CN100467506C - Method for preparing temperature-sensitive polyvinylidene fluoride intelligent membrane material and its product - Google Patents
Method for preparing temperature-sensitive polyvinylidene fluoride intelligent membrane material and its product Download PDFInfo
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- CN100467506C CN100467506C CN 200510015298 CN200510015298A CN100467506C CN 100467506 C CN100467506 C CN 100467506C CN 200510015298 CN200510015298 CN 200510015298 CN 200510015298 A CN200510015298 A CN 200510015298A CN 100467506 C CN100467506 C CN 100467506C
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Abstract
This invention relates to a method for prparing temperature-sensitive polyvinylidene flourine intelligent membrane. The method is: NIPA as grafted monomer, PVDF as macromelocular initiator, cuprous chloride as catalyst,4,4 demethyl 2,2 bipyridine as ligand, using atom transfer free radical process, preparation of temperature-sensitive polyvinylidene flourine intelligent membrane comprising: in reaction kettle, adding 7-13% PVDF(WT%) and solvent N-methyl-2-pyrrolidone,heating to 50 deg. C to make it solve completely; then adding grafted monomer NIPA, its mol ratio with cuprous chloride is 2000:1-2500:1,filling nitrogen gas 30mins. at stirring, and separately adding 0.20-025g ligand 4,4-dimethyl 2,2-bipyridine and 0.04-0.06g catalyst cupous chloride, stirring and heating to 80-120deg.C,constant reaction 19-25 hrs; then washing reaction product using pure water to obtain light brown solid, filtering and 80 C degree drying to obtain finish product.
Description
Technical field
The present invention relates to a kind of mould material preparation method and product technology, be specially preparation method of the temperature-sensitive polyvinylidene fluoride intelligent membrane material that a kind of N-N-isopropylacrylamide (NIPA) to temperature sensitive and temperature response type and polyvinylidene difluoride (PVDF) (PVDF) graft copolymerization obtains and products thereof, belong to functional high polymer material field, international Patent classificating number intends being Int.Cl
7C08F 20/54.
Background technology
Film is the membrane technique core.The chemical property of mould material and membrane structure play decisive role to the membrane sepn process.Mould material must have following basic function: select perviousness good; Certain hydrophobicity or wetting ability are arranged; Chemical proofing and anti-biological degradability are good, can use lastingly and never degenerate; Good heat resistance; Certain mechanical strength and good processibility are arranged.
Polyvinylidene difluoride (PVDF) good heat resistance, life-time service temperature can reach 140 ℃; Gamma ray resistant, ultraviolet radiation; Resistance to acids and bases is strong, life-time service scope pH2-12 under the room temperature; Organic solvent-resistant is as halohydrocarbon, aliphatic hydrocarbon, aromatic hydrocarbons, alcohol, aldehyde etc.It is the good material of system film.
Although the many advantages of polyvinylidene difluoride (PVDF), but because it has strong-hydrophobicity, its film product is being used for the aqueous phase system separation (as oily water separation, protein matter separates) time, still can produce absorption and pollute, cause membrane flux to descend, membrane sepn efficient reduces, be a big weakness of polyvinylidene fluoride film, also can't satisfy the requirement of some special film process and special dimension.Therefore, lot of domestic and foreign scholar begins one's study and changes the wetting ability of PVDF, promptly compound one deck can improve the wetting ability on film surface or improve the PVDF composite membrane that basement membrane is selected diactinic ultra-thin top layer on porous PVDF basement membrane, or use a kind of hydroaropic substance and PVDF graft copolymerization to generate the PVDF graft copolymer, prepare the hydrophilic PVDF film by the method that changes mutually again.At present, have much as improving PVDF basement membrane hydroaropic substance, the N-N-isopropylacrylamide is exactly wherein a kind of.
The polymkeric substance of N-N-isopropylacrylamide is a kind of intelligent material.Its polymkeric substance has good temperature sensitive characteristic, and promptly its volume can change along with variation of temperature.Contain oh group (OH) in addition on the PNIPA long-chain, have good wetting ability.Therefore a lot of researchs all are NIPA to be grafted to prepare pvdf membrane on the PVDF, so not only improve the wetting ability of pvdf membrane, also give pvdf membrane simultaneously and have temperature-responsive.Relevant at present is material with the N-N-isopropylacrylamide, and the relevant report of preparation PVDF intelligence film mainly concentrates on external magazine, the domestic relevant report of also not seeing at present.The preparation method of PVDF intelligence film mainly contains following several:
1. phase transition method: at first PVDF and NIPA monomer are sent out by thermal initiation and are carried out polymerization, form the PVDF multipolymer, passing through phase transition method, preparation has the PVDF intelligence flat sheet membrane of temperature response type (referring to document: novel PNIPA and the temperature sensitive property of PVDF copolymer microfiltration membrane, Lei Ying, En T.Kang.NovelPoly (N-isopropylacrylamide)-graft-Poly (vinylidenefluoride) Copolymer for Temperature-Sensitive MicrofiltraionMembranes.Macromol.Mater.Eng.2003.288.11～16).
2. irradiation grafting copolymerization method: energetic ray can replace catalyzer to make initiator form the free radical activity center on the molecular chain of polymer surfaces.This active centre can cause polymerisable monomers such as alkene in the graft polymerization of polymer surfaces (referring to document: prepare composite membrane at pvdf membrane surface grafting NIPA by the irradiation grafting copolymerization, Rben Mazzei, Eduardo Smolko, Radiation grafting of NIPAAm onPVDF nuclear track membranes.Nrclear Instrument and Methods in PhysicsResearch B 170 (2000) 419～426).
3. alkali treatment method: make the pvdf membrane surface modification by alkaline purification, contain the monomer of two keys in the PVDF surface reaction with NIPA, vinylformic acid etc. again, generation has the pvdf membrane (referring to applicant patent (200410049992.9): Chen Li formerly, a kind of temperature sensitive polyvinylidene difluoride (PVDF) tubular fibre intelligence membrane preparation method of Wang Wenyu and products thereof) of certain environment temperature-responsive.
In the prior art, adopt the method for PVDF surface modification to prepare PVDF intelligence film, shortcoming is that polymers grafted comes off easily, if flat sheet membrane also can reduce owing to grafting polymer long-chain on film surface or fenestra makes the flux of film, changes the filtration rank of former film.Adopt the phase method of converting to prepare PVDF intelligence film, though can pass through original liquid concentration, precipitation bath, conditions such as temperature are controlled the pvdf membrane aperture, are gone out parameters such as porosity, but when preparation PVDF graft copolymer, reaction conditions, percentage of grafting, molecular structure and molecular weight are difficult to control, and the variation to research PNIPA swelling degree and fenestra just has very big difficulty like this.Applicant's patent application (200410019992.9) formerly also relates to the preparation method of temperature sensitive PVDF intelligence film, but also there are problems such as intelligent layer comes off easily in this method.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined provides preparation method of a kind of temperature-sensitive polyvinylidene fluoride intelligent membrane material and products thereof.Characteristics such as this preparation method collects the advantage of radical polymerization and living polymerization, has controllability well, and technology is simple, and cost is low, does not need specific installation, and industrializing implementation is easy.Adopting the PVDF intelligence film of this preparation method's manufacturing not only can improve the wetting ability of pvdf membrane, and can make this film product have good temperature sensitivity or responsiveness, is a kind of novel temperature sensitive type PVDF intelligence film.Compare with patent formerly, the phenomenon that the present invention has avoided intelligent material to come off, prepared product is the starting material of intelligent film, in addition, intelligent film by this film section product preparation not only can prepare flat sheet membrane, also can prepare hollow-fibre membrane simultaneously, has enlarged use range like this.
The technical scheme that the present invention solves described preparation method's technical problem is: the preparation method who designs a kind of temperature-sensitive polyvinylidene fluoride intelligent membrane material, this method is to be grafted monomer with the N-N-isopropylacrylamide, polyvinylidene difluoride (PVDF) is a macromole evocating agent, with the cuprous chloride is catalyzer, 4,4 dimethyl, 2,2 dipyridyls are ligand, adopt the method for atom transferred free radical to prepare temperature-sensitive polyvinylidene fluoride intelligent membrane material, comprise the steps:
1 to add weight ratio in the reactor that thermometer, agitator are housed be polyvinylidene difluoride (PVDF) and the solvent N-N-methyl-2-2-pyrrolidone N-of 7-13%, is heated to 50 ℃ it is dissolved fully;
2 add grafted monomer N-N-isopropylacrylamide then, the mol ratio of itself and cuprous chloride is 2000:1-2500:1, under agitation inflated with nitrogen is 30 minutes, the ligand 4 that adds 0.20-0.25g more respectively, 4-dimethyl 2, the catalyzer cuprous chloride of 2-dipyridyl and 0.04-0.06g is stirred and heated to 80-120 ℃, isothermal reaction 19-25 hour;
3 wash reaction product with pure water then, obtain the solid of light brown, filter, and 80 ℃ of oven dry can obtain temperature-sensitive polyvinylidene fluoride intelligent membrane material.
The technical scheme that the present invention solves described product technology problem is: design a kind of temperature-sensitive polyvinylidene fluoride intelligent membrane material, it is characterized in that this temperature-sensitive polyvinylidene fluoride intelligent membrane material is obtained by preparation method of the present invention.
Compared with prior art, preparation method's technology of temperature-sensitive polyvinylidene fluoride intelligent membrane material of the present invention is simple, under atmospheric pressure state, just can carry out, used reagent is conventional reagent, and equipment mainly uses common equipments such as reactor, heating tank, belong to the chemical plant the basic equipment that should possess, therefore do not need additionally to increase equipment, just can carry out industrial continuous production, so have characteristics such as industrializing implementation is easy.Compare with the method for previous alkaline purification, preparation method of the present invention is the method for atom transfer radical polymerization, just PVDF and NIPA are dissolved in the solution of response, under the effect of catalyzer and coordination agent, graft copolymerization obtains the PVDF-g-NIPA multipolymer, mainly preparation is the intelligent membrane material material, re-uses this intelligent membrane material material and prepares tubular fibre intelligence film, perhaps flat sheet membrane by the method that changes mutually.So just can avoid when the flat sheet membrane surface grafting, the fenestra aperture being diminished and flux being reduced, can also prevent the phenomenon that graft product comes off simultaneously.Applicant's patent application (200410019992.9) formerly also relates to the preparation method of temperature sensitive PVDF intelligence film, but this method is the PVDF tubular fibre intelligence film that utilizes ready-made PVDF hollow-fibre membrane directly to obtain by the method graft copolymerization of alkaline purification on the film surface.The key distinction of two kinds of methods is, the first, and preparation method's difference, the method that the present invention takes are the method for atom transfer radical polymerization, and previous patent is the direct method by surface modification on film; The second, the product difference, the prepared product of the present invention is a mould material, i.e. the multipolymer of PVDF and NIPA, rather than film is though can further prepare intelligent film (comprising tubular fibre intelligence film or dull and stereotyped intelligent film) by traditional method again; The 3rd, intelligent mechanism difference, formerly the intelligent source of patent is the NIPA gel on PVDF tubular fibre surface, is the temperature sensitivity that the NIPA gel is given film, and of the present invention intelligent be the NIPA polymkeric substance that derives from the PVDF long-chain; The 4th, the quality product difference, formerly the shortcoming of patent is that intelligent layer comes off easily, and this patent this phenomenon can not occur owing to be multipolymer, and temperature sensitive performance is better, and quality is more stable, and range of application is wider.
Embodiment
Further narrate the present invention below in conjunction with embodiment:
The preparation method of a kind of temperature-sensitive polyvinylidene fluoride intelligent membrane material of the present invention's design, be to be grafted monomer with the N-N-isopropylacrylamide, polyvinylidene difluoride (PVDF) is a macromole evocating agent, with the cuprous chloride is catalyzer, 4,4 dimethyl, 2,2 dipyridyls are ligand, adopting the method preparation of atom transferred free radical to have temperature sensitive PVDF graft copolymer, also is temperature-sensitive polyvinylidene fluoride intelligent membrane material.It comprises the steps:
1. adding weight ratio in the reactor that thermometer, agitator are housed is polyvinylidene difluoride (PVDF) and the solvent N-N-methyl-2-2-pyrrolidone N-of 7-13%, is heated to 50 ℃ it is dissolved fully;
2. add grafted monomer N-N-isopropylacrylamide then, the mol ratio of itself and cuprous chloride is 2000:1-2500:1, under agitation inflated with nitrogen is 30 minutes, the ligand 4 that adds 0.20-0.25g more respectively, 4-dimethyl 2, the catalyzer cuprous chloride of 2-dipyridyl and 0.04-0.06g is stirred and heated to 80-120 ℃, isothermal reaction 19-25 hour;
3. wash reaction product with pure water then, obtain the solid of light brown, filter, 80 ℃ of oven dry can obtain temperature-sensitive polyvinylidene fluoride intelligent membrane material.
Temperature-sensitive polyvinylidene fluoride intelligent membrane material of the present invention (hereinafter to be referred as intelligent membrane material) is obtained by preparation method of the present invention, also promptly passes through the atom transfer radical polymerization gained by N-N-isopropylacrylamide (hereinafter to be referred as NIPA) and polyvinylidene difluoride (PVDF) (hereinafter to be referred as PVDF).The PVDF intelligence film that utilizes this intelligent membrane material to make comprises the dull and stereotyped intelligent film of temperature sensitive PVDF tubular fibre intelligence film or temperature sensitive PVDF.Which kind of intelligent film all can improve the wetting ability of pvdf membrane, have tensile strength, shock strength, wear resisting property preferably simultaneously, weathering resistance and chemical stability, the aperture that is a kind of film can change along with variation of temperature, can reach the novel temperature sensitive type PVDF intelligence film that only can carry out fractional separation with a kind of film to the different molecular weight mixture by attemperation.
The preparation method of intelligent membrane material of the present invention selects PVDF and NIPA for use, adopts atom transfer radical polymerization to get method and prepares the PVDF graft copolymer.Its principle of design is: with PVDF is macromole evocating agent, is polymerization single polymerization monomer with NIPA, is catalyzer with the cuprous chloride, and 4,4 dimethyl, 2,2 dipyridyls are ligand, under nitrogen atmosphere, carries out polymerization under the certain temperature.Under the effect of ligand, can capture the fluorin radical on the PVDF long-chain, make on the PVDF long-chain and produce free radical, again with the NIPA monomer polymerization.Preparation method of the present invention can be according to the quantity of ligand, and monomeric quantity realizes that molecular weight is controlled, helps controlling the percentage of grafting of NIPA.Therefore film product of the present invention not only can keep original PVDF characteristic, also has good hydrophilicity and environment-responsive simultaneously.
Though it is polymerization single polymerization monomer that preparation method of the present invention preferentially selects NIPA for use, but it is equally applicable to other material that contains two keys, can prepare graft copolymer according to the characteristics of this material, and make corresponding PVDF intelligence film with this with specific function.
The place that preparation method of the present invention does not address is applicable to prior art.
Introduce specific embodiments of the invention below:
Embodiment 1:
1 adds the PVDF of 5g and the solvent N-N-methyl-2-2-pyrrolidone N-of 70mL in the there-necked flask that thermometer, agitator are housed, be heated to 50 ℃ it is dissolved fully;
2 add grafted monomer NIPA10g then, and under agitation inflated with nitrogen is 30 minutes, adds ligand 4 again, 4-dimethyl 2, and 2-dipyridyl 0.25g, cuprous chloride 0.04g is stirred and heated to 120 ℃, isothermal reaction 18 hours.
3 wash reaction product with pure water then, obtain the solid of light brown, filter, and after 80 ℃ of oven dry, can obtain temperature sensitive type PVDF intelligent membrane material product.
Embodiment 2:
1 in the there-necked flask that thermometer, agitator are housed polyvinylidene difluoride (PVDF) (PVDF) and the solvent N-N-methyl-2-2-pyrrolidone N-60mL of 6g, be heated to 50 ℃ it dissolved fully.
2 grafted monomer NIPA10g then, under agitation inflated with nitrogen is 20 minutes, adds ligand 4 again, 4-dimethyl 2,2-dipyridyl 0.20g, cuprous chloride 0.04 is stirred and heated to 80 ℃, isothermal reaction 18 hours.
3 with embodiment 1
Embodiment 3:
1 in the there-necked flask that thermometer, agitator are housed polyvinylidene difluoride (PVDF) (PVDF) and the solvent N-N-methyl-2-2-pyrrolidone N-50mL of 4g, be heated to 50 ℃ it dissolved fully.
2 grafted monomer NIPA 8g then, under agitation inflated with nitrogen is 30 minutes, adds ligand 4 again, 4-dimethyl 2,2-dipyridyl 0.25g, cuprous chloride 0.05g is stirred and heated to 100 ℃, isothermal reaction 25 hours.
3 with embodiment 1.
Embodiment 4:
1 with embodiment 1
2 grafted monomer NIPA 11.5g then, under agitation inflated with nitrogen is 30 minutes, adds ligand 4 again, 4-dimethyl 2,2-dipyridyl 0.25g, cuprous chloride 0.06g is stirred and heated to 100 ℃, isothermal reaction 22 hours.
3 with embodiment 1
Embodiment 5
1 with embodiment 1
2 grafted monomer NIPA9g then, under agitation inflated with nitrogen is 30 minutes, adds ligand 4 again, 4-dimethyl 2,2-dipyridyl 0.22g, cuprous chloride 0.04 is stirred and heated to 110 ℃, isothermal reaction 19 hours.
Claims (3)
1. the preparation method of a temperature sensitive polyvinylidene fluoride intelligent membrane material, this method is to be grafted monomer with the N-N-isopropylacrylamide, polyvinylidene difluoride (PVDF) is a macromole evocating agent, with the cuprous chloride is catalyzer, 4,4-dimethyl 2,2-dipyridyl are ligand, the method of employing atom transferred free radical prepares and gets, and comprises the steps:
(1) in the there-necked flask that thermometer, agitator are housed, adds the polyvinylidene difluoride (PVDF) of 5g and the solvent N-N-methyl-2-2-pyrrolidone N-of 70mL, be heated to 50 ℃ it is dissolved fully;
(2) add grafted monomer N-N-isopropylacrylamide 10g then, under agitation inflated with nitrogen is 30 minutes, adds ligand 4 again, 4-dimethyl 2, and 2-dipyridyl 0.25g, cuprous chloride 0.04g is stirred and heated to 120 ℃, isothermal reaction 18 hours;
(3) wash reaction product with pure water then, obtain the solid of light brown, filter, after 80 ℃ of oven dry, can obtain the temperature-sensitive polyvinylidene fluoride intelligent membrane material product.
2. a temperature sensitive polyvinylidene fluoride intelligent membrane material is characterized in that this temperature sensitive polyvinylidene fluoride intelligent membrane material product is made by the described preparation method of claim 1.
3. temperature sensitive polyvinylidene fluoride intelligent membrane material according to claim 2 is characterized in that this temperature sensitive polyvinylidene fluoride intelligent membrane material is used to make temperature sensitive polyvinylidene difluoride (PVDF) tubular fibre intelligence film or temperature sensitive polyvinylidene fluoride flat intelligence film.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EE00894U1 (en) * | 2009-02-05 | 2010-01-15 | Visitret Displays O | A method for surface adsorbing fluoropolymers |
| CN101985086B (en) * | 2009-11-23 | 2013-04-03 | 天津工业大学 | Temperature response hollow fiber separation membrane |
| CN101864039B (en) * | 2009-11-23 | 2012-10-17 | 天津工业大学 | Preparation method of temperature-sensitive graft copolymers based on polyvinylidene fluoride |
| CN101711951B (en) * | 2009-11-23 | 2012-01-11 | 天津工业大学 | Method for preparing fiber separation film |
| WO2011060631A1 (en) * | 2009-11-23 | 2011-05-26 | 天津工业大学 | Temperature responsive membrane and preparation method thereof |
| CN101711950B (en) * | 2009-11-23 | 2011-08-31 | 天津工业大学 | Flat separation membrane |
| CN101824122B (en) * | 2010-04-15 | 2012-07-25 | 南京工业大学 | Hydrophilic PVDF material and preparation method thereof |
| CN102061049B (en) * | 2010-11-30 | 2013-03-27 | 天津工业大学 | Temperature sensitive polyvinylidene fluoride gel film and preparation method thereof |
| CN102140181B (en) * | 2011-01-19 | 2013-04-17 | 天津工业大学 | Polyvinylidene fluoride (PVDF) hydrophilic modified membrane and preparation method thereof |
| CN105153371B (en) * | 2015-07-24 | 2018-02-27 | 北京科技大学 | A kind of manufacture method of cationic polyelectrolyte and the application in ultracapacitor |
| CN110898686A (en) * | 2018-09-17 | 2020-03-24 | 天津工业大学 | Preparation method of hydrophilic temperature-sensitive polyvinyl chloride separation membrane and product |
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