out2- CTFE copolymer hollow-fibre membrane.
Embodiment 9
The modification PVDF-CTFE copolymer hollow-fibre membrane that embodiment 8 is obtained immerses three second of 80 DEG C of 1.0mol/L
In four amine aqueous solution of alkene, react 6 hours.With 50% (v/v) ethanol water sufficiently rinses, pure water embathes, dries after reaction.
Prepare CF2- CTFE copolymer lotus positive electricity hollow-fibre membrane.
Embodiment 10
The modification PVDF-CTFE copolymer hollow-fibre membrane that embodiment 2 is obtained, is immersed into aqueous gluconic acid,
It is reacted 2 hours at 80 DEG C, prepares the CF of surface electroneutrality2- CTFE copolymer hollow-fibre membrane.
Embodiment 11
The modification PVDF-CTFE copolymer hollow-fibre membrane that embodiment 2 is obtained, is immersed into aqueous citric acid solution, 80
It is reacted 2 hours at DEG C, prepares the CF of surface electroneutrality2- CTFE copolymer hollow-fibre membrane.
Embodiment 12
By vinylidene-chlorotrifluoroethylene hollow fiber porous film, in the temperature range condition of room temperature to 90 DEG C
Under, it contacts, is reacted with ethanol amine liquid, the reaction time 8 hours, directly obtain vinylidene-trifluoro of surface hydrophilicity
Vinyl chloride copolymer hollow fiber porous film.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those of ordinary skill in the art
For, under the premise of not departing from inventive concept, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.
Claims (10)
1. a kind of method for preparing porous film of functionalized surface, it is characterised in that: use chain element structure feature forVinylidene-chlorotrifluoroethylene as basement membrane, wherein m:n be 95:5~
80:20 is reacted using the cl radical having in copolymer molecule structure with aminated compounds, and surface lotus positive electricity is prepared
Vinylidene-chlorotrifluoroethylene perforated membrane.
2. method for preparing porous film according to claim 1, it is characterised in that: the aminated compounds be ethylenediamine,
Diethylenetriamine, triethylene tetramine, tetraethylenepentamine one or more kinds of mixtures.
3. method for preparing porous film according to claim 2, it is characterised in that: the aminated compounds concentration is 0.1-
3.0mol/L reacts 2~48 hours at 20~90 DEG C with vinylidene-chlorotrifluoroethylene.
4. method for preparing porous film according to claim 1 or 2 or 3, it is characterised in that: just by the surface lotus being prepared
Vinylidene-chlorotrifluoroethylene perforated membrane of electricity is reacted again with the compound containing carboxylic group, prepares bear
Electrical antipollution perforated membrane or with selection adsorption function perforated membrane, the compound containing carboxylic group be oxalic acid,
Malic acid, citric acid, itaconic acid, maleic anhydride, fumaric acid, maleic anhydride, glue acid anhydrides, below 5000 dalton of molecular weight
Polyacrylic acid one or more kinds of mixtures.
5. method for preparing porous film according to claim 1 or 2 or 3, it is characterised in that: just by the surface lotus being prepared
Vinylidene-chlorotrifluoroethylene perforated membrane of electricity reacts preparation electroneutral perforated membrane with hydracrylic acid or gluconic acid.
6. method for preparing porous film according to claim 1 or 2 or 3, it is characterised in that: just by the surface lotus being prepared
Vinylidene-chlorotrifluoroethylene perforated membrane of electricity continues to react with the compound containing epoxy group, obtains table
The perforated membrane of face hydrophiling.
7. method for preparing porous film according to claim 6, it is characterised in that: the compound containing epoxy group
For the bisphenol F type resin of low molecular weight liquid, bisphenol S type resin, alicyclic diepoxide, glycidyl ester type epoxy tree
One or more kinds of mixtures of rouge, hydantoin epoxy.
8. method for preparing porous film according to claim 7, it is characterised in that: by the perforated membrane of obtained surface hydrophilic
It carries out reacting preparation lotus electropositive with aminated compounds or selects the perforated membrane of adsorption function, the aminated compounds is second two
Amine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine one or more kinds of mixtures.
9. method for preparing porous film according to claim 7, it is characterised in that: by the perforated membrane of obtained surface hydrophilic
Preparation bear is reacted with carboxyl compound electrically or the perforated membrane of selection adsorption function, the carboxyl compound are oxalic acid, apple
Tartaric acid, citric acid, itaconic acid, maleic anhydride, fumaric acid, maleic anhydride, glue acid anhydrides, 5000 dalton of molecular weight are below
One or more kinds of mixtures of polyacrylic acid.
10. method for preparing porous film according to claim 1, it is characterised in that: the aminated compounds is ethanol amine
Or diethanol amine, concentration 0.1-3.0mol/L react 2~48 with vinylidene-chlorotrifluoroethylene at 20~90 DEG C
Hour directly obtains the perforated membrane of surface hydrophilicity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910326736.0A CN110066415B (en) | 2019-04-23 | 2019-04-23 | Preparation method of porous membrane with functionalized surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910326736.0A CN110066415B (en) | 2019-04-23 | 2019-04-23 | Preparation method of porous membrane with functionalized surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110066415A true CN110066415A (en) | 2019-07-30 |
| CN110066415B CN110066415B (en) | 2021-07-20 |
Family
ID=67368391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910326736.0A Active CN110066415B (en) | 2019-04-23 | 2019-04-23 | Preparation method of porous membrane with functionalized surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110066415B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111195485A (en) * | 2020-02-17 | 2020-05-26 | 天津工业大学 | Preparation method of polyvinyl chloride blood purification membrane |
| CN111659267A (en) * | 2020-07-23 | 2020-09-15 | 天津海龙津阳材料科技有限公司 | Pollution-resistant modified porous membrane and preparation method thereof |
| CN113083032A (en) * | 2021-04-26 | 2021-07-09 | 贵州省材料产业技术研究院 | Positively charged blended ultrafiltration membrane and preparation method thereof |
| CN114534525A (en) * | 2021-12-31 | 2022-05-27 | 山东华夏神舟新材料有限公司 | Amination modified anti-pollution porous membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3463921B2 (en) * | 1999-02-18 | 2003-11-05 | セントラル硝子株式会社 | Stain-resistant laminated sheet |
| CN102101021A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院大连化学物理研究所 | Alkaline anionic membrane and preparation method thereof |
| CN102140181A (en) * | 2011-01-19 | 2011-08-03 | 天津工业大学 | Polyvinylidene fluoride (PVDF) hydrophilic modified membrane and preparation method thereof |
| CN105727770A (en) * | 2014-12-08 | 2016-07-06 | 中国石油天然气股份有限公司 | Fluorine-containing antipollution ultrafiltration membrane preparation method, fluorine-containing antipollution ultrafiltration membrane, and application thereof |
-
2019
- 2019-04-23 CN CN201910326736.0A patent/CN110066415B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3463921B2 (en) * | 1999-02-18 | 2003-11-05 | セントラル硝子株式会社 | Stain-resistant laminated sheet |
| CN102101021A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院大连化学物理研究所 | Alkaline anionic membrane and preparation method thereof |
| CN102140181A (en) * | 2011-01-19 | 2011-08-03 | 天津工业大学 | Polyvinylidene fluoride (PVDF) hydrophilic modified membrane and preparation method thereof |
| CN105727770A (en) * | 2014-12-08 | 2016-07-06 | 中国石油天然气股份有限公司 | Fluorine-containing antipollution ultrafiltration membrane preparation method, fluorine-containing antipollution ultrafiltration membrane, and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| FU LIU等: "Hydrophilic modification of P(VDF-co-CTFE) porous membranes", 《CHEMICAL ENGINEERING SCIENCE》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111195485A (en) * | 2020-02-17 | 2020-05-26 | 天津工业大学 | Preparation method of polyvinyl chloride blood purification membrane |
| CN111659267A (en) * | 2020-07-23 | 2020-09-15 | 天津海龙津阳材料科技有限公司 | Pollution-resistant modified porous membrane and preparation method thereof |
| CN113083032A (en) * | 2021-04-26 | 2021-07-09 | 贵州省材料产业技术研究院 | Positively charged blended ultrafiltration membrane and preparation method thereof |
| CN114534525A (en) * | 2021-12-31 | 2022-05-27 | 山东华夏神舟新材料有限公司 | Amination modified anti-pollution porous membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110066415B (en) | 2021-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110066415A (en) | A kind of preparation method of the perforated membrane of functionalized surface | |
| CN105363353B (en) | A kind of charged type chlorine-containing polymer NF membrane and preparation method thereof | |
| CN105435656B (en) | A kind of composite nanometer filtering film and preparation method thereof | |
| CN112275140B (en) | Polyamide nanofiltration membrane with patterned surface and preparation method thereof | |
| CN109304106B (en) | Janus forward osmosis membrane and preparation method and application thereof | |
| CN105148750B (en) | A kind of method that polyamide composite film surface is modified | |
| KR101630208B1 (en) | A preparation method of hydrophilic membrane and a hydrophilic membrane prepared by the same | |
| CN105617882A (en) | Chitosan modified graphene oxide nano composite positive osmotic membrane and preparation method thereof | |
| CN107899432B (en) | A kind of plate compounding nanofiltration membrane and preparation method thereof for water filter purification | |
| CN111921388B (en) | Borate intercalation modified graphene oxide composite nanofiltration membrane and preparation method thereof | |
| CN107261871A (en) | A kind of preparation method of polyethyleneimine/sodium lignin sulfonate composite membrane | |
| CN112108020B (en) | Polyamide nanofiltration membrane and preparation method and application thereof | |
| CN109621738A (en) | A kind of preparation method of multilevel structure bilayer membrane distillation film | |
| CN107020017A (en) | A kind of antipollution composite distillation film and preparation method and application | |
| CN108939951A (en) | A kind of self-assembled modified polyamide reverse osmosis composite film and its application | |
| CN110449049A (en) | A kind of nanofiltration membrane, preparation method and its purposes in the separation of pigment wastewater monovalence salt-mixture | |
| CN111286068A (en) | Method for preparing hydrophilic-hydrophobic composite membrane by grafting zwitterion on surface | |
| EP0436720B1 (en) | Hydrolyzed membrane and process for its production | |
| CN111545083B (en) | Nanofiltration membrane, preparation method and application of nanofiltration membrane in fermentation liquor concentration | |
| CN109012232B (en) | Preparation method of anti-shrinkage polytetrafluoroethylene composite nanofiltration membrane | |
| CN107158974B (en) | High-strength hydrophilic nanofiltration membrane, preparation method thereof and application thereof in protein solution desalination process | |
| CN110743383A (en) | Modification method for improving permeation flux of polyamide composite membrane | |
| KR100322235B1 (en) | Fabrication of high permeable reverse osmosis membranes | |
| CN1481409A (en) | Modified sulfonamide polymers | |
| CN109157986B (en) | Pervaporation composite membrane with step crosslinking degree and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |