CN100544809C - A kind of polyvinylidene fluoride film hydrophilically modified method - Google Patents
A kind of polyvinylidene fluoride film hydrophilically modified method Download PDFInfo
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- CN100544809C CN100544809C CNB200710058333XA CN200710058333A CN100544809C CN 100544809 C CN100544809 C CN 100544809C CN B200710058333X A CNB200710058333X A CN B200710058333XA CN 200710058333 A CN200710058333 A CN 200710058333A CN 100544809 C CN100544809 C CN 100544809C
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Abstract
The present invention relates to a kind of polyvinylidene fluoride film hydrophilically modified method, its technology is: prepare casting solution: press following mass concentration formulation blended liquid: Kynoar 10-18% 1.; Polyvinyl alcohol 2-10%; Dimethyl sulfoxide (DMSO) 80% places 98 ℃ of water-baths with described blended liquid, stirs after 6 hours, and standing and defoaming promptly obtains even casting solution; 2. preparation film: described casting solution behind striking flat sheet membrane or wet method spinning hollow-fibre membrane under the room temperature, is immersed in the coagulating bath immediately, keep the 24h solidified forming; Described coagulating bath is that water, mass concentration are a kind of in 20% ethanol water or the 5mol/L sodium-chloride water solution; After the film that is shaped washed with clear water, being immersed in mass concentration again was 12h in 60% glycerine water solution, takes out air dry in air, promptly can be made into hydrophily good polyvinylidene fluoride flat film or hollow-fibre membrane.
Description
Technical field
The present invention relates to a kind of modification technology of film product, be specially a kind of method that is intended to improve polyvinylidene fluoride film hydrophilically, international Patent classificating number intends being Int.Cl.C08J7/12 (2006.01) I.
Background technology
Kynoar is a kind of semicrystalline polymer.Because its C-F bond distance is short, bond energy strong (486kJ/mol) is so heat-resisting, corrosion-resistant, radiation hardness and intensity height, good toughness are the preferred materials of preparation film.Yet its strong-hydrophobicity can cause two problems: the one, and separation process needs bigger driving force; The 2nd, be easy to generate absorption and pollute, make two of membrane flux and rejection mainly separate index and descend, shorten the service life of film, restricted its application in aqueous phase systems such as biochemical pharmacy, food and drink and water body purification.Therefore, the hydrophilic modification of polyvinylidene fluoride film has important and practical meanings.
During the preparation hydrophilic high molecular material, can adopt following three kinds of methods: (1). the little molecule that will have hydrophilic radical obtains hydrophilic macromolecule through polymerisation; (2). the high polymer skeleton that does not contain hydrophilic radical is carried out the hydrophiling reaction, macromolecular chain is hung go up hydrophilic radical; (3). common high molecular materials is carried out physical modification, make its possess hydrophilic property.Relatively Chang Yong hydrophilic modification method has surface modification, blend, grafting, copolymerization and crosslinked etc.Above three kinds of methods, first kind implements difficulty the most, because it will progressively obtain end product through the complicated organic synthesis and the polymerisation of monomer, may also need the protection of functional group to conciliate the protection process therebetween; Though second method implements more easily than first method, but high molecular hydrophiling reaction also exists many insoluble technical problems, and the functional material that this method obtains exists the functional group skewness, do not reach the defective of theoretical content; And described the third method still all is easier to realize in research on commercial Application than preceding two kinds of methods.
Many researchs all show, blend system film be a kind of on the current material basis, learn from other's strong points to offset one's weaknesses improve the short-cut method of film properties.With a kind of polymer and other polyblend, performance that can each polymers compositions of aggregative equilibrium, learn from other's strong points to offset one's weaknesses, eliminate the weakness on each single polymers component property, and, can also improve the processing characteristics of polymer by blend, to the remarkable but expensive engineering plastics of some performance, not influencing under the instructions for use condition, can reduce the cost of raw material by blend.Prepare membrane material co-mixing system commonly used at Kynoar at present and Kynoar/polymethyl methacrylate is arranged (referring to S.P.Nunes, Deng, the PVDF/PMMA blended ultrafiltration membrane, membrane science magazine .73 (1992) 25), Kynoar/polyacrylonitrile (is illustrated in will brightness etc., the research of Kynoar/polyacrylonitrile blended milipore filter, membrane science and technology .20 (2000) 10), Kynoar/SPSF is (referring to grandson's drench green grass or young crops etc., doing of Kynoar polysulfones comixing compatibility and milipore filter research, membrane science and technology .21 (2001) 1) and Kynoar/polyvinyl acetate (referring to F.M.Ksei etc., the method .US Patent4 for preparing perforated membrane, 772,440,1998) etc.Above-mentioned technical literature is only simple from the effect of hydrophilic angle discussion to film properties, and has ignored the influence of interface pore structure to film properties.
Polyvinyl alcohol is a kind of good hydrophilicity polymer, and it as blend components, is used to improve the interface pore structure of polyvinylidene fluoride film, and combines the report of research with hydrophilic modifying, does not see as yet so far.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is, a kind of polyvinylidene fluoride film hydrophilically modified method is provided, this method adopts the wet method phase inversion to prepare Kynoar/polyvinyl alcohol binary blend film, can improve the hydrophily of polyvinylidene fluoride film effectively, utilizes polyblend interface phase separation principle to enrich the pore structure of film simultaneously, and it is simple to have technology, appointed condition is not had specific (special) requirements, and cost is lower, is convenient to the characteristics of industrial applications.
The technical scheme that the present invention solve the technical problem is: design a kind of polyvinylidene fluoride film hydrophilically modified method, its technology is as follows:
1. preparation casting solution: by following mass concentration formulation blended liquid:
Kynoar 10-18%;
Polyvinyl alcohol 2-10%
Dimethyl sulfoxide (DMSO) 80%,
Described blended liquid is placed 98 ℃ of water-baths, stir after 6 hours, standing and defoaming promptly obtains even casting solution;
2. preparation film: described casting solution behind striking flat sheet membrane or wet method spinning hollow-fibre membrane under the room temperature, is immersed in the coagulating bath immediately, keep the 24h solidified forming; Described coagulating bath is that water, mass concentration are a kind of in 20% ethanol water or the 5mol/L sodium-chloride water solution; After the film that is shaped washed with clear water, being immersed in mass concentration again was 12h in 60% glycerine water solution, takes out air dry in air, promptly can be made into hydrophily good polyvinylidene fluoride flat film or hollow-fibre membrane.
Compared with prior art, the inventive method combines hydrophilic modifying first with the interface pore structure, study its influence to the film hydrophilicity, not only can improve the hydrophily of polyvinylidene fluoride film effectively, also utilize the interface phase separation principle to enrich the pore structure of film, and technology is simple, and appointed condition is not had specific (special) requirements, cost is lower, is convenient to industrial applications.
The specific embodiment
The present invention is further elaborated below in conjunction with specific embodiment:
The present invention designs a kind of polyvinylidene fluoride film hydrophilically modified method (hereinafter to be referred as method), and its technology is as follows:
1. preparation casting solution: by following mass concentration formulation blended liquid:
Kynoar 10-18%;
Polyvinyl alcohol 2-10%;
Dimethyl sulfoxide (DMSO) 80%,
Described blended liquid is placed 98 ℃ of water-baths, stir after 6 hours, standing and defoaming promptly obtains even casting solution;
2. preparation film: described casting solution behind striking flat sheet membrane or wet method spinning doughnut under the room temperature, is immersed in the coagulating bath immediately, keep the 24h solidified forming; Described coagulating bath is that water, mass concentration are a kind of in 20% ethanol water or the 5mol/L sodium-chloride water solution; After the film that is shaped washed with clear water, being immersed in mass concentration again was 12h in 60% glycerine water solution, takes out air dry in air, promptly can be made into hydrophily good polyvinylidene fluoride flat film or hollow-fibre membrane.
The basal lamina material of the described film of the inventive method or matrix phase are Kynoar.
Polyvinylidene fluoride film of the present invention comprises flat sheet membrane and hollow-fibre membrane.Key technology of the method for its hydrophilic modifying is the blend with it of a kind of hydroaropic substance of choose reasonable.It is selected according to being: be that non-thermodynamic compatibility or part are compatible with the matrix phase Kynoar 1.; 2. with polyvinylidene blending after, casting solution has good film or fiberizing and processing characteristics; 3. final gained film there are not physics damage or chemical damage.In view of the above, the blend components of film of the present invention has been selected and Kynoar part perhaps inconsistent mutually hydroaropic substance---polyvinyl alcohol.Test shows that in the prescription of the present invention, within the specific limits, with the increase of polyvinyl alcohol content, the water flux of gained blend film increases afterwards earlier and reduces, and the ovalbumin rejection is then reduced afterwards raising earlier.Studies show that, though the polyvinyl alcohol mass concentration proportioning in described blended liquid can be 2-10%, preferred 3-5%, effect is more satisfactory.
For further increasing the flux of film, perhaps for satisfying the requirement of different purposes, the further feature of the inventive method is to add the 3rd component or additive in described blended liquid prescription.The 3rd components selection of the present invention is according to being: after 1. preparing the blend casting solution with described Kynoar/polyvinyl alcohol, should have good film or fiberizing and processing characteristics; 2. after film forming, can be removed, make film form loose structure; 3. the final molding film there are not physics damage and chemical damage.The 3rd component described in the blended liquid prescription of the present invention or additive are Macrogol 600.After adding the 3rd component, the mass concentration prescription of described blended liquid is adjusted into:
Kynoar 10-18%;
Polyvinyl alcohol 2-10%;
Macrogol 600 3-15%
Dimethyl sulfoxide (DMSO) 65-77%,
Although the mass concentration proportioning of additive is 3-15% in the described blended liquid, general preferred 3-10%, too high additive mass concentration proportioning will influence the viscosity of casting solution.
Need explanation to be, although can add described additive in the prescription of the present invention to increase the water flux of gained film, it is nonessential.The present invention can not add any other component fully in film-forming process, can solve technical problem to be solved by this invention.
The inventive method has been investigated the influence to the film hydrophilicity of process conditions such as Kynoar/polyvinyl alcohol blending ratio, solid content, additive concentration, curing condition and post processing or parameter.Studies show that, during the following design of the mass concentration of described blended liquid prescription, prepared film combination property is more satisfactory: the mass ratio of Kynoar/polyvinyl alcohol is 80/20, the mass concentration proportioning is 20%, Macrogol 600 mass concentration proportioning is 6%, dimethyl sulfoxide (DMSO) mass concentration proportioning is 74%, and coagulating bath is 20 ℃ a water.Research also shows, prepared film is with 40 ℃ water treatment 10min, and its rejection obviously improves, and handles 180min with alcohol, and its water flux obviously increases, and rejection is constant substantially.
The further feature of the inventive method is that the employing glass plate is a supporter in preparation or striking flat sheet membrane process.Because have strong interaction between polyvinyl alcohol and the glass, therefore, the upper and lower surface of the flat sheet membrane of formation has hydrophilic otherness.Test shows, adopts the hydrophily of the blend flat sheet membrane lower surface of this method preparation to be better than its upper surface.
The inventive method adopts the wet method phase inversion to prepare Kynoar/polyvinyl alcohol binary blend film, Kynoar and polyvinyl alcohol blending, can balanced both performances, learn from other's strong points to offset one's weaknesses, eliminate the weakness of Kynoar hydrophily difference, and reduce the cost of raw material not influencing under the instructions for use condition; Utilizing Kynoar/polyvinyl alcohol simultaneously is incompatible system, the interface takes place after the blend be separated and form the hole, interface.The inventive method combines with the interface pore structure film hydrophilically modified first, study its influence to film properties, and it is simple to have technology, and appointed condition is not had specific (special) requirements, is convenient to characteristics such as industrial applications.
Provide specific embodiments of the invention below, but specific embodiment does not limit the present invention.
Embodiment 1:
Be Kynoar/polyvinyl alcohol of 20% with the mass concentration proportioning with the mass concentration proportioning be that 80% dimethyl sulfoxide (DMSO) mixes; Said mixture is placed 98 ℃ of water-baths, stir after 6 hours, standing and defoaming obtains even casting solution; With casting solution under the room temperature with glass plate striking flat sheet membrane after, immersing 20 ℃, mass concentration immediately is solidified forming in 20% alcohol water blend; After treating that film comes off voluntarily, take out glass plate, film remains on 24h in the coagulating bath; Flat sheet membrane after the shaping is with after the clear water flushing, is immersed in mass concentration and is in 60% glycerine water solution behind the 12h, takes out air dry in air, promptly can be made into the PVDF flat sheet membrane with excellent hydrophilic.
The mass ratio of the described Kynoar/polyvinyl alcohol of said method is respectively 100/0,90/10, and 80/20,70/30,50/50,0/100, the flat sheet membrane of institute's striking is measured its water flux respectively and to the ovalbumin rejection under 20 ℃, 0.1Mpa, resultant water flux (mLcm
-2H
-1) analog value is respectively 0.61,1.88,4.13,2.62,0.22,0.10; Ovalbumin rejection (%) analog value is respectively 83.8,72.6,63.3,70.74,87.1,91.2 (%).The result shows that the mass ratio of Kynoar/polyvinyl alcohol flat sheet membrane is at 80/20 o'clock, and the combination property of film is better.
Further measure polyvinylidene fluoride flat film and Kynoar/polyvinyl alcohol mass ratio respectively and be 80/20 flat sheet membrane antifouling property, obtain its resistance enhancement coefficient (%) and be respectively 42.42,22.78 ovalbumin.The result shows, the Kynoar after the modification, and its resistance tocrocking obviously improves.
Embodiment 2:
Prepare casting solution by embodiment 1 described method; After using glass plate striking flat sheet membrane under the room temperature, place 20 ℃ of air sets to be shaped casting solution, adopt solvent evaporated method system film, can avoid the influence of surface micropore contact angle; Be dipped in after the shaping in the clear water, treat that film comes off voluntarily after, take out glass plate, film remains on 24h in the clear water; Take out air dry in air.Measuring Kynoar/polyvinyl alcohol mass ratio respectively is 100/0,90/10,80/20,70/30, the upper surface of 50/50,0/100 made flat sheet membrane and lower surface contact angle, resultant film upper surface contact angle (°) analog value is respectively 98.2,96.8,92.1,71.2,67.3,38.7; Film lower surface contact angle (°) analog value is respectively 98.2,79.1,77.8,48.3,58.0,38.7.The result shows that the mass ratio of Kynoar/polyvinyl alcohol is at 80/20 o'clock, and contact angle is less, and hydrophily is better, and there is difference in the upper and lower surface contact angle of film, therefore has lamination.
Embodiment 3:
Be Kynoar/polyvinyl alcohol (mass ratio 80/20) of 20% with the mass concentration proportioning with mass concentration be that 80% dimethyl sulfoxide (DMSO) mixes; Said mixture is immersed solidified forming in the following coagulating bath after by embodiment 1 method mixing, deaeration and knifing immediately; After treating that film comes off voluntarily, take out glass plate, film remains on 24h in the coagulating bath; Film after the shaping is made dry film by embodiment 1 method.Described coagulating bath is respectively 20 ℃ water, and 20 ℃, mass concentration are 20% alcohol water blend and 20 ℃, the 5mol/LNaCl aqueous solution.In three kinds of coagulating baths made flat sheet membrane under 20 ℃, 0.1Mpa, measure respectively its water flux with to the ovalbumin rejection, can obtain water flux (mLcm
-2H
-1) analog value is respectively 2.67,4.13,2.45; Ovalbumin rejection (%) analog value is respectively 80.0,63.3,81.0 (%).The result shows, selects for use 20 ℃ water to do coagulating bath, and the combination property of film is better.
Embodiment 4:
To solidify bath water temperature (℃) be designed to 0,20,40 and 60, surplus with embodiment 3, made flat sheet membrane under 20 ℃, 0.1Mpa, measure respectively its water flux with to the ovalbumin rejection, obtain water flux (mLcm
-2H
-1) analog value is respectively 0.63,2.67,3.54 and 8.75; Ovalbumin rejection (%) analog value is respectively 87.8,80.0,50.9 and 22.1.The result shows, selects for use 20 ℃ water to do coagulating bath, and the combination property of film is better.
Embodiment 5:
After making film according to the method for embodiment 3, under following temperature film is heat-treated, the processing time is 10min.Described heat treated temperature (℃) be respectively 20,40,50,60 and 80, the corresponding prepared flat sheet membrane of different temperatures under 20 ℃, 0.1Mpa, measure respectively its water flux with to the ovalbumin rejection, obtain water flux (mLcm
-2H
-1) analog value is respectively 2.67,1.98,1.91,1.87 and 3.27; Ovalbumin rejection (%) analog value is respectively 80.0,84.2,85.0,85.2 and 65.2.The result shows that heat treatment can make membrane structure densified, with film with 40 ℃ water treatment 10min after, its rejection obviously improves, and 80 ℃ water treatment makes the membrane structure instability.
Embodiment 6:
After making film according to embodiment 3 described methods, at room temperature film is carried out alcohol and handle.The alcohol processing time (min) is 0,30,60,120,180 and 300, the flat sheet membrane of different disposal time gained under 20 ℃, 0.1Mpa, measure respectively its water flux with to the ovalbumin rejection, obtain water flux (mLcm
-2H
-1) analog value is respectively 2.67,2.93,3.00,3.27,3.28 and 3.30; Ovalbumin rejection (%) analog value is respectively 80.0,80.2,80.1,80.9,81.2 and 80.3.The result shows that alcohol is handled water flux is obviously improved, but does not influence rejection, and the alcohol processing time, water flux improved bigger when being 180min.
Embodiment 7:
With the mass concentration proportioning is the Kynoar/polyvinyl alcohol (mass ratio 80/20) of 15,20 and 25 (%), and the mass concentration proportioning is 6% Macrogol 600, and the mass concentration proportioning is that 79,74 and 69 (%) dimethyl sulfoxide (DMSO) mixes; With said mixture by example 1 method mixing, deaeration and make dry film.With Kynoar/polyvinyl alcohol mass concentration be the flat sheet membrane of 15,20,25 (%) under 20 ℃, 0.1Mpa, measure respectively its water flux with to the ovalbumin rejection, obtain water flux (mLcm
-2H
-1) analog value is respectively 7.09,4.57,0.76; Ovalbumin rejection (%) analog value is respectively 30.2,68.5,79.7.The result shows, the mass ratio of Kynoar/polyvinyl alcohol is 80/20, the mass concentration proportioning is 20% o'clock, and the combination property of film is better.
Embodiment 8:
With the mass concentration proportioning is Kynoar/polyvinyl alcohol (mass ratio 80/20) of 20%, and the mass concentration proportioning is 0,3,6,10, the Macrogol 600 of 15 (%), and the mass concentration proportioning is that the dimethyl sulfoxide (DMSO) of 80,77,74,70 and 65 (%) mixes; With said mixture by example 1 method mixing, deaeration and make dry film.With Macrogol 600 mass concentration proportioning is 0,3,6,10, the flat sheet membrane of 15 (%) under 20 ℃, 0.1Mpa, measure respectively its water flux with to the ovalbumin rejection, obtain water flux (mLcm
-2H
-1) analog value is respectively 2.67,2.93,4.57,3.68,1.27; Ovalbumin rejection (%) analog value is respectively 80.0,78.2,68.5,73.77,83.11.The result shows that the 3rd component Macrogol 600 mass concentration proportioning is at 6% o'clock, and the combination property of film is better.
Embodiment 9:
With the mass concentration proportioning is Kynoar/polyvinyl alcohol of 20%, and the mass concentration proportioning is 6% polyvinylidene alcohol 600, and the mass concentration proportioning is that 74% dimethyl sulfoxide (DMSO) mixes; Said mixture is placed 98 ℃ of water-baths, stirred 12 hours; Casting solution is added the wet spinning autoclave pressure, after the vacuum defoamation, carry out wet method spinning doughnut, spinning temperature all is controlled at 78 ℃, and coagulating bath is 20 ℃ of water.Kynoar/polyvinyl alcohol mass ratio is respectively 100/0,90/10,80/20,70/30 prepared hollow-fibre membrane under 20 ℃, 0.1Mpa, measure respectively its water flux with to the ovalbumin rejection, obtain water flux (mLcm
-2H
-1) analog value is respectively 2.78,3.67,12.76,7.78; Ovalbumin rejection (%) analog value is respectively 80.4,71.3,54.2,55.8.The result shows, the mass ratio of Kynoar/polyvinyl alcohol is 80/20, the polymer quality concentration proportioning is 20% o'clock, and the combination property of gained hollow-fibre membrane is better.
Claims (7)
1. polyvinylidene fluoride film hydrophilically modified method, its technology is as follows:
(1). preparation casting solution: press following mass concentration formulation blended liquid:
Kynoar 10-18%;
Polyvinyl alcohol 2-10%;
Dimethyl sulfoxide (DMSO) 80%,
Above-mentioned blended liquid is placed 98 ℃ of water-baths, stir after 6 hours, standing and defoaming promptly obtains even casting solution;
(2). preparation film: described casting solution behind striking flat sheet membrane or wet method spinning hollow-fibre membrane under the room temperature, is immersed in the coagulating bath immediately, keep the 24h solidified forming; Described coagulating bath is that water, mass concentration are a kind of in 20% ethanol water or the 5mol/L sodium-chloride water solution; After the film that is shaped washed with clear water, being immersed in mass concentration again was 12h in 60% glycerine water solution, takes out air dry in air, promptly can be made into hydrophily good polyvinylidene fluoride flat film or hollow-fibre membrane.
2. polyvinylidene fluoride film hydrophilically modified method, its technology is as follows:
(1). preparation casting solution: press following mass concentration formulation blended liquid:
Kynoar 10-18%;
Polyvinyl alcohol 2-10%;
Macrogol 600 3-15%;
Dimethyl sulfoxide (DMSO) 65-77%,
(2). preparation film: described casting solution behind striking flat sheet membrane or wet method spinning hollow-fibre membrane under the room temperature, is immersed in the coagulating bath immediately, keep the 24h solidified forming; Described coagulating bath is that water, mass concentration are a kind of in 20% ethanol water or the 5mol/L sodium-chloride water solution; After the film that is shaped washed with clear water, being immersed in mass concentration again was 12h in 60% glycerine water solution, takes out air dry in air, promptly can be made into hydrophily good polyvinylidene fluoride flat film or hollow-fibre membrane.
3. polyvinylidene fluoride film hydrophilically modified method according to claim 2 is characterized in that the Macrogol 600 mass concentration proportioning in the described blended liquid is 3-10%.
4. polyvinylidene fluoride film hydrophilically modified method according to claim 2, the mass concentration prescription that it is characterized in that described blended liquid is: the concentration proportioning of Kynoar and polyvinyl alcohol quality is 20%, wherein the mass ratio of Kynoar/polyvinyl alcohol is 80/20, Macrogol 600 mass concentration proportioning is 6%, and dimethyl sulfoxide (DMSO) mass concentration proportioning is 74%; Described coagulating bath is 20 ℃ a water.
5. according to each described polyvinylidene fluoride film hydrophilically modified method among the claim 1-4, it is characterized in that prepared polyvinylidene fluoride flat film or hollow-fibre membrane with 40 ℃ water treatment 10min, or handle 180min with alcohol.
6. according to each described polyvinylidene fluoride film hydrophilically modified method among the claim 1-4, it is characterized in that in striking flat sheet membrane process, the employing glass plate is a supporter.
7. polyvinylidene fluoride film hydrophilically modified method according to claim 5 is characterized in that in striking flat sheet membrane process, the employing glass plate is a supporter.
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| CN103127841A (en) * | 2011-11-28 | 2013-06-05 | 中化蓝天集团有限公司 | Polyvinylidene fluoride hydrophilic modified membrane and preparation method thereof |
| CN102600733B (en) * | 2012-03-28 | 2014-03-19 | 天津工业大学 | Preparation method for homogeneously-enhanced polyvinylidene fluoride hollow fiber membrane |
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| CN102872732A (en) * | 2012-10-22 | 2013-01-16 | 浙江理工大学 | Hydrophilic modification method for polytetrafluoroethylene microporous material |
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| CN105327624A (en) * | 2015-11-30 | 2016-02-17 | 上海应用技术学院 | Preparation method of modified polyvinylidene fluoride-polyvinyl alcohol binary composite ultrafiltration membrane |
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