CN102190761B - Fluorine-containing amphipathic modifying material for preparing antifouling membrane and preparation method thereof - Google Patents
Fluorine-containing amphipathic modifying material for preparing antifouling membrane and preparation method thereof Download PDFInfo
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- CN102190761B CN102190761B CN201110062406A CN201110062406A CN102190761B CN 102190761 B CN102190761 B CN 102190761B CN 201110062406 A CN201110062406 A CN 201110062406A CN 201110062406 A CN201110062406 A CN 201110062406A CN 102190761 B CN102190761 B CN 102190761B
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- fluorine
- terepthaloyl moietie
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- modifying material
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Abstract
The invention relates to a fluorine-containing amphipathic modifying material for preparing an antifouling membrane and a preparation method thereof. The fluorine-containing amphipathic modifying material has a structure formula shown in the specification. The preparation method of the fluorine-containing amphipathic modifying material comprises the following steps of: feeding a polyethylene glycol-polymethoxy propylene-polyethylene glycol segmented copolymer and methacrylic acid hexafluorobutyl according to mole ratio into deionized water to obtain an emulsified liquid; feeding ammonium ceric nitrate as an initiator under the protection of nitrogen gas, stirring and reacting to obtain a reaction solution containing a product; and carrying out water removal, impurity removal and drying on the reaction solution to obtain the fluorine-containing amphipathic modifying material. The invention has the advantages that the preparation method has mild process and conditions and is simple and feasible; and the obtained fluorine-containing amphipathic modifying material is used for preparing the antifouling membrane with excellent performances.
Description
Technical field
The present invention relates to a kind of the fluorine-containing amphipathic material modified and preparation method thereof of pollution-resistant membrane that be used to prepare, belong to the material of preparing technology.
Background technology
An important factor that influences the film pollution is exactly a mould material, and major part is the hydrophobic polymer film in the existing mould material, and the hydrophobicity of film causes that easily serious film pollutes; Though some hydrophilic film materials have good anti pollution property, relatively poor stalling characteristic and tolerance have limited the widespread use of these materials.Thereby at present, the attention that solves the film pollution concentrates on and prepares low the pollution on the separatory membrane, comprises the development of new macromolecular material, and it is surperficial that existing mould material of modification and modification have film now.The above two costs are higher, and on large-scale application, have difficulties; And the existing film surface of modification can be on the basis of not destroying original polymeric membrane good characteristic, and improving film suppresses pollution capacity, therefore becomes the effective way that solves membrane pollution problem.
Hence one can see that, and the pollution-resistant membrane of designing and preparing efficient general is material modified, and it is extremely important for suppressing the film pollution to be used for existing film surface, and can realize simultaneously in the membrane prepare process as if modifying process, both need not subsequent disposal, must be better selection.Membrane surface modification require to increase the film surface hydrophilicity, and through discovering that two types of materials possess good antifouling property: one type is the material that has the zwitter-ion group for example phosphatide, sulphur ammonium polymer; Another kind of is T 46155 (PEO) or polyoxyethylene glycol (PEG) etc.Yet this type of modification molecule generally has higher wetting ability, and higher wetting ability can cause the modification molecule to have than highly water-soluble, and this will make most surfaces modification molecule in membrane prepare and use, run off, and has reduced modified effect.Thereby; In recent years, based on above-mentioned zwitter-ion and PEO/PEG material etc., investigators have designed the Amphipathilic block polymer that a series of hydrophilic/hydrophobic segments are inlayed; Not only realized the surface enrichment of hydrophilic section; Hydrophobic segment can be suppressed at the loss of surface-modified molecules in the film process on the one hand simultaneously, can make film have comparatively stable modified effect through with the interaction of film material of main part that surface-modified molecules " grappling " is surperficial at film on the other hand.But, make a general survey of the research of existing modification pollution-resistant membrane performance, simple hydrophilic modifying does not obviously reach gratifying antipollution effect, although the cleaning restorability of film is improved, the flux decay is still serious.When this just requires that pollution-resistant membrane is material modified to possess hydrophobic " grappling section ", hydrophilic " antipollution section "; Also should possess effective segment of giving film good " pollution releasability "; And can realize the common enrichment of hydrophilic " antipollution section " and " pollution releasing section " simultaneously on the film surface; With further reduction flux decay, realize the efficient hardening of membrane sepn process.
Summary of the invention
The object of the present invention is to provide a kind of the fluorine-containing amphipathic material modified and preparation method thereof of pollution-resistant membrane that be used to prepare.This fluorine-containing amphipathic material modified system is one of preparation pollution-resistant membrane film good material, and its preparation method is simple.
The present invention realizes that through following technical proposals a kind of being used to prepares the fluorine-containing amphipathic material modified of pollution-resistant membrane, it is characterized in that, this fluorine-containing amphipathic material modified be polyoxyethylene glycol (EO)
a-gather methoxy propylene (PO)
b-polyoxyethylene glycol (EO)
aThe multipolymer of segmented copolymer (formal name used at school is Prist (Poloxamer), and commodity are called pluronic Pluronic) and methylacrylic acid hexafluoro butyl ester (HFBMA), molecular-weight average M
w=1250～16500, its structural formula is suc as formula shown in 1, in the formula: a=15～100, and b=40～69, n=1～20, the infrared absorption spectrum charateristic avsorption band is :-CH
3Stretching vibration absorption peak 2846cm
-1-CH
2Stretching vibration absorption peak 2776cm
-1C-O-C stretching vibration absorption peak 1259cm
-1And 1134cm
-1C=O stretching vibration absorption peak 1700cm
-1C-F rocking vibration absorption peak 692cm
-1Its character: normal temperature is down white sticky shape solid, soluble in water, ethanol, N, ethanamide, methyl-sulphoxide polar solvent.
Above-mentioned fluorine-containing amphipathic material modified preparation method is characterized in that may further comprise the steps:
1) with polyoxyethylene glycol (EO)
a-gather methoxy propylene (PO)
b-polyoxyethylene glycol (EO)
aSegmented copolymer (Prist) is 1: 0.01～1 with methylacrylic acid hexafluoro butyl ester (HFBMA) by the mole proportioning; Add deionized water and process emulsion; Under nitrogen protection, slowly drip the salpeter solution of initiator ceric ammonium nitrate to emulsion, the consumption of ceric ammonium nitrate by and T 46155 (EO)
a-methoxy propylene (PO)
b-T 46155 (EO)
aThe mass ratio of segmented copolymer is 1: 0.2～0.8, and the concentration of nitric acid is 1mol/L, obtains containing the reaction soln of product at 60 ℃ of following stirring reaction 20～24h of temperature;
2) reaction soln that contains product of step 1) system is anhydrated, after dissolve with ethanol impurity elimination, revaporization remove ethanol, in 50 ℃ of vacuum-dryings of temperature, obtains (HFBMA) through evaporation
n-(EO)
a-(PO)
b-(EO)
a-(HFBMA)
nFluorine-containing amphipathic material modified.
The invention has the advantages that: this preparing method's process condition is gentle, simple, and the water soap-free emulsion synthesizes green non-pollution, can not produce harm to human body; Gained is material modified various in style, is used to prepare pollution-resistant membrane, and film properties is superior; And wherein hydrophobic PPO is as " grappling section "; Hydrophilic PEO is as " antipollution section ", and low surface energy is as PDFHMA " pollution releasing section ", thereby gives film lasting stability, antifouling property efficiently.
Description of drawings
Fig. 1 is (a methylacrylic acid hexafluoro butyl ester)
n-(terepthaloyl moietie)
a-(methoxy propylene)
b-(terepthaloyl moietie)
a-(methylacrylic acid hexafluoro butyl ester)
nFluorine-containing amphipathic material modified ir spectra spectrogram.
Embodiment
Embodiment 1
Prist F127 block macromolecular (EO) with 5g
98-(PO)
67-(EO)
98Reach 0.80g methylacrylic acid hexafluoro butyl ester (HFBMA) and place the there-necked flask that has whisking appliance, add the 100mL deionized water, 0.5h is stirred in nitrogen protection, forms stable emulsion, and (the 0.49g ceric ammonium nitrate is dissolved in 20mL 1mol/L HNO to add initiator solution
3In); After stirring 24h under 60 ℃; Reaction solution is that evaporation anhydrates, uses thereafter that washing with alcohol to solid matter dissolves fully, 40 ℃ then, vacuum tightness remove ethanol as evaporating 0.1MPa under under the 0.1MPa at 50 ℃, vacuum tightness, and 50 ℃ of vacuum-drying 24h obtain white sticky shape solid (HFBMA)
4-(EO)
98-(PO)
67-(EO)
98-(HFBMA)
4Graft copolymer, productive rate is near 95%.
Embodiment 2
Prist F127 block macromolecular (EO) with 5g
98-(PO)
67-(EO)
98Reach 1.60g methylacrylic acid hexafluoro butyl ester (HFBMA) and place the there-necked flask that has whisking appliance, add the 100mL deionized water, 0.5h is stirred in nitrogen protection, forms stable emulsion, and (the 0.49g ceric ammonium nitrate is dissolved in 20mL 1mol/L HNO to add initiator solution
3In); After stirring 24h under 60 ℃; Reaction solution is that evaporation anhydrates, uses thereafter that washing with alcohol to solid matter dissolves fully, 40 ℃ then, vacuum tightness remove ethanol as evaporating 0.1MPa under under the 0.1MPa at 50 ℃, vacuum tightness, and 50 ℃ of vacuum-drying 24h obtain white sticky shape solid (HFBMA)
8-(EO)
98-(PO)
67-(EO)
98-(HFBMA)
8Graft copolymer, productive rate is near 95%.
Embodiment 3
Prist F127 block macromolecular (EO) with 5g
98-(PO)
67-(EO)
98Reach 2.00g methylacrylic acid hexafluoro butyl ester (HFBMA) and place the there-necked flask that has whisking appliance, add the 100mL deionized water, 0.5h is stirred in nitrogen protection, forms stable emulsion, and (the 0.49g ceric ammonium nitrate is dissolved in 20mL 1mol/LHNO to add initiator solution
3In); After stirring 24h under 60 ℃; Reaction solution is that evaporation anhydrates, uses thereafter that washing with alcohol to solid matter dissolves fully, 40 ℃ then, vacuum tightness remove ethanol as evaporating 0.1MPa under under the 0.1MPa at 50 ℃, vacuum tightness, and 50 ℃ of vacuum-drying 24h obtain white sticky shape solid (HFBMA)
10-(EO)
98-(PO)
67-(EO)
98-(HFBMA)
10Graft copolymer, productive rate is near 95%.
Embodiment 4
Prist F127 block macromolecular (EO) with 5g
98-(PO)
67-(EO)
98Reach 2.40g methylacrylic acid hexafluoro butyl ester (HFBMA) and place the there-necked flask that has whisking appliance, add the 100mL deionized water, 0.5h is stirred in nitrogen protection, forms stable emulsion, and (the 0.49g ceric ammonium nitrate is dissolved in 20mL 1mol/L HNO to add initiator solution
3In); After stirring 24h under 60 ℃; Reaction solution is that evaporation anhydrates, uses thereafter that washing with alcohol to solid matter dissolves fully, 40 ℃ then, vacuum tightness remove ethanol as evaporating 0.1MPa under under the 0.1MPa at 50 ℃, vacuum tightness, and 50 ℃ of vacuum-drying 24h obtain white sticky shape solid (HFBMA)
16-(EO)
98-(PO)
67-(EO)
98-(HFBMA)
16Graft copolymer, productive rate is near 95%.
Claims (2)
1. one kind is used to prepare the fluorine-containing amphipathic material modified of pollution-resistant membrane, it is characterized in that, this fluorine-containing amphipathic material modified be (terepthaloyl moietie)
a-(oxypropylene)
b-(terepthaloyl moietie)
aThe multipolymer of segmented copolymer and methylacrylic acid hexafluoro butyl ester, molecular-weight average M
w=1250～16500, its structural formula is suc as formula shown in 1, in the formula: a=15～100, and b=40～69, n=1～20, the infrared absorption spectrum charateristic avsorption band is :-CH
3Stretching vibration absorption peak 2846cm
-1-CH
2Stretching vibration absorption peak 2776cm
-1C-O-C stretching vibration absorption peak 1259cm
-1And 1134cm
-1C=O stretching vibration absorption peak 1700cm
-1C-F rocking vibration absorption peak 692cm
-1Its character: normal temperature is down white sticky shape solid, soluble in water, ethanol, N, ethanamide, methyl-sulphoxide polar solvent,
Formula 1
。
2. press the described fluorine-containing amphipathic material modified preparation method of claim 1 for one kind, it is characterized in that may further comprise the steps:
1) with (terepthaloyl moietie)
a-(oxypropylene)
b-(terepthaloyl moietie)
aSegmented copolymer and methylacrylic acid hexafluoro butyl ester are 1: 0.01～1 by the mole proportioning, add deionized water and process emulsion, under nitrogen protection, slowly drip the salpeter solution of initiator ceric ammonium nitrate to emulsion, the consumption of ceric ammonium nitrate by and (terepthaloyl moietie)
a-(oxypropylene)
b-(terepthaloyl moietie)
aThe mass ratio of segmented copolymer is 0.49: 5, and the concentration of nitric acid is 1mol/L, obtains containing the reaction soln of product at 60 ℃ of following stirring reaction 20～24h of temperature;
2) reaction soln that contains product of step 1) system is anhydrated, after dissolve with ethanol impurity elimination, revaporization remove ethanol,, obtains (methylacrylic acid hexafluoro butyl ester) in 50 ℃ of vacuum-dryings of temperature through evaporation
n-(terepthaloyl moietie)
a-(oxypropylene)
b-(terepthaloyl moietie)
a-(methylacrylic acid hexafluoro butyl ester) n's is fluorine-containing amphipathic material modified.
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| CN102746477B (en) * | 2012-07-05 | 2014-04-16 | 天津大学 | Fluorine-containing amphiphilic modification material used for preparation of membrane with excellent performances and preparation method |
| CN104474931B (en) * | 2014-12-04 | 2016-03-23 | 天津大学 | A kind of preparation method of Kynoar hybridized film of modification and application thereof |
| CN110548420B (en) * | 2019-08-06 | 2021-12-17 | 天津大学 | Preparation method of zero-flux attenuation chemical heterogeneous hydrogel ultrafiltration membrane |
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| CN101250369B (en) * | 2008-03-25 | 2010-12-15 | 中国科学院广州化学研究所 | Aqueous composite paint containing amphiphilic fluorine-containing acrylate blocking copolymer and preparation thereof |
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Non-Patent Citations (3)
| Title |
|---|
| O. Iguerb.Antifouling Properties of Poly(methyl methacrylate) Films Grafted with Poly(ethylene glycol) Monoacrylate Immersed in Seawater.《Langmuir》.2008,第24卷(第21期),第12272-12281页. * |
| Yan-Qiang Wang.Pluronic polymers and polyethersulfone blend membranes with improved fouling-resistant ability and ultrafiltration performance.《Journal of Membrane Science》.2006,第283卷(第1-2期),第440-447页. |
| Yan-Qiang Wang.Pluronic polymers and polyethersulfone blend membranes with improved fouling-resistant ability and ultrafiltration performance.《Journal of Membrane Science》.2006,第283卷(第1-2期),第440-447页. * |
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