CN106179003B - It is a kind of to be used to adsorb polyetheramine/Kynoar composite porous film of dyestuff in water and preparation method thereof - Google Patents
It is a kind of to be used to adsorb polyetheramine/Kynoar composite porous film of dyestuff in water and preparation method thereof Download PDFInfo
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- CN106179003B CN106179003B CN201610717247.4A CN201610717247A CN106179003B CN 106179003 B CN106179003 B CN 106179003B CN 201610717247 A CN201610717247 A CN 201610717247A CN 106179003 B CN106179003 B CN 106179003B
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- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
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- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28035—Membrane, sheet, cloth, pad, lamellar or mat with more than one layer, e.g. laminates, separated sheets
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
- C08G83/006—After treatment of hyperbranched macromolecules
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
The invention discloses a kind of polyetheramine/Kynoar composite porous film for being used to adsorb dyestuff in water and preparation method thereof.The present invention is first grafted to small molecule photocrosslinking agent hyperbranched polyetheramine chain on and containing fluorocarbon chain, then the crosslinking of the hyperbranched polyetheramine after grafting is obtained polyetheramine/Kynoar composite porous film on polyvinylidene fluoride film surface by the method for photo-crosslinking.Preparation technology of the present invention is simple, it is easy to operate；Polyetheramine/Kynoar composite porous film of the present invention, due to introducing hyperbranched polyetheramine, with good hydrophily and Dye Adsorption performance；Due to loose structure, therefore can quick separating contaminant water.
Description
Technical field
The invention belongs to the modified high-molecular technology field of membrane materials in water treatment field, specifically, the present invention relates to
It is a kind of to be used to adsorb polyetheramine/Kynoar composite porous film of dyestuff in water and preparation method thereof.
Background technology
Dyestuff obtains universal application in fields such as fabric, printing, coating, food, but it is bringing great economic benefit
While, also become the important sources of water pollution.Most of dyestuff all has toxicity, and most of dyestuff can not be by biology drop
Solution, therefore it all brings existence threat to animals and humans.Absorption method is a kind of effective ways for removing dyestuff in water.Polyethers
Amine is a kind of good dye sorbent, can be acted on by being compounded in gel, playing its on membrane material.
Kynoar has good mechanical performance, thermodynamic stability, resistance to chemical corrosion, ageing resistance due to it
Deng being gradually valued by people in membrane separation technique.Itself has hydrophobicity, limits it in water treatment field
Using., can be by adding polymethyl methacrylate, polyacrylonitrile, cellulose acetate, polyethylene in order to improve its hydrophily
The high molecular polymers such as base pyrrolidones.For the hydrophilically modified of Kynoar, exist material compatibility, stability with
And it is cumbersome the problems such as, thus remain in the laboratory research stage, therefore exploitation has new hydrophily polyvinylidene fluoride
Alkene membrane material is imperative.And functional modification is carried out to polyvinylidene fluoride film, it is the effective way for expanding its application field.
The content of the invention
It is an object of the invention to the deficiency for currently available technology, there is provided a kind of polyethers for being used to adsorb dyestuff in water
Amine/Kynoar composite porous film and preparation method thereof.The composite porous film has good hydrophily, can quick separating water
In dyestuff, preparation technology is simple, is adapted to industrialized production.
To achieve the above object, the present invention is grafted to hyperbranched polyetheramine chain by small molecule photocrosslinking agent and containing fluorocarbon chain
On, make the crosslinking of the hyperbranched polyetheramine after grafting that polyetheramine/poly- be made on polyvinylidene fluoride film surface by the method for photo-crosslinking
Vinylidene composite porous film.
Technical scheme is specifically described as follows.
The present invention provides a kind of polyetheramine/Kynoar composite porous film for being used to adsorb dyestuff in water, and this is compound more
Pore membrane is obtained by Kynoar and the crosslinking of graft polyether amine；Wherein：Shown in the structure such as formula (1) of the graft polyether amine：
Wherein, X represents polyether chain；A isOr be not present；B represents that fluorine atom partly or completely replaces
Carbon number be 1-30 alkyl or oxyalkyl chain；U represents photocrosslinking agent molecule residues；
Y represents coinitiator amine molecule residue, and it has structure shown in formula (3)：
Wherein, R2For C2-C10Straight or branched alkyl, C2-C10Alkoxy, cycloalkyl or the piperazine for being replaced hydrogen by alkyl；R3
For hydrogen, halogen atom, the C replaced completely1-C30Alkyl or oxyalkyl chain or hetero ring type base, hydroxyl, carboxyl, ester group, cycloalkyl,
Phenyl or naphthyl.
In the present invention, in the graft polyether amine, X has structure shown in following (2)：
Wherein, R1For C1-C20Straight or branched alkyl, C1-C20Alkoxy, cycloalkyl, phenyl, naphthyl, hetero ring type base or
The product that these group hydrogen atoms are substituted with a substituent, 0<n<20.
In the present invention, in the graft polyether amine, U has structure shown in formula (4)：
Wherein, R4、R5、R6、R7、R8Separately it is selected from hydrogen, halogen, C1-C20Straight or branched alkyl, C1-C20Alcoxyl
Base, epoxy radicals, nitro, amino, hydroxyl, carboxyl, itrile group, sulfonic group, ester group, cycloalkyl, phenyl or naphthyl；X1For methylene,
Oxygen, sulphur or nitrogen-atoms；N1, n2 are integer, 0<n1,2<5.
The present invention also provides a kind of above-mentioned polyetheramine/Kynoar composite porous film for being used to adsorb dyestuff in water
Preparation method, is comprised the following steps that：
(1) it is 1 according to mol ratio:10~10:1 by the organic amine containing primary amine and secondary amine and the polyethers containing diepoxy group
It is dissolved in alcohol, under the protection of inert gas, then stirring at normal temperature mixing 12h~60h reacts 12h~60h at 60~120 DEG C,
After reaction terminates, organic solvent is rotated and removed, dried, obtain hyperbranched polyetheramine；Wherein：It is described containing primary amine and secondary amine
The structural formula of organic amide monomer is such as shown in (5)：
Wherein, R2For C2-C10Straight or branched alkyl, C2-C10Alkoxy, cycloalkyl or the piperazine for being replaced hydrogen by alkyl；R3
For hydrogen, C1-C10Straight or branched alkyl, C1-C10Alkoxy, hydroxyl, carboxyl, ester group, cycloalkyl, phenyl, naphthyl or hetero ring type
Base；
(2) hyperbranched polyetheramine is dissolved in alcohol with the small molecule photocrosslinking agent with functional group, it is anti-at 60~120 DEG C
12h~60h is answered, the monomer containing fluorocarbon chain is added, after reaction terminates, revolving removes organic solvent, is sunk in precipitating reagent
Form sediment, dry, obtain graft polyether amine；Wherein：Hyperbranched polyetheramine, the small molecule photocrosslinking agent with functional group and containing fluorocarbon chain
Monomer mol ratio be (1~10)：(1~10)：(1~10)；
(3) by Kynoar be dissolved in dimethyl acetamide be made mass fraction for 1%~50% Kynoar it is molten
Liquid, the graft polyether amine for then obtaining step (2) and Kynoar solution blending so that graft polyether amine is in blended liquid
Mass fraction be 1~20wt%, mass fraction of the Kynoar in blended liquid be 1~15wt%, at 30~100 DEG C
12h~60h is stirred, casting solution is made；
(4) casting solution obtained by step (3) is scraped on glass plate, being immersed in 10~40 DEG C of tank, after 5~30s
It will take off, dried at a temperature of 10~150 DEG C on film glass plate, 12~60h of illumination under ultraviolet light after drying produces polyethers
Amine/Kynoar composite porous film.
In above-mentioned steps (1), the structural formula of the polyethers containing diepoxy group is such as shown in (6)：
Wherein, R1For C1-C20Straight or branched alkyl, C1-C20Alkoxy, cycloalkyl, phenyl, naphthyl, hetero ring type base or
The product that these group hydrogen atoms are substituted with a substituent, 0<n<20.
In above-mentioned steps (2), the structural formula of the small molecule photocrosslinking agent with functional group is such as shown in (7)：
Wherein, U represents photocrosslinking agent molecule residues, R9For epoxide group, carboxyl or ester group.
In above-mentioned steps (2), the structural formula of the monomer containing fluorocarbon chain is such as shown in (8)：
Wherein, B represents the alkyl or oxyalkyl chain that the carbon number that fluorine atom partly or completely replaces is 1-30, R10For
Epoxide group, carboxyl or ester group.
In above-mentioned steps (2), precipitating reagent is n-hexane or petroleum ether.
In above-mentioned steps (2), inert gas is nitrogen.
Advantages of the present invention is as follows：
1st, polyetheramine/Kynoar composite porous film prepared by the present invention, due to wherein containing polyetheramine, so phase
Than in polyvinylidene fluoride film, its hydrophily is improved；Polyetheramine has the function of adsorpting dye molecule, therefore this is compound more
Pore membrane also possesses the performance of absorption dyestuff.It has a loose structure to Kynoar, can quick separating contaminant water, with polyetheramine
With reference to rear, dyestuff that can be in quick separating contaminant water.Polyetheramine/Kynoar composite porous film of the present invention, can be used for
Dyestuff in water is adsorbed, dyestuff includes erythrosine (ETB), eosin (EB), 3,4,5,6- tetra- chlorofluoresceins (TCF) and rose-red
(RB) etc..
2nd, the technique of the invention for preparing polyetheramine/Kynoar composite porous film is simple, it is easy to operate, therefore in Shui Chu
Reason field has broad application prospects.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the graft polyether amine (hPEA211-EC-CF6) synthesized by embodiment 1.
Fig. 2 is the complete of polyetheramine/Kynoar composite porous film (P10.00-hPEA3.33) synthesized by embodiment 6
Compose scanning figure.
In Fig. 3, (a1) is polyvinylidene fluoride film cross-section morphology electromicroscopic photograph, and (a2) is Kynoar environmental microbes electricity
Mirror photo；(b1) it is polyetheramine/Kynoar composite porous film (P10.00-hPEA2.50) section synthesized by embodiment 5
Pattern electromicroscopic photograph, (b2) is polyetheramine/Kynoar composite porous film (P10.00- synthesized by embodiment 5
HPEA2.50) surface topography electromicroscopic photograph；(c1) it is polyetheramine/Kynoar composite porous film synthesized by embodiment 6
(P10.00-hPEA3.33) cross-section morphology electromicroscopic photograph, (c2) is that polyetheramine/Kynoar synthesized by embodiment 6 is combined
Perforated membrane (P10.00-hPEA3.33) surface topography electromicroscopic photograph；(d1) it is polyetheramine/polyvinylidene fluoride synthesized by embodiment 7
Alkene composite porous film (P10.00-hPEA5.00) cross-section morphology electromicroscopic photograph, (d2) is polyetheramine synthesized by embodiment 7/poly-
Vinylidene composite porous film (P10.00-hPEA5.00) surface topography electromicroscopic photograph；(e1) it is polyethers synthesized by embodiment 8
Amine/Kynoar composite porous film (P10.00-hPEA10.00) cross-section morphology electromicroscopic photograph, (e2) is synthesized by embodiment 8
Polyetheramine/Kynoar composite porous film (P10.00-hPEA10.00) surface topography electromicroscopic photograph；(f1) it is embodiment 9
Synthesized polyetheramine/Kynoar composite porous film (P15.00-hPEA5.00) cross-section morphology electromicroscopic photograph, (f2) is real
Apply polyetheramine/Kynoar composite porous film (P15.00-hPEA5.00) surface topography electromicroscopic photograph synthesized by example 9.
Fig. 4 is polyetheramine/Kynoar composite porous film (P10.00-hPEA2.50) of the synthesis of embodiment 5, embodiment
The polyetheramine that polyetheramine/Kynoar composite porous film (P10.00-hPEA3.33) of 6 synthesis, embodiment 7 are synthesized/poly- inclined
Polyetheramine/Kynoar composite porous film that PVF composite porous film (P10.00-hPEA5.00), embodiment 8 are synthesized
(P10.00-hPEA10.00) and embodiment 9 synthesize polyetheramine/Kynoar composite porous film (P15.00-hPEA5.00)
For the saturated extent of adsorption figure of different dyes.
Embodiment
Below, present invention is further illustrated with embodiment, but protection scope of the present invention is not limited to reality
Apply example.Other changes for being made to those skilled in the art in the case of without departing substantially from spirit and scope of the present invention and
Modification, is included within the scope of the present invention.
The infrared spectrum of the present invention is measured by REAL TIME INFRARED THERMAL IMAGE instrument (Thermo IS10 Fourier infrared spectrographs device)
's.
The x-ray photoelectron power spectrum of the present invention is by x-ray photoelectron spectroscopy (AXIS ULTRA DLDX ray light
Electron spectrometer) measure.
The surface topography map of the present invention is measured by electron microscope (SM-7401 electron microscopes), and voltage is
5kV, all polyetheramine/Kynoar composite porous films are both needed to metal spraying before observation.
The saturated extent of adsorption figure of the present invention is by dual-beam ultraviolet-uisible spectrophotometer (UV-2550 spectrophotometers)
Measure.
Embodiment 1
(a) by 2 moles of NEEDs (NEED), 1 mole of polyethyleneglycol diglycidylether (PEGDE) and 1 mole
PPOX diglycidyl ether (PPGDE), which is dissolved in ethanol, to be placed in three-necked flask, and under the protection of nitrogen, normal temperature is stirred
Mixing 48h is mixed, 24h is then reacted at 78 DEG C, after reaction terminates, revolving removes ethanol, is dried in 60 DEG C of constant-temperature vacuum baking ovens
Obtain hyperbranched polyetheramine (hPEA211)；
(b) it is 1 mole of hyperbranched polyetheramine (hPEA211) is fragrant with 0.33 mole of 7- (2,3- glycidoxies) -4- methyl
Legumin (EC), which is dissolved in ethanol, to be placed in three-necked flask, and 24h, then 0.67 mole of the addition in three-necked flask are reacted at 80 DEG C
3- (2- perfluoro hexyls ethyoxyl) -1,2- expoxy propane (CF6), after reaction terminates, revolving removes ethanol, is carried out in n-hexane
Precipitation, dries in 60 DEG C of constant-temperature vacuum baking ovens, obtains graft polyether amine (hPEA211-EC-CF6).
Fig. 1 is the structure chart and infrared spectrum of target product：FT-IR(KBr)：1726cm-1,1614cm-1(phenyl ring),
1241cm-1,1203cm-1(C-F)。
Embodiment 2
(a) by 3 moles of NEEDs (NEED), 2 moles of polyethyleneglycol diglycidylethers (PEGDE) and 1 mole
PPOX diglycidyl ether (PPGDE), which is dissolved in ethanol, to be placed in three-necked flask, and under the protection of nitrogen, normal temperature is stirred
Mixing 48h is mixed, 24h is then reacted at 78 DEG C, after reaction terminates, revolving removes ethanol, is dried in 60 DEG C of constant-temperature vacuum baking ovens
Obtain hyperbranched polyetheramine (hPEA321)；
(b) it is 1 mole of hyperbranched polyetheramine (hPEA321) is fragrant with 0.33 mole of 7- (2,3- glycidoxies) -4- methyl
Legumin (EC), which is dissolved in ethanol, to be placed in three-necked flask, and 24h, then 0.67 mole of the addition in three-necked flask are reacted at 80 DEG C
3- (2- perfluoro hexyls ethyoxyl) -1,2- expoxy propane (CF6), after reaction terminates, revolving removes ethanol, is carried out in n-hexane
Precipitation, dries in 60 DEG C of constant-temperature vacuum baking ovens, obtains graft polyether amine (hPEA321-EC-CF6).
Embodiment 3
(a) by 2 moles of NEEDs (NEED), 1 mole of polyethyleneglycol diglycidylether (PEGDE) and 1 mole
PPOX diglycidyl ether (PPGDE), which is dissolved in ethanol, to be placed in three-necked flask, and under the protection of nitrogen, normal temperature is stirred
Mixing 48h is mixed, 24h is then reacted at 78 DEG C, after reaction terminates, revolving removes ethanol, is dried in 60 DEG C of constant-temperature vacuum baking ovens
Obtain hyperbranched polyetheramine (hPEA211)；
(b) it is 1 mole of hyperbranched polyetheramine (hPEA211) is fragrant with 0.33 mole of 7- (2,3- glycidoxies) -4- methyl
Legumin (EC), which is dissolved in ethanol, to be placed in three-necked flask, and 24h, then 0.67 mole of the addition in three-necked flask are reacted at 80 DEG C
3- (2- perfluoro capryls ethyoxyl) -1,2- expoxy propane (CF8), after reaction terminates, revolving removes ethanol, is carried out in n-hexane
Precipitation, dries in 60 DEG C of constant-temperature vacuum baking ovens, obtains graft polyether amine (hPEA211-EC-CF8).
Embodiment 4
(a) by 2 moles of NEEDs (NEED), 1 mole of polyethyleneglycol diglycidylether (PEGDE) and 1 mole
PPOX diglycidyl ether (PPGDE), which is dissolved in ethanol, to be placed in three-necked flask, and under the protection of nitrogen, normal temperature is stirred
Mixing 48h is mixed, 24h is then reacted at 78 DEG C, after reaction terminates, revolving removes ethanol, is dried in 60 DEG C of constant-temperature vacuum baking ovens
Obtain hyperbranched polyetheramine (hPEA211)；
(b) it is 1 mole of hyperbranched polyetheramine (hPEA211) and 0.33 mole of 9- anthracene methoxyl group glycidol ether (E-AN) is molten
It is placed in ethanol in three-necked flask, 24h, then 0.67 mole of 3- (2- perfluor of addition in three-necked flask is reacted at 80 DEG C
Hexyl ethyoxyl) -1,2- expoxy propane (CF6), after reaction terminates, revolving removes ethanol, is precipitated in n-hexane, in 60
Dried in DEG C constant-temperature vacuum baking oven, obtain graft polyether amine (hPEA211-AN-CF6).
Embodiment 5
(a) it is the poly- inclined of 17wt% to be dissolved in dimethyl acetamide (DMAc) mass fraction is made by Kynoar (PVDF)
PVF solution, then graft polyether amine (hPEA211-EC-CF6) and Kynoar solution is blended so that graft polyether
Mass fraction of the amine in blended liquid is 2.50wt%, and mass fraction of the Kynoar in blended liquid is 10wt%, 40
24h is stirred at DEG C, casting solution is made；
(b) casting solution obtained by step (a) is scraped on glass plate, being immersed in 20 DEG C of tank, by film glass after 5s
Take off, dried at 20 DEG C on plate, dry after under 365nm ultraviolet light illumination 12h, produce polyetheramine/Kynoar be combined
Perforated membrane (P10.00-hPEA2.50).
In Fig. 3, (a1) is polyvinylidene fluoride film cross-section morphology electromicroscopic photograph, and (a2) is Kynoar environmental microbes electricity
Mirror photo；Fig. 3 (b1) is that polyetheramine/Kynoar composite porous film (P10.00-hPEA2.50) synthesized by embodiment 5 breaks
Face pattern electromicroscopic photograph, (b2) is polyetheramine/Kynoar composite porous film (P10.00- synthesized by embodiment 5
HPEA2.50) surface topography electromicroscopic photograph.
Embodiment 6
(a) it is the poly- inclined of 17wt% to be dissolved in dimethyl acetamide (DMAc) mass fraction is made by Kynoar (PVDF)
PVF solution, then graft polyether amine (hPEA211-EC-CF6) and Kynoar solution is blended so that graft polyether
Mass fraction of the amine in blended liquid is 3.33wt%, and mass fraction of the Kynoar in blended liquid is 10wt%, 40
24h is stirred at DEG C, casting solution is made；
(b) casting solution obtained by step (a) is scraped on glass plate, being immersed in 20 DEG C of tank, by film glass after 5s
Take off, dried at 20 DEG C on plate, dry after under 365nm ultraviolet light illumination 12h, produce polyetheramine/Kynoar be combined
Perforated membrane (P10.00-hPEA3.33).
Fig. 3 (c1) is polyetheramine/Kynoar composite porous film (P10.00-hPEA3.33) synthesized by embodiment 3
Cross-section morphology electromicroscopic photograph, (c2) is polyetheramine/Kynoar composite porous film (P10.00- synthesized by embodiment 6
HPEA3.33) surface topography electromicroscopic photograph；Fig. 2 is polyetheramine/Kynoar composite porous film synthesized by embodiment 6
(P10.00-hPEA3.33) full spectrum scanning figure.
Embodiment 7
(a) it is the poly- inclined of 17wt% to be dissolved in dimethyl acetamide (DMAc) mass fraction is made by Kynoar (PVDF)
PVF solution, then graft polyether amine (hPEA211-EC-CF6) and Kynoar solution is blended so that graft polyether
Mass fraction of the amine in blended liquid is 5.00wt%, and mass fraction of the Kynoar in blended liquid is 10wt%, 40
24h is stirred at DEG C, casting solution is made；
(b) casting solution obtained by step (a) is scraped on glass plate, being immersed in 20 DEG C of tank, by film glass after 5s
Take off, dried at 20 DEG C on plate, dry after under 365nm ultraviolet light illumination 12h, produce polyetheramine/Kynoar be combined
Perforated membrane (P10.00-hPEA5.00).
Fig. 3 (d1) is polyetheramine/Kynoar composite porous film (P10.00-hPEA5.00) synthesized by embodiment 7
Cross-section morphology electromicroscopic photograph, (d2) is polyetheramine/Kynoar composite porous film (P10.00- synthesized by embodiment 7
HPEA5.00) surface topography electromicroscopic photograph.
Embodiment 8
(a) it is the poly- inclined of 17wt% to be dissolved in dimethyl acetamide (DMAc) mass fraction is made by Kynoar (PVDF)
PVF solution, then graft polyether amine (hPEA211-EC-CF6) and Kynoar solution is blended so that graft polyether
Mass fraction of the amine in blended liquid is 10.00wt%, and mass fraction of the Kynoar in blended liquid is 10wt%, 40
24h is stirred at DEG C, casting solution is made；
(b) casting solution obtained by step (a) is scraped on glass plate, being immersed in 20 DEG C of tank, by film glass after 5s
Take off, dried at 20 DEG C on plate, dry after under 365nm ultraviolet light illumination 12h, produce polyetheramine/Kynoar be combined
Perforated membrane (P10.00-hPEA10.00).
Fig. 3 (e1) is polyetheramine/Kynoar composite porous film (P10.00-hPEA10.00) synthesized by embodiment 8
Cross-section morphology electromicroscopic photograph, (e2) is polyetheramine/Kynoar composite porous film (P10.00- synthesized by embodiment 8
HPEA10.00) surface topography electromicroscopic photograph.
Embodiment 9
(a) it is the poly- inclined of 17wt% to be dissolved in dimethyl acetamide (DMAc) mass fraction is made by Kynoar (PVDF)
PVF solution, then graft polyether amine (hPEA211-EC-CF6) and Kynoar solution is blended so that graft polyether
Mass fraction of the amine in blended liquid is 5.00wt%, and mass fraction of the Kynoar in blended liquid is 15wt%, 40
24h is stirred at DEG C, casting solution is made；
(b) casting solution obtained by step (a) is scraped on glass plate, being immersed in 20 DEG C of tank, by film glass after 5s
Take off, dried at 20 DEG C on plate, dry after under 365nm ultraviolet light illumination 12h, produce polyetheramine/Kynoar be combined
Perforated membrane (P15.00-hPEA5.00).
Fig. 3 (f1) is polyetheramine/Kynoar composite porous film (P15.00-hPEA5.00) synthesized by embodiment 9
Cross-section morphology electromicroscopic photograph, (f2) is polyetheramine/Kynoar composite porous film (P15.00- synthesized by embodiment 9
HPEA5.00) surface topography electromicroscopic photograph.
Embodiment 10
Polyetheramine/Kynoar composite porous film of the present invention is compared with traditional polyvinylidene fluoride film, and hydrophily is obtained
Raising has been arrived, and due to wherein containing polyetheramine, so also having had the performance of adsorpting dye molecule concurrently.Therefore this is compound porous
Film can be for the dyestuff in separation water.The present invention is carried out to film Dye Adsorption performance, and specific method is as follows：
12 kinds of hydrophilic dyes have been used in an experiment：Fluorescein (FR), 4 ', 5 '-two bromo fluoresceins (DBF), Eosin B
(EB), erythrosine (ETB), the chlorofluoresceins of 3,4,5,6- tetra- (TCF), rose-red (RB), calcium flavin (Cal), Ponceau S
(PS), bismarck brown (BBY), acid red (AR), methylene blue (MB), Evans blue (EVB)., will under conditions of 25 DEG C
15mg composite membranes are added in 15ml dye solutions, and the initial concentration of dyestuff is 300 μm of ol/L, and absorption dyestuff is up to balance.Pass through
Uv-vis spectra, measures the concentration of dyestuff before and after absorption, and the molal quantity of absorption dyestuff is calculated accordingly, adsorbs the molal quantity of dyestuff
Divided by composite porous film graft polyether amine quality, produce saturated extent of adsorption.
Fig. 4 is that the saturation of the dyestuff in the aqueous solution is inhaled using polyetheramine/Kynoar composite porous film of the present invention
Attached spirogram.Saturated extent of adsorption refers to the amount of every gram of graft polyether amine absorption dyestuff in the state of the equilibrium, in actual applications, saturation
Adsorbance is to weigh the important parameter of adsorbent adsorption effect.Specifically, Fig. 4 is polyetheramine/poly- inclined fluorine that embodiment 5 is synthesized
Ethene composite porous film P10.00-hPEA2.50, polyetheramine/Kynoar composite porous film that case study on implementation 6 is synthesized
P10.00-hPEA3.33, polyetheramine/Kynoar composite porous film P10.00-hPEA5.00 that embodiment 7 is synthesized, implement
The polyetheramine that the polyetheramine/Kynoar composite porous film P10.00-hPEA10.00 and embodiment 9 that example 8 is synthesized are synthesized/poly-
Vinylidene composite porous film P15.00-hPEA5.00 is to dyestuff saturated extent of adsorption figure in the aqueous solution.
As can be seen from Figure 4, polyetheramine/Kynoar composite porous film has preferable adsorbance to ETB, EB, TCF, RB, inhales
Attached amount is in 500 μm of ol/L or so；And it is less for the Dye Adsorption amount such as Cal, MB.The composite porous film positively charged, but it is negative to band
But adsorbance is less by the Cal of electricity, and this shows suction of the electrostatic force to dyestuff between the composite porous film subject and object dyestuff
It is attached to have not significant impact.In addition from figure, it was also found that for the overall adsorbance of all dyestuffs, P15.00-hPEA5.00
Saturated extent of adsorption it is maximum, and P10.00-hPEA10.00 saturated extent of adsorption is minimum, because P15.00-hPEA5.00 tools
There is very high specific surface area so being conducive to adsorbing dyestuff.
Claims (10)
1. a kind of polyetheramine/Kynoar composite porous film for being used to adsorb dyestuff in water, it is characterised in that this is compound porous
Film is obtained by Kynoar and the crosslinking of graft polyether amine；Wherein：Shown in the structure such as formula (1) of the graft polyether amine：
Wherein, X represents polyether chain；A isOr be not present；B represents the carbon that fluorine atom partly or completely replaces
Atomicity is 1-30 alkyl or oxyalkyl chain；U represents photocrosslinking agent molecule residues；
Y represents coinitiator amine molecule residue, and it has structure shown in formula (3)：
Wherein, R2For C2-C10Straight or branched alkyl, R3The C replaced for hydrogen or completely1-C30Alkyl.
2. polyetheramine according to claim 1/Kynoar composite porous film, it is characterised in that Kynoar and
The mass ratio of graft polyether amine is 1:15~20:1.
3. polyetheramine according to claim 1/Kynoar composite porous film, it is characterised in that the graft polyether
In amine, X has structure shown in following (2)：
Wherein, R1For C1-C20Straight or branched alkyl, 0<n<20.
4. polyetheramine according to claim 1/Kynoar composite porous film, it is characterised in that the graft polyether
In amine, U has structure shown in formula (4)：
Wherein, R4、R5Separately it is selected from hydrogen, C1-C20Straight or branched alkyl.
5. polyetheramine/Kynoar that a kind of being used for according to one of Claims 1 to 4 adsorbs dyestuff in water is compound more
The preparation method of pore membrane, it is characterised in that comprise the following steps that：
(1) it is 1 according to mol ratio:10~10:1 is dissolved in the organic amine containing primary amine and secondary amine and the polyethers containing diepoxy group
In alcohol, under the protection of inert gas, then stirring at normal temperature mixing 12h~60h reacts 12h~60h, reaction at 60~120 DEG C
After end, organic solvent is rotated and removed, dried, obtain hyperbranched polyetheramine；Wherein：It is described organic containing primary amine and secondary amine
The structural formula of amine monomers is such as shown in (5)：
Wherein, R2For C2-C10Straight or branched alkyl, R3The C replaced for hydrogen or completely1-C30Alkyl；
(2) hyperbranched polyetheramine is dissolved in alcohol with the small molecule photocrosslinking agent with functional group, reacted at 60~120 DEG C
12h~60h, adds the monomer containing fluorocarbon chain, and after reaction terminates, revolving removes organic solvent, is precipitated in precipitating reagent,
Dry, obtain graft polyether amine；Wherein：Hyperbranched polyetheramine, the small molecule photocrosslinking agent with functional group and containing fluorocarbon chain
The mol ratio of monomer is (1~10)：(1~10)：(1~10)；
(3) Kynoar is dissolved in dimethyl acetamide and the Kynoar solution that mass fraction is 1%~50% is made, so
Graft polyether amine and the Kynoar solution blending that step (2) is obtained afterwards so that matter of the graft polyether amine in blended liquid
Amount fraction is 1~20wt%, and mass fraction of the Kynoar in blended liquid is 1~15wt%, is stirred at 30~100 DEG C
12h~60h, is made casting solution；
(4) casting solution obtained by step (3) is scraped on glass plate, being immersed in 10~40 DEG C of tank, by film after 5~30s
Take off, dried at a temperature of 10~150 DEG C on glass plate, 12~60h of illumination under ultraviolet light after drying produces polyetheramine/poly-
Vinylidene composite porous film.
6. preparation method according to claim 5, it is characterised in that in step (1), the knot of the polyethers containing diepoxy group
Structure formula is such as shown in (6)：
Wherein, R1For C1-C20Straight or branched alkyl, 0<n<20.
7. preparation method according to claim 5, it is characterised in that in step (2), the small molecule photo-crosslinking with functional group
The structural formula of agent is such as shown in (7)：
R9-U (7)
Wherein, U represents photocrosslinking agent molecule residues, R9For epoxide group.
8. preparation method according to claim 5, it is characterised in that in step (2), the structural formula of the monomer containing fluorocarbon chain
As shown in (8)：
Rl0-B (8)
Wherein, B represents the alkyl or oxyalkyl chain that the carbon number that fluorine atom partly or completely replaces is 1-30, R10For epoxy
Group.
9. preparation method according to claim 5, it is characterised in that in step (2), precipitating reagent is n-hexane or oil
Ether.
10. preparation method according to claim 5, it is characterised in that in step (1), inert gas is nitrogen.
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