CN109499385A - A kind of antipollution grape wine film and preparation method thereof - Google Patents
A kind of antipollution grape wine film and preparation method thereof Download PDFInfo
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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Abstract
The invention discloses a kind of antipollution grape wine films and preparation method thereof, belong to membrane material preparation field.The supporting layer of the grape wine film is sulfonated poly aryl ether ketone film, and the active layer of support layer surface, the active layer includes hydrophobic nano-titanium dioxide and Amino End Group dimethyl silicone polymer.Preparation is the following steps are included: (1) prepares sulfonated poly aryl ether ketone；(2) preparation of sulfonated poly aryl ether ketone casting solution；(3) preparation of sulfonated poly aryl ether ketone supporter；(4) preparation of Amino End Group dimethyl silicone polymer casting solution；(5) the antipollution grape wine film is prepared using knife coating in the casting solution by step (4) preparation.The preparation method of antipollution grape wine film prepared by the present invention is simple, the grape wine composite membrane of preparation not only has the characteristics that high temperature resistant, higher thermal stability, super-hydrophobicity and mechanical strength, there is antipollution, corrosion resistant characteristic simultaneously, suitable for grape wine application.
Description
Technical field
The invention belongs to technology field of membrane materials, and in particular to a kind of antipollution grape wine film and preparation method thereof.
Background technique
Currently, grape wine has sizable consumption market, nutritive value with higher has multiple health care.But
It is containing many ethyl alcohol in grape wine, ethyl alcohol usually reduces Portugal by distillation technique to human body toxic side effect, the prior art
Ethanol content in grape wine.The production technology of grape wine routine is kettle formula or tower distillation, passes through what is heated and vacuumize
Mode is by the ethanol distillation in grape wine, but energy consumption is high for distillation, and the fragrance matter of low volatilization point also can be with second in grape wine
Alcohol is distilled together, so as to cause the flavor change of grape wine, loses its original quality characteristic.
In UF membrane field, infiltration evaporation is a kind of novel membrane separation technique, it has also become industrial development and scientific and technological progress
One of the important signs that, main application includes organics dehydration, is separated from the water three sides of separation of organic matter and organic solution
Face.In recent years, preferential organic matter Pervaporation Technology thoroughly is reported the Separation Research of alcohols material very much.Research both at home and abroad,
It is dimethyl silicone polymer (PDMS) material using more alcohol permselective membrane material, special-Si-O- is alternately arranged structure imparting
The preferable backbone flexibility of PDMS and higher free volume, it is preferable to the permeability of most of molecules.Industrial application is more
Saturating alcohol seperation film is mostly the composite membrane that inorganic membrane surface coats one layer of PDMS separating layer, and there is PDMS in actual application
Film layer and inorganic basement membrane associativity are poor, and membrane surface aperture is excessive to cause PDMS film layer to coat easy to leak, plug-hole, and composite membrane is easily dirty
The separating property and service life of the problems such as dye reduction composite membrane.
In addition, due to during the separation process can containing impurity such as pectin, pigments in raw material wine in wine making process
Fouling membrane is caused, the separating property of film is influenced.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of antipollution grape wine film, i.e. Amino End Group dimethyl silicone polymer-sulphur
Change poly (arylether ketone) compound membrane and preparation method thereof.The composite membrane not only has high temperature resistant, compared with heat-flash stability and mechanical strength
Feature also has resistant to pollution characteristic.
To reach above-mentioned technical purpose, the present invention adopts the following technical scheme:
A kind of antipollution grape wine film, the supporting layer of the grape wine film are sulfonated poly aryl ether ketone film, support layer surface tool
Active layer, the active layer include Amino End Group dimethyl silicone polymer and hydrophobic nano-titanium dioxide.
The sulfonation degree of the sulfonated poly aryl ether ketone is preferably 40%~90%.
The sulfonated poly aryl ether ketone is in sulfonated polyether ketone (SPEK) or sulfonated polyether ether ketone ketone ketone (SPEKEKK)
It is a kind of.
Preferably, the Amino End Group dimethyl silicone polymer active layer with a thickness of 1~10 μm.
Preferably, the ammonia value of the Amino End Group dimethyl silicone polymer is 0.2~0.8.
Further, the mass ratio of the hydrophobic nano-titanium dioxide and the Amino End Group dimethyl silicone polymer is 0.5
~2:100.
The present invention also provides a kind of preparation methods of antipollution grape wine film, comprising the following steps:
(1) sulfonated poly aryl ether ketone is prepared；
(2) preparation of sulfonated poly aryl ether ketone casting solution: the sulfonated poly aryl ether ketone that step (1) obtains is matched in organic solvent
The sulfonated poly aryl ether ketone casting solution that mass percent concentration is 5%~30% is made, it is spare after filtering, deaeration；
(3) preparation of sulfonated poly aryl ether ketone film support: the scraper of the casting solution of step (2) preparation is scratched in cleaning
Plate on, be then placed in 20~60 DEG C hydrogel bath in gel film forming, gel time be 1~10min, be then placed in water
8~36h of middle immersion is finally dried in vacuo 2~12h at 30~100 DEG C, sulfonated poly aryl ether ketone film support is prepared；
(4) preparation of Amino End Group dimethyl silicone polymer casting solution: a certain amount of Amino End Group dimethyl silicone polymer is weighed
Organic solvent is dissolved in hydrophobic nano-titanium dioxide and forms evenly dispersed mixed liquor, crosslinking agent, catalyst is then added, sufficiently
It stirs, its cross-linking reaction is made to form coating liquid at 20~50 DEG C, it is spare after filtering, deaeration；
(5) casting solution of step (4) preparation the preparation of grape wine film: is applied to the sulphur of step (3) preparation using knife coating
Change on poly(aryl ether ketone) film support outer surface, the film time is 20~60 seconds, and the supporter after film is true at 30~60 DEG C
Dry 6~the 48h of sky, 1~10h is then heat-treated at 60~150 DEG C, the antipollution grape wine film is prepared.
Wherein, sulfonated poly aryl ether ketone described in step (1) is by forming or passing through sulfonation with sulfonic monomer polymerization
Agent Direct Sulfonation poly aryl ether ketone polymer obtains.
Above-mentioned poly(aryl ether ketone) can be the polymer-modified of polyether-ketone (PEK) polyetherketoneetherketoneketone (PEKEKK) or previous materials
One of.
Preferably, sulfonating agent described in above-mentioned steps (1) is the concentrated sulfuric acid, oleum, chlorosulfonic acid, acetyl group sulfonic acid, three
One of sulfur oxide-triethyl phosphate composition is a variety of.
Preferably, the concentrated sulfuric acid mass percent is 95~98%；The oleum mass percent be 102~
103%.Sulfonating agent used in the present invention and poly(aryl ether ketone) reactivity with higher, so as in the time short as far as possible
It is interior to introduce certain density sulfonic group, while the chain rupture of poly(aryl ether ketone) macromolecular can also be reduced to the greatest extent.
Step (2) organic solvent is dimethyl sulfoxide, N-Methyl pyrrolidone, tetrahydrofuran, N, N- dimethyl second
One of amide, N,N-dimethylformamide.
Scraper described in step (3) with a thickness of 150~300 μm, preferably 250 μm.
Plate described in step (3) is preferably glass plate.
Step (4) the Amino End Group dimethyl silicone polymer viscosity is 3000~10000cp.
Catalyst in step (4) be dibutyl tin acetate, diethyl tin dilaurate tin, dibutyl tin dilaurate,
One or more of dibutyl disuccinic acid tin, iron chloride, aluminium chloride, aniline, dibutylamine or chlorine molybdic acid, preferably dibutyl
One or both of tin dilaurate tin or chlorine molybdic acid.
Organic solvent in step (4) is normal heptane, normal octane, n-hexane, hexamethylene, toluene, ethyl acetate, positive penta
One or more of alkane, benzene, dimethylbenzene and petroleum ether, preferably one or both of normal heptane or n-hexane.
Crosslinking agent in step (4) is glutaraldehyde, chlorethanol, epoxychloropropane, ethyl orthosilicate, vinyl trimethoxy
Silane, phenyltrimethoxysila,e, octyl trimethoxy silane, methyltriethoxysilane, tartaric acid, 1,6-HD dipropyl
Olefin(e) acid ester, ethylene glycol dimethacrylate, divinylbenzene, silicic acid propyl ester, butyl silicate, tetramethoxy-silicane, four ethoxies
One or more of base silane, vinyltriethoxysilane, gamma-methyl allyl acyloxypropyl trimethoxysilane.
Preferably, the crosslinking agent in step (4) is three ethoxy of ethyl orthosilicate, phenyltrimethoxysila,e or vinyl
One or more of base silane.
Obtained film fluid viscosity is 7~25cp in step (4).
Preferably, film fluid viscosity obtained in step (4) is 9~20cp.
It is multiple using the casting solution of different viscosities, different coating times or different dip times, gained in above-mentioned steps
The active layer thickness for closing film is different.
The invention has the benefit that
Poly(aryl ether ketone) is a kind of high-temperature-resistant thermoplastic special engineering plastics, mechanical property, chemical stability, thermal stability etc.
It has excellent performance.After carrying out sulfonation modifying to poly(aryl ether ketone), it is not only able to keep original excellent properties, and there is high corrosion resistant
Corrosion and thermal stability.
Amino modified polydimethyl siloxane material also has anti-in addition to separating property with higher, heat resistance etc.
The seperation film of the performances such as wrinkle, shrinkproof, preparation has preferable antifouling property.
The mechanical strength, corrosion resistance and ultra-hydrophobicity of active layer can be improved in the addition of hydrophobic nano-titanium dioxide,
The separation factor of film is also improved to a certain extent.
Chemical bond occurs for the amino of the sulfonate radical of sulfonated poly aryl ether ketone and composite layer, so that supporter and composite layer
In conjunction with stronger, the service life is longer for film.
Grape wine film of the present invention is the Amino End Group dimethyl silicone polymer-sulphur for filling hydrophobic nano-titanium dioxide
Change poly (arylether ketone) compound membrane, by the performance of poly(aryl ether ketone), hydrophobic nano-titanium dioxide and Amino End Group dimethyl silicone polymer it is comprehensive and
Get up, have many advantages, such as good high temperature resistant, high mechanical strength, anti-fouling performance and corrosion resistance, can be applied to grape wine film
Ethyl alcohol is removed in production.The preparation method of the composite membrane is simple, and repeatability is strong, can industrialized production.
Specific embodiment
The present invention is further discussed below below with reference to embodiment:
The present invention is a kind of resistant to pollution grape wine film i.e. Amino End Group dimethyl silicone polymer-sulfonated poly (arylether ketone) compound membrane
And preparation method thereof.The film is to use sulfonated poly aryl ether ketone film as support layer material, use Amino End Group dimethyl silicone polymer as
Surface separation membrane layer.Its design principle is to prepare sulfonated poly aryl ether ketone first, is then dissolved in casting film organic solvent and is configured to
A certain proportion of casting solution prepares sulfonated poly aryl ether ketone film support；Then the end of filling hydrophobic nano-titanium dioxide is prepared
Coating liquid is finally applied to sulfonated poly aryl ether ketone film support outer surface using knife coating by amino polydimethyl siloxane coating liquid
On prepare filling hydrophobic nano-titanium dioxide Amino End Group dimethyl silicone polymer-sulfonated poly (arylether ketone) compound membrane.As this
Poly aryl ether ketone and sulfonated polyether ketone in invention can also be bought in addition to laboratory chemical synthesis by marketable material.
The polymer molecular weight of the sulfonated poly aryl ether ketone is not specifically limited, and the sulfonic group content of the sulfonated poly aryl ether ketone does not have
Body limitation.
Embodiment 1
(1) poly(aryl ether ketone) selects polyether-ketone (PEK), and dry polyether-ketone (PEK) is placed in 98% dense H2SO4In, wherein
PEK and dense H2SO4Mass volume ratio be 1:20g/mL, continue stirring until PEK and be completely dissolved, sulfonation at a temperature of 55 DEG C
Reaction 24 hours, acquired solution is added in ice water and stops sulfonating reaction, and the solid of sedimentation, solid warp are filtered out after standing
Washing, drying obtain the sulfonated polyether ketone (SPEK) that sulfonation degree is 80%.
(2) sulfonated polyether ketone is dissolved in casting solvent as casting solvent using n,N-dimethylacetamide, is prepared
Casting solution at sulfonated polyether ketone mass percent 10%, it is spare after filtering, deaeration.
(3) by the casting solution of step (2) preparation with 200 μm of scraper blade coating on the glass plate of cleaning, then by film
Sulfonated polyether ketone supporter afterwards be put into 20 DEG C hydrogel bath in gel film forming, gel time 1min, be then placed in from
36h is impregnated in sub- water, is dried in vacuo 12h at last 40 DEG C, sulfonated polyether ketone film support is prepared；
(4) weighing a certain amount of viscosity is 6000cp, and it is molten that the Amino End Group dimethyl silicone polymer of ammonia value 0.2 is dissolved in normal heptane
Agent, and hydrophobic nano-titanium dioxide is added and forms evenly dispersed mixed liquor, hydrophobic nano-titanium dioxide and the poly- diformazan of Amino End Group
The mass ratio of radical siloxane is 1:100, crosslinking agent ethyl orthosilicate, catalyst dibutyl tin dilaurate is then added, sufficiently
It stirs, makes its cross-linking reaction to viscosity 15cp at 30 DEG C, form coating liquid, filter, is spare after deaeration；
(5) coating liquid of step (4) preparation is applied to the sulfonated polyether ketone film support of step (3) preparation using knife coating
On outer surface, the film time is 60s, is dried in vacuo for 24 hours at 30 DEG C, is then heat-treated 4h at 80 DEG C, it is poly- that Amino End Group is prepared
Dimethyl siloxane-sulfonation polyalkylene polyether ketone composite membrane, that is, grape wine film.
The grape wine film being prepared, Amino End Group dimethyl silicone polymer active layer thickness are 3 μm.
Embodiment 2
(1) poly(aryl ether ketone) selects polyether-ketone (PEK), using the mixed acid of 102% oleum and 95% concentrated sulfuric acid
As sulfonated reagent, wherein the mass volume ratio of PEK and mixed acid is 1:10g/mL, and sulfonating reaction 12 is small at a temperature of 35 DEG C
When, acquired solution is added in ice water and stops sulfonating reaction, the solid of sedimentation is filtered out after standing, solid is washed, dry
It is dry, obtain the sulfonated polyether ketone (SPEK) that sulfonation degree is 70%.
(2) sulfonated polyether ketone is dissolved in casting solvent, is configured to as casting solvent using N-Methyl pyrrolidone
Casting solution of the sulfonated polyether ketone mass percent 10%, it is spare after filtering, deaeration.
(3) by the casting solution of step (2) preparation with 250 μm of scraper blade coating on the glass plate of cleaning, then by film
Sulfonated polyether ketone supporter afterwards be put into 40 DEG C hydrogel bath in gel film forming, gel time 3min, be then placed in from
It is impregnated in sub- water for 24 hours, is dried in vacuo 12h at last 40 DEG C, sulfonated polyether ketone film support is prepared；
(4) it weighs the Amino End Group dimethyl silicone polymer that a certain amount of viscosity is 10000cp, ammonia value is 0.3 and is dissolved in hexamethylene
Alkane solvents, and hydrophobic nano-titanium dioxide is added and forms evenly dispersed mixed liquor, hydrophobic nano-titanium dioxide and Amino End Group are poly-
The mass ratio of dimethyl siloxane is 1.5:100, and crosslinking agent epoxychloropropane, catalyst dibutyl disuccinic acid is then added
Tin is sufficiently stirred, and makes its cross-linking reaction to viscosity 9cp at 20 DEG C, forms coating liquid, filter, is spare after deaeration.
(5) coating liquid by step (4) preparation is applied to outside the sulfonated polyether ketone supporter of step (3) preparation using knife coating
On surface, the film time is 20s, is dried in vacuo for 24 hours at 30 DEG C, is then heat-treated 2h at 100 DEG C, Amino End Group poly- two is prepared
Methylsiloxane-sulfonated polyether ketone composite membrane.The grape wine film being prepared, sulfonated polyether ketone active layer thickness are 2.4 μm.
Embodiment 3
(1) poly(aryl ether ketone) selects polyether-ketone (PEK), using chlorosulfonic acid as sulfonated reagent, wherein PEK and chlorosulfonic acid
Mass volume ratio is 1:15g/mL, and sulfonating reaction 48 hours, acquired solution is added in ice water and stops sulfonation at a temperature of 30 DEG C
It reacts, the solid of sedimentation is filtered out after standing, solid is washed, dry, obtains the sulfonated polyether ketone that sulfonation degree is 90%
(SPEK)。
(2) sulfonated polyether ketone is dissolved in casting solvent as casting solvent using n,N-Dimethylformamide, is prepared
Casting solution at sulfonated polyether ketone mass percent 30%, it is spare after filtering, deaeration.
(3) by the casting solution of step (2) preparation with 180 μm of scraper blade coating on the glass plate of cleaning, then by film
Sulfonated polyether ketone supporter afterwards be put into 60 DEG C hydrogel bath in gel film forming, gel time 1min, be then placed in from
36h is impregnated in sub- water, is dried in vacuo 2h at last 100 DEG C, sulfonated polyether ketone film support is prepared.
(4) weighing a certain amount of viscosity is 5000cp, and the Amino End Group dimethyl silicone polymer of ammonia value 0.6 is dissolved in ethyl acetate
Solvent, and hydrophobic nano-titanium dioxide is added and forms evenly dispersed mixed liquor, hydrophobic nano-titanium dioxide and Amino End Group poly- two
The mass ratio of methylsiloxane is 0.5:100, crosslinking agent phenyltrimethoxysila,e, catalyst chlorine molybdic acid is then added, sufficiently
It stirs, makes its cross-linking reaction to viscosity 20cp at 40 DEG C, form coating liquid, filter, is spare after deaeration；
(5) coating liquid of step (4) preparation is applied to the sulfonated polyether ketone film support of step (3) preparation using knife coating
On outer surface, the film time is 30s, is dried in vacuo 48h at 30 DEG C, is then heat-treated 6h at 60 DEG C, it is poly- that Amino End Group is prepared
Dimethyl siloxane-sulfonated polyether ketone composite membrane.The grape wine film being prepared, Amino End Group dimethyl silicone polymer active layer
With a thickness of 10 μm.
Embodiment 4
(1) poly(aryl ether ketone) selects polyetherketoneetherketoneketone (PEKEKK), using acetyl group sulfonic acid as sulfonated reagent, wherein
The mass volume ratio of PEKEKK and mixed acid is 1:15g/mL, the sulfonating reaction 12 hours at a temperature of 30 DEG C, by acquired solution plus
Stop sulfonating reaction into ice water, the solid of sedimentation is filtered out after standing, solid is washed, dry, and obtaining sulfonation degree is
60% sulfonated polyether ether ketone ketone ketone (SPEKEKK).
(2) sulfonated polyether ether ketone ketone ketone is dissolved in casting solvent as casting solvent using dimethyl sulfoxide, is prepared
Casting solution at sulfonated polyether ether ketone ketone ketone mass percent 10%, it is spare after filtering, deaeration.
(3) by the casting solution of step (2) preparation with 280 μm of scraper blade coating on the glass plate of cleaning, then by film
Sulfonated poly aryl ether ketone supporter afterwards is put into gel film forming in 30 DEG C of hydrogel bath, and gel time 10min is then placed in
8h is impregnated in ionized water, is dried in vacuo 8h at last 80 DEG C, sulfonated poly aryl ether ketone film support is prepared.
(4) weighing a certain amount of viscosity is 10000cp, and the Amino End Group dimethyl silicone polymer of ammonia value 0.6 is dissolved in n-hexane
Solvent, and hydrophobic nano-titanium dioxide is added and forms evenly dispersed mixed liquor, hydrophobic nano-titanium dioxide and Amino End Group poly- two
The mass ratio of methylsiloxane is 2:100, and crosslinking agent vinyltriethoxysilane, catalyst aniline is then added, sufficiently stirs
It mixes, makes its cross-linking reaction to viscosity 7cp at 30 DEG C, form coating liquid, filter, is spare after deaeration；
(5) coating liquid of step (4) preparation is supported using the sulfonated poly aryl ether ketone film that knife coating is applied to step (3) preparation
On external surface, the film time is 20s, is dried in vacuo 18h at 50 DEG C, is then heat-treated 3h at 100 DEG C, Amino End Group is prepared
Dimethyl silicone polymer-sulfonated polyether ether ketone ketone ketone composite membrane.The grape wine film being prepared, Amino End Group polydimethylsiloxanes
Alkane active layer thickness is 2 μm.
Embodiment 5
(1) sulfonated polyether ketone (SPEK) is prepared with sulfonic monomer polymerization.
(2) using tetrahydrofuran as casting solvent, the sulfonated polyether ketone (SPEK) that sulfonation degree is 65% is dissolved in casting
In membrane solvent, it is configured to casting solution of the sulfonated polyether ketone mass percent 10%, it is spare after filtering, deaeration.
(3) by the casting solution of step (2) preparation with 300 μm of scraper blade coating on the glass plate of cleaning, then by film
Sulfonated poly aryl ether ketone supporter afterwards is put into gel film forming in 30 DEG C of hydrogel bath, and gel time 5min is then placed in
36h is impregnated in ionized water, is dried in vacuo 12h at last 60 DEG C, sulfonated polyether ketone film support is prepared.
(4) weighing a certain amount of viscosity is 8000cp, and it is molten that the Amino End Group dimethyl silicone polymer of ammonia value 0.8 is dissolved in dimethylbenzene
Agent, and hydrophobic nano-titanium dioxide is added and forms evenly dispersed mixed liquor, hydrophobic nano-titanium dioxide and the poly- diformazan of Amino End Group
The mass ratio of radical siloxane is 1.2:100, and crosslinking agent tartaric acid, catalyst aluminum chloride is then added, is sufficiently stirred, makes at 30 DEG C
Its cross-linking reaction forms coating liquid, filters, is spare after deaeration to viscosity 20cp；
(5) coating liquid by step (4) preparation is applied to outside the sulfonated polyether ketone supporter of step (3) preparation using knife coating
On surface, the film time is 45s, is dried in vacuo 6h at 60 DEG C, is then heat-treated 10h at 100 DEG C, it is poly- that Amino End Group is prepared
Dimethyl siloxane-sulfonated polyether ketone composite membrane.The grape wine film being prepared, Amino End Group dimethyl silicone polymer active layer
With a thickness of 4 μm.
Embodiment 6
(1) polyetherketoneetherketoneketone (PEKEKK) is chosen, is tried using sulfur trioxide-triethyl phosphate composition as sulfonation
Agent obtains the sulfonated polyether ether ketone ketone ketone (SPEKEKK) that sulfonation degree is 40%.
(2) sulfonated polyether ether ketone ketone ketone is dissolved in as casting solvent by casting solvent using n,N-Dimethylformamide
In, it is configured to casting solution of the sulfonated polyether ether ketone ketone ketone mass percent 5%, it is spare after filtering, deaeration.
(3) by the casting solution of step (2) preparation with 150 μm of scraper blade coating on the glass plate of cleaning, then by film
Sulfonated polyether ether ketone ketone ketone supporter afterwards is put into gel film forming in 30 DEG C of hydrogel bath, then gel time 10min is put
Enter and impregnate 36h in deionized water, be dried in vacuo 12h at last 30 DEG C, sulfonated polyether ether ketone ketone ketone film support is prepared.
(4) weighing a certain amount of viscosity is 3000cp, and it is molten that the Amino End Group dimethyl silicone polymer of ammonia value 0.3 is dissolved in petroleum ether
Agent, and hydrophobic nano-titanium dioxide is added and forms evenly dispersed mixed liquor, hydrophobic nano-titanium dioxide and the poly- diformazan of Amino End Group
The mass ratio of radical siloxane is 0.8:100, and cross-linker divinylbenzene, catalyst dibutylamine is then added, is sufficiently stirred, 50
Make its cross-linking reaction to viscosity 25cp at DEG C, forms coating liquid, filter, is spare after deaeration；
(5) coating liquid of step (4) preparation is applied to the sulfonated polyether ether ketone ketone ketone film of step (3) preparation using knife coating
It supports on external surface, the film time is 60s, is dried in vacuo 36h at 40 DEG C, is then heat-treated 1h at 150 DEG C, end is prepared
Amino polydimethyl siloxane-sulfonated polyether ether ketone ketone ketone composite membrane.The grape wine film being prepared, Amino End Group poly dimethyl
Siloxane active layer is with a thickness of 1 μm.
Embodiment 7
(1) it chooses polyetherketoneetherketoneketone (PEKEKK) and obtains sulfonation using 103% oleum as sulfonated reagent
The sulfonated polyether ether ketone ketone ketone (SPEKEKK) that degree is 60%.
(2) sulfonated polyether ether ketone ketone ketone is dissolved in as casting solvent by casting solvent using n,N-dimethylacetamide
In, it is configured to casting solution of the sulfonated polyether ether ketone ketone ketone mass percent 20%, it is spare after filtering, deaeration.
(3) by the casting solution of step (2) preparation with 250 μm of scraper blade coating on the glass plate of cleaning, then by film
Sulfonated polyether ether ketone ketone ketone supporter afterwards is put into gel film forming in 30 DEG C of hydrogel bath, then gel time 7min is put
Enter and impregnate 30h in deionized water, be dried in vacuo 10h at last 30 DEG C, sulfonated polyether ether ketone ketone ketone supporter is prepared.
(4) a certain amount of viscosity 5000cp is weighed, it is molten that the Amino End Group dimethyl silicone polymer of ammonia value 0.8 is dissolved in normal heptane
Agent, and hydrophobic nano-titanium dioxide is added and forms evenly dispersed mixed liquor, hydrophobic nano-titanium dioxide and the poly- diformazan of Amino End Group
The mass ratio of radical siloxane is 0.5:100, crosslinking agent butyl silicate, catalyst dibutyl tin dilaurate is then added, sufficiently
It stirs, makes its cross-linking reaction to viscosity 18cp at 40 DEG C, form coating liquid, filter, is spare after deaeration；
(5) coating liquid of step (4) preparation is applied to the sulfonated polyether ether ketone ketone ketone film of step (3) preparation using knife coating
It supports on external surface, the film time is 30s, is dried in vacuo 12h at 30 DEG C, is then heat-treated 10h at 120 DEG C, is prepared
Amino End Group dimethyl silicone polymer-sulfonated polyether ether ketone ketone ketone composite membrane.The grape wine film being prepared, the poly- diformazan of Amino End Group
Radical siloxane active layer thickness is 8 μm.
Embodiment 8 (comparative example)
(1) Kynoar (PVDF) material for choosing molecular weight 630,000, using n,N-dimethylacetamide as casting film
Kynoar is dissolved in casting solvent by solvent, is configured to casting solution of the Kynoar mass percent 20%, mistake
It is spare after filter, deaeration.
(2) by the casting solution of step (1) preparation with 250 μm of scraper blade coating on the glass plate of cleaning, then by film
Kynoar supporter afterwards be put into 30 DEG C hydrogel bath in gel film forming, gel time 7min, be then placed in from
30h is impregnated in sub- water, is dried in vacuo 10h at last 30 DEG C, Kynoar film support is prepared.
(3) weigh a certain amount of viscosity be 5000cp dimethyl silicone polymer be dissolved in normal heptane solvent formed it is evenly dispersed
Mixed liquor, then be added crosslinking agent benzene ethyl orthosilicate, catalyst dibutyl tin dilaurate, be sufficiently stirred, make at 40 DEG C
Its cross-linking reaction forms coating liquid, filters, is spare after deaeration to viscosity 18cp；
(4) coating liquid of step (3) preparation is applied to the Kynoar film support of step (2) preparation using knife coating
On outer surface, the film time is 30s, is dried in vacuo 12h at 30 DEG C, is then heat-treated 10h at 120 DEG C, poly- diformazan is prepared
Radical siloxane-poly-vinylidene-fluoride composite film.Dimethyl silicone polymer-the poly-vinylidene-fluoride composite film being prepared, poly- diformazan
Radical siloxane active layer thickness is 8 μm.
Embodiment 9
The composite membrane prepared in Examples 1 to 8 is tested to it on the experiment porch of designed, designed and removes second in grape wine
Permeance property in alcohol application.Experiment is raw material with 12.5 ° of alcoholic strength of red wine, and experimental temperature is 40 DEG C, vacuum degree
5000pa.Experimental result such as table 1:
1 Examples 1 to 8 experimental result of table
The composite membrane prepared in the embodiment 7 and 8 is tested it on the experiment porch of designed, designed and is removed in grape wine
Antifouling property in ethyl alcohol application.Experiment is raw material with 12.5 ° of alcoholic strength of red wine, and experimental temperature is 40 DEG C, vacuum
Spend 5000pa.Experimental result such as the following table 2:
The 2 antipollution experimental result of embodiment 7 and 8 of table
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Several alternative or obvious variations are made under the premise of not departing from present inventive concept, and performance or use is identical, all should be considered as
It belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of antipollution grape wine film, which is characterized in that the supporting layer of the antipollution grape wine film is sulfonated poly aryl ether ketone
Film, the active layer of support layer surface, the active layer include hydrophobic nano-titanium dioxide and Amino End Group dimethyl silicone polymer,
Preferably, the sulfonation degree of the sulfonated poly aryl ether ketone is 40% ~ 90%；Preferably, the ammonia of the Amino End Group dimethyl silicone polymer
Value is 0.2 ~ 0.8；Preferably, the mass ratio of the hydrophobic nano-titanium dioxide and the Amino End Group dimethyl silicone polymer is
0.5~2:100。
2. antipollution grape wine film according to claim 1, which is characterized in that the sulfonated poly aryl ether ketone is poly- for sulfonation
One of ether ketone or sulfonated polyether ether ketone ketone ketone.
3. antipollution grape wine film according to claim 1, which is characterized in that the Amino End Group dimethyl silicone polymer is living
Property layer with a thickness of 1 ~ 10 μm.
4. a kind of preparation method of any antipollution grape wine film of claim 1-3, which is characterized in that including following step
It is rapid:
(1) sulfonated poly aryl ether ketone is prepared；
(2) it is dense that sulfonated poly aryl ether ketone the preparation of sulfonated poly aryl ether ketone casting solution: is configured to mass percent in organic solvent
The sulfonated poly aryl ether ketone casting solution that degree is 5%~30%, it is spare after filtering, deaeration；
(3) preparation of sulfonated poly aryl ether ketone supporter: the casting solution scraper of step (2) preparation is scratched in clean plate
On, be then placed in 20 ~ 60 DEG C hydrogel bath in gel film forming, gel time be 1 ~ 10min, be then placed in water impregnate 8 ~
36h is finally dried in vacuo 2 ~ 12h at 30 ~ 100 DEG C, sulfonated poly aryl ether ketone supporter is prepared；Preferably, the scraper
With a thickness of 150 ~ 300 μm, optimal is 250 μm；
(4) it the preparation of Amino End Group dimethyl silicone polymer casting solution: weighs a certain amount of Amino End Group dimethyl silicone polymer and dredges
Water nano-titanium dioxide is dissolved in organic solvent and forms evenly dispersed mixed liquor, and crosslinking agent, catalyst is then added, sufficiently stirs
It mixes, its cross-linking reaction is made to form coating liquid at 20 ~ 50 DEG C, it is spare after filtering, deaeration；
(5) preparation of grape wine film: the sulfonation that the casting solution of step (4) preparation is applied to step (3) preparation using knife coating is poly-
On aryl ether ketone film support outer surface, the film time is 20~60s, and the supporter after film is dried in vacuo 6 at 30 ~ 60 DEG C
Then ~ 48h is heat-treated 1 ~ 10h at 60 ~ 150 DEG C, the antipollution grape wine film is prepared.
5. according to the method described in claim 4, it is characterized in that, sulfonated poly aryl ether ketone described in step (1) is by having sulfonic acid
The monomer polymerization of base is formed or is obtained by sulfonating agent Direct Sulfonation poly aryl ether ketone polymer.
6. according to the method described in claim 5, it is characterized in that, the sulfonating agent is the concentrated sulfuric acid, oleum, chlorine sulphur
One of acid, acetyl group sulfonic acid, sulfur trioxide-triethyl phosphate are a variety of；Preferably, the concentrated sulfuric acid mass percent is
95~98%；Preferably, the oleum mass percent is 102 ~ 103%.
7. according to the method described in claim 4, it is characterized in that, the catalyst in the step (4) is dibutyl oxalic acid
Tin, diethyl tin dilaurate tin, dibutyl tin dilaurate, dibutyl disuccinic acid tin, iron chloride, aluminium chloride, aniline, two fourths
One or more of base amine or chlorine molybdic acid, preferably one or both of dibutyl tin dilaurate or chlorine molybdic acid.
8. according to the method described in claim 4, it is characterized in that, organic solvent in the step (4) be normal heptane, it is just pungent
Alkane, n-hexane, one or more of hexamethylene, toluene, ethyl acetate, pentane, benzene, dimethylbenzene and petroleum ether, preferably just
One or both of heptane or n-hexane.
9. according to the method described in claim 4, it is characterized in that, the crosslinking agent in the step (4) is glutaraldehyde, chloroethene
Alcohol, epoxychloropropane, ethyl orthosilicate, vinyltrimethoxysilane, phenyltrimethoxysila,e, octyl trimethoxy silicon
Alkane, methyltriethoxysilane, tartaric acid, 1,6 hexanediol diacrylate, ethylene glycol dimethacrylate or divinyl
Base benzene, silicic acid propyl ester and butyl silicate, tetramethoxy-silicane, tetraethoxysilane, vinyltriethoxysilane, γ-methyl
One or more of acryloxypropyl trimethoxy silane, preferably ethyl orthosilicate, phenyltrimethoxysila,e or second
One or more of alkenyl triethoxysilane.
10. according to the method described in claim 4, it is characterized in that, Amino End Group dimethyl silicone polymer described in step (4) applies
The viscosity of film liquid is 7 ~ 25cp.
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| CN102949943A (en) * | 2011-08-19 | 2013-03-06 | 东丽纤维研究所（中国）有限公司 | Organic-inorganic hybridized sulfonated polyaryletherketone proton exchange membrane and preparation method thereof |
| CN104010718A (en) * | 2011-10-18 | 2014-08-27 | 帝国创新有限公司 | Membranes for separation |
| CN107880294A (en) * | 2017-12-19 | 2018-04-06 | 长春工业大学 | Sulfonated poly aryl ether ketone sulfone containing amino/amino-acid functional inorganic particulate compoiste proton exchange film |
| CN108434995A (en) * | 2018-03-19 | 2018-08-24 | 清华大学 | It is a kind of to desorb CO from the aqueous solution containing saleratus2Film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102949943A (en) * | 2011-08-19 | 2013-03-06 | 东丽纤维研究所（中国）有限公司 | Organic-inorganic hybridized sulfonated polyaryletherketone proton exchange membrane and preparation method thereof |
| CN104010718A (en) * | 2011-10-18 | 2014-08-27 | 帝国创新有限公司 | Membranes for separation |
| CN107880294A (en) * | 2017-12-19 | 2018-04-06 | 长春工业大学 | Sulfonated poly aryl ether ketone sulfone containing amino/amino-acid functional inorganic particulate compoiste proton exchange film |
| CN108434995A (en) * | 2018-03-19 | 2018-08-24 | 清华大学 | It is a kind of to desorb CO from the aqueous solution containing saleratus2Film and preparation method thereof |
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Effective date of registration: 20201022 Address after: 211808 Jiangsu Film Technology Industrial Park No.1, R & D Park, Nanjing area, China (Jiangsu) pilot Free Trade Zone, Nanjing, Jiangsu Province Applicant after: Jiangsu jiumo Hi Tech Co., Ltd Address before: 211808 Nanjing City, Jiangsu Province, Jiangbei new District Garden train of thought No. 1 Applicant before: NANJING JIUSI HIGH-TECH Co.,Ltd. |