CN104289118A - In situ polymerization method for controlling polyvinylidene fluoride ultrafiltration membrane structure - Google Patents
In situ polymerization method for controlling polyvinylidene fluoride ultrafiltration membrane structure Download PDFInfo
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- CN104289118A CN104289118A CN201310302895.XA CN201310302895A CN104289118A CN 104289118 A CN104289118 A CN 104289118A CN 201310302895 A CN201310302895 A CN 201310302895A CN 104289118 A CN104289118 A CN 104289118A
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Abstract
The invention relates to an in situ polymerization method for controlling a polyvinylidene fluoride ultrafiltration membrane structure. The method of the invention has the advantages of environmental-friendliness, mild reaction conditions, simple preparation method and one-step preparation modification and preparation. The prepared PVDF membrane does not require further modification, has good repeatability, and is not limited to the form of the ultrafiltration membrane; and no additional pore forming agent is needed to obtain the hydrophilic polyvinylidene fluoride ultrafiltration membrane with narrow pore size distribution.
Description
[technical field]
The invention belongs to technical field of membrane separation, relate to the method for a kind of in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure.
[background technology]
Kynoar (PVDF) is as a kind of membrane material of comprehensive function admirable, because of chemical stability, heat endurance, mechanical property and dielectric properties that it is outstanding, receive increasing concern, be with a wide range of applications in UF membrane field.Although membrane science worker is devoted to prepare the pvdf membrane with high flux, very good mechanical properties always, the strong-hydrophobicity of pvdf membrane limits its application in seawater cleaning, production, sanitary wastewater process etc.Therefore, by hydrophilic modifying, increase water flux, reduce the fouling membrane that organic matter, protein etc. cause, prolonging service lifetime of film seems very necessary.Wherein, surface hydrophilic modification and blending and modifying are two kinds of methods commonly used the most.The surface modification of, complicated operation, modification result poor stability high compared to cost, blending and modifying is more practical and convenient, is not limited to form membrane, and do not need pretreatment or post processing (Hester, J.F., Mayes, A.M., J.Membr.Sci.202,119-135; Hashim, N.A., Liu, F., Li, K., J.Membr.Sci.2002.345,134-141; Shi, F., Ma, Y., Ma, J., Wang, P., Sun, W., J.Membr.Sci.2013,427,259-269; Chinese patent " a kind of method of in-situ polymerization modification of polyvinylidene fluoride microporous membrane ", publication number: CN102553465A) in recent years, one of study hotspot of pvdf membrane surface modification realizes the pore of film, modification and structure regulating with the amphipathic copolymer of oneself synthesis.Simultaneously amphipathic polymer has hydrophilic and particular molecule that is hydrophobic chain, can be self-assembled into various structure (Ping-Yun Zhang, Hu Yang, Zhen-Liang Xu.Ind.Eng.Chem.Res.2012,51,4388-4396 in polar solvent; Hester, J.F., Banerjee, P., Mayes, A.M., Macromolecules, 1999,32,1643-1650).Although amphipathic polymer and polymeric matrix have good compatibility, but its preparation process is comparatively loaded down with trivial details, often need chemical reaction through complexity as ATRP (ATRP) (Hashim, N.A., Liu, F., Li, K., J.Membr.Sci.2004,345,134-141; Hussain, H., Tan, B.H., Gudipati, C.S., He, C.B., Liu, Y., Davis, T.P., 2009.Langmuir25,5557-5564) further, because the general molecular weight of amphipathic polymer of synthesis is larger, its meeting is in organic solvent tangled mutually with polymer chain, thus forms large-sized amphipathic polymer-polymer aggregation.These large-sized macromolecular limit the pore of amphipathic polymer in PVDF film forming procedure, modifying function (Ping-Yun Zhang, Zhen-Liang Xu, Hu Yang, Yong-Ming Wei, Wen-Zhi Wu, Desalination, 2013; Ping-Yun Zhang, Zhen-Liang Xu, Hu Yang, Yong-Ming Wei, Wen-Zhi Wu, Chem.Eng.Sci, 2013).Even the simple blend method of report, large-sized micella (size: 10 ~ 100 nanometers) that amphipathic polymer and polymer self assembles are formed and nanometer spherical (100 ~ 200nm), make amphipathic polymer to the obtained flux of PVDF ultrafiltration membrane and the limited use of improved strength.
[summary of the invention]
The object of this invention is to provide the method for a kind of in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure, to improve stain resistance, the separative efficiency of diffusion barrier and to increase the service life.
A method for in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure, concrete steps are:
(1) be dissolved in triethyl phosphate TEP by monomer 1 and monomer 2, stir and make it dissolve completely, make monomer mixture solution, the ratio of monomer 1 and the amount of substance of monomer 2 in TEP is 5: 1 ~ 1: 5;
Described monomer 1 and monomer 2 are the one in methyl methacrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, or methyl methacrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, acrylic acid, polyethylene glycol methyl methacrylate, multiple mixture in poly glycol monomethyl ether methyl methacrylate, at least comprise in methyl methacrylate, hydroxy propyl methacrylate, poly glycol monomethyl ether methyl methacrylate in mixture one or both;
Described monomer 1 is methyl methacrylate;
Described monomer 2 is hydroxy propyl methacrylate;
As preferably, the ratio of monomer 1 and the amount of substance of monomer 2 in TEP is 4: 1 ~ 1: 4;
(2) by Kynoar, monomer dissolved mixture in the mixed solvent of triethyl phosphate TEP and DMA DMAc, in 50 ~ 100 DEG C of baking ovens, place 1 ~ 15 hour, make casting solution precursor solution; In film forming precursor solution, the mass percent of Kynoar is 10 ~ 30%, and the triethyl phosphate TEP in mixed solvent and DMA DMAc mass ratio are 10: 1 ~ 1: 10;
As preferably, oven temperature is 40 ~ 80 DEG C, places 6 ~ 12 hours; TEP and DMAc mass content ratio in mixed solvent is 9: 1 ~ 1: 9;
(3) when casting solution precursor solution is cooled to room temperature, add initator, magnetic agitation is after 1 ~ 6 hour, and by casting solution as 50 ~ 90 DEG C of baking oven situ reactions 1 ~ 8 hour, deaeration under room temperature, obtains casting solution; The added quality of initator and the mass ratio of film forming precursor solution are 0.001: 1 ~ 0.100: 1;
As preferably, initator used is the one in benzoyl peroxide (BPO), isopropyl benzene hydroperoxide (CHPO), azo-bis-isobutyl cyanide (AIBN), azo two cyanogen in different heptan (ABVN);
As preferably, initator magnetic agitation jitter time is 2 ~ 5 hours; The precursor solution reaction temperature of in-situ polymerization is 60 ~ 80 DEG C, and the reaction time is 2 ~ 5 hours;
(4) casting solution is scraped on the glass plate of clean, no marking, glass plate to be immersed in coagulation bath 3 ~ 5 minutes, to make primary membrane;
The ethanol-water solution that described coagulation bath is deionized water, ethanol mass fraction is 10 ~ 100%, ethanol mass fraction are the one in the mixed solvent ethanol-water solution of 5% ~ 90%;
The temperature of described coagulation bath is 10 ~ 80 DEG C;
As preferably, the film formation time of primary membrane in coagulating bath is 3.5 ~ 4.5 minutes;
The Immersion time of primary membrane in deionization water-bath is 1 ~ 8 day, changes water every day 1 ~ 6 time;
(5) obtained primary membrane is transferred in deionization water-bath, soak 5 ~ 8 days, except desolventizing, naturally dry under normal temperature in air, obtained high performance polyvinylidene fluoride (PVDF) ultrafiltration membrane;
As preferably, the temperature in coagulation bath and deionization water-bath is 10 ~ 50 DEG C.
Compared with prior art, good effect of the present invention is:
The present invention by carrying out the in-situ polymerization of hydrophilic monomer in PVDF casting solution, then high performance polyvinylidene fluoride (PVDF) ultrafiltration membrane is prepared by microphase-separated means, without the need to using extra pore-foaming agent in preparation process, narrow ditribution, high-performance, milipore filter that structure is excellent just can be obtained.The inventive method environmental friendliness, reaction condition are gentle, preparation method is simple, and modification, preparation and membrane structure regulate and control a step and complete, reproducible; The method is not limited to the form of milipore filter, just can realize structure regulating and the performance improvement of milipore filter without the need to extra pore-foaming agent.
[accompanying drawing explanation]
Fig. 1 is high-performance PVDF ultrafiltration membrane surface texture scanning electron microscope (SEM) photograph (10000 times) prepared by embodiment 1 in-situ polymerization;
Fig. 2 is the cross section structure scanning electron microscope (SEM) photograph (350 times) of the high-performance PVDF ultrafiltration membrane of embodiment 1 situ polymerization preparation
Fig. 3 is the cross section structure scanning electron microscope (SEM) photograph (10000 times) of the high performance ultra filtration film of embodiment 1 situ polymerization preparation
[detailed description of the invention]
The detailed description of the invention of a kind of in-situ polymerization regulation and control of the present invention polyvinylidene fluoride (PVDF) ultrafiltration membrane structure is below provided.
Embodiment 1
(1) poly glycol monomethyl ether methyl methacrylate and methyl methacrylate are dissolved in TEP, are made into monomer mixture solution;
In above-mentioned monomer mixture solution, the ratio of the amount of substance of poly glycol monomethyl ether methyl methacrylate and methyl methacrylate is 5: 3;
(2) 18.0g Kynoar and 6.0g monomer mixture solution are dissolved in triethyl phosphate and DMA mixed solvent, dissolve in 60 DEG C of baking ovens, make film forming precursor solution;
In above-mentioned mixed solvent, the mass ratio of triethyl phosphate and DMA is 7: 3;
(3) casting solution is cooled to room temperature, adds initiator A IBN wherein, magnetic agitation 2 hours, makes initator be uniformly dispersed.Then casting solution is placed in 70 DEG C of baking ovens, reacts after 2 hours, by casting solution in left at room temperature deaeration 8 hours;
The component of described monomer mixture solution is the poly glycol monomethyl ether methyl methacrylate of the ratio 5: 3 of amount of substance, the triethyl phosphate solution of methyl methacrylate;
The mass ratio of added initator quality and film forming precursor solution is 0.01;
(4) scraped by casting solution on the glass plate of clean, drying, no marking, being immersed in ethanol content is film forming in the coagulation bath of 50%;
(5) shaping primary membrane to be immersed in the deionization water-bath of 25 DEG C 7 days, change water every day three times.Naturally dry under obtained film is placed in air at room temperature, obtain the polyvinylidene fluoride (PVDF) ultrafiltration membrane of structure regulating.
Fig. 1 is the surface structure surface sweeping Electronic Speculum figure (10000 times) of obtained milipore filter, and Fig. 2 and 3 is respectively section structure surface sweeping Electronic Speculum Figure 35 0 times and 10000 times.As seen from the figure, the patellate physical dimension of the arrangement of PVDF ultrafiltration membrane surface compact, rule increases, and occurs obvious crackle between patellate structure.Section is spongelike structure, the display of Electronic Speculum result under 10000 multiples, and the string that the polymer grain shape of film section presents rule is spherical.These design features make the milipore filter obtained while meeting separation requirement, have excellent mechanical property.
Test result shows: the narrow ditribution effective aperture of above-mentioned polyvinylidene fluoride (PVDF) ultrafiltration membrane is 50.22nm, and pure water flux is 160L.m
-2.h
-1, cow's serum flux recovery rate reaches 70.9%, and fracture strength is 8.0MPa, and elongation at break is 290%.
Embodiment 2
(1) poly glycol monomethyl ether methyl methacrylate and methyl methacrylate are dissolved in TEP, are made into monomer mixture solution;
In above-mentioned monomer mixture solution, the ratio of the amount of substance of poly glycol monomethyl ether methyl methacrylate and methyl methacrylate is 5: 3;
(2) 18.0g Kynoar and 3.0g methyl methacrylate and the mixed solution of poly glycol monomethyl ether methyl methacrylate in triethyl phosphate are dissolved in triethyl phosphate and N, in N-dimethylacetylamide mixed solvent, dissolve in 60 DEG C of baking ovens, make film forming precursor solution;
In above-mentioned mixed solvent, the mass ratio of triethyl phosphate and DMA is 7: 3;
(3) casting solution is cooled to room temperature, adds initiator A IBN wherein, magnetic agitation 2 hours, makes initator be uniformly dispersed.Then casting solution is placed in 70 DEG C of baking ovens, reacts after 2 hours, by casting solution in left at room temperature deaeration 8 hours;
The mass ratio of added initator quality and film forming precursor solution is 0.01;
(4) scraped by casting solution on the glass plate of clean, drying, no marking, being immersed in ethanol content is film forming in the coagulation bath of 50%;
(5) shaping primary membrane to be immersed in the deionization water-bath of 25 DEG C 7 days, change water every day three times.Naturally dry under obtained film is placed in air at room temperature, obtain the polyvinylidene fluoride (PVDF) ultrafiltration membrane of structure regulating.
Test result shows: the narrow ditribution effective aperture of above-mentioned polyvinylidene fluoride (PVDF) ultrafiltration membrane is 50.89nm, and pure water flux is 350L.m
-2.h
-1, the flux recovery rate of cow's serum reaches 69.9%, and fracture strength is 7.1MPa, and elongation at break is 280%.
Embodiment 3
(1) poly glycol monomethyl ether methyl methacrylate and methyl methacrylate are dissolved in TEP, are made into monomer mixture solution;
In above-mentioned monomer mixture solution, the ratio of the amount of substance of poly glycol monomethyl ether methyl methacrylate and methyl methacrylate is 5: 3;
(2) 18.0g Kynoar and 9.0g methyl methacrylate and the mixed solution of poly glycol monomethyl ether methyl methacrylate in triethyl phosphate are dissolved in triethyl phosphate and N, in N-dimethylacetylamide mixed solvent, dissolve in 60 DEG C of baking ovens, make film forming precursor solution;
In above-mentioned mixed solvent, the mass ratio of triethyl phosphate and DMA is 7: 3;
(3) casting solution is cooled to room temperature, adds initiator A IBN wherein, magnetic agitation 2 hours, makes initator be uniformly dispersed.Then casting solution is placed in 70 DEG C of baking ovens, reacts after 2 hours, by casting solution in left at room temperature deaeration 8 hours;
The mass ratio of added initator quality and film forming precursor solution is 0.01;
(4) scraped by casting solution on the glass plate of clean, drying, no marking, being immersed in ethanol content is film forming in the coagulation bath of 50%;
(5) shaping primary membrane to be immersed in the deionization water-bath of 25 DEG C 7 days, change water every day three times.Naturally dry under obtained film is placed in air at room temperature, obtain the polyvinylidene fluoride (PVDF) ultrafiltration membrane of structure regulating.
Test result shows: the narrow ditribution effective aperture of above-mentioned polyvinylidene fluoride (PVDF) ultrafiltration membrane is 30.16nm, and pure water flux is 110L.m
-2.h
-1, flux recovery rate reaches 72.8%, and fracture strength is 9.0MPa, and elongation at break is 350%.
The inventive method environmental friendliness, reaction condition are gentle, preparation method is simple, modification completes with preparation one step, obtained pvdf membrane does not need further modification, reproducible, be not limited to the form of milipore filter, just can obtain narrow pore-size distribution, hydrophilicity kynoar milipore filter without the need to extra pore-foaming agent.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (10)
1. a method for in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure, it is characterized in that, its concrete steps are:
(1) be dissolved in triethyl phosphate TEP by monomer 1 and monomer 2, stir and make it dissolve completely, make monomer mixture solution, the ratio of monomer 1 and the amount of substance of monomer 2 in triethyl phosphate TEP is 5: 1 ~ 1: 5;
(2) by Kynoar, monomer dissolved mixture in the mixed solvent of triethyl phosphate TEP and DMA DMAc, in 50 ~ 100 DEG C of baking ovens, place 1 ~ 15 hour, make casting solution precursor solution; In film forming precursor solution, the mass percent of Kynoar is 10 ~ 30%, and the triethyl phosphate TEP in mixed solvent and DMA DMAc mass ratio are 10: 1 ~ 1: 10;
(3) when casting solution precursor solution is cooled to room temperature, add initator, magnetic agitation is after 1 ~ 6 hour, and by casting solution as 50 ~ 90 DEG C of baking oven situ reactions 1 ~ 8 hour, deaeration under room temperature, obtains casting solution; The added quality of initator and the mass ratio of film forming precursor solution are 0.001: 1 ~ 0.100: 1;
(4) casting solution is scraped on the glass plate of clean, no marking, glass plate to be immersed in coagulation bath 3 ~ 5 minutes, to make primary membrane;
(5) obtained primary membrane is transferred in deionization water-bath, soak 5 ~ 8 days, except desolventizing, naturally dry under normal temperature in air, obtained high performance polyvinylidene fluoride (PVDF) ultrafiltration membrane.
2. the method for a kind of in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure as claimed in claim 1, it is characterized in that, in described step (1), described monomer 1 and monomer 2 are methyl methacrylate, hydroxyethyl methacrylate, one in hydroxy propyl methacrylate, or methyl methacrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate, acrylic acid, polyethylene glycol methyl methacrylate, multiple mixture in poly glycol monomethyl ether methyl methacrylate, at least methyl methacrylate is comprised in mixture, hydroxy propyl methacrylate, one or both in poly glycol monomethyl ether methyl methacrylate.
3. the method for a kind of in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure as claimed in claim 1, it is characterized in that, in described step (1), the ratio of monomer 1 and the amount of substance of monomer 2 in triethyl phosphate TEP is 4: 1 ~ 1: 4.
4. the method for a kind of in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure as claimed in claim 1, it is characterized in that, in described step (2), oven temperature is 40 ~ 80 DEG C, places 6 ~ 12 hours; TEP and DMAc mass content ratio in mixed solvent is 9: 1 ~ 1: 9.
5. the method for a kind of in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure as claimed in claim 1, it is characterized in that, in described step (3), initator used is the one in benzoyl peroxide BPO, isopropyl benzene hydroperoxide CHPO, azo-bis-isobutyl cyanide AIBN, azo two cyanogen ABVN in different heptan.
6. the method for a kind of in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure as claimed in claim 1, it is characterized in that, in described step (3), initator magnetic agitation jitter time is 2 ~ 5 hours; The precursor solution reaction temperature of in-situ polymerization is 60 ~ 80 DEG C, and the reaction time is 2 ~ 5 hours.
7. the method for a kind of in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure as claimed in claim 1, it is characterized in that, in described step (4), the ethanol-water solution that described coagulation bath is deionized water, ethanol mass fraction is 10 ~ 100%, ethanol mass fraction are the one in the mixed solvent ethanol-water solution of 5% ~ 90%.
8. the method for a kind of in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure as claimed in claim 1, it is characterized in that, in described step (4), the temperature of described coagulation bath is 10 ~ 80 DEG C.
9. the method for a kind of in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure as claimed in claim 1, it is characterized in that, in described step (4), the film formation time of primary membrane in coagulating bath is 3.5 ~ 4.5 minutes; The Immersion time of primary membrane in deionization water-bath is 1 ~ 8 day, changes water every day 1 ~ 6 time.
10. the method for a kind of in-situ polymerization regulation and control polyvinylidene fluoride (PVDF) ultrafiltration membrane structure as claimed in claim 1, is characterized in that, in described step (5), the temperature in coagulation bath and deionization water-bath is 10 ~ 50 DEG C.
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Cited By (5)
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| CN105148743A (en) * | 2015-09-30 | 2015-12-16 | 江苏通瑞环保科技发展有限公司 | Preparation method of composite membrane with activated carbon added |
| CN106731900A (en) * | 2017-01-12 | 2017-05-31 | 常州大学 | In-situ sol-gel high-strength polyvinylidene fluoride milipore filter and preparation method |
| WO2017121169A1 (en) * | 2016-01-13 | 2017-07-20 | 厦门理工学院 | Method for preparing anthraquinone-functionalized poly(vinylidene fluoride) membrane |
| CN109647229A (en) * | 2019-01-30 | 2019-04-19 | 自然资源部天津海水淡化与综合利用研究所 | A kind of the anti-pollution polyvinylidene fluoride film and preparation method of co-electrodeposition method preparation |
| CN112108015A (en) * | 2020-10-10 | 2020-12-22 | 天津工业大学 | Preparation method of structurally controllable amphiphilic hyperbranched polymer in-situ modified ultrafiltration membrane |
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| CN109647229A (en) * | 2019-01-30 | 2019-04-19 | 自然资源部天津海水淡化与综合利用研究所 | A kind of the anti-pollution polyvinylidene fluoride film and preparation method of co-electrodeposition method preparation |
| CN112108015A (en) * | 2020-10-10 | 2020-12-22 | 天津工业大学 | Preparation method of structurally controllable amphiphilic hyperbranched polymer in-situ modified ultrafiltration membrane |
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Application publication date: 20150121 |