CN108636131A - Hydrophilized porous membrane and preparation method thereof - Google Patents
Hydrophilized porous membrane and preparation method thereof Download PDFInfo
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- CN108636131A CN108636131A CN201810418291.4A CN201810418291A CN108636131A CN 108636131 A CN108636131 A CN 108636131A CN 201810418291 A CN201810418291 A CN 201810418291A CN 108636131 A CN108636131 A CN 108636131A
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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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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
- B01D71/26—Polyalkenes
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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
- B01D2325/02—Details relating to pores or porosity of the membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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Abstract
A kind of hydrophilic film of present invention offer and preparation method thereof, preparation method includes：One polymeric acceptor is provided, and is prepared into curtain coating ribbon；Curtain coating ribbon is stretched so that membrane structure is prepared, and processing is carried out shaping to membrane structure；Membrane structure after sizing is placed in the first solvent containing assistant crosslinking agent and is handled；It previous step is obtained structure is placed in the second solvent containing hydrophilic polymer to handle；And radiation treatment is carried out to structure obtained in the previous step, to prepare the Hydrophilized porous membrane, Pass through above-mentioned technical proposal, a kind of Hydrophilized porous membrane of present invention offer and preparation method, by the solvent soaking processing containing hydroaropic substance in its preparation process, meanwhile, assistant crosslinking agent is used in preparation process, play the role of connecting perforated membrane matrix and hydroaropic substance, so as to characteristics such as the pure water fluxs that significantly improves Hydrophilized porous membrane.
Description
Technical field
The invention belongs to perforated membrane preparing technical fields, more particularly to a kind of Hydrophilized porous membrane and preparation method thereof.
Background technology
Currently, perforated membrane is used widely in the fields such as gas treatment, liquid handling, especially water treatment field.
The industry being related to is varied, includes mainly, oil, chemical industry, pharmacy, food, electronics, biotechnology etc..Plumbing
Purification, sewage purification, the core component of sea water desalination is exactly to be carried out using the screening principle of perforated membrane.
In order to enable perforated membrane preferably to play sieving actoion, in addition to needing it to have certain porosity and pore size
Outside, it is also necessary to which its outer surface and hole surface have good wellability to medium to be treated (such as water), to ensure to locate
During managing medium, medium can be smoothly through duct, effectively reduce through resistance, prevent the residual of medium and cause to block up
Treatment effeciency is improved in hole.For the perforated membrane for water process, it is desirable to which its outer surface and hole surface have good hydrophilic
Property, i.e., lower contact angle, during handling aqueous medium, water can rapidly infiltrate and pass through, that is, possess prodigious pure
Water flux.But conventional porous membrane material is mostly hydrophobic polymer, such as wants to be used for water treatment field, it is necessary to carry out parent to it
Watersoluble modified processing, modifying process not only complex process improve cost, and the problems such as original micropore can be caused to block.
Therefore, how a kind of Hydrophilized porous membrane and its manufacturing method are provided, perforated membrane is made to keep original aperture and hole
On the basis of gap rate, possess permanent hydrophilic surface layer, and is able to maintain that prodigious pure water flux is necessary.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of Hydrophilized porous membrane and its systems
Preparation Method, for solving perforated membrane modified in the prior art, there are the reductions of aperture and porosity, cannot obtain permanent hydrophilic
The problems such as property multilayer film and relatively low existing perforated membrane pure water flux.
In order to achieve the above objects and other related objects, the present invention provides a kind of preparation method of Hydrophilized porous membrane, packet
Include step：
1) polymeric acceptor is provided, and is prepared into curtain coating ribbon；
2) the curtain coating ribbon is stretched so that membrane structure is prepared, and place is carried out shaping to the membrane structure
Reason；
3) membrane structure after sizing is placed in the first solvent containing assistant crosslinking agent and is handled；
4) it step 3) is obtained structure is placed in the second solvent containing hydrophilic polymer to handle；And
5) radiation treatment is carried out to the structure that step 4) obtains, to prepare the Hydrophilized porous membrane.
As a preferred embodiment of the present invention, further include between step 1) and step 2)：The curtain coating ribbon is set
First time extraction is carried out in the extraction tank containing dichloromethane, to remove the mineral oil in the curtain coating ribbon.
As a preferred embodiment of the present invention, in step 2), after stretching obtains the membrane structure and carrying out
Before the sizing treatment, the membrane structure is carried out second in the extraction tank containing dichloromethane and is extracted and to described
The membrane structure obtained after second of extraction is cleaned.
As a preferred embodiment of the present invention, in step 1), prepare to form the curtain coating ribbon using casting technique,
The temperature of the casting technique is between 60 DEG C~100 DEG C；In step 2), the temperature of the sizing treatment is carried out between 100
DEG C~120 DEG C between, the time is between 10min~20min；The technique handled in first solvent in step 3)
Including impregnating, soaking time is between 50min~80min；The technique handled in second solvent in step 4)
Including impregnating, soaking time is between 50min~80min.
As a preferred embodiment of the present invention, in step 5), using at least one of gamma ray and electron beam into
The row radiation treatment, and the irradiation dose for carrying out the radiation treatment is not higher than 10kGy.
As a preferred embodiment of the present invention, in step 1), the polymeric acceptor includes at least one high-molecular-weight poly
Ethylene, wherein the average molecular weight of the High molecular weight polyethylene is between 1.0 × 105~10.0 × 106Between, the macromolecule
The density of weight northylen is between 0.940g/cm3~0.976g/cm3Between.
As a preferred embodiment of the present invention, in step 1), the polymeric acceptor includes pore former and antioxidant
At least one of.
As a preferred embodiment of the present invention, when the polymeric acceptor includes the pore former, the pore former choosing
From in crude mineral oils, C6-15 alkane, C8-15 aliphatic carboxylic acids, C8-15 aliphatic carboxylic acid C1-4 alkyl esters, C2-6 halogenated alkanes, neighbour
Phthalic acid ester, trimellitate, adipate ester, sebacate, maleate, benzoic ether, epoxidized vegetable oil, benzene sulfonyl
In amine, phosphotriester, glycol ether, acetylated monoglyceride, citrate and hexamethylene -1,2- dicarboxylic acids dinonyls
At least one.
As a preferred embodiment of the present invention, 40 DEG C of kinematic viscosity of the pore former are between 10mm2/ s~100mm2/s
Between；The initial boiling point of the pore former is not less than 110 DEG C.
It is described anti-oxidant when the polymeric acceptor includes the antioxidant as a preferred embodiment of the present invention
Agent is selected from 4,4- thiobis (6- tert-butyl-m-cresols), dibutyl hydroxy toluene, phosphite ester, tert-butylhydroquinone, β-
Positive ten caprylate of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, 1,1,3- tri- (- 4 hydroxyl -5- 2-methyl-2-phenylpropanes base of 2- methyl) fourth
Alkane, 2- tertiary butyl -6- methylphenols, N, N '-two-betanaphthyls p-phenylenediamine, thio-2 acid double lauryl, three (nonyls of phosphorous acid
Base phenyl) at least one of ester and triphenyl phosphite.
As a preferred embodiment of the present invention, in step 3), the assistant crosslinking agent is selected from mercaptobenzothiazoler, two sulphur
Change benzothiazole, N- cyclohexylbenzothiazoles sulfenamide, divinyl oxide base benzothiazole sulfenamide, a vulcanization tetramethyl autumn
Lan Mu, tetramethylthiuram disulfide, zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, diphenylguanidine,
Di-o-tolylguanidine, ethylene thiourea, N, N '-diethyl thioureas, hexa, zinc isopropyl xanthate, trihydroxy methyl third
Alkane trimethyl acrylic ester, trimethylolpropane trimethacrylate, cyanuric acid tripropylene and triallyl isocyanuric acid
At least one of ester.
As a preferred embodiment of the present invention, in step 4), the hydrophilic polymer is selected from carboxymethyl starch, vinegar
Acid-starch, hydroxymethyl cellulose, carboxymethyl cellulose, polyacrylamide, hydrolyzed polyacrylamide, ethyl cellulose, poly- Malaysia
Acid anhydrides, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol oxide, ethylene-vinyl alcohol copolymer, acrylic acid-second
Enol copolymer, vinyl alcohol-vinyl acetate copolymer, polyvinyl formal, polyvinyl acetal, polyvinyl alcohol contracting first
At least one of the segmented polymer containing vinyl alcohol of acetaldehyde, polyvinyl butyral.
As a preferred embodiment of the present invention, in step 3), first solvent is selected from isopropanol, isopropanol and first
At least one of mixture, ethyl alcohol and normal propyl alcohol of alcohol；In step 4), second solvent is selected from isopropanol, isopropyl
At least one of the mixture of alcohol and methanol, ethyl alcohol and normal propyl alcohol.
As a preferred embodiment of the present invention, first solvent is identical as second solvent.
Include High molecular weight polyethylene in the polymeric acceptor, by the high score as a preferred embodiment of the present invention
The weight of sub- weight northylen is 100 parts of meters, and the weight of the assistant crosslinking agent is between 0.1~5 part, the hydrophilic polymer
Weight between 0.1~5 part, the total weight of first solvent and second solvent is between 800~1200 parts.
As a preferred embodiment of the present invention, in step 5), the micropore size of the obtained Hydrophilized porous membrane is situated between
Between 10nm~100nm, porosity is between 20%~60%, and for surface contact angle between 50 °~60 °, pure water is logical
Amount is between 1000L/m2H0.1MPa~2000L/m2Between h0.1MPa.
The present invention also provides a kind of Hydrophilized porous membrane, the raw material for preparing of the Hydrophilized porous membrane includes high-molecular-weight poly
Ethylene, assistant crosslinking agent, hydrophilic polymer, the first solvent and the second solvent, wherein first solvent is described for dissolving
Assistant crosslinking agent, second solvent is for dissolving the hydrophilic polymer.
It as a preferred embodiment of the present invention, counts in parts by weight, and is by the weight of the High molecular weight polyethylene
100 parts of meters, the weight of the assistant crosslinking agent is between 0.1~5 part, and the weight of the hydrophilic polymer is between 0.1~5 part, institute
The total weight of the first solvent and second solvent is stated between 800~1200 parts.
As a preferred embodiment of the present invention, the raw material for preparing of the Hydrophilized porous membrane further includes pore former and antioxygen
At least one of agent, wherein by the weight of the High molecular weight polyethylene be 100 parts based on, when containing the pore former,
The weight of the pore former is between 100~500 parts, and when containing the antioxidant, the weight of the antioxidant is between 0.1
~10 parts.
As a preferred embodiment of the present invention, the micropore size of the Hydrophilized porous membrane between 10nm~100nm it
Between, porosity is between 20%~60%, and surface contact angle is between 50 °~60 °, and pure water flux is between 1000L/m2·
H0.1MPa~2000L/m2Between h0.1MPa.
As described above, the Hydrophilized porous membrane and preparation method of the present invention, have the advantages that：
A kind of Hydrophilized porous membrane of present invention offer and preparation method, by containing hydroaropic substance in its preparation process
Solvent carry out immersion treatment, meanwhile, assistant crosslinking agent is used in preparation process, there is connection perforated membrane matrix and hydrophily object
The effect of matter, so as to characteristics such as the pure water fluxs of the Hydrophilized porous membrane significantly improved.
Description of the drawings
Fig. 1 is shown as the preparation technology flow chart of the Hydrophilized porous membrane of the present invention.
Component label instructions
S1~S5 steps 1)~step 5)
Specific implementation mode
Illustrate that embodiments of the present invention, those skilled in the art can be by this specification below by way of specific specific example
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Shown in please referring to Fig.1.It should be noted that the diagram provided in the present embodiment only illustrates this hair in a schematic way
Bright basic conception, though in diagram only display and related component in the present invention rather than component count when according to actual implementation,
Shape and size are drawn, when actual implementation form, quantity and the ratio of each component can be a kind of random change, and its component
Arrangement form may also be increasingly complex.
As shown in Figure 1, the present invention provides a kind of preparation method of Hydrophilized porous membrane, include the following steps：
1) polymeric acceptor is provided, and is prepared into curtain coating ribbon；
2) the curtain coating ribbon is stretched membrane structure is prepared, and to the membrane structure sizing treatment；
3) membrane structure after sizing is placed in the first solvent containing assistant crosslinking agent and is handled；
4) it step 3) is obtained structure is placed in the second solvent containing hydrophilic polymer to handle；And
5) radiation treatment is carried out to the structure that step 4) obtains, to obtain the Hydrophilized porous membrane.
The preparation process of the Hydrophilized porous membrane of the present invention is described more detail below.
First, as shown in the S1 in Fig. 1, step 1) is carried out, a polymeric acceptor is provided, and be prepared into curtain coating ribbon.
As an example, in step 1), the polymeric acceptor includes at least one High molecular weight polyethylene, wherein the height
The density of molecular weight polyethylene is between 0.940g/cm3~0.976g/cm3Between, average molecular weight is between 1.0 × 105~10.0
×106Between.
Specifically, providing a kind of polymeric acceptor first, in one example, the polymeric acceptor includes high-molecular-weight poly second
Alkene, wherein High molecular weight polyethylene can be a kind of High molecular weight polyethylene, can also be two or more high molecular weight
The mixture of polyethylene, type difference for example can be that the ratio for the ingredient for constituting High molecular weight polyethylene is different, excellent one
It selects in example, the density of the High molecular weight polyethylene is between 0.940g/cm3~0.966g/cm3Between, the high-molecular-weight poly
The average molecular weight of ethylene is 1.0 × 105~5.0 × 106, namely when containing there are many when High molecular weight polyethylene, it is preferably each described
The average molecular weight of High molecular weight polyethylene is within above-mentioned numberical range, in further preferred example, the height
The density of molecular weight polyethylene is between 0.950g/cm3~0.966g/cm3Between, the mean molecule of the High molecular weight polyethylene
Amount is 1.0 × 105~2.0 × 106, to further prepare the Hydrophilized porous membrane of good performance such as pure water flux, porosity.
As an example, in step 1), the polymeric acceptor includes at least one of pore former and antioxidant.
As an example, when the polymeric acceptor includes the pore former, the pore former selected from crude mineral oils,
C6-15 alkane, C8-15 aliphatic carboxylic acids, C8-15 aliphatic carboxylic acid C1-4 alkyl esters, C2-6 halogenated alkanes, phthalic acid ester, inclined benzene
Three acid esters, adipate ester, sebacate, maleate, benzoic ether, epoxidized vegetable oil, benzsulfamide, phosphotriester, binary
At least one of alcohol ether, acetylated monoglyceride, citrate and hexamethylene -1,2- dicarboxylic acids dinonyls.
As an example, 40 DEG C of kinematic viscosity of the pore former are between 10mm2/ s~100mm2Between/s, it is preferably based on
20mm2/ s~80mm2Between/s, further preferably between 30mm2/ s~70mm2Between/s.
As an example, the initial boiling point of the pore former is not less than 110 DEG C.
As an example, when the polymeric acceptor includes the antioxidant, the antioxidant is thio selected from 4,4-
Bis- (6- tert-butyl-m-cresols), dibutyl hydroxy toluene, phosphite ester, tert-butylhydroquinone, β-(3,5- di-t-butyls -4-
Hydroxy phenyl) positive ten caprylate of propionic acid, 1,1,3- tri- (- 4 hydroxyl -5- 2-methyl-2-phenylpropanes base of 2- methyl) butane, 2- tertiary butyl -6- first
Base phenol, N, the double lauryls of N '-two-betanaphthyls p-phenylenediamine, thio-2 acid, (nonyl phenyl) ester of phosphorous acid three and phosphorous
At least one of triphenyl phosphate ester.
As an example, in step 1), prepare to form the curtain coating ribbon, the temperature of the casting technique using casting technique
Degree is between 60 DEG C~100 DEG C.
Specifically, in one example, during the polymeric acceptor is formed, also adding mineral oil, further, also wrapping
Addition pore former, antioxidant or both of pore former and antioxidant is included to add, in actual mechanical process, polymerization
Compositions (such as High molecular weight polyethylene, antioxidant and mineral oil) are continuously squeezed out by extruder, enter slot die
Interior, mixture is expressed into curtain coating chill roll by slot die, and be preferably cast under conditions of 80 DEG C ribbon to get to
The curtain coating ribbon.
Then, as shown in the S2 in Fig. 1, step 2) is carried out, the curtain coating ribbon is stretched so that film knot is prepared
Structure, and to the membrane structure sizing treatment.
As an example, in step 2), carry out the temperature of the sizing treatment between 100 DEG C~140 DEG C, the time between
Between 10min~20min.
Specifically, after the curtain coating ribbon is prepared in previous step, in one example, preferably in 120 DEG C of conditions
The lower ribbon that will pass through extraction be continuously introduced into biaxial orientation stretching machine and be drawn into film, i.e., the described membrane structure then preferably exists
Thermal finalization 15 minutes under the conditions of 120 DEG C, to carry out lower step processing.
As an example, further including between step 1) and step 2)：The curtain coating ribbon is placed in extraction tank and carries out
Single extraction, to remove the mineral oil in the curtain coating ribbon.
As an example, in step 2), it, will after stretching obtains the membrane structure and before carrying out the sizing treatment
The membrane structure carries out the membrane structure after extracting and being extracted to described second in extraction tank second and cleans.
Specifically, in a preferable example, after the curtain coating ribbon is formed, the merging of obtained ribbon is contained into dichloro
First time extraction is carried out in the extraction tank of methane, to remove the mineral oil in ribbon, it is further preferred that first will be passed through
The ribbon of secondary extraction is continuously introduced into biaxial orientation stretching machine and is drawn into after film, then with dichloromethane to gained thin-film material into
Second of extraction of row, and deionized water is preferably used to clean gained film.Furthermore it is preferred that containing when in the polymeric acceptor
When the pore former, pore former extraction is fallen during first time extraction or second extract.
Then, as shown in the S3 in Fig. 1, step 3) is carried out, the membrane structure after sizing is placed in containing helping crosslinking
It is handled in first solvent of agent.
As an example, the technique handled in first solvent in step 3) include impregnate, soaking time between
Between 50min~80min.
As an example, in step 3), first solvent is selected from isopropanol, the mixture of isopropanol and methanol, ethyl alcohol
And at least one of normal propyl alcohol.
As an example, in step 3), the assistant crosslinking agent is selected from mercaptobenzothiazoler, benzothiazole disulfide, N- rings
Hexyl benzo thiazolesulfenamide, divinyl oxide base benzothiazole sulfenamide, tetramethylthiuram monosulfide, curing tetramethyl
Base thiuram, zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, diphenylguanidine, di-o-tolylguanidine, sub- second
Base thiocarbamide, N, N '-diethyl thioureas, hexa, zinc isopropyl xanthate, trimethylol propane trimethyl acrylic acid
At least one of ester, trimethylolpropane trimethacrylate, cyanuric acid tripropylene and Triallyl isocyanurate.
Specifically, in the step, in one example, by the membrane structure after sizing in first containing assistant crosslinking agent
Immersion 1h is carried out in solvent, and it is further preferred that the membrane structure after immersion is dried into 1h in the environment of 50 DEG C.Its
In, the assistant crosslinking agent plays connection perforated membrane matrix (membrane structure that previous step obtains) and the hydroaropic substance (parent
Waterborne polymeric) effect.It is further the weight of the assistant crosslinking agent based on 100 parts by the weight of the High molecular weight polyethylene
Amount is preferably between 0.1~5 part between 0.2~2 part, further preferably between 0.5~1 part, to which control is suitable
The assistant crosslinking agent weight so that the weight for adding the assistant crosslinking agent to improve connection effect, and makes pure water flux
It is obviously improved, and further prevents self-crosslinking plug-hole, help to improve the improvement of pure water flux.
Continue, as shown in the S4 in Fig. 1, carries out step 4), step 3) is obtained into structure and is placed in containing hydrophilic polymer
The second solvent in handled.
As an example, the technique handled in second solvent in step 4) include impregnate, soaking time between
Between 50min~80min.
As an example, in step 4), the hydrophilic polymer is fine selected from carboxymethyl starch, acetic starch, methylol
It ties up element, carboxymethyl cellulose, polyacrylamide, hydrolyzed polyacrylamide, ethyl cellulose, polymaleic anhydride, polyacrylic acid, gather
Vinylpyrrolidone, polyvinyl alcohol, polyethylene glycol oxide, ethylene-vinyl alcohol copolymer, acrylic-ethylene alcohol copolymer, ethylene
Alcohol-vinyl acetate co-polymer, polyvinyl formal, polyvinyl acetal, polyvinyl formal acetal, polyvinyl alcohol contracting
At least one of the segmented polymer containing vinyl alcohol of butyraldehyde.
As an example, in step 4), second solvent is selected from isopropanol, the mixture of isopropanol and methanol, ethyl alcohol
And at least one of normal propyl alcohol.
Specifically, after the membrane structure impregnated in the first solvent containing the assistant crosslinking agent, placed
It is impregnated in the second solvent containing hydrophilic polymer, preferably impregnates 1h, and it is further preferred that by the institute after immersion
It states membrane structure and dries 1h in the environment of 50 DEG C.
Preferably, first solvent is identical as the type of substance that second solvent selects, so that close
The overall performance of the stable preparation process of aqueous perforated membrane, finally obtained Hydrophilized porous membrane is stablized.
Finally, as shown in the S5 in Fig. 1, step 5) is carried out, radiation treatment is carried out to the structure that step 4) obtains, to prepare
The Hydrophilized porous membrane.
As an example, in step 5), the radiation treatment is carried out using at least one of gamma ray and electron beam, and
The irradiation dose for carrying out the radiation treatment is not higher than 10kGy.
Specifically, to using in the first solvent containing assistant crosslinking agent and the second solvent containing hydrophilic polymer into
After row processing, low dosage gamma ray then is carried out to gained film or electron beam irradiation is handled, it is preferable that irradiation dose
5kGy finally obtains permanent hydrophilic porous film it is further preferred that the film after irradiation is wound with 50 ms/min of speed.
As an example, including High molecular weight polyethylene in the polymeric acceptor, by the weight of the High molecular weight polyethylene
It is counted for 100 parts, the weight of the assistant crosslinking agent is between 0.1~5 part, and the weight of the hydrophilic polymer is between 0.1~5
Between part, the total weight of first solvent and second solvent is between 800~1200 parts.
Specifically, in this example, a kind of composition of the hydrophilic film is provided, by the weight of the High molecular weight polyethylene
Amount is 100 parts of meters, and the weight of the assistant crosslinking agent is preferably between 0.2~2 part, further preferably between 0.5~1 part；
The weight of the hydrophilic polymer is preferably between 0.5~3 part, further preferably between 1~2 part；First solvent
And the total weight of second solvent is preferably between 900~1100 parts, further preferably 1000 parts.
As an example, in step 5), the micropore size of the obtained Hydrophilized porous membrane between 10nm~100nm it
Between, porosity is between 20%~60%, and surface contact angle is between 50 °~60 °, and pure water flux is between 1000L/m2·
H0.1MPa~2000L/m2Between h0.1MPa.
Specifically, based on Hydrophilized porous membrane prepared by method provided by the invention, micropore size is preferably between 20nm
Between~60nm, porosity is preferably between 30%~50%, and surface contact angle is preferably between 52 °~58 °, and pure water is logical
Amount is between 1500L/m2H0.1MPa~1800L/m2Between h0.1MPa, perforated membrane is made to keep original aperture and hole
On the basis of gap rate, possess permanent hydrophilic surface layer, and is able to maintain that prodigious pure water flux.
The present invention also provides a kind of Hydrophilized porous membranes, wherein the Hydrophilized porous membrane is preferably provided using the present invention
The preparation method of Hydrophilized porous membrane be prepared, the raw material for preparing of the Hydrophilized porous membrane includes high-molecular-weight poly second
Alkene, assistant crosslinking agent, hydrophilic polymer, the first solvent and the second solvent, wherein first solvent is for dissolving described help
Crosslinking agent, second solvent is for dissolving the hydrophilic polymer.
In one example, the polymeric acceptor includes High molecular weight polyethylene, wherein High molecular weight polyethylene can be
A kind of High molecular weight polyethylene can also be the mixture of two or more High molecular weight polyethylene, type difference example
Such as can be the ratio difference for the ingredient for constituting High molecular weight polyethylene, in a preferable example, the High molecular weight polyethylene
Density between 0.940g/cm3~0.966g/cm3Between, the average molecular weight of the High molecular weight polyethylene is 1.0 × 105
~5.0 × 106, namely when containing there are many when High molecular weight polyethylene, the average of preferably each High molecular weight polyethylene is divided
Son amount is within above-mentioned numberical range, in further preferred example, the density of the High molecular weight polyethylene between
0.950g/cm3~0.966g/cm3Between, the average molecular weight of the High molecular weight polyethylene is 1.0 × 105~2.0 × 106,
To further prepare the Hydrophilized porous membrane of good performance such as pure water flux, porosity.
As an example, count in parts by weight, and by the weight of the High molecular weight polyethylene it is based on 100 parts, it is described to help friendship
Join the weight of agent between 0.1~5 part, the weight of the hydrophilic polymer is between 0.1~5 part, first solvent and described
The weight of second solvent is between 800~1200 parts.
As an example, the raw material for preparing of the Hydrophilized porous membrane further includes at least one in pore former and antioxidant
Kind, wherein by the weight of the High molecular weight polyethylene be 100 parts based on, when containing the pore former, the weight of the pore former
Amount is between 100~500 parts, and when containing the antioxidant, the weight of the antioxidant is between 0.1~10 part.
As an example, when the polymeric acceptor includes the pore former, the pore former selected from crude mineral oils,
C6-15 alkane, C8-15 aliphatic carboxylic acids, C8-15 aliphatic carboxylic acid C1-4 alkyl esters, C2-6 halogenated alkanes, phthalic acid ester, inclined benzene
Three acid esters, adipate ester, sebacate, maleate, benzoic ether, epoxidized vegetable oil, benzsulfamide, phosphotriester, binary
At least one of alcohol ether, acetylated monoglyceride, citrate and hexamethylene -1,2- dicarboxylic acids dinonyls.
As an example, 40 DEG C of kinematic viscosity of the pore former are between 10mm2/ s~100mm2Between/s, it is preferably based on
20mm2/ s~80mm2Between/s, further preferably between 30mm2/ s~70mm2Between/s.
As an example, the initial boiling point of the pore former is not less than 110 DEG C.
As an example, when the polymeric acceptor includes the antioxidant, the antioxidant is thio selected from 4,4-
Bis- (6- tert-butyl-m-cresols), dibutyl hydroxy toluene, phosphite ester, tert-butylhydroquinone, β-(3,5- di-t-butyls -4-
Hydroxy phenyl) positive ten caprylate of propionic acid, 1,1,3- tri- (- 4 hydroxyl -5- 2-methyl-2-phenylpropanes base of 2- methyl) butane, 2- tertiary butyl -6- first
Base phenol, N, the double lauryls of N '-two-betanaphthyls p-phenylenediamine, thio-2 acid, (nonyl phenyl) ester of phosphorous acid three and phosphorous
At least one of triphenyl phosphate ester.
Specifically, in one example, during the polymeric acceptor is formed, also adding mineral oil, further, also wrapping
It includes addition pore former, antioxidant or both of pore former and antioxidant to add, it is preferable that when the polymeric acceptor
In when containing the pore former, pore former extraction is fallen during first time extraction or second extract.
As an example, in step 3), first solvent is selected from isopropanol, the mixture of isopropanol and methanol, ethyl alcohol
And at least one of normal propyl alcohol.
As an example, in step 3), the assistant crosslinking agent is selected from mercaptobenzothiazoler, benzothiazole disulfide, N- rings
Hexyl benzo thiazolesulfenamide, divinyl oxide base benzothiazole sulfenamide, tetramethylthiuram monosulfide, curing tetramethyl
Base thiuram, zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, diphenylguanidine, di-o-tolylguanidine, sub- second
Base thiocarbamide, N, N '-diethyl thioureas, hexa, zinc isopropyl xanthate, trimethylol propane trimethyl acrylic acid
At least one of ester, trimethylolpropane trimethacrylate, cyanuric acid tripropylene and Triallyl isocyanurate.
As an example, in step 4), the hydrophilic polymer is fine selected from carboxymethyl starch, acetic starch, methylol
It ties up element, carboxymethyl cellulose, polyacrylamide, hydrolyzed polyacrylamide, ethyl cellulose, polymaleic anhydride, polyacrylic acid, gather
Vinylpyrrolidone, polyvinyl alcohol, polyethylene glycol oxide, ethylene-vinyl alcohol copolymer, acrylic-ethylene alcohol copolymer, ethylene
Alcohol-vinyl acetate co-polymer, polyvinyl formal, polyvinyl acetal, polyvinyl formal acetal, polyvinyl alcohol contracting
At least one of the segmented polymer containing vinyl alcohol of butyraldehyde.
As an example, in step 4), second solvent is selected from isopropanol, the mixture of isopropanol and methanol, ethyl alcohol
And at least one of normal propyl alcohol.
Specifically, in this example, a kind of composition of the hydrophilic film is provided, by the weight of the High molecular weight polyethylene
Amount is 100 parts of meters, and the weight of the assistant crosslinking agent is preferably between 0.2~2 part, further preferably between 0.5~1 part；
The weight of the hydrophilic polymer is preferably between 0.5~3 part, further preferably between 1~2 part；First solvent
And the total weight of second solvent is preferably between 900~1100 parts, further preferably 1000 parts.
The assistant crosslinking agent plays connection perforated membrane matrix (membrane structure that preparation process obtains) and hydroaropic substance (institute
State hydrophilic polymer) effect.It is further the assistant crosslinking agent based on 100 parts by the weight of the High molecular weight polyethylene
Weight between 0.1~5 part, be preferably between 0.2~2 part, further preferably between 0.5~1 part, to control
The weight of the suitable assistant crosslinking agent so that the weight for adding the assistant crosslinking agent to improve connection effect, and makes pure water
Flux is obviously improved, and further prevents self-crosslinking plug-hole, helps to improve the improvement of pure water flux.
Preferably, first solvent is identical as the type of substance that second solvent selects, so that close
The overall performance of the stable preparation process of aqueous perforated membrane, finally obtained Hydrophilized porous membrane is stablized.
As an example, the micropore size of the Hydrophilized porous membrane is between 10nm~100nm, porosity is between 20%
Between~60%, surface contact angle is between 50 °~60 °, and pure water flux is between 1000L/m2H0.1MPa~2000L/
m2Between h0.1MPa.
Specifically, based on Hydrophilized porous membrane prepared by method provided by the invention, micropore size is preferably between 20nm
Between~60nm, porosity is preferably between 30%~50%, and surface contact angle is preferably between 52 °~58 °, and pure water is logical
Amount is between 1500L/m2H0.1MPa~1800L/m2Between h0.1MPa, perforated membrane is made to keep original aperture and hole
On the basis of gap rate, possess permanent hydrophilic surface layer, and is able to maintain that prodigious pure water flux.
The technique effect further illustrated the present invention with reference to specific example data, wherein hole in following each example
Rate automatically presses water instrument to measure using PMIAAQ-3K-A-1；Water instrument is automatically pressed to measure using PMIAAQ-3K-A-1 in aperture；It connects
Feeler is measured using Kruss DSA25 contact angle instruments；Pure water flux is measured using the Amicon ultrafiltration cups of Merck Mi Libo.
Embodiment 1：
It is 0.957g/cm by 100 grams of density3, average molecular weight is 5.0 × 105High molecular weight polyethylene, 0.5 gram of antioxygen
Agent, 250 grams of mineral oil are added in continuous batching coppers, are stirred with 50 revs/min of speed, raw material is uniformly mixed.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, the High molecular weight polyethylene, antioxidant
Continuous-dissolution is continuously squeezed out in mineral oil, then by double screw extruder with 200 revs/min of speed in double screw extruder, is mixed
It closes object to continuously enter in slot die, mixture is expressed into curtain coating chill roll by slot die, is cast under the conditions of 80 DEG C
Become band object.
Obtained ribbon is placed in the extraction tank containing dichloromethane and is extracted, to remove the mine in ribbon
Object oil.Biaxial orientation stretching machine will be continuously introduced under the conditions of 120 DEG C by the ribbon of extraction later and be drawn into film, then with two
Chloromethanes carries out reextraction to gained thin-film material, and gained film is cleaned with deionized water.Then heat is fixed under the conditions of 120 DEG C
Film after thermal finalization is placed in the 1000g solvents containing 0.1g assistant crosslinking agent Triallyl isocyanurates by type 15 minutes
Impregnate 1h, later again 50 DEG C drying 1h.Then film is again placed in containing 1.5g hydrophilic polymer polyvinylpyrrolidones
Solvent in impregnate 1h, later again 50 DEG C drying 1h.Low dosage gamma ray or electron beam irradiation then are carried out to gained film
Film after irradiation is wound with 50 ms/min of speed, finally obtains permanent hydrophilic porous film by processing, irradiation dose 5kGy.
Embodiment 2：
On the basis of keeping 1 other conditions of embodiment constant, assistant crosslinking agent is increased into 0.5g, it is finally obtained permanent
Hydrophilized porous membrane, performance are as follows：
| Porosity | 47% |
| Aperture | 0.045μm |
| Contact angle | 51° |
| Pure water flux | 1900L/m2·h·0.1MPa |
Embodiment 3
On the basis of keeping 1 other conditions of embodiment constant, assistant crosslinking agent is increased into 5g, finally obtained permanent parent
Aqueous perforated membrane, performance are as follows：
| Porosity | 42% |
| Aperture | 0.040μm |
| Contact angle | 60° |
| Pure water flux | 1000L/m2·h·0.1MPa |
Embodiment 4
It is 0.957g/cm by 100 grams of density3, average molecular weight is 5.0 × 105High molecular weight polyethylene, 0.5 gram of antioxygen
Agent, 250 grams of mineral oil are added in continuous batching coppers, are stirred with 50 revs/min of speed, raw material is uniformly mixed.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, the High molecular weight polyethylene, antioxidant
Continuous-dissolution is continuously squeezed out in mineral oil, then by double screw extruder with 200 revs/min of speed in double screw extruder, is mixed
It closes object to continuously enter in slot die, mixture is expressed into curtain coating chill roll by slot die, is cast under the conditions of 80 DEG C
Become band object.
Obtained ribbon is placed in the extraction tank containing dichloromethane and is extracted, to remove the mine in ribbon
Object oil.Biaxial orientation stretching machine will be continuously introduced under the conditions of 120 DEG C by the ribbon of extraction later and be drawn into film, then with two
Chloromethanes carries out reextraction to gained thin-film material, and gained film is cleaned with deionized water.Then heat is fixed under the conditions of 120 DEG C
Film after thermal finalization is placed in the 1000g solvents containing 0.5g assistant crosslinking agent Triallyl isocyanurates by type 15 minutes
Impregnate 1h, later again 50 DEG C drying 1h.Then film is again placed in containing 0.1g hydrophilic polymer polyvinylpyrrolidones
Solvent in impregnate 1h, later again 50 DEG C drying 1h.Low dosage gamma ray or electron beam irradiation then are carried out to gained film
Film after irradiation is wound with 50 ms/min of speed, finally obtains permanent hydrophilic porous film by processing, irradiation dose 5kGy.
| Porosity | 49% |
| Aperture | 0.048μm |
| Contact angle | 59° |
| Pure water flux | 1100L/m2·h·0.1MPa |
Embodiment 5：
On the basis of keeping 4 other conditions of embodiment constant, hydrophilic polymer is increased into 5g, it is finally obtained forever
Long Hydrophilized porous membrane, performance are as follows：
| Porosity | 46% |
| Aperture | 0.046μm |
| Contact angle | 50° |
| Pure water flux | 1500L/m2·h·0.1MPa |
Embodiment 6：
It is 0.957g/cm by 100 grams of density3, average molecular weight is 5.0 × 105High molecular weight polyethylene, 0.5 gram of antioxygen
Agent, 250 grams of mineral oil are added in continuous batching coppers, are stirred with 50 revs/min of speed, raw material is uniformly mixed.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, the High molecular weight polyethylene, antioxidant
Continuous-dissolution is continuously squeezed out in mineral oil, then by double screw extruder with 200 revs/min of speed in double screw extruder, is mixed
It closes object to continuously enter in slot die, mixture is expressed into curtain coating chill roll by slot die, is cast under the conditions of 80 DEG C
Become band object.
Obtained ribbon is placed in the extraction tank containing dichloromethane and is extracted, to remove the mine in ribbon
Object oil.Biaxial orientation stretching machine will be continuously introduced under the conditions of 120 DEG C by the ribbon of extraction later and be drawn into film, then with two
Chloromethanes carries out reextraction to gained thin-film material, and gained film is cleaned with deionized water.Then heat is fixed under the conditions of 120 DEG C
Film after thermal finalization is placed in the 1000g solvents containing 0.5g assistant crosslinking agent cyanuric acid tripropylenes and soaks by type 15 minutes
Steep 1h, later again 50 DEG C drying 1h.Then film is again placed in the solvent containing 1.5g hydrophilic polymer polyvinyl alcohol
Impregnate 1h, later again 50 DEG C drying 1h.Low dosage gamma ray then is carried out to gained film or electron beam irradiation is handled, irradiation
Film after irradiation is wound with 50 ms/min of speed, finally obtains permanent hydrophilic porous film by dosage 5kGy.
Embodiment 7：
On the basis of keeping 6 other conditions of embodiment constant, hydrophilic polymer is replaced with ethylene vinyl alcohol copolymer
Object, finally obtained permanent hydrophilic porous film, performance are as follows：
| Porosity | 51% |
| Aperture | 0.048μm |
| Contact angle | 50° |
| Pure water flux | 2000L/m2·h·0.1MPa |
Comparative example：
It is 0.957g/cm by 100 grams of density3, average molecular weight is 5.0 × 105High molecular weight polyethylene, 0.5 gram of antioxygen
Agent, 250 grams of mineral oil are added in continuous batching coppers, are stirred with 50 revs/min of speed, raw material is uniformly mixed.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, the High molecular weight polyethylene, antioxidant
Continuous-dissolution is continuously squeezed out in mineral oil, then by double screw extruder with 200 revs/min of speed in double screw extruder, is mixed
It closes object to continuously enter in slot die, mixture is expressed into curtain coating chill roll by slot die, is cast under the conditions of 80 DEG C
Become band object.
Obtained ribbon is placed in the extraction tank containing dichloromethane and is extracted, to remove the mine in ribbon
Object oil.Biaxial orientation stretching machine will be continuously introduced under the conditions of 120 DEG C by the ribbon of extraction later and be drawn into film, then with two
Chloromethanes carries out reextraction to gained thin-film material, and gained film is cleaned with deionized water.Then heat is fixed under the conditions of 120 DEG C
Obtained film is wound with 50 ms/min of speed, finally obtains perforated membrane by type 15 minutes.
| Porosity | 48% |
| Aperture | 0.048μm |
| Contact angle | 110° |
| Pure water flux | 100L/m2·h·0.1MPa |
It can be seen that compared with conventional porous membranes from the above experimental result, by the solvent soaking containing hydroaropic substance
Processed perforated membrane all there is extraordinary pure water flux to be connect with perforated membrane matrix more although hydroaropic substance is excessive
It is likely to cause plug-hole, to influence pure water flux, but still far better than conventional porous membranes.In addition, assistant crosslinking agent is being implemented
Play the role of connecting perforated membrane matrix and hydroaropic substance in example, less assistant crosslinking agent, connection effect is relatively poor, pure water
Flux improves unobvious；Assistant crosslinking agent is using more, it is possible to occur self-crosslinking and plug-hole, can equally influence changing for pure water flux
It is kind.
The technology contents and technical characterstic of the present invention have revealed that as above washing extraction polymer according to the present invention is isolated
The component of film is not limited to the different materials mentioned by the present invention, does not also limit several formulas mentioned by the present invention,
There is the material of similar characteristics and formula also to be covered by the present invention for he.However those skilled in the art is still potentially based on this
The announcement of invention and make various substitutions and modifications without departing substantially from spirit of that invention.Therefore, protection scope of the present invention is answered unlimited
It in the revealed content of embodiment, and should include the various substitutions and modifications without departing substantially from the present invention, and be the attached claims
Book is covered.
In conclusion a kind of hydrophilic film of present invention offer and preparation method thereof, preparation method includes：One polymerization is provided
Object, and it is prepared into curtain coating ribbon；The curtain coating ribbon is stretched membrane structure is prepared, and to described thin
Membrane structure carries out shaping processing；The membrane structure after sizing is placed in the first solvent containing assistant crosslinking agent
Reason；It previous step is obtained structure is placed in the second solvent containing hydrophilic polymer to handle；And previous step is obtained
Structure carry out radiation treatment, to prepare the Hydrophilized porous membrane, through the above technical solutions, the present invention provide it is a kind of hydrophilic
Property perforated membrane and preparation method, by the solvent soaking processing containing hydroaropic substance in its preparation process, meanwhile, preparing
Assistant crosslinking agent is used in the process, plays the role of connecting perforated membrane matrix and hydroaropic substance, it is hydrophilic so as to significantly improve
The characteristics such as the pure water flux of property perforated membrane.So the present invention effectively overcomes various shortcoming in the prior art and has height and produce
Industry utility value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (18)
1. a kind of preparation method of Hydrophilized porous membrane, which is characterized in that include the following steps：
1) polymeric acceptor is provided, and is prepared into curtain coating ribbon；
2) the curtain coating ribbon is stretched so that membrane structure is prepared, and processing is carried out shaping to the membrane structure；
3) membrane structure after sizing is placed in the first solvent containing assistant crosslinking agent and is handled；
4) it step 3) is obtained structure is placed in the second solvent containing hydrophilic polymer to handle；And
5) radiation treatment is carried out to the structure that step 4) obtains, to prepare the Hydrophilized porous membrane.
2. the preparation method of Hydrophilized porous membrane according to claim 1, which is characterized in that between step 1) and step 2)
Further include：The curtain coating ribbon is placed in progress first time extraction in extraction tank, to remove the mine in the curtain coating ribbon
Object oil.
3. the preparation method of Hydrophilized porous membrane according to claim 2, which is characterized in that in step 2), stretching
After to the membrane structure and before carrying out the sizing treatment, the membrane structure is carried out second in extraction tank
It extracts and the membrane structure obtained after being extracted to described second cleans.
4. the preparation method of Hydrophilized porous membrane according to claim 1, which is characterized in that in step 1), using curtain coating
Technique prepares to form the curtain coating ribbon, and the temperature of the casting technique is between 60 DEG C~100 DEG C；In step 2), into
The temperature of the row sizing treatment is between 100 DEG C~140 DEG C, and the time is between 10min~20min；In step 3)
The technique handled in first solvent includes impregnating, and soaking time is between 50min~80min；In step 4)
The technique handled in second solvent includes impregnating, and soaking time is between 50min~80min.
5. the preparation method of Hydrophilized porous membrane according to claim 1, which is characterized in that in step 5), using gamma
At least one of ray and electron beam carry out the radiation treatment, and the irradiation dose during the progress radiation treatment is not
Higher than 10kGy.
6. the preparation method of Hydrophilized porous membrane according to claim 1, which is characterized in that in step 1), the polymerization
Object includes at least one High molecular weight polyethylene, wherein the average molecular weight of the High molecular weight polyethylene between 1.0 ×
105~10.0 × 106Between, the density of the High molecular weight polyethylene is between 0.940g/cm3~0.976g/cm3Between.
7. the preparation method of Hydrophilized porous membrane according to claim 1, which is characterized in that in step 1), the polymerization
Object includes at least one of pore former and antioxidant.
8. the preparation method of Hydrophilized porous membrane according to claim 7, which is characterized in that when the polymeric acceptor includes
When the pore former, the pore former is selected from crude mineral oils, C6-15Alkane, C8-15Aliphatic carboxylic acid, C8-15Aliphatic carboxylic acid C1-4
Alkyl ester, C2-6Halogenated alkane, phthalic acid ester, trimellitate, adipate ester, sebacate, maleate, benzoic ether,
Epoxidized vegetable oil, benzsulfamide, phosphotriester, glycol ether, acetylated monoglyceride, citrate and hexamethylene -1,
At least one of 2- dicarboxylic acids dinonyls.
9. the preparation method of Hydrophilized porous membrane according to claim 8, which is characterized in that 40 DEG C of fortune of the pore former
Kinetic viscosity is between 10mm2/ s~100mm2Between/s；The initial boiling point of the pore former is not less than 110 DEG C.
10. the preparation method of Hydrophilized porous membrane according to claim 7, which is characterized in that when the polymeric acceptor packet
When including the antioxidant, the antioxidant selected from 4,4- thiobis (6- tert-butyl-m-cresols), dibutyl hydroxy toluene,
Phosphite ester, tert-butylhydroquinone, positive ten caprylate of β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid, 1,1,3- tri-
(- 4 hydroxyl -5- 2-methyl-2-phenylpropanes base of 2- methyl) butane, 2- tertiary butyl -6- methylphenols, N, it is N '-two-betanaphthyls p-phenylenediamine, thio
Dipropionic acid double lauryl, phosphorous acid three (nonyl phenyl) at least one of esters and triphenyl phosphite.
11. the preparation method of Hydrophilized porous membrane according to claim 1, which is characterized in that described to help friendship in step 3)
Join agent selected from mercaptobenzothiazoler, benzothiazole disulfide, N- cyclohexylbenzothiazoles sulfenamide, divinyl oxide base benzo
Thiazolesulfenamide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, zinc dimethyl dithiocarbamate, two
Zinc diethyl dithiocarbamate, diphenylguanidine, di-o-tolylguanidine, ethylene thiourea, N, N '-diethyl thioureas, hexa-methylene four
Amine, zinc isopropyl xanthate, trimethylol-propane trimethacrylate, trimethylolpropane trimethacrylate, cyanuric acid
At least one of three acrylic esters and Triallyl isocyanurate.
12. the preparation method of Hydrophilized porous membrane according to claim 1, which is characterized in that described hydrophilic in step 4)
Property polymer it is poly- selected from carboxymethyl starch, acetic starch, hydroxymethyl cellulose, carboxymethyl cellulose, polyacrylamide, hydrolysis
Acrylamide, ethyl cellulose, polymaleic anhydride, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol oxide, second
Alkene-ethenol copolymer, vinyl alcohol-vinyl acetate copolymer, polyvinyl formal, gathers acrylic-ethylene alcohol copolymer
At least one of the segmented polymer containing vinyl alcohol of vinyl acetal, polyvinyl formal acetal, polyvinyl butyral.
13. the preparation method of Hydrophilized porous membrane according to claim 1, which is characterized in that in step 3), described first
Solvent is selected from least one of isopropanol, the mixture of isopropanol and methanol, ethyl alcohol and normal propyl alcohol；In step 4), institute
The second solvent is stated selected from least one of isopropanol, the mixture of isopropanol and methanol, ethyl alcohol and normal propyl alcohol.
14. the preparation method of the Hydrophilized porous membrane according to any one of claim 1~13, which is characterized in that institute
State in polymeric acceptor include High molecular weight polyethylene, and by the weight of the High molecular weight polyethylene be 100 parts based on, it is described to help friendship
Join the weight of agent between 0.1~5 part, for the weight of the hydrophilic polymer between 0.1~5 part, described first is molten
The total weight of agent and second solvent is between 800~1200 parts.
15. the preparation method of Hydrophilized porous membrane according to claim 14, which is characterized in that step 5) obtains described
The micropore size of Hydrophilized porous membrane is between 10nm~100nm, and porosity is between 20%~60%, surface contact angle
Between 50 °~60 °, pure water flux is between 1000L/m2H0.1MPa~2000L/m2Between h0.1MPa.
16. a kind of Hydrophilized porous membrane, which is characterized in that the raw material for preparing of the Hydrophilized porous membrane includes high-molecular-weight poly second
Alkene, assistant crosslinking agent, hydrophilic polymer, the first solvent and the second solvent, wherein first solvent is for dissolving described help
Crosslinking agent, second solvent is for dissolving the hydrophilic polymer.
17. Hydrophilized porous membrane according to claim 16, which is characterized in that count in parts by weight, and press the high score
The weight of sub- weight northylen is 100 parts of meters, and the weight of the assistant crosslinking agent is between 0.1~5 part, the weight of the hydrophilic polymer
Amount is between 0.1~5 part, and the total weight of first solvent and second solvent is between 800~1200 parts.
18. the Hydrophilized porous membrane according to any one of claim 16~17, which is characterized in that the hydrophily is more
The raw material for preparing of pore membrane further includes at least one of pore former and antioxidant, wherein by the High molecular weight polyethylene
Weight is 100 parts of meters, and when containing the pore former, the weight of the pore former is between 100~500 parts, when containing described anti-
When oxidant, the weight of the antioxidant is between 0.1~10 part.
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