CN108568221A - A kind of bear electricity type chlorine-containing polymer group compound film and preparation method thereof based on the enhancing of interlayer covalent effect - Google Patents
A kind of bear electricity type chlorine-containing polymer group compound film and preparation method thereof based on the enhancing of interlayer covalent effect Download PDFInfo
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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
- B01D71/30—Polyalkenyl halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/08—Flat membrane modules
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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
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/48—Polyesters
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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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/14—Membrane materials having negatively charged functional groups
Abstract
The invention discloses a kind of bear electricity type chlorine-containing polymer group compound films and preparation method thereof based on the enhancing of interlayer covalent effect.The bear electricity type chlorine-containing polymer group compound film is made of supporting layer and functional layer, and wherein supporting layer is enhancement layer containing polyester fiber, and functional layer is made of chlorine-containing polymer and bear electricity type polymer, and supporting layer and functional layer are combined with covalent bond effect.The preparation method includes：It is configured to preparation liquid after dissolving is blended in chlorine-containing polymer and bear electricity type polymer；Heat treatment modification is carried out to supporting layer polymer fiber using the solution of aminated compounds and catalyst as modifying agent；Enter coagulating bath film-forming after preparation liquid is coated in polymeric fiber surface；After composite membrane obtained is heat-treated again, clean up to the bear electricity type chlorine-containing polymer group compound film enhanced based on interlayer covalent effect.Composite membrane flux at 0.1MPa reaches 660 L/hm2, and operation peel strength reaches 1MPa, while having good hydrophily and resistance tocrocking.
Description
Technical field
The invention belongs to technical field of membrane separation more particularly to a kind of bear electricity type based on the enhancing of interlayer covalent effect to contain
Chlorine polyalcohol group compound film and preparation method thereof.
Background technology
Membrane separation technique is a kind of emerging isolation technics, using external energy or chemical potential difference as driving force, seperation film
Material may be implemented to the bi-component function that either multi-component liquid or gas are detached, be classified, purified or is enriched with, phase
There is unrivaled advantage compared with traditional handicraft.Membrane separation technique is general in being widely used for water treatment field, mainly there is sewage
Purification, water purification purifying, sea water desalination etc..
In numerous potential polymeric film materials, chlorine-containing polymer has excellent resistance to acid and alkali and resistant to chemical etching
The advantages that property, preferable comprehensive mechanical property and electrical insulation capability and anti-flammability, weatherability, the room temperature such as ultrafiltration, micro-filtration in China
There are larger application potentials in UF membrane field.Wherein, polyvinyl chloride is cheap, and about the 1/20 of only PVDF, therefore by
Great concern has had ripe film product to enter market at present.
Homogeneous membrane product strength to solve the problems, such as PVC is low, is enhanced at present frequently with composite supporting layer, Neng Gouxian
The raising film strength of work.It is woven tube that patent US 4061821 and US 5472607, which individually discloses a kind of internal layer for preparing,
The method of PAN hollow-fibre membranes and PVDF hollow-fibre membranes makes the mechanical property of film be significantly improved.Patent CN
It is woven tube that 103949166A, which also describes a kind of outer layer, and internal layer coats preparation liquid, and central tube, which is passed through inner core liquid, to carry out phase and turn
It is melted into the preparation method of the internal air pressure type hollow fiber compound film of film.In addition to this, successively original is blended in coating also outside woven tube
Liquid and preparation liquid realize that the double-deck coating prepares hollow fiber composite membrane (CN 102160967A), compiles fiber on spinneret die
It is made into after pipe synchronous coating preparation liquid and prepares outside in hollow fiber composite membrane (CN 101543731A), woven tube and be coated with system
Film liquid, then occur by technologies such as phase inversion preparative separation film layers (CN 1864828A).However, being applied using braiding pipe surface
The technology of preparative separation film layer is covered, it is poor inevitably to encounter adhesive property between the supporting layer of product and separation membrane layer, uses
Exist in the process and fall off, remove, the problems such as intolerant to backwash.
Due to the solvent resistant that polyester system itself has, the characteristics such as high intensity are widely used in the branch of membrane material at present
Support layer.To solve the problems, such as that supporting layer and separation membrane layer adhesive property are poor, method more commonly used at present is to polyester support
Layer is pre-processed, to improve the caking property of composite membrane supporting layer and function interlayer.CN 102553463A are first boiling woven tube
The dipping by lye of boiling is to degrease, and then woven tube dipping modification liquid is modified processing so that product supporting layer and coating
Layer is not easily disconnected from, and the resistance to backwash ability of film has also obtained apparent improvement；CN102512990A is to prepare Kynoar hollow
Atmospheric pressure plasma jet treatment hollow braided rope is used when fiber coating film, improve kernmantle and cortex polyvinylidene fluoride material it
Between interfacial wettability and hydrogen bond bonding force；CN102784566A is pre- by the pretreatment of woven tube, Kynoar weak solution
The technologies such as coating prepare a kind of heterogeneous enhancing Pvdf Microporous Hollow Fiber Membrane with high-adhesion.In addition,
Penetration degrees of the CN2103691327A by raising preparation liquid in support tube, increases the contact area of preparation liquid and support tube,
To improve bond effect between the two.
In conclusion the prior art is not involved with the modification of woven tube the change between supporting layer and functional layer
Learn reaction.In contrast, the specific surface area of polyester fiber is much smaller than polyester powder, corresponding, to improve to polyester fiber
Modification degree is also more difficult.And since in composite membrane, polyester fiber plays a part of supporting layer, there is intensity to supporting layer
It is required that modified condition grasp is bad, it be easy to cause a large amount of molecular chain ruptures of polyester and loses due intensity, destroys composite membrane
Performance.The good stability that polyester itself has makes it that can not often be chemically reacted with raw material with functional layer.The prior art
Modification to polyester fiber all improves inter-layer bonding force by improving the compatibility of surface of polyester and functional layer to realize substantially
The new functional group reactions activity of purpose, generation is all relatively low, can not often be chemically reacted with raw material with functional layer, therefore difficult
Covalent bonding together is generated to be formed between supporting layer and functional layer.So the composite membrane product prepared using techniques described above,
There is the interface for only leaning on physical action to bond, in prolonged practical application, physical action between its supporting layer and functional layer
It is possible that can gradually fail.So the adhesion problem between composite film fails to obtain solution fundamentally.
Invention content
For overcome the deficiencies in the prior art, it is covalent based on interlayer that technical problem to be solved by the invention is to provide one kind
Act on the bear electricity type chlorine-containing polymer group compound film of enhancing.
The technical solution adopted by the present invention is as follows：
A kind of bear electricity type chlorine-containing polymer group compound film based on the enhancing of interlayer covalent effect, it is characterised in that：It is described
Composite membrane be made of supporting layer and functional layer, the supporting layer be enhancement layer containing polyester fiber, the functional layer is by containing
Chlorine polymer and bear electricity type polymer composition, mass percentage of the bear electricity type polymer in functional layer are 10
~50%, combined with covalent bond effect between the supporting layer and functional layer, the composite film surface with carboxyl or
Sulfonic acid group, the composite membrane bear electricity, the covalent bond is C-O keys and C-N keys, and the composite membrane is bear electricity type
Microfiltration membranes or ultrafiltration membrane.
Further, the interlayer covalent effect is to form it into active group by carrying out amination modifying to supporting layer
Group, and chemically reacted with the active group of bear electricity type polymer, it forms C-O and C-N covalent bonds and realizes, it is described
The amination modifying extent of reaction is 1~5%.The amination modifying extent of reaction refers to the ratio that aminating reaction occurs for polyester.
Further, the composite membrane is any one of plate membrane, hollow-fibre membrane.
Further, the enhancement layer containing polyester fiber is selected from polyester fiber, cotton polyester blend fibre, polyester/fiber
In plain blend fibre, polyester/polyamide blend fibre, polyester/polyurethane blend fibre, polyester/polypropylene nitrile blend fibre
Any one.
Further, the chlorine-containing polymer is selected from polyvinyl chloride (PVC), Vingon (PVDC), chlorinated polyethylene
Alkene (CPE), chliorinated polyvinyl chloride (CPVC), vinyl chloride-vinylidene chloride copolymer (P (VC-VDC)), vinyl chloride-vinyl acetate are total
In polymers (LC), polychlorobutadiene (CR), chlorinated polypropylene (CPP) any one or it is arbitrary a variety of.
Further, described is the polymer containing carboxylic acid group, sulfonic acid group with bear electricity type polymer, preferably
, the bear electricity type polymer is selected from Eudragit S100 (P (MMA-MAA)), propylene
Acid-acrylonitrile copolymer (P (AA-AN)), acrylic acid-acrylic acid hydroxypropyl ester copolymer (P (AA-HPA)), acrylic acid-acrylic acyl
Amine copolymer object (P (AA-AM)), vinyl alcohol-acrylic copolymer (P (VA-AA)), sulfonic group modified polyvinyl alcohol (sulfonation PVA),
Acrylicstyrene sulfonic acid copolymer (P (AA-SSA)), maleic acid-Styrene Sulfonic Acid Copolymer (P (MA-SSA)), acrylic acid-
Sodium Allyl Sulfonate copolymer (P (AA-SAS)), acrylic acid-(2- acrylamido -2- methyl propane sulfonic acids) copolymer (P
(AA-AMPS)), acrylic acid-acrylic acid methyl esters-(2- acrylamido -2- methyl propane sulfonic acids) terpolymer (P (AA-MA-
AMPS in)) any one or it is a variety of.
The present invention also provides a kind of systems of the bear electricity type chlorine-containing polymer group compound film based on the enhancing of interlayer covalent effect
Preparation Method, preparation process include the following steps：
(1) preparation liquid is configured to after dissolving being blended in chlorine-containing polymer and bear electricity type polymer；
(2) supporting layer modifying agent is prepared；
(3) supporting layer initially enters modifying agent, and carries out first time heat treatment, and polyester fiber is made to be issued in modifying agent effect
Raw aminating reaction, it is hydroxyl or the polyester macromolecule of primary amine groups to generate one end；
(4) preparation liquid is coated in the supporting layer outer surface by modification that step (3) obtains, and passes through immersion precipitation
Inversion of phases film-forming；
(5) film that step (4) obtains is placed in saturated steam environment and carries out second of heat treatment, made one in supporting layer
End be hydroxyl or primary amine groups polyester macromolecule under modifying agent effect with the carboxyl in bear electricity type polymer in functional layer
It reacts to form C-O and C-N covalent bonds, then by Membrane cleaning, the support type chlorine-containing polymer with high strong adhesive power is made
Group compound film.
Further, the mass percentage of bear electricity type polymer is 1~10% in the preparation liquid.
Further, the modifying agent is the solution containing aminated compounds and catalyst, and the solvent of the solution is
The mass percentage of the mixture of water or water and ethyl alcohol, the aminated compounds is 5%~40%, the catalyst
Mass percentage is 0.01%~1%, and the mass percentage of solvent is 59~94.99% in the modifying agent, the water
Mass percentage with ethyl alcohol in the mixture of ethyl alcohol is 10~30%.
Further, the aminated compounds be the amine monomers containing primary amine group, selected from methylamine, ethamine, ethanol amine,
Ethylenediamine, propane diamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylene hexamine, polyethylene polyamine,
In p-phenylenediamine, m-phenylene diamine (MPD) any one or it is arbitrary a variety of.
Further, one kind in aluminium chloride, iron chloride, titanium tetrachloride, boron trifluoride of the catalyst or
It is arbitrary a variety of.
Further, the amination modifying extent of reaction is 1~5%.
Further, the first time heat treatment temperature described in step (3) is 50~200 DEG C, and heat treatment time is 0.1~10
Minute.
Further, second of heat treatment temperature described in step (5) is 50~90 DEG C, and heat treatment time is 1~24 small
When.
Different from the prior art, bear electricity type chlorine-containing polymer group compound film provided by the invention is not influencing composite membrane
Originally have the characteristics that flux is high, flux stability is good, retention and resistance tocrocking are excellent, good mechanical properties while, improve
The resistance to stripping ability and antifouling property of film.Each Coating combination is highly stable in its film, therefore comprehensive during the film use
Performance is stablized, and membrane lifetime is long, resistance to backwash.Meanwhile the film itself bear electricity, it is based on electrical charge rejection effect, the composite membrane is to certain
Charged pollutant has better choice, has widened the application range of film product.
In the technology of existing enhanced composite membrane, interlayer binding ability is applied with functional form commonly used to improve filament support layer
Method have：1, the chemical treatments such as atmospheric plasma, lye are carried out to supporting layer, to make interface performance and the painting of supporting layer
Layer is similar, to improve its adhesive property；2, the dilute coating solution of support layer surface precoating or there is preferable phase with film material
The substance of capacitive, to improve its similitude with coating, to improve caking property；3, the phase by improving supporting layer with applying interlayer
It is oozed in mutually to improve caking property.And in the above-mentioned methods, supporting layer can inevitably occur being based on physical bond with interlayer is applied
The coating of interface physics or physical entanglement, stability is not so good as to establish by force in supporting layer and coating interlayer
Covalent bonding together.By the supporting layer and coat of Covalent bonding together, cohesive force between the two can effectively improve, to
Make film that there is higher burst strength and stronger resistance to backwash ability, service life to greatly improve.
The raising of each interlayer adhesion of the enhanced composite membrane of chlorine-containing polymer base of the present invention, is based primarily upon the change of each interlayer
The Covalent bonding together of strong molecular level is established in effect enhancing, i.e. supporting layer and function coating interlayer.First, by polymer
The pretreatment of filament support layer makes the chemical constitution of polyester fiber change, and hydroxyl, amino isoreactivity base are introduced on surface
Group.The present invention is by aminated compounds mass percentage in considered critical modifying agent, the mass percentage of catalyst, and
The temperature and time of heat treatment controls the amination modifying extent of reaction 1~5% for the first time.Meanwhile it being blended and carrying in preparation liquid
The bear electricity type polymer of active group.Therefore, the composite membrane is during film forming and post-processing, the work introduced on supporting layer
Property group and bear electricity type polymer active group react, formed covalent bond, improve the bonding force of interlayer.Meanwhile
In order to further increase the bonding force of interlayer, certain crosslinking agent can be added in preparation liquid, ensureing and promoting interlayer chemistry anti-
While should occurring, it is possible to intermolecular interpenetrating networks are formed in interlayer, to make bonding force further increase.
Chlorine-containing polymer group compound film of the present invention, is made of supporting layer and functional layer, and functional layer is polymerize by containing chlorine
Object and bear electricity type polymer composition.Wherein, the bear electricity type polymer is one kind having good phase with chlorine-containing polymer
Capacitive, while having both certain hydrophilic polymer.The bear electricity type polymer other than having reactive active group,
There is carboxylic acid or sulfonic acid group simultaneously, it is electrical to assign film bear after film forming.Therefore, the chlorine-containing polymer group compound film
In separation process exceptionally in addition to aperture sieve, also electrical charge rejection acts on, to make the composite membrane have some special absorption
And stalling characteristic, there is better cutoff performance to certain charged type pollutants, the removal of protein, humic acid etc. in water is made
With apparent, therefore the resistance tocrocking of film significantly improves.
The realization of each functional layer performance of composite membrane of the present invention and stabilisation, are based primarily upon the active group of filament support layer
It reacts with the active group of bear electricity type polymer, forms C-O and C-N covalent bonds (Fig. 1), to which one side can be effective
Raising supporting layer and function interlayer adhesion strength, meanwhile, promote stability of the bear electricity type polymer in film, assign film
Sufficient charge.Specifically：
(1) studies have shown that with primary amine aminating reaction can occur for polyester fiber (PET) under heating conditions.The present invention
Based on this is reacted, using the solution of the amine monomers containing primary amine group as modifying agent, under the effect of the catalyst, to branch
In the polyester fiber first time heat treatment process for supportting layer, it can make fiber that aminating reaction occur and generate containing terminal hydroxy group, amino etc.
The PET of active group.(Fig. 1-1)
The key problem in technology of the present invention is strictly to control the aminating reaction degree of PET.The present invention is modified by considered critical
Aminated compounds mass percentage is 5~40% in agent, and the mass percentage of catalyst is 0.01%~1%, for the first time
Heat treatment temperature is 50~200 DEG C, and heat treatment time, come the control for realizing to the PET extents of reaction, was realized for 0.1~10 minute
The aminating reaction degree of PET reaches 1~5%.
Because along with molecule chain break while PET fiber generation aminating reaction.If the degree of reaction is excessively high, meeting
Cause the PET strands of fracture excessive, to make the intensity of supporting layer substantially reduce, the support to functional layer can not be played and made
With；If the extent of reaction is too low, terminal hydroxy group, the amino isoreactivity group generated is less, and supporting layer can not provide enough work
Property group reacted with the bear electric polymer in functional layer and generate covalent bond, binding force do not enhanced, the peel resistance of film
It cannot can just improve.
(2) bear electricity type polymer of the present invention is other than having reactive active group, at the same have carboxylic acid,
Sulfonic acid group.It is electrical to assign film bear for the presence of carboxyl and sulfonic acid group.And carboxyl etc. has the presence of reaction active groups,
Make the bear electricity type polymer in preparation liquid that can react with modified PET, it is strong to be established in supporting layer and functional layer
Covalent key connection.Such as, in the hydroxyl and preparation liquid in modified PET P (MMA-MAA) carboxyl, at film forming and second heat
During reason, esterification occurs, forms the bonded companies of C-O (Fig. 1-2)；P (MMA- in amino and preparation liquid in modified PET
In film forming and second of heat treatment process amidation process occurs for carboxyl MAA), forms C-N key connections (Fig. 1-3).
(3) composite membrane supporting layer and functional layer of the invention are combined with covalent bond effect, when chlorine-containing polymer base preparation liquid
It is middle when different bear electricity type polymer are blended, supporting layer and functional layer can be formed C-O keys, C-N keys it is one or more covalently
Key connection；Meanwhile charged film surface contains the carboxyl, sulfonic one or more of bear electricity.Therefore, it is blended different charged
Type polymer, will make film that different interlayer adhesions and charge be presented, and the microstructure of composite membrane is also different (Fig. 2).
The key problem in technology of the present invention is strictly to control content of the bear electric polymer in functional layer.The present invention passes through tight
The mass percentage that lattice limit bear electric polymer in preparation liquid is realized to bear electric polymer as 1~10% in functional layer
The control of middle content.
Because if the content of bear electric polymer is too low, it will be unable to provide enough bear electric groups, can not also provide
Enough active group reacts with modified supporting layer generates C-O keys and C-N keys, film obtained had not both been shown obviously
Bear electrical feature, flux, hydrophily, resistance tocrocking etc. is all unable to get improvement, also do not have stronger antistripping property；Such as
The too high levels of fruit bear electric polymer will make to change by the function film structure of skeleton of chlorine-containing polymer, to make
Variation beyong contemplation occurs for the overall performance of film.
The key problem in technology of the present invention is strictly to control bear electric polymer in the active group of supporting layer and functional layer
The extent of reaction.The present invention by considered critical bear electric polymer content in functional layer, second of heat treatment temperature be 50~
90 DEG C, heat treatment time is 1~24 hour, to realize the anti-of bear electric polymer in active group and functional layer to supporting layer
Answer the control of degree.Wherein, the present invention by the mass percentage of bear electric polymer in considered critical preparation liquid be 1~
10% realizes the control to bear electric polymer content in functional layer.
Because if the extent of reaction is excessively high, then the carboxyl or sulfonic group of bear electric polymer in functional layer can be consumed significantly
Etc. bears electric group, composite membrane can not show bear electrical characteristics, flux, hydrophily, resistance tocrocking etc. is all unable to get improvement；
If the extent of reaction is too low, enough C-O and C-N covalent bonds can not be formed, binding force is not enhanced, the resistance to stripping of film
Performance cannot just improve.The extent of reaction of bear electric polymer in the active group and functional layer of stringent control supporting layer,
Purpose is to realize electrical to the bear of film and peel resistance balance.
The present invention also provides a kind of membrane module, the membrane module includes the composite membrane of any one form of the invention.
The beneficial effects of the present invention are：
(1) a kind of bear electricity type chlorine-containing polymer group compound film based on the enhancing of interlayer covalent effect disclosed by the invention,
It is made of, and supporting layer and functional layer are combined with covalent bond effect, therefore interlayer adhesion is strong, is using supporting layer and functional layer
While filament support layer improves film dynamic performance, solves the problems, such as in use ablation between film inner layer, improve the steady of film
Qualitative and service life enhances the resistance to backwash ability of film；
(2) functional layer of the invention is made of chlorine-containing polymer and bear electricity type polymer.Bear electricity type polymer draws
Enter, the composite membrane made to have certain bear electrical, while improving membrane flux, make the composite membrane have special absorption with
Stalling characteristic there is better removal capacity, the resistance tocrocking of film to significantly improve certain charged type pollutants.
(3) present invention is modified the masking technique of realization synchronous with inversion of phases film forming using supporting layer, and production process is simple.And
When using different structural support layer and filming technology, the masking technique is simultaneously suitable for preparing plate membrane and doughnut
Film.
Description of the drawings
Fig. 1 is chemical reaction schematic diagram according to the present invention
Wherein, 1-1 is the aminating reaction schematic diagram of PET；Ester occurs for the carboxyl of the hydroxyl that 1-2 is PET and P (MMA-MAA)
Change reaction schematic diagram；Amidation process schematic diagram occurs for the carboxyl of the amino that 1-3 is PET and P (MMA-MAA).
Fig. 2 is the filter membrane microstructure schematic diagram of the present invention.
Wherein, supporting layer is the non-woven fabrics or woven tube of polymer fiber composition, and functional layer is chlorine-containing polymer and lotus
Inversion of phases is formed after negative electricity type polymer is blended, and passes through a variety of covalent bonds such as C-O keys, C-N singly-bounds between supporting layer and functional layer
Connection, function layer surface have the carboxyl, sulfonic one or more of bear electricity.
Specific implementation mode：
The present invention will be described in detail with reference to the accompanying drawings and examples.Following embodiment be merely to illustrate the present invention rather than
It limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art can be right
The present invention makes various changes or modifications, and these equivalent forms also fall within the scope of the appended claims of the present application.
The present invention provides a kind of bear electricity type chlorine-containing polymer group compound film enhanced based on interlayer covalent effect, described
Composite membrane is made of supporting layer and functional layer, and the supporting layer is enhancement layer containing polyester fiber, and the functional layer is by containing chlorine
Polymer and bear electricity type polymer composition, the supporting layer and functional layer are combined with covalent bond effect, the composite membrane
Bear electricity.
The present invention prepares a kind of the specific of the bear electricity type chlorine-containing polymer group compound film enhanced based on interlayer covalent effect
Implementation is as follows：
(1) preparation liquid containing chlorine-containing polymer and bear electricity type polymer is prepared.Wherein, preparation liquid includes to polymerize containing chlorine
Object, bear electricity type polymer, pore former and several components of solvent.Specifically, the chlorine-containing polymer be selected from polyvinyl chloride,
Vingon, chliorinated polyvinyl chloride, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-olefin copolymer, gathers haloflex
In chlorobutadiene, chlorinated polypropylene any one or it is arbitrary a variety of, mass percentage is 10~25%；Negative electricity type polymerize
Object is the polymer containing carboxylic acid group, sulfonic acid group, selected from Eudragit S100, acrylic acid-
Acrylonitrile copolymer, acrylic acid-acrylic acid hydroxypropyl ester copolymer, acrylic acid-acrylamide copolymer, vinyl alcohol-acrylic acid are total
Polymers, acrylicstyrene sulfonic acid copolymer, maleic acid-Styrene Sulfonic Acid Copolymer, acrylic acid-Sodium Allyl Sulfonate copolymerization
Object, acrylic acid-(2- acrylamido -2- methyl propane sulfonic acids) copolymer, acrylic acid-acrylic acid methyl esters-(2- acrylamides
Base -2- methyl propane sulfonic acids) in terpolymer any one or it is a variety of, mass percentage is 1~10%；Pore-forming
Agent be selected from water, ethyl alcohol, glycerine, ethylene glycol, the polyethylene glycol (PEG) that molecular weight is 200~8000 any one or it is arbitrary
A variety of, mass percentage is 0.1~10%；Solvent is selected from N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide
(DMAC), any one or a few mixing in N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), gross mass hundred
It is 55~88.9% to divide content；The preparation of preparation liquid and dwell temperature are 25~90 DEG C.
(2) modifying agent is prepared.Modifying agent is the solution containing aminated compounds and catalyst, the solvent of solution be water or
The mixture of water and ethyl alcohol.Wherein, aminated compounds is the amine monomers containing primary amine group, selected from methylamine, ethamine, ethyl alcohol
Amine, ethylenediamine, propane diamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylene hexamine, more ethylene are more
In amine, p-phenylenediamine, m-phenylene diamine (MPD) any one or it is arbitrary a variety of, mass percentage is 5~40%；Catalyst is selected from
It is one or any a variety of in aluminium chloride, iron chloride, titanium tetrachloride, boron trifluoride, mass percentage be 0.01%~
1%；If solvent is the mixture of water and ethyl alcohol, the mass percentage of ethyl alcohol is 10~30% in solvent.
(3) supporting layer initially enters modifying agent, and carries out first time heat treatment.Supporting layer is containing polyester material containing poly-
Ester fiber enhancement layer, it is blended selected from polyester fiber, cotton polyester blend fibre, polyester/cellulose blends fiber, polyester/polyamide
Any one in fiber, polyester/polyurethane blend fibre, polyester/polypropylene nitrile blend fibre.Supporting layer initially enters modification
Agent, and carry out first time heat treatment.At once the pretreatment tank for being equipped with modifying agent is immersed after filament support layer coil stripping, enters back into heating
Drying tunnel carries out first time heat treatment, while making filament support layer that aminating reaction introducing active group occur, dries its surface water
Point.The temperature of heating drying tunnel is 50~200 DEG C, and the supporting layer residence time is 0.1~10 minute.
(4) preparation liquid is coated in the supporting layer outer surface by modification that step (3) obtains, and passes through immersion precipitation
Inversion of phases film-forming.Wherein, solidification liquid is water, and temperature is 20~60 DEG C.Above-mentioned filament support layer coil stripping-modifying agent is located in advance
It is continuous process, the i.e. movement velocity of filament support layer that reason-drying tunnel first time heat treatment-supporting layer, which enters film head-film-forming,
Always consistent with spinning speed, the masking technique of realization synchronous with inversion of phases film forming is modified using supporting layer.
(5) film that step (4) obtains is placed in saturated steam environment and carries out second of heat treatment, be subsequently placed in water
The support type bear electricity chlorine-containing polymer group compound film with high strong adhesive power is made in soaking and washing.Second of heat treatment temperature
It it is 50~90 DEG C, heat treatment time is 1~24 hour；The Membrane cleaning time is 10~24 hours, at least changes water in the process 3 times.
The performance characterization of bear electricity type chlorine-containing polymer group compound film based on the enhancing of interlayer covalent effect：
Pure water flux is measured using homemade flux measuring device.25 DEG C are measured, under 0.1MPa pressure when unit
The pure water transit dose of interior per membrane area；
The amination modifying extent of reaction of polyester fiber supporting layer is calculated using surface infrared spectrum measurement result.Such as figure
Shown in 1-1, in the aminating reaction of polyester fiber, a polyester molecule and amine substance react and generate an Amino End Group point
Son and a terminal hydroxy group molecule, therefore modified polyester fibre surface Amino End Group and ester group are measured by surface infrared spectrum
Ratio, you can calculate the amination modifying extent of reaction of polyester fiber supporting layer.
The peel strength of enhanced composite membrane is measured using homemade test device.Film wire is packaged into widgets, adopts
The mode intake with internal pressure, test pressure-flux detector.Operating pressure is slowly promoted, while monitoring the internal pressure flux of film, when
When cataclysm occurs for flux, that is, illustrate that situations such as rupture, cortex stripping occurs in film wire, operating pressure at this time can be used to description film
Peel strength.When there is covalently key connection between the supporting layer and functional layer of composite membrane, the peel strength of film can be shown
It writes and increases；
Bear electrically measures the isoelectric point of film, the pH value that isoelectric point is film surface charge when being 0 by zeta potentiometers.One
As not charged polymer film isoelectric point be about 6, when isoelectric point is less than 6, that is, show that this film shows bear under normal conditions
Electrical characteristics, isoelectric point is smaller, shows that the bear electrical characteristics of film are stronger；
Hydrophily measures the first contact angle that pure water is contacted with film surface by contact angle instrument, and the number of degrees of contact angle are got over
It is low, then illustrate that water is easier in surface spreading, hydrophily is better；
Resistance tocrocking is measured using the Static Adsorption experiment of bovine serum albumin (BSA).The phosphoric acid that BSA is dissolved in 0.01M delays
Rush the protein solution that solution (PBS, pH=7.4) is configured to 10mg/mL.Film wire is packaged into certain effectively membrane area and size
Component is fully cleaned repeatedly with water and ethyl alcohol.Be sufficiently injected protein solution in assembly chambeies body, after in shaking bath at 37 DEG C
Absorption is for 24 hours.It after the completion of absorption, takes the film out, is fully rinsed with PBS and deionized water.Then film is immersed a concentration of 1wt%'s
Oscillation desorption 2h in lauryl sodium sulfate (SDS) solution.Protein concentration in SDS solution is existed using UV spectrophotometers
The absorbance measurement of 280nm.Protein solution concentration-absorbance standard curve is existed by measuring 0.1~2mg/mL protein
Absorbance in SDS solution determines.With the BSA adsorbances of this unit of account membrane area.The adsorbance of bovine serum albumin is lower, says
The resistance tocrocking of bright film is better.
Embodiment 1：
Prepare a kind of fibre-reinforced bear electricity type chlorine-containing polymer base hollow-fibre membrane specific steps：
(1) preparation of preparation liquid：By polyvinyl chloride (PVC, 18wt%), methyl methacrylate-methacrylic acid copolymer
Object (P (MMA-MAA), 3wt%), polyethylene glycol (PEG400,7wt%), H2O (0.6wt%), DMAC (71.4wt%) are at 70 DEG C
Lower stirring is filtered after 24 hours, deaeration set aside for use at 70 DEG C.
(2) preparation of supporting layer modifying agent：Soluble in water, the room by diethylenetriamine (50wt%) and aluminium chloride (0.1%)
It is configured to modification liquid under temperature.
(3) supporting layer is braided polyester pipe.Immersed at once after woven tube coil stripping and be equipped with the pretreatment tank of modifying agent, after pass through again
Excess temperature is 90 DEG C, and the residence time is the heating drying tunnel of 5min, carries out first time heat treatment.
(4) the braided polyester tube outer surface by modification obtained in step (3) coats preparation liquid, rear to immerse 40 DEG C
Film-forming in water.
(5) film that step (4) obtains is placed in saturated steam environment and carries out second of heat treatment, heat treatment temperature is
70 DEG C, the time is 12 hours, is subsequently placed in soaking and washing 24 hours in water, and the support type bear electricity with high strong adhesive power is made
Chlorine-containing polymer base hollow-fibre membrane.
It is as follows to be film-made design parameter：
Test result, pure water flux is 660L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 4%, and operating pressure peeling occurs when reaching 1MPa.The isoelectric point of film is 3.5, and film surface first contact angle is
65 °, the adsorbance of bovine serum albumin is 8.4 μ g/cm2。
Comparative example 1：
Specific steps are the same as embodiment 1, the design parameter such as following table of film：
Explanation：Compared to embodiment 1, comparative example 1 does not carry out first time heat treatment, i.e., is not modified place to supporting layer
Reason.
Test result, pure water flux is 630L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 0%, and operating pressure peeling occurs when reaching 0.44MPa.The isoelectric point of film is 3.7, film surface first contact angle
It it is 73 °, the adsorbance of bovine serum albumin is 15.9 μ g/cm2。
Comparative example 2：
Specific steps are the same as embodiment 1, the design parameter such as following table of film：
Explanation：Compared to embodiment 1, aminated compounds is dense in the modifying agent that comparative example 2 uses when being heat-treated for the first time
Degree is less than the present invention, i.e., not stringent control condition when being modified processing to supporting layer.
Test result, pure water flux is 600L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 0.2%, and operating pressure peeling occurs when reaching 0.48MPa.The isoelectric point of film is 4.3, film surface first contact
Angle is 76 °, and the adsorbance of bovine serum albumin is 17.1 μ g/cm2。
Comparative example 3：
Specific steps are the same as embodiment 1, the design parameter such as following table of film：
Explanation：Compared to embodiment 1, aminated compounds is dense in the modifying agent that comparative example 2 uses when being heat-treated for the first time
Degree is less than the present invention, i.e., not stringent control condition when being modified processing to supporting layer.
Test result, pure water flux is 640L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 0.6%, and operating pressure peeling occurs when reaching 0.49MPa.The isoelectric point of film is 4.4, film surface first contact
Angle is 78 °, and the adsorbance of bovine serum albumin is 18.3 μ g/cm2。
Comparative example 4：
Specific steps are the same as embodiment 1, the design parameter such as following table of film：
Explanation：Compared to embodiment 1, temperature when comparative example 3 is heat-treated for the first time less than the present invention, i.e., to supporting layer into
Not stringent control condition when row modification.
Test result, pure water flux is 620L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 0.1%, and operating pressure peeling occurs when reaching 0.45MPa.The isoelectric point of film is 3.8, film surface first contact
Angle is 74 °, and the adsorbance of bovine serum albumin is 16.2 μ g/cm2。
Compared to embodiment 1, comparative example 1 is not modified processing to supporting layer, and comparative example 2 to comparative example 4 is to supporting layer
It is modified not stringent control condition when processing.The amination modifying extent of reaction of polyester fiber supporting layer is very low, supporting layer without
Method provides enough active groups and reacts generation covalent bond with the bear electric polymer in functional layer, and binding force is not increased
By force, the antistripping property of film is markedly less than embodiment 1.
Comparative example 5：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Explanation：Compared to embodiment 1, bear electricity type polymer is not blended in 4 preparation liquid of comparative example.
Test result, pure water flux is 430L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 3.8%, and operating pressure peeling occurs when reaching 0.52MPa.The isoelectric point of film is 6.2, film surface first contact
Angle is 105 °, and the adsorbance of bovine serum albumin is 41.5 μ g/cm2。
Compared to embodiment 1, it is not blended bear electricity type polymer in 5 preparation liquid of comparative example, it can be in functional layer
The substance that modified supporting layer reacts, binding force are not enhanced, and the antistripping property of film is markedly less than embodiment
1.Meanwhile the isoelectric point of film is 6 or so, does not also have bear electrical feature, flux, hydrophily, stain resistance is markedly less than reality
Apply example 1.
Comparative example 6：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Explanation：Compared to embodiment 1, second of heat treatment is not carried out in comparative example 5, i.e., does not promote modified PET and film
Bear electricity type polymer, which reacts, in liquid generates C-O keys and C-N keys.
Test result, pure water flux is 650L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 3.9%, and operating pressure peeling occurs when reaching 0.54MPa.The isoelectric point of film is 4.7, film surface first contact
Angle is 84 °, and the adsorbance of bovine serum albumin is 21.7 μ g/cm2。
Comparative example 7：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Explanation：Compared to embodiment 1, the temperature that second of heat treatment is carried out in comparative example 6 is far below claim 11 institute
It states, that is, is not controlled strictly when modified PET being promoted to react with bear electricity type polymer in preparation liquid and generate C-O keys and C-N keys
Condition.
Test result, pure water flux is 640L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 3.9%, and operating pressure peeling occurs when reaching 0.5MPa.The isoelectric point of film is 5.1, film surface first contact angle
It it is 82 °, the adsorbance of bovine serum albumin is 22.5 μ g/cm2。
Compared to embodiment 1, second of heat treatment is not carried out in comparative example 6, when carrying out second of heat treatment in comparative example 7
Not stringent control condition.The active group that modified supporting layer provides can not be fully anti-with the bear electric polymer in functional layer
Covalent bond should be generated, binding force is not enhanced significantly, and the antistripping property of film is weaker than embodiment 1.
Embodiment 2：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Test result, pure water flux is 620L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 5.0%, and operating pressure peeling occurs when reaching 1.23MPa.The isoelectric point of film is 4.3, film surface first contact
Angle is 63 °, and the adsorbance of bovine serum albumin is 18.5 μ g/cm2。
Embodiment 3：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Test result, pure water flux is 690L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 4.2%, and operating pressure peeling occurs when reaching 0.9MPa.The isoelectric point of film is 3.9, film surface first contact angle
It it is 67 °, the adsorbance of bovine serum albumin is 19.2 μ g/cm2。
Embodiment 4：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Test result, pure water flux is 600L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 1.0%, and operating pressure peeling occurs when reaching 0.88MPa.The isoelectric point of film is 3.5, film surface first contact
Angle is 81 °, and the adsorbance of bovine serum albumin is 12.6 μ g/cm2。
Embodiment 5：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Test result, pure water flux is 630L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 1.5%, and operating pressure peeling occurs when reaching 0.75MPa.The isoelectric point of film is 2.8, film surface first contact
Angle is 79 °, and the adsorbance of bovine serum albumin is 9.7 μ g/cm2。
Embodiment 6：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Test result, pure water flux is 480L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 2.8%, and operating pressure peeling occurs when reaching 0.83MPa.The isoelectric point of film is 3.7, film surface first contact
Angle is 89 °, and the adsorbance of bovine serum albumin is 20.6 μ g/cm2。
Embodiment 7：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Test result, pure water flux is 510L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 3.6%, and operating pressure peeling occurs when reaching 0.77MPa.The isoelectric point of film is 3.2, film surface first contact
Angle is 80 °, and the adsorbance of bovine serum albumin is 14.2 μ g/cm2。
Embodiment 8：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Test result, pure water flux is 390L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 4.0%, and operating pressure peeling occurs when reaching 0.8MPa.The isoelectric point of film is 3.7, film surface first contact angle
It it is 66 °, the adsorbance of bovine serum albumin is 19.5 μ g/cm2。
Embodiment 9：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Test result, pure water flux is 420L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 4.3%, and operating pressure peeling occurs when reaching 0.79MPa.The isoelectric point of film is 3.6, film surface first contact
Angle is 74 °, and the adsorbance of bovine serum albumin is 23.5 μ g/cm2。
Embodiment 10：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Test result, pure water flux is 350L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 3.1%, and operating pressure peeling occurs when reaching 0.76MPa.The isoelectric point of film is 2.5, film surface first contact
Angle is 95 °, and the adsorbance of bovine serum albumin is 29.5 μ g/cm2。
Embodiment 11：
Specific steps are the same as embodiment 1, the following table of design parameter of film：
Test result, pure water flux is 390L/hm at 0.1MPa2, the amination modifying reaction of polyester fiber supporting layer
Degree is 1.8%, and operating pressure peeling occurs when reaching 0.76MPa.The isoelectric point of film is 3.2, film surface first contact
Angle is 91 °, and the adsorbance of bovine serum albumin is 26.3 μ g/cm2。
Claims (10)
1. a kind of bear electricity type chlorine-containing polymer group compound film based on the enhancing of interlayer covalent effect, it is characterised in that：Described
Composite membrane is made of supporting layer and functional layer, and the supporting layer is enhancement layer containing polyester fiber, and the functional layer is by containing chlorine
Polymer and bear electricity type polymer composition, mass percentage of the bear electricity type polymer in functional layer be 10~
50%, it is combined with covalent bond effect between the supporting layer and functional layer, the composite film surface carries carboxyl or sulfonic acid
Group, the composite membrane bear electricity, the covalent bond is C-O keys and C-N keys, and the composite membrane is bear electricity type micro-filtration
Film or ultrafiltration membrane.
2. a kind of bear electricity type chlorine-containing polymer base based on the enhancing of interlayer covalent effect according to claim 1 is compound
Film, it is characterised in that：The interlayer covalent effect be by supporting layer carry out amination modifying form it into active group, and
It is chemically reacted with the active group of bear electricity type polymer, forms C-O and C-N covalent bonds and realize, the amination
Modified-reaction degree is 1~5%.
3. a kind of bear electricity type chlorine-containing polymer base based on the enhancing of interlayer covalent effect according to claim 1 is compound
Film, it is characterised in that：The composite membrane is any one of plate membrane, hollow-fibre membrane.
4. a kind of bear electricity type chlorine-containing polymer base based on the enhancing of interlayer covalent effect according to claim 1 is compound
Film, it is characterised in that：The enhancement layer containing polyester fiber is selected from polyester fiber, cotton polyester blend fibre, polyester/cellulose
Appointing in blend fibre, polyester/polyamide blend fibre, polyester/polyurethane blend fibre, polyester/polypropylene nitrile blend fibre
Meaning is a kind of.
5. a kind of bear electricity type chlorine-containing polymer base based on the enhancing of interlayer covalent effect according to claim 1 is compound
Film, it is characterised in that：The chlorine-containing polymer is selected from polyvinyl chloride, Vingon, haloflex, chlorinated polyvinyl chloride second
It is arbitrary in alkene, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, polychlorobutadiene, chlorinated polypropylene
It is a kind of or arbitrary a variety of.
6. a kind of bear electricity type chlorine-containing polymer base based on the enhancing of interlayer covalent effect according to claim 1 is compound
Film, it is characterised in that：The bear electricity type polymer is the polymer containing carboxylic acid group, sulfonic acid group, it is preferred that described
Bear electricity type polymer be selected from Eudragit S100, AA-AN copolymerization object, propylene
Acid-hydroxypropyl acrylate copolymer, acrylic acid-acrylamide copolymer, vinyl alcohol-acrylic copolymer, acrylicstyrene
Sulfonic acid copolymer, maleic acid-Styrene Sulfonic Acid Copolymer, acrylic acid-Sodium Allyl Sulfonate copolymer, acrylic acid-（2- acryloyls
Amido -2- methyl propane sulfonic acids）Copolymer, acrylic acid-acrylic acid methyl esters-（2- acrylamido -2- methyl propane sulfonic acids）Three
In membered copolymer any one or it is a variety of.
7. a kind of bear electricity type chlorine-containing polymer group compound film based on the enhancing of interlayer covalent effect according to claim 1
Preparation method, it is characterised in that include the following steps：
It is configured to preparation liquid after dissolving is blended in chlorine-containing polymer and bear electricity type polymer；
Prepare supporting layer modifying agent；
Supporting layer initially enters modifying agent, and carries out first time heat treatment, makes polyester fiber that amination occur under modifying agent effect
Reaction, it is hydroxyl or the polyester macromolecule of primary amine groups to generate one end；
In step（3）The obtained supporting layer outer surface coating preparation liquid by modification, and pass through immersion precipitation inversion of phases
Film-forming；
By step（4）Obtained film, which is placed in saturated steam environment, carries out second of heat treatment, and it is hydroxyl to make one end in supporting layer
It reacts with the carboxyl in bear electricity type polymer in functional layer under base or the effect of the polyester macromolecule modifying agent of primary amine groups
C-O and C-N covalent bonds are formed, then by Membrane cleaning, the bear electricity type chlorine-containing polymer enhanced based on interlayer covalent effect is made
Group compound film.
8. preparation method according to claim 7, it is characterised in that：Step（1）Described in preparation liquid in bear electricity type
The mass percentage of polymer is 1~10%.
9. preparation method according to claim 7, it is characterised in that：Step（3）And step（5）The modifying agent be containing
It is the mixture of water or water and ethyl alcohol, the amine to have the solution of aminated compounds and catalyst, the solvent of the solution
The mass percentage of compound is 5%~40%, and the mass percentage of the catalyst is 0.01%~1%, the modifying agent
The mass percentage of middle solvent is 59~94.99%, and the mass percentage of ethyl alcohol is 10 in the mixture of the water and ethyl alcohol
~30%.
10. preparation method according to claim 8, it is characterised in that：The aminated compounds is to contain primary amine group
Amine monomers, selected from methylamine, ethamine, ethanol amine, ethylenediamine, propane diamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, tetrem
In five amine of alkene, pentaethylene hexamine, polyethylene polyamine, p-phenylenediamine, m-phenylene diamine (MPD) any one or it is arbitrary a variety of.
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