CN108727628A - A kind of nano silver tiny balloon/PVDF ultrafiltration membrane and preparation method thereof - Google Patents
A kind of nano silver tiny balloon/PVDF ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN108727628A CN108727628A CN201810611267.2A CN201810611267A CN108727628A CN 108727628 A CN108727628 A CN 108727628A CN 201810611267 A CN201810611267 A CN 201810611267A CN 108727628 A CN108727628 A CN 108727628A
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
The present invention provides one kind using A-co-B copolymers as core, and C-co-D cross-linked copolymers are the polymer microballoon of shell, and hollow polymer microsphere is obtained by the hydrolysis of copolymer, then loads metal nano silver particles on surface, obtains nano silver tiny balloon.Nano silver tiny balloon has unique hollow-core construction, it is light, large specific surface area, the advantages that Surface Permeability is good, itself and PVDF are subjected to blending extrusion, curtain coating obtains nano silver tiny balloon/PVDF ultrafiltration membrane, aquaporin of the nano silver tiny balloon as ultrafiltration membrane has good antibacterial and resistant to pollution effect.
Description
Technical field
The invention belongs to the preparing technical field of ultrafiltration membrane, more particularly to a kind of nano silver tiny balloon/PVDF ultrafiltration membrane
And preparation method thereof.
Background technology
Hyperfiltration technique has good removal effect to particulate matter in source water and protozoan, is effectively guaranteed place
Reason water quality and the safety for drinking aquatic organism, do not chemically react during ultrafiltration, do not need heat input, also do not need
Regeneration treatment is carried out to processing medium.Ultrafiltration technology floor space is small, it is easy to accomplish scale, high degree of automation.These are excellent
Point allows hyperfiltration technique to apply in membrane for water treatment on a large scale.But ultrafiltration membrane is in use, inevitably
Pollution can be encountered, fouling membrane phenomenon is relative complex, it is difficult to theoretically analyzed, the influence factor of fouling membrane include mainly with
Under several aspects：
(1) property of film itself, the property of film itself includes the material of film, pore size, hydrophobicity, porosity, coarse
Degree and charging property etc..Contamination class, the attainable degree of fouling membrane institute and the Membrane cleaning of film are determined to a certain extent
Complexity.
(2) external operation condition, external operation condition is different, is polluted caused by film different.
How to slow down the pollution problem that ultrafiltration membrane occurs in use, currently, researchers mainly propose it is following several
Kind measure is improved：(1) feed liquid pre-processes；(2) operation conditions optimization；(3) selection and modification of Membrane cleaning and membrane material.
PVDF has good thermal stability and mechanical performance relative to other membrane materials, becomes and is led in sewage disposal
The excellent membrane material of preparative separation film in domain.Nano-Ag particles are since it is with excellent catalysis, optics, electricity and biology biography
The performances such as sense, thus it is widely used in the fields such as chemistry, biology, material.Due to silver nano-grain performance with
Its structure is closely related, common nano silver shape be mainly nanometer rods, nano wire and various scales cube.Sheet with
And triangular shape particle.Research at present about nano silver/PVDF ultrafiltration membrane is relatively fewer, and horse army etc. is in patent《A kind of conjunction in situ
The preparation method of PVDF ultrafiltration membrane is modified at nano silver》Middle proposition is existed by PVDF ultrafiltration membrane, can mainly improve nano silver
The contamination resistance of dispersibility and raising film in PVDF ultrafiltration membrane.But the nano silver being prepared is only in ultrafiltration membrane
Play the role of antibacterial.
Invention content
The present invention is prepared for a kind of nano silver tiny balloon, and itself and PVDF are carried out melt blending extrusion, and curtain coating obtains
Nano silver tiny balloon/PVDF ultrafiltration membrane, since nano silver tiny balloon has unique hollow-core construction, light, specific surface area
Greatly, the advantages that Surface Permeability is good, can be as the aquaporin of ultrafiltration membrane, while having good antibacterial and resistant to pollution effect
Fruit.
Nano silver tiny balloon/PVDF ultrafiltration membrane provided by the invention, according to parts by weight consisting of：
100 parts of PVDF
10~30 parts of PMMA
0.1~1 part of nano silver tiny balloon.
Be added PMMA can improve the mechanical property of PVDF, hydrophilicity etc., then with the compound system of nano silver tiny balloon
For the good ultrafiltration membrane of a kind of antibacterial and antipollution effect, which has higher water flux and flux recovery rate.
PVDF described in patent of the present invention, such as 6008, Kynar 740, DS201,720, FR906,6010NC etc..It is a kind of
Semicrystalline polymer is not easy to be corroded by the strong oxidizers such as halogen and acid, alkali at room temperature, and PVDF is in 200~400nm of wavelength
Ultraviolet irradiation under performance kept stable, have excellent ageing-resistant performance, have good film forming.
PMMA described in patent of the present invention, such as CM-201,8N, IRG-504, HI855H, HI835H, 80N etc..With good
The transparency, stability and weatherability, can effectively improve the filming performance of PVDF, improve the mechanical property of its ultrafiltration membrane.
Nano silver tiny balloon described in patent of the present invention is a kind of nucleocapsid for the special construction that kernel is air,
Has many advantages, such as higher specific surface area, lower density.It is prepared using template, using previously prepared template ball as core, so
It is shell that polymerization, which obtains cross-linked copolymer, afterwards, forms the complex microsphere of core/shell structure, removes template kernel by hydrolysis, then pass through
It is assembled in template ball surface and coats certain thickness elemental silver, obtain nano silver tiny balloon.
Nano silver tiny balloon described in patent of the present invention, preparation process key step include two steps：
(1) first step prepares the polymer microballoon of nucleocapsid first；
(2) polymer microballoon that step (1) obtains is hydrolyzed second step, falls kernel mould by physical method extracting
Plate obtains hollow polymer microsphere, then loads metal nano silver particles, nano silver tiny balloon is prepared.
The first step, the preparation of polymer microballoon：
(1) template ball is prepared first, and steps are as follows for specific experiment：
Using dimethylacetylamide as solvent, initiator is added, (A is added drop-wise in reactor after being mixed with monomer B with monomer A
It is 2 with B molar ratios：8~8：Between 2) free radicals copolymerization reaction generation A-co-B type copolymers are carried out, reaction temperature is 70~80
DEG C, the reaction time is 8~10h, leads to nitrogen protection in entire reaction process.Wherein, initiator is azo-initiator, main to wrap
Azodiisobutyronitrile, azobisisoheptonitrile etc. are included, dosage is the 0.3~0.5% of monomer gross mass, dissolves list in a solvent
Body is added drop-wise in reactor with the speed of 40~60 drops/min.Product is used into petroleum ether and deionization respectively after reaction
Water is respectively washed three times, and 60~80 DEG C of dry 10~12h are to get to white A-co-B types copolymer in vacuum drying oven.Take out grinding
Template particles are obtained at particle.
(2) on the basis of first step template ball prepares, the polymer microballoon of nucleocapsid is prepared：
Take 3~5 parts of the template particles A-co-B types copolymer powder prepared (by mass fraction relative to the total of reactant
Dosage.).(C and D molar ratios are 2 with monomer C and monomer D：8~8：Between 2) mixing, crosslinking agent is added, with 1,1,2- tri- chloroethene
Alkane is solvent, and suitable initiator is added, and carries out solution free radical polymerization, and polymerisation carries out in a nitrogen atmosphere, reaction temperature
For degree at 70~80 DEG C, the reaction time is 8~10h.It is prepared using C-co-D types cross-linked copolymer as shell, A-co-B type copolymers
For the polymer microballoon of core.
Wherein, crosslinking agent be 1,4-butanediol diacrylate, divinylbenzene, trimethylolpropane trimethacrylate,
Pentaerythritol tetraacrylate, bisphenol-A-methyl methacrylate etc., dosage are 3 ‰~the 5 ‰ of monomer gross mass；Cause
Agent is azo-initiator, includes mainly azodiisobutyronitrile, azobisisoheptonitrile etc., and dosage is the 3 ‰ of monomer gross mass
~5 ‰.
Above-mentioned monomer A and B, mainly acrylic acid and its homologue.Acrylic acid and its homologue it is common as：Methyl-prop
E pioic acid methyl ester, butyl methacrylate, methyl acrylate, ethyl acrylate, 2- methyl methacrylates, ethyl methacrylate
Or isobornyl methacrylate, it optionally two kinds therein, is compounded to obtain monomer A and B according to arbitrary proportion.
Above-mentioned monomer C and D, mainly chooses the monomer of fluorine-containing esters of acrylic acid, the monomer of fluorine-containing esters of acrylic acid
Such as acrylic acid trifluoro ethyl ester, trifluoroethyl methacrylate, hexafluorobutyl acrylate, perfluoroethyl n-octyl, octafluoro methyl
The fluorine-containing acrylic ester monomers such as butyl acrylate, methacrylic acid pentafluorophenyl esters, tetrafluoropropyl ethyl ester.Optionally its
In two kinds, compounded to obtain monomer C and D according to arbitrary proportion.This crosslinked fluorine-containing copolymer has non yellowing, and
The advantages that being resistant to gasoline, salt, oil and anti-icing fluid has many advantages, such as low-down surface tension.
Second step, hydrolysis load metal nano silver particles after obtaining hollow polymer microsphere.
The hydrolysis of copolymer：The copolymer pellet that the first step is prepared is put into ultrasonic vibration in excessive acetone soln
Centrifuged after 30~60min, repeatedly for three times, extracting fall all kernel template A-co-B (since stratum nucleare copolymer is uncrosslinked structure,
It is exactly simple A-co-B types copolymer, acetone solution can be used, filtered), obtain hollow polymer microsphere C-co-D.
Surface loads metal nano silver particles：By hollow polymer microsphere 1~2h of ultrasonic disperse after above-mentioned hydrolysis, successively
Silver nitrate, PVP and sodium chloride, ultrasonic disperse is added and is dissolved into milk-white coloured suspension.The milky that ultrasonic disperse obtains is hanged
Supernatant liquid is put into microwave reactor (500~800W of reaction power, 5~10min of microwave time), microwave treatment.To the end of reaction
Solution is taken out into room temperature cooling afterwards, the acetone washing of 3 times of volumes is added, then is detached through centrifuge, the rotating speed for controlling centrifuge is
5000r/min, centrifugation time t=20min.Lower layer's solids after separation is washed with deionized again to be dried afterwards twice, is obtained
To nano silver tiny balloon.
Additive amount according to the above-mentioned tiny balloon of parts by weight is 5~10 parts；The additive amount of silver nitrate is 30~50 parts；PVP
50~100 parts of additive amount；The additive amount of sodium chloride is 0.1~1 part.
The polymer polymerizing method of patent selection of the present invention is fairly simple, and cost is relatively low, the C-co-D type shell materials of selection,
It is a kind of fluorine-containing copolymer, has many advantages, such as non yellowing, and be resistant to gasoline, salt, oil and anti-icing fluid, there is low-down table
The advantages that face tension.It is helpful to the film forming of the PVDF ultrafiltration membrane in later stage, and the service life of film can be improved, it is super to widen PVDF
The use scope of filter membrane.
The present invention also provides a kind of preparation methods of nano silver tiny balloon/PVDF ultrafiltration membrane, weigh according to proportioning, into
Row melt blending squeezes out, and curtain coating obtains nano silver tiny balloon/PVDF ultrafiltration membrane.Wherein, the temperature of extrusion is 200 DEG C, ultrafiltration
The thickness of film is in 20~30um.
Presently embodied advantageous effect major embodiment is in the following areas：
(1) patent of the present invention is put forward for the first time using A-co-B copolymers as core, and C-co-D cross-linked copolymers are the polymer of shell
Microballoon, special nucleocapsid can effectively improve the thermal stability and glass transition temperature of polymer microballoon, improve material
The mechanical property of material improves the compatibility with PVDF matrix resins.
(2) the C-co-D type shell materials selected, which are a kind of fluorine-containing copolymers, has non yellowing, and be resistant to gasoline, salt,
The advantages that oil and anti-icing fluid, has many advantages, such as low-down surface tension.The toughness of PVDF ultrafiltration membrane can be preferentially improved, is improved
Its filming performance has widened the use scope of PVDF ultrafiltration membrane and has extended the service life of PVDF ultrafiltration membrane.
(3) nano silver tiny balloon/PVDF ultrafiltration membrane that patent of the present invention provides, since nano silver tiny balloon has solely
It the advantages that special hollow-core construction, light, large specific surface area, Surface Permeability is good, can be as the aquaporin of ultrafiltration membrane.With very
Good antibacterial and resistant to pollution effect.
Description of the drawings
Fig. 1 prepares schematic diagram for polymer hollow microsphere.
Fig. 2 is the scanning electron microscope for the nano silver tiny balloon that the embodiment of the present invention 1 is prepared.
Specific implementation mode
Embodiment 1
The specific preparation method of nano silver tiny balloon is as follows：
The first step, the preparation of polymer microballoon.
(1) template ball is prepared first, and steps are as follows for specific experiment：
Using dimethylacetylamide as solvent, azodiisobutyronitrile is initiator, and (A and B molar ratios are 2 with A and B：8,
In, A is methyl methacrylate, and B is butyl methacrylate) it is added drop-wise in reactor and carries out free radicals copolymerization reaction after mixing
Polymethyl methacrylate-co- butyl methacrylate type copolymers are generated, reaction temperature is 70 DEG C, reaction time 8h, whole
Lead to nitrogen protection in a reaction process.Wherein, the dosage of azodiisobutyronitrile is the 0.3% of monomer gross mass, is dissolved in solvent
In monomer be to be added drop-wise in reactor with the speed of 40 drops/min.After reaction by product respectively with petroleum ether and go from
Sub- water is respectively washed three times, and 60 DEG C of dry 10h are to get to white polymethyl methacrylate-co- methacrylic acids in vacuum drying oven
Butyl ester type copolymer.It is spare that taking-up is ground into particle.
(2) on the basis of first step template ball prepares, the polymer microballoon of nucleocapsid is prepared.
Take 3 parts of the template particles polymethyl methacrylate-co- butyl methacrylate types copolymer powder prepared.
By monomer C and D, (C and D molar ratios are 2：8, C be perfluoroethyl n-octyl, and D is octafluoro butyl methacrylate) mixing, with
Bisphenol-A-methyl methacrylate is crosslinking agent, and 1,1,2- trichloroethanes is solvent, is to draw with azodiisobutyronitrile (AIBN)
Agent is sent out, solution free radical polymerization is carried out, polymerisation carries out in a nitrogen atmosphere, and reaction temperature is at 70 DEG C, reaction time 8h.
It is prepared using polyacrylic acid perfluor n-octyl-co- octafluoro butyl methacrylate type cross-linked copolymers as shell, polymethyl
Sour methyl esters-co- butyl methacrylates type copolymer is the hollow sphere polymer of core, wherein bisphenol-A-dimethacrylate first
The dosage of ester and azodiisobutyronitrile (AIBN) is respectively the 3 ‰ of monomer gross mass.
Second step loads metal nano silver particles after copolymer hydrolysis.
The hydrolysis of copolymer：The polyacrylic acid perfluor n-octyl-co- octafluoro methacrylic acid fourths that the first step is prepared
Ester type cross-linked copolymer is shell, and polymethyl methacrylate-co- butyl methacrylate type copolymers are the polymer microballoon of core
Particle is put into excessive acetone soln and is centrifuged after 30~60min of ultrasonic vibration, and repeatedly for three times, all kernel templates are fallen in extracting,
Obtain the hollow polymer microsphere that polyacrylic acid perfluor n-octyl-co- octafluoro butyl methacrylate type cross-linked copolymers are shell.
Surface loads metal nano silver particles：By the polyacrylic acid perfluor n-octyl-co- octafluoro methyl-props after above-mentioned hydrolysis
Olefin(e) acid butyl ester type cross-linked copolymer is the hollow polymer hollow ball ultrasonic disperse 1h of shell, sequentially adds silver nitrate, PVP and chlorine
Change sodium, ultrasonic disperse is dissolved into milk-white coloured suspension.The milk-white coloured suspension that ultrasonic disperse is obtained, is put into microwave reactor
In (reaction power 500W, microwave time 5min), microwave treatment.It waits for that solution is taken out room temperature cooling after reaction, is added 3 times
The acetone of volume washs, then is detached through centrifuge, and the rotating speed for controlling centrifuge is 5000r/min, centrifugation time t=20min.
Lower layer's solids after separation is washed with deionized again to be dried afterwards twice, obtains nano silver tiny balloon.
Fig. 2 is microscopic appearance figure and the surface for the nano silver tiny balloon particle that embodiment 1 is prepared.
According to parts by weight, the additive amount of above-mentioned tiny balloon is 5 parts；The additive amount of silver nitrate is 30 parts；The addition of PVP
50 parts of amount；The additive amount of sodium chloride is 0.1 part.
Prepare nano silver tiny balloon/PVDF ultrafiltration membrane
6,008 100 parts of PVDF
10 parts of PMMA CM-201
0.1 part of nano silver tiny balloon
It according to above-mentioned formula, weighs, carries out blending extrusion, curtain coating obtains a kind of nano silver tiny balloon/PVDF ultrafiltration
Film.The temperature wherein squeezed out is 200 DEG C, and the thickness of ultrafiltration membrane is 20um.
Embodiment 2
The specific preparation method of nano silver tiny balloon is as follows：
The first step, the preparation of polymer microballoon.
Template ball is prepared first.Steps are as follows for specific experiment：Using dimethylacetylamide as solvent, azobisisoheptonitrile is to draw
Agent is sent out, (A is 5 with B molar ratios with A and B：5, wherein A is 2- methyl methacrylates, and B is ethyl methacrylate, methyl-prop
Olefin(e) acid isobornyl thiocyanoacetate) it is added drop-wise in reactor after mixing and carries out free radicals copolymerization reaction and generate poly- 2- methyl methacrylates-co-
Isobornyl methacrylate type copolymer, reaction temperature are 75 DEG C, reaction time 9h, and leading to nitrogen in entire reaction process protects
Shield.Wherein, the dosage of azobisisoheptonitrile is the 0.4% of monomer gross mass, and the monomer dissolved in a solvent is with 50 drops/min
Speed be added drop-wise in reactor.Product is respectively washed with petroleum ether and deionized water three times, in vacuum respectively after reaction
70 DEG C of dry 11h are to get to the poly- 2- methyl methacrylates-co- isobornyl methacrylate type copolymers of white in baking oven.
It is spare that taking-up is ground into particle.
(2) on the basis of first step template ball prepares, the polymer microballoon of nucleocapsid is prepared.
Take the poly- 2- methyl methacrylates-co- isobornyl methacrylates type copolymer powder of the template particles prepared
4 parts of end.By monomer C and D, (C and D molar ratios are 5：5, C acrylic acid trifluoro ethyl esters, D are trifluoroethyl methacrylate) mixing,
Using 1,4-butanediol diacrylate as crosslinking agent, 1,1,2- trichloroethanes is solvent, using azobisisoheptonitrile as initiator, into
Row solution free radical polymerization, polymerisation carry out in a nitrogen atmosphere, and reaction temperature is at 70 DEG C, reaction time 8h.It is prepared into
To using polyacrylic acid trifluoro ethyl ester-co- trifluoroethyl methacrylate type cross-linked copolymers as shell, poly- 2- methyl methacrylates
Ester-co- isobornyl methacrylate type copolymers are the polymer hollow microsphere of core, wherein 1,4-butanediol diacrylate
The dosage of ester and azobisisoheptonitrile is respectively the 4 ‰ of monomer gross mass.
Second step loads metal nano silver particles after copolymer hydrolysis.
The hydrolysis of copolymer：Polyacrylic acid trifluoro ethyl ester-co- the trifluoroethyl methacrylates that the first step is prepared
Type cross-linked copolymer is shell, and poly- 2- methyl methacrylates-co- isobornyl methacrylate type copolymers are the polymer of core
Tiny balloon particle is put into excessive acetone soln and is centrifuged after 30~60min of ultrasonic vibration, and repeatedly for three times, extracting is fallen in all
Core template obtains the polymeric hollow that polyacrylic acid trifluoro ethyl ester-co- trifluoroethyl methacrylate type cross-linked copolymers are shell
Microballoon.
Surface loads metal nano silver particles：By the hollow ball ultrasonic disperse 1.5h after above-mentioned hydrolysis, nitric acid is sequentially added
Silver, PVP and sodium chloride, ultrasonic disperse are dissolved into milk-white coloured suspension.The milk-white coloured suspension that ultrasonic disperse is obtained, is put into
In microwave reactor (reaction power 600W, microwave time 8min), microwave treatment.It waits for after reaction that solution taking-up room temperature is cold
But, the acetone washing of 3 times of volumes is added, then is detached through centrifuge, the rotating speed for controlling centrifuge is 5000r/min, centrifugation time
For t=20min.Lower layer's solids after separation is washed with deionized again to be dried afterwards twice, obtains hollow Nano silver microballoon.
According to parts by weight, the additive amount of above-mentioned tiny balloon is 8 parts；The additive amount of silver nitrate is 40 parts；The addition of PVP
80 parts of amount；The additive amount of sodium chloride is 0.5 part.
The preparation of nano silver tiny balloon/PVDF ultrafiltration membrane
100 parts of PVDF kynar740
20 parts of PMMA 8N
0.5 part of nano silver tiny balloon
It according to above-mentioned formula, weighs, carries out blending extrusion, curtain coating obtains a kind of nano silver tiny balloon/PVDF ultrafiltration
Film.The temperature wherein squeezed out is at 200 DEG C, and the thickness of ultrafiltration membrane is in 25um.
Embodiment 3
Nano silver tiny balloon is prepared as follows：
The first step, the preparation of polymer microballoon.
(1) template ball is prepared first, and steps are as follows for specific experiment：
Using dimethylacetylamide as solvent, azodiisobutyronitrile is initiator, and (A and B molar ratios are 8 with A and B：2, wherein
A is methyl acrylate, and B is ethyl acrylate) mixing after be added drop-wise in reactor carry out free radicals copolymerization reaction generate polypropylene
Sour methyl esters-co- ethyl acrylates type copolymer, reaction temperature are 80 DEG C, reaction time 10h, lead to nitrogen in entire reaction process
Gas shielded.Wherein, the dosage of azodiisobutyronitrile is the 5 ‰ of monomer gross mass, the monomer for dissolving in a solvent be with 60 drops/
The speed of min is added drop-wise in reactor.Product is respectively washed with petroleum ether and deionized water three times, true respectively after reaction
80 DEG C of dry 12h are to get to white polypropylene acid methyl esters-co- ethyl acrylate type copolymers in empty baking oven.Take out grinding granulating
Son is spare.
(2) on the basis of first step template ball prepares, the polymer microballoon of nucleocapsid is prepared.Take the mould prepared
5 parts of plate particle polymethyl acrylate-co- ethyl acrylate types copolymer powder.By monomer C and D, (C and D molar ratios are 8：2, C
For methacrylic acid pentafluorophenyl esters, D is tetrafluoropropyl ethyl ester) mixing, using divinylbenzene as crosslinking agent, 1,1,2- tri-
Chloroethanes is solvent, using azobisisoheptonitrile as initiator, carry out solution free radical polymerization, polymerisation in a nitrogen atmosphere into
Row, reaction temperature is at 70 DEG C, reaction time 8h.It is prepared with polymethylacrylic acid pentafluorophenyl esters-co- methacrylic acids four
Fluorine ethyl ester type cross-linked copolymer be shell, polymethyl acrylate-co- ethyl acrylate type copolymers be core polymer microballoon, two
Vinyl benzene is respectively the 5 ‰ of monomer gross mass for the dosage of crosslinking agent and azobisisoheptonitrile.
Second step loads metal nano silver particles after copolymer hydrolysis.
The hydrolysis of copolymer：Polymethylacrylic acid pentafluorophenyl esters-co- the tetrafluoropropyls that the first step is prepared
Ethyl ester type cross-linked copolymer is shell, and polymethyl acrylate-co- ethyl acrylate type copolymers are that the polymer microballoon particle of core is put
Enter in excessive acetone soln and centrifuged after 30~60min of ultrasonic vibration, repeatedly for three times, all kernel templates are fallen in extracting, are gathered
Methacrylic acid pentafluorophenyl esters-co- tetrafluoropropyl ethyl ester type cross-linked copolymers are the hollow polymer microsphere of shell.
Surface loads metal nano silver particles：By the hollow ball ultrasonic disperse 2h after above-mentioned hollow hydrolysis, nitre is sequentially added
Sour silver, PVP and sodium chloride, ultrasonic disperse are dissolved into milk-white coloured suspension.The milk-white coloured suspension that ultrasonic disperse is obtained, puts
Enter in microwave reactor (reaction power 800W, microwave time 10min), microwave treatment.It waits for after reaction taking out solution normal
Temperature is cooling, and the acetone washing of 3 times of volumes is added, then is detached through centrifuge, and the rotating speed for controlling centrifuge is 5000r/min, centrifugation
Time is t=20min.Lower layer's solids after separation is washed with deionized again to be dried afterwards twice, and it is micro- to obtain hollow Nano silver
Ball.
According to parts by weight, the additive amount of above-mentioned tiny balloon is 10 parts；The additive amount of silver nitrate is 50 parts；The addition of PVP
100 parts of amount；The additive amount of sodium chloride is 1 part.
The preparation of nano silver tiny balloon/PVDF ultrafiltration membrane
100 parts of PVDF DS201
30 parts of PMMA IRG-504
1 part of nano silver tiny balloon
It according to above-mentioned formula, weighs, carries out blending extrusion, curtain coating obtains a kind of nano silver tiny balloon/PVDF ultrafiltration
Film.The temperature wherein squeezed out is at 200 DEG C, and the thickness of ultrafiltration membrane is in 30um.
Embodiment 4
A and B molar ratios in embodiment 1 are changed to 3：8, wherein A are methyl methacrylate, and B is 2- methyl methacrylates
Ester, C and D molar ratios are changed to 8：3, C be methacrylic acid pentafluorophenyl esters, and D is perfluoroethyl n-octyl.Other conditions are constant.
Embodiment 5
A and B molar ratios in embodiment 1 are changed to 4：6, wherein A are methyl acrylate, and B is butyl methacrylate, C and D
Molar ratio is 6：4, C be tetrafluoropropyl ethyl ester, and D is perfluoroethyl n-octyl.Other conditions are constant.
Comparative example 1
6,008 100 parts of PVDF
10 parts of PMMA CM-201
It according to above-mentioned formula, weighs, carries out blending extrusion, curtain coating obtains a kind of nano silver tiny balloon/PVDF ultrafiltration
Film.The temperature wherein squeezed out is at 200 DEG C, and the thickness of ultrafiltration membrane is in 20um.
Comparative example 2
6,008 100 parts of PVDF
10 parts of PMMA CM-201
0.1 part of nano silver powder
It according to above-mentioned formula, weighs, carries out blending extrusion, curtain coating obtains a kind of nano silver tiny balloon/PVDF ultrafiltration
Film.The temperature wherein squeezed out is at 200 DEG C, and the thickness of ultrafiltration membrane is in 20um.
Comparative example 3
6,008 100 parts of PVDF
0.5 part of nano silver tiny balloon
The preparation method of nano silver tiny balloon is the same as embodiment 2.
Comparative example 4
Monomer C in embodiment 1 is changed to methyl methacrylate, D is changed to ethyl methacrylate, and other conditions are not
Become.
Dependence test：
The measurement of pure water flux：Formula ultrafilter is carried on the back using Millipore 8200, takes the wet film sample of certain area super
It is fixed in filter membrane, carry out the measurement of water flux.Before experiment 30min is compacted with deionized water under room temperature and 0.15Mpa.Then
At 0.1Mpa, the online volume for noting down the water in 1min by film, effective membrane area is 28.4cm2.Film is calculated according to formula (1)
Pure water flux J0：
J0=V/ (At)
Wherein, V is infiltration water volume, and A is effective membrane area, and t is minute.
The measurement of flux recovery rate：Precompressed 30min is carried out to film with deionized water under room temperature and 0.15Mpa,
The pure water flux J of film is measured under 0.1Mpa0.The BSA solution that deionized water is changed into 500mg/L filters one section at 0.1Mpa
The permeation flux J of test film after timep.By the ultrafiltration membrane of BSA pollutions 30min will be cleaned with deionized water.Then exist
Test the pure water flux J of ultrafiltration membrane under 0.1Mpa again with deionized water1, then the flux recovery rate of ultrafiltration membrane be：
M=J1/J0× 100%
Above-described embodiment and comparative example the result shows that：Nano silver tiny balloon has unique hollow-core construction, light, than
The advantages that surface area is big, and Surface Permeability is good, can be as the aquaporin of ultrafiltration membrane, and water flux is relative to being not added with nano silver
PVDF ultrafiltration membrane bigger.The yellowness index of the copolymerization microsphere of fluorine-containing monomer is larger.
Claims (10)
1. a kind of nano silver tiny balloon/PVDF ultrafiltration membrane, it is characterised in that：The ultrafiltration membrane is according to its composition of parts by weight
For：
100 parts of PVDF
10~30 parts of PMMA
0.1~1 part of nano silver tiny balloon；
Wherein, the nano silver tiny balloon is using air as core, and cross-linked copolymer is the polymer microballoon of shell, on surface
Load metal nano silver particles, obtained nano silver tiny balloon.
2. nano silver tiny balloon/PVDF ultrafiltration membrane as described in claim 1, it is characterised in that：The PVDF is 6008,
Kynar 740, DS201,720, FR906 or 6010NC；The PMMA be CM-201,8N, IRG-504, HI855H, HI835H or
80N。
3. nano silver tiny balloon/PVDF ultrafiltration membrane as described in claim 1, it is characterised in that：The nano silver is hollow micro-
Steps are as follows for the preparation method of ball：
(1) polymer microballoon of nucleocapsid is prepared；
(2) polymer microballoon that step (1) obtains is hydrolyzed, extracting falls kernel template and obtains hollow polymer microsphere, so
Metal nano silver particles are loaded afterwards, and nano silver tiny balloon is prepared.
4. nano silver tiny balloon/PVDF ultrafiltration membrane as claimed in claim 3, it is characterised in that：Step (1) described polymer
The preparation method of microballoon is：
(1) template ball is prepared：
Using dimethylacetylamide as solvent, initiator is added, is added drop-wise in reactor and is carried out certainly after being mixed with monomer B with monomer A
A-co-B type copolymers are generated by base copolyreaction, lead to nitrogen protection in entire reaction process, after reaction by product point
It is not washed respectively three times with petroleum ether and deionized water, 60~80 DEG C of dry 10~12h are to get to white A-co-B in vacuum drying oven
Type copolymer；It takes out grinding and obtains template particles；
(2) polymer microballoon of nucleocapsid is prepared：
3~5 parts of the template particles A-co-B types copolymer powder prepared is taken, is mixed with monomer C and monomer D, crosslinking agent is added
And initiator carries out solution free radical polymerization with 1,1,2- trichloroethanes for solvent, polymerisation carries out in a nitrogen atmosphere,
It is prepared using C-co-D types cross-linked copolymer as shell, A-co-B type copolymers are the polymer microballoon of the nucleocapsid of core.
5. nano silver tiny balloon/PVDF ultrafiltration membrane as claimed in claim 4, it is characterised in that：The monomer A and monomer B
For acrylic acid and its homologue, the molar ratio of monomer A and monomer B are 2：8~8：2；Initiator is azodiisobutyronitrile or azo
Two different heptonitriles, dosage are the 0.3~0.5% of monomer gross mass, and monomer is added drop-wise to reactor with the speed of 40~60 drops/min
In；Polymeric reaction temperature is 70~80 DEG C, and polymerization reaction time is 8~10h；
Monomer C and monomer D is fluorine-containing acrylic ester monomer；The molar ratio of monomer C and monomer D are 2：8~8：2；Crosslinking agent
For 1,4 butanediol diacrylate, divinylbenzene, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate or
Bisphenol-A-methyl methacrylate, dosage are 3 ‰~the 5 ‰ of monomer gross mass；Initiator is azodiisobutyronitrile or idol
Two different heptonitrile of nitrogen, dosage are 3 ‰~the 5 ‰ of monomer gross mass；Polymeric reaction temperature is 70~80 DEG C, and polymerization reaction time is
8~10h.
6. nano silver tiny balloon/PVDF ultrafiltration membrane as claimed in claim 5, it is characterised in that：The acrylic acid and its same
Be object be methyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, 2- methyl methacrylates or
Any one in ethyl 2-methacrylate；The fluorine-containing acrylic ester monomer is acrylic acid trifluoro ethyl ester, methyl-prop
Olefin(e) acid trifluoro ethyl ester, hexafluorobutyl acrylate, perfluoroethyl n-octyl, octafluoro butyl methacrylate, methacrylic acid five
Any one in fluorobenzene ester or tetrafluoropropyl ethyl ester.
7. nano silver tiny balloon/PVDF ultrafiltration membrane as claimed in claim 3, it is characterised in that：Step (2) described nano silver
The preparation method of tiny balloon is：
(1) hydrolysis of copolymer：
The polymer microballoon being prepared is put into excessive acetone soln after 30~60min of ultrasonic vibration and is centrifuged, repeatedly three
Secondary, all kernel template A-co-B are fallen in extracting, obtain hollow polymer microsphere C-co-D；
(2) surface loads metal nano silver particles：
Hollow polymer microsphere 1~2h of ultrasonic disperse that step (1) is obtained, sequentially adds silver nitrate, PVP and sodium chloride,
Ultrasonic disperse is dissolved into milk-white coloured suspension, and the milk-white coloured suspension that ultrasonic disperse is obtained is put into microwave reactor, microwave
Processing waits for that solution is taken out room temperature cooling after reaction, the acetone washing of 3 times of volumes is added, then detached through centrifuge, detaches
Lower layer's solids afterwards is washed with deionized again to be dried afterwards twice, obtains nano silver tiny balloon.
8. nano silver tiny balloon/PVDF ultrafiltration membrane as claimed in claim 7, it is characterised in that：According to empty described in mass parts
The additive amount of heart microballoon is 5~10 parts；The additive amount of silver nitrate is 30~50 parts；50~100 parts of the additive amount of PVP；Sodium chloride
Additive amount be 0.1~1 part；The rotating speed of centrifuge is 5000r/min, centrifugation time 20min.
9. a kind of preparation method of nano silver tiny balloon/PVDF ultrafiltration membrane as described in claim 1, it is characterised in that：Institute
Stating preparation method is：
Raw material is weighed according to formula, then carries out melt blending extrusion, curtain coating obtains nano silver tiny balloon/PVDF ultrafiltration membrane.
10. the preparation method of nano silver tiny balloon/PVDF ultrafiltration membrane as claimed in claim 9, it is characterised in that：It is described to squeeze
It is 200 DEG C to go out temperature, and the thickness of obtained ultrafiltration membrane is 20~30um.
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