CN106178987A - A kind of Kynoar/nano silicon dioxide hybridization film and preparation method thereof - Google Patents
A kind of Kynoar/nano silicon dioxide hybridization film and preparation method thereof Download PDFInfo
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- CN106178987A CN106178987A CN201610595016.0A CN201610595016A CN106178987A CN 106178987 A CN106178987 A CN 106178987A CN 201610595016 A CN201610595016 A CN 201610595016A CN 106178987 A CN106178987 A CN 106178987A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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Abstract
The present invention relates to a kind of Kynoar/nano silicon dioxide hybridization film and preparation method thereof, the composition of described hybridized film includes: Kynoar, porogen, tetraethyl orthosilicate TEOS and silane coupler.Preparation method includes: in Kynoar, adds porogen, dissolves in a solvent, stirs, obtain Kynoar solution at 40～60 DEG C；TEOS is mixed with silane coupler, is dissolved in solvent, be then added under stirring condition in the solution of Kynoar, instill hydrochloric acid, at 60～80 DEG C, continue stirring 12～24h, standing and defoaming, knifing, solidifies 24～48h, obtains Kynoar/nano silicon dioxide hybridization film.The method of the present invention is simple, and prepared hybridized film combines the stalling characteristic of organic membrane and the enhancing of inorganic nano-particle and hydrophilic advantage, has preferable mechanical property, separating property and hydrophilicity, is a kind of promising separation membrane material.
Description
Technical field
The invention belongs to separate film and preparation field thereof, particularly to a kind of Kynoar/nano silicon dioxide hybridization
Film and preparation method thereof.
Background technology
Kynoar (PVDF) is the high-molecular organic material of a kind of function admirable, have prominent chemical stability and
Heat stability, the decomposition temperature of PVDF, more than 316 DEG C, is at room temperature difficult to be corroded by acid, alkali, strong oxidizer etc., and hydro carbons,
It also without impact, is had excellent heat-resisting, corrosion-resistant by the organic solvent such as alcohol, aldehyde.Due in PVDF chemical constitution with fluoro-carbonization
Bond is closed, and intermolecular arrangements is tight, has again stronger hydrogen bond so that it is not only have excellent wearability and impact resistance, and
The highest anti-ultraviolet property is had in rugged environment.But PVDF has extremely strong hydrophobicity, in actual application, easily
Produce absorption to pollute on film surface, shorten the service life of film.Nano silicon (SiO2) it is a kind of conventional inorganic nano
Granule, SiO2Specific surface area big, there is the highest surface chemistry energy and there is higher hydrophilic, can the antipollution of reinforcing membrane
Property.SiO2Hydroxy functional group is contained on surface, can functionalization, SiO further2Also there is corrosion resistance, non-oxidizability, chemical property
Stably wait premium properties.
Polyvinylidene fluoride film and modification thereof are reported by existing patent and document.Chinese Patent Application No. is
CN201610000907.7, it is a kind of with Graphene-rely that application publication date is that the patent application document on March 23rd, 2016 discloses
Propylhomoserin (GO-lysine) is the former film of additive agent modified PVDF and prepared PVDF/GO-lysine composite membrane, and research shows initial
Contact angle drops to about 80 ° of hybridized film from 102 ° of former film, makes hybridized film hydrophilicity and antifouling property obtain the biggest
Raising；Superhydrophilic nano silicon dioxide granule, by simple dipping process, is irreversibly attached to first by Liang S etc.
The polyvinylidene fluoride film surface of base acrylic graft copolymer, result improves the wettability of film, prepares a kind of super hydrophilic
PVDF ultrafiltration membrane.(Liang S,Kang Y,Tiraferri A,Giannelis E P,Huang X,Elimelech
M.Highly Hydrophilic Polyvinylidene Fluoride(PVDF)Ultrafiltration Membranes
via Postfabrication Grafting of Surface-Tailored Silica Nanoparticles.Acs
Applied Materials&Interfaces,2013,5(14):6694-6703.)；Ruan Wenxiang etc. use solution grafting to close
Become ionic liquid graft type nano silicon (IL-SiO2), and it is prepared for PVDF/IL-SiO with phase inversion2Hybridized film,
Have studied IL-Si O2The content impact on hybridized film performance, result shows, IL-SiO2Addition significantly improve hybridized film
Hydrophilic, hybridized film pure water flux reaches 427L.m-2.h-1, 182L.m-higher than the pure water flux of pure film2.h-1, and to egg
The adsorbance of white matter and rejection all have raising to a certain extent.(Ruan Wenxiang, Liao Junbin, Wang Guoqing, Zhang Xianwei, Wang Jianli,
Meter is built bright. and the hydrophilic modification of polyvinylidene fluoride film is studied [J] by ionic liquid graft type nano silicon. colleges and universities' chemistry work
Journey journal, 2015,29 (01): 185-194.)
Summary of the invention
The technical problem to be solved is to provide a kind of Kynoar/nano silicon dioxide hybridization film and system thereof
Preparation Method, the method is simple to operate, mild condition.Preparation hybridized film water flux improves, and hydrophilic strengthens, and has a wide range of applications
Prospect.
A kind of Kynoar/nano silicon dioxide hybridization the film of the present invention, percent mass pressed by the raw material of described hybridized film
Ratio includes: Kynoar is 10～18wt%, and porogen is 3～10wt% and tetraethyl orthosilicate TEOS is 1～7wt%, remaining
Amount is silane coupler, water and hydrochloric acid.
Described porogen is polyvinylpyrrolidone PVP and lithium chloride LiCl, and wherein, the mass ratio of PVP and LiCl is 1:1
～5:1.
Described silane coupler is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560), γ-metering system
One in propyl propionate base trimethoxy silane (KH570), 3-aminopropyl triethoxysilane (KH550), can increase from intramolecular
Strong organic facies and the compatibility of inorganic phase；Tetraethyl orthosilicate is 13:1～17:1 with the mass ratio of silane coupler.
A kind of preparation method of the Kynoar/nano silicon dioxide hybridization film of the present invention, including:
(1) in 10～18wt% Kynoar, add the porogen of 3～10wt%, dissolve in a solvent, 40～
Stir at 60 DEG C, obtain Kynoar solution；
(2) TEOS is mixed with silane coupler, be dissolved in solvent, obtain mixed solution；Then join under stirring condition
In the solution of the Kynoar in step (1), instilling hydrochloric acid, stirring, 60～80 DEG C are continued stirring 12～24 hours, take out and produce
Thing (polymer) standing and defoaming afterwards, forms casting solution, knifing, resolidification 24～48h in water, obtains Kynoar/nanometer
SiO 2 hybrid film；Wherein, the content of TEOS is 1～7wt%；Above-mentioned mass percent is that each raw material accounts for all raw materials quality
The mass percent of summation.
Solvent in described step (1) is 1-Methyl-2-Pyrrolidone NMP and dimethyl acetylamide DMAc；Wherein, NMP
It is 1:1～9:1 with the mass ratio of DMAc.
In described step (2), tetraethyl orthosilicate hydrolyzable in acid condition becomes silicon dioxide.
In described step (2), silane coupler can improve the interface performance between Kynoar and silicon dioxide, strengthens two
The compatibility between person.
In described step (2), solvent is NMP.
In described step (2), the concentration of hydrochloric acid is 0.15～2mol/L；In mixed solution the volume fraction of hydrochloric acid be 0.1～
1%.
The time stirred after instilling hydrochloric acid in described step (2) is 1h.
In described step (2) at 60～80 DEG C during stirring, the rotating speed of stirring is 280r/min；Speed of agitator before is
200r/min。
In described step (2), the time of standing and defoaming is 12～24h.
In described step (2), Kynoar/nano silicon dioxide hybridization film has good permeability and mechanical property,
Water flux reaches 500～1300L.m-2.h-1, hot strength reaches 7～8.5MPa, elongation at break reach 10.5%～
15.3%.
The present invention takes phase inversion and sol-gel process one step to prepare PVDF/SiO2Hybridized film, simple to operate, condition
Gentle.
Beneficial effect
The method of the present invention is simple to operate, mild condition；Preparation hybridized film has good permeability, and water flux carries
Height, hydrophilic strengthens, is with a wide range of applications.
The hybridized film that the present invention obtains combines the stalling characteristic of organic membrane and the enhancing of inorganic nano-particle and hydrophilic
Advantage, there is preferable mechanical property, separating property and hydrophilicity, be a kind of promising separation membrane material.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, people in the art
The present invention can be made various changes or modifications by member, and these equivalent form of values fall within the application appended claims equally and limited
Scope.
Embodiment 1
The porogen LiCl taking the PVDF of 12wt%, 3wt% porogen PVP K90 and 1wt% puts into dry three mouthful burning
In Ping, pour in same there-necked flask by after solvent mix homogeneously that NMP:DMAc mass ratio is 8:2, there-necked flask is being inserted
Entering stirring rod and put into stirring in oil bath pan, arranging parameter is 45 DEG C, 200r/min.In whipping process, preparation mass ratio is 17:1
Tetraethyl orthosilicate (TEOS) and γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560) mix homogeneously, mixed
Close solution；Wherein the content of TEOS is 1wt%；Above-mentioned mass percent is the quality hundred that each raw material accounts for all raw materials quality summations
Proportion by subtraction.Under conditions of stirring, instill in there-necked flask slowly, be then slowly added dropwise 0.1% and (account for the volume integral of mixed solution
Number) hydrochloric acid solution of 0.15mol/L that configured.Stirring about 1h under this condition so that polymer is swelling, then 65
DEG C, 280r/min, stirring 15h, taking-up polymer, standing and defoaming 15h, formation casting solution, knifing, resolidification 28h in water, i.e.
PVDF/ Nano-meter SiO_2 can be obtained2Hybridized film；The water flux of this film is 1300L.m-2.h-1, hot strength is 7.1MPa, elongation at break
It is 12.1%.
Embodiment 2
The porogen LiCl taking the PVDF of 14wt%, 4wt% porogen PVP K90 and 2wt% puts into dry three mouthful burning
In Ping, pour in same there-necked flask by after solvent mix homogeneously that NMP:DMAc mass ratio is 7:3, there-necked flask is being inserted
Entering stirring rod and put into stirring in oil bath pan, arranging parameter is 50 DEG C, 200r/min.In whipping process, preparation mass ratio is 15:1
Tetraethyl orthosilicate (TEOS) mix homogeneously with γ-propyl methacrylate base trimethoxy silane (KH570), obtain mixing molten
Liquid；Wherein the content of TEOS is 3wt%；Above-mentioned mass percent is the percent mass that each raw material accounts for all raw materials quality summations
Ratio.Under conditions of stirring, instill in there-necked flask slowly, be then slowly added dropwise 0.3% and (account for the volume integral of mixed solution
Number) hydrochloric acid solution of 0.5mol/L that configured.Stirring about 1h under this condition so that polymer is swelling, then at 70 DEG C,
280r/min, stirs 18h, takes out polymer, standing and defoaming 18h, forms casting solution, knifing, resolidification 32h in water.?
Obtain PVDF/ Nano-meter SiO_22Hybridized film；The water flux of this film is 800L.m-2.h-1, hot strength is 8.5MPa, and elongation at break is
10.5%.
Embodiment 3
The porogen LiCl taking the PVDF of 16wt%, 5wt% porogen PVP K90 and 3wt% puts into dry three mouthful burning
In Ping, pour in same there-necked flask by after solvent mix homogeneously that NMP:DMAc mass ratio is 6:4, there-necked flask is being inserted
Entering stirring rod and put into stirring in oil bath pan, arranging parameter is 55 DEG C, 200r/min.In whipping process, preparation mass ratio is 13:1
Tetraethyl orthosilicate (TEOS) mix homogeneously with 3-aminopropyl triethoxysilane (KH550), obtain mixed solution；Wherein TEOS
Content be 5wt%；Above-mentioned mass percent is the mass percent that each raw material accounts for all raw materials quality summations.Bar in stirring
Under part, instill in there-necked flask slowly, be then slowly added dropwise what 0.5% (accounting for the volume fraction of mixed solution) had configured
The hydrochloric acid solution of 1mol/L.Stirring about 1h under this condition so that polymer is swelling, then at 75 DEG C, 280r/min, stirring
21h, takes out polymer, standing and defoaming 21h, forms casting solution, knifing, resolidification 40h in water.PVDF/ nanometer
SiO2Hybridized film；The water flux of this film is 600L.m-2.h-1, hot strength is 8.3MPa, and elongation at break is 10.9%.
Embodiment 4
The porogen LiCl taking the PVDF of 18wt%, 5wt% porogen PVP K90 and 5wt% puts into dry three mouthful burning
In Ping, pour in same there-necked flask by after solvent mix homogeneously that NMP:DMAc mass ratio is 1:1, there-necked flask is being inserted
Entering stirring rod and put into stirring in oil bath pan, arranging parameter is 60 DEG C, 200r/min.In whipping process, preparation mass ratio is 11:1
Tetraethyl orthosilicate (TEOS) mix homogeneously with γ-propyl methacrylate base trimethoxy silane (KH570), obtain mixing molten
Liquid；Wherein the content of TEOS is 7wt%；Above-mentioned mass percent is the percent mass that each raw material accounts for all raw materials quality summations
Ratio.Under conditions of stirring, instill in there-necked flask slowly, be then slowly added dropwise 1% (accounting for the volume fraction of mixed solution)
The hydrochloric acid solution of the 2mol/L configured.Stirring about 1h under this condition so that polymer is swelling, then at 80 DEG C, 280r/
Min, stirs 24h, takes out polymer, standing and defoaming 24h, forms casting solution, knifing, resolidification 48h in water.?
PVDF/ Nano-meter SiO_22Hybridized film.The water flux of this film is 500L.m-2.h-1, hot strength is 8.0MPa, and elongation at break is
11.4%.
Claims (8)
1. Kynoar/nano silicon dioxide hybridization film, it is characterised in that percent mass pressed by the raw material of described hybridized film
Ratio includes: Kynoar is 10～18wt%, and porogen is 3～10wt% and tetraethyl orthosilicate TEOS is 1～7wt%, remaining
Amount is silane coupler, water and hydrochloric acid.
A kind of Kynoar/nano silicon dioxide hybridization film the most according to claim 1, it is characterised in that described cause
Hole agent is polyvinylpyrrolidone PVP and lithium chloride LiCl, and wherein, the mass ratio of PVP and LiCl is 1:1～5:1.
A kind of Kynoar/nano silicon dioxide hybridization film the most according to claim 1, it is characterised in that described silicon
Alkane coupling agent is γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane KH560, γ-propyl methacrylate base trimethoxy
One in silane KH570,3-aminopropyl triethoxysilane KH550；Tetraethyl orthosilicate with the mass ratio of silane coupler is
11:1～17:1.
4. a preparation method for Kynoar/nano silicon dioxide hybridization film, including:
(1) in 10～18wt% Kynoar, add the porogen of 3～10wt%, dissolve in a solvent, at 40～60 DEG C
Lower stirring, obtains Kynoar solution；
(2) TEOS is mixed with silane coupler, be dissolved in solvent, obtain mixed solution；Then step is joined under stirring condition
Suddenly in the solution of the Kynoar in (1), instilling hydrochloric acid, stirring, 60～80 DEG C are continued stirring 12～24h, are taken out by product,
Standing and defoaming, knifing, solidify 24～48h, obtain Kynoar/nano silicon dioxide hybridization film；Wherein, the content of TEOS is
1～7wt%；
Above-mentioned mass percent is the mass percent that each raw material accounts for all raw materials quality summations.
The preparation method of a kind of Kynoar/nano silicon dioxide hybridization film the most according to claim 4, its feature exists
In, the solvent in described step (1) is 1-Methyl-2-Pyrrolidone NMP and dimethyl acetylamide DMAc；Wherein, NMP and DMAc
Mass ratio be 1:1～9:1.
The preparation method of a kind of Kynoar/nano silicon dioxide hybridization film the most according to claim 4, its feature exists
In, in described step (2), solvent is NMP.
The preparation method of a kind of Kynoar/nano silicon dioxide hybridization film the most according to claim 4, its feature exists
In, in described step (2), the concentration of hydrochloric acid is 0.15～2mol/L；In mixed solution, the volume fraction of hydrochloric acid is 0.1～1%.
The preparation method of a kind of Kynoar/nano silicon dioxide hybridization film the most according to claim 4, its feature exists
In, in described step (2), the time of standing and defoaming is 12～24h.
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Cited By (10)
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|---|---|---|---|---|
| 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 |
| CN108499363A (en) * | 2018-04-28 | 2018-09-07 | 广西民族大学 | The method of the nano-silicon dioxide modified PVDF dewatering microporous films of fabricated in situ |
| CN109772182A (en) * | 2018-12-29 | 2019-05-21 | 清大国华环境集团股份有限公司 | A kind of preparation method of modified polyvinilidene fluoride film |
| CN111298660A (en) * | 2020-02-27 | 2020-06-19 | 浙江理工大学 | Preparation method of anti-fouling composite nanofiltration membrane with strong stability |
| CN111533642A (en) * | 2020-05-30 | 2020-08-14 | 青岛森晨环保科技有限责任公司 | Method for recovering ethanol from ethanol/water solution |
| CN111569673A (en) * | 2020-05-30 | 2020-08-25 | 青岛森晨环保科技有限责任公司 | SiO with preferential alcohol permeability2Preparation method of PVDF hybrid membrane |
| CN113318603A (en) * | 2021-05-18 | 2021-08-31 | 浙江工业大学 | Organic-inorganic hybrid separation membrane and preparation method thereof |
| CN114159982A (en) * | 2021-12-10 | 2022-03-11 | 江苏巨之澜科技有限公司 | Hollow fiber braided tube filter membrane for sewage reduction and preparation method and application thereof |
| CN114425241A (en) * | 2020-09-29 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method and application of copolymer film material containing silicon dioxide |
| CN115591416A (en) * | 2021-06-28 | 2023-01-13 | 上海斯纳普膜分离科技有限公司（Cn） | Casting solution, flat ultrafiltration membrane, preparation method and application thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108499363A (en) * | 2018-04-28 | 2018-09-07 | 广西民族大学 | The method of the nano-silicon dioxide modified PVDF dewatering microporous films of fabricated in situ |
| CN109772182A (en) * | 2018-12-29 | 2019-05-21 | 清大国华环境集团股份有限公司 | A kind of preparation method of modified polyvinilidene fluoride film |
| CN109772182B (en) * | 2018-12-29 | 2021-11-26 | 清大国华环境集团股份有限公司 | Preparation method of modified polyvinylidene fluoride membrane |
| CN111298660A (en) * | 2020-02-27 | 2020-06-19 | 浙江理工大学 | Preparation method of anti-fouling composite nanofiltration membrane with strong stability |
| CN111298660B (en) * | 2020-02-27 | 2021-12-07 | 浙江理工大学 | Preparation method of anti-fouling composite nanofiltration membrane with strong stability |
| CN111569673B (en) * | 2020-05-30 | 2021-10-19 | 杨笃云 | SiO with preferential alcohol permeability2Preparation method of PVDF hybrid membrane |
| CN111533642B (en) * | 2020-05-30 | 2021-06-11 | 广西英和药业有限公司 | Method for recovering ethanol from ethanol/water solution |
| CN111569673A (en) * | 2020-05-30 | 2020-08-25 | 青岛森晨环保科技有限责任公司 | SiO with preferential alcohol permeability2Preparation method of PVDF hybrid membrane |
| CN111533642A (en) * | 2020-05-30 | 2020-08-14 | 青岛森晨环保科技有限责任公司 | Method for recovering ethanol from ethanol/water solution |
| CN114425241A (en) * | 2020-09-29 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method and application of copolymer film material containing silicon dioxide |
| CN114425241B (en) * | 2020-09-29 | 2023-07-21 | 中国石油化工股份有限公司 | Preparation method and application of copolymer film material containing silicon dioxide |
| CN113318603A (en) * | 2021-05-18 | 2021-08-31 | 浙江工业大学 | Organic-inorganic hybrid separation membrane and preparation method thereof |
| CN113318603B (en) * | 2021-05-18 | 2022-05-27 | 浙江工业大学 | Organic-inorganic hybrid separation membrane and preparation method thereof |
| CN115591416A (en) * | 2021-06-28 | 2023-01-13 | 上海斯纳普膜分离科技有限公司（Cn） | Casting solution, flat ultrafiltration membrane, preparation method and application thereof |
| CN114159982A (en) * | 2021-12-10 | 2022-03-11 | 江苏巨之澜科技有限公司 | Hollow fiber braided tube filter membrane for sewage reduction and preparation method and application thereof |
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