CN102500241B - Preparation method for anti-pollution permeable vaporization film - Google Patents
Preparation method for anti-pollution permeable vaporization film Download PDFInfo
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- CN102500241B CN102500241B CN201110375074.XA CN201110375074A CN102500241B CN 102500241 B CN102500241 B CN 102500241B CN 201110375074 A CN201110375074 A CN 201110375074A CN 102500241 B CN102500241 B CN 102500241B
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Abstract
The invention relates to a preparation method for an anti-pollution permeable vaporization film. A film coating solution formed by reaction of polysiloxane and fluorine-containing silane is coated on the surface of a permeable vaporization film; and a fluorine-containing group in the coating has low surface energy, so pollutants is attached to the surface of the film difficultly and the permeable vaporization film has a high anti-pollution property. The chemical bond action is formed between the coating and the surface of the permeable vaporization film, so the permeable vaporization film prepared by the method has a high structural stability. Compared with the unmodified permeable vaporization film, the anti-pollution permeable vaporization film prepared by the anti-pollution modification method can maintain stable permeation flux and selectivity when is operated continuously for a long time in a system comprising microorganisms.
Description
Technical field
The invention belongs to infiltrating and vaporizing membrane preparation field, relate in particular to a kind of preparation method of anti-pollution permeable vaporization film.
Background technology
In recent years, membrane separation technique is widely used in water treatment, beverage processing, biochemical industry, medicine and other fields.Wherein, infiltration evaporation is as a kind of novel membrane separation technique, because it has energy-saving and environmental protection, the advantage such as efficient, in fields such as biomass fuel preparation, organic solvent recovery, dehydration of organic solvent, organic mixture separation, has increasing application.
When infiltrating and vaporizing membrane is for the treatment of the system that contains microorganism during as biomass ferment liquid, sanitary wastewater, it is the critical problem of puzzlement film application that film pollutes, and film pollutes and will cause film properties to decline and reduce the stability of membrane material itself.Antipollution modification for film at present mainly concentrates on hydrophilically modified aspect, and the pollution-resistant membrane of these hydrophilic modifyings is used to micro-filtration, ultrafiltration, nanofiltration and counter-infiltration field.But, for infiltrating and vaporizing membrane, because requiring film, a lot of application systems there is stronger hydrophobicity, as reclaimed alcohol organic solvent in biomass ferment liquid, reclaim various organic solvents etc. in waste water, hydrophilically modified method is prepared resistant to pollution infiltrating and vaporizing membrane and is just had significant limitation.Therefore, how to keep under the hydrophobic prerequisite of film, preparing resistant to pollution infiltrating and vaporizing membrane is the challenge that we face.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of anti-pollution permeable vaporization film.The present invention is by applying the thin and stable hydrophobic antipollution organic coating of one deck on existing infiltrating and vaporizing membrane surface, thus the contamination resistance of raising infiltrating and vaporizing membrane.
Technical scheme of the present invention: a kind of preparation method of anti-pollution permeable vaporization film, its concrete steps are as follows: in container, add organic solvent, polysiloxane, fluorine containing silane and catalyst, wherein the quality that adds of organic solvent is 5～35 times of polysiloxane quality, the quality that adds of fluorine containing silane is 0.05～0.3 times of polysiloxane quality, the quality that adds of catalyst is 0.005～0.01 times of polysiloxane quality, obtains uniform coating solution after stirring; Then coating solution is coated in to infiltrating and vaporizing membrane surface equably, after Overheating Treatment, on infiltrating and vaporizing membrane surface, forms the thin and stable antipollution rete of one deck, thereby prepare anti-pollution permeable vaporization film.
Preferably described organic solvent is hexane, heptane, toluene or oxolane; Also can be the mixture of the arbitrary proportion of above-mentioned several organic solvents.
Described polysiloxane is the polysiloxane of hydroxyl, chlorine or hydrogen end-blocking; Preferably polysiloxane is dihydroxy-PSI, dihydroxy-dimethyl silicone polymer, two chloro-dimethyl silicone polymer or diethoxy-dimethyl silicone polymers; Also can be the mixture of the arbitrary proportion of above-mentioned several polysiloxane.
Described fluorine containing silane is for containing CF
3or CF
2the silane of segment; Preferably (3,3,3-trifluoro propyl) trimethoxy silane, (3,3,3-trifluoro propyl) trichlorosilane, 1H, 1H, 2H, 2H-perfluor decyl triethoxysilane or trichlorine (1H, 1H, 2H, 2H-perfluoro capryl) silane; Also can be the mixture of the arbitrary proportion of above-mentioned several fluorine containing silanes.
Preferably described catalyst is dibutyl tin acetate, diethyl two tin laurates, dibutyl tin dilaurate, aniline, dibutylamine or chloroplatinic acid, more preferably dibutyl tin dilaurate or chloroplatinic acid.
Described is coated in coating solution behind infiltrating and vaporizing membrane surface equably, and preferred heat treated temperature is 80～140 ℃, and heat treatment time is 6～24h.
Described infiltrating and vaporizing membrane is all applicable infiltrating and vaporizing membranes.Preferably infiltrating and vaporizing membrane moral separating layer material is any in following a few class: 1) various organic film materials: as: silicon rubber, butadiene-styrene rubber, acrylonitrile-butadiene rubber, EPDR, poly-trimethyl silicane propine, polypropylene, polybutadiene, Kynoar, polytetrafluoroethylene (PTFE), polyether amide block copolymer or derivatives thereof; 2) various inorganic material films: as: carbon, hydrophobic type molecular sieve, organometallic skeletal; 3) mixed-matrix membrane material: the silicon rubber being adulterated by various inorganic particulates, butadiene-styrene rubber, acrylonitrile-butadiene rubber, EPDR, poly-trimethyl silicane propine, polypropylene, polybutadiene, Kynoar, polytetrafluoroethylene (PTFE), polyether amide block copolymer or derivatives thereof.
Preferably the thickness of the described antipollution rete forming on infiltrating and vaporizing membrane surface is 0.2～10 micron.
Beneficial effect:
Fluoro-containing group in face coat has very low surface energy, causes microorganism to be difficult in film surface attachment, thereby has good antifouling property, makes infiltrating and vaporizing membrane can keep the stability of long-time operation in containing the system of microorganism.Meanwhile, this coating can combine by the effect of chemical bond with infiltration evaporation rete, therefore also has good structural stability.In addition, the coating of the fluoro-containing group that surface applies not only can not reduce the hydrophobicity of infiltrating and vaporizing membrane, can increase to the hydrophobicity of film on the contrary, thus the separation selectivity of raising film; And this antipollution coating has nano level thickness, to the permeation flux of infiltrating and vaporizing membrane, can impact hardly.The present invention also has the advantages such as easy, easy row, universality, can realize the quick and serialization of production technology.
The specific embodiment
Embodiment 1
In container, adding mass ratio is 20: 1: 0.2: 0.01 hexane, dihydroxy-PSI, (3,3,3-trifluoro propyl) trimethoxy silane and dibutyl tin dilaurate, be configured to coating solution after stirring under room temperature.Then the coating liquid configuring is coated in equably to the surface of silicon rubber infiltrating and vaporizing membrane, heat treatment 12h at 90 ℃, forms a layer thickness on film surface and is about the antipollution rete of 3 microns, thereby prepare resistant to pollution silicone rubber membrane.
Comparative example 1
The infiltrating and vaporizing membrane adopting is the silicone rubber membrane in embodiment 1.
Embodiment 2
Coating solution collocation method is with embodiment 1, the coating liquid configuring is coated in to hydrophobic type molecular screen membrane surface equably, heat treatment 24h at 120 ℃, forms a layer thickness on film surface and is about the antipollution rete of 1 micron, thereby prepare resistant to pollution hydrophobic type molecular screen membrane.
Comparative example 2
The infiltrating and vaporizing membrane adopting is the hydrophobic type molecular screen membrane in embodiment 2.
Embodiment 3
Coating solution collocation method is with embodiment 1, the coating liquid configuring is coated in to polyether amide block copolymer film surface equably, cross-linking reaction 18h at 120 ℃, on film surface, form a layer thickness and be about the antipollution rete of 9 microns, thereby prepare resistant to pollution polyether amide block copolymer film.
Comparative example 3
The infiltrating and vaporizing membrane adopting is the polyether amide block copolymer film in embodiment 3.
Embodiment 4
In container, adding mass ratio is 5: 1: 0.3: 0.008 oxolane, dihydroxy-dimethyl silicone polymer, (3,3,3-trifluoro propyl) trichlorosilane and chloroplatinic acid, be configured to coating solution after stirring under room temperature.Then the coating liquid configuring is coated in equably to the surface of silicon rubber infiltrating and vaporizing membrane, heat treatment 12h at 120 ℃, forms a layer thickness on film surface and is about the antipollution rete of 7 microns, thereby prepare resistant to pollution silicone rubber membrane.
Comparative example 4
The infiltrating and vaporizing membrane adopting is the silicone rubber membrane in embodiment 4.
Embodiment 5
Coating solution collocation method is with embodiment 4, the coating liquid configuring is coated in to hydrophobic type molecular screen membrane surface equably, heat treatment 12h at 140 ℃, forms a layer thickness on film surface and is about the antipollution rete of 5 microns, thereby prepare resistant to pollution hydrophobic type molecular screen membrane.
Comparative example 5
The infiltrating and vaporizing membrane adopting is the hydrophobic type molecular screen membrane in embodiment 5.
Embodiment 6
In container, adding mass ratio is 10: 1: 0.3: 0.008 heptane, two chloro-dimethyl silicone polymers, 1H, and 1H, 2H, 2H-perfluor decyl triethoxysilane and chloroplatinic acid, be configured to coating solution after stirring under room temperature.Then the coating liquid configuring is coated in equably to the surface of silicon rubber infiltrating and vaporizing membrane, heat treatment 12h at 80 ℃, forms a layer thickness on film surface and is about the antipollution rete of 0.5 micron, thereby prepare resistant to pollution silicone rubber membrane.
Comparative example 6
The infiltrating and vaporizing membrane adopting is the silicone rubber membrane in embodiment 6.
Embodiment 7
Coating solution collocation method is with embodiment 6, the coating liquid configuring is coated in to polyether amide block copolymer film surface equably, heat treatment 16h at 100 ℃, on film surface, form a layer thickness and be about the antipollution rete of 5.5 microns, thereby prepare resistant to pollution polyether amide block copolymer film.
Comparative example 7
The infiltrating and vaporizing membrane adopting is the polyether amide block copolymer film in embodiment 7.
Embodiment 8
In container, adding mass ratio is 35: 1: 0.05: 0.01 toluene, diethoxy-dimethyl silicone polymer, trichlorine (1H, 1H, 2H, 2H-perfluoro capryl) silane and dibutyl tin dilaurate, be configured to coating solution after stirring under room temperature.Then the coating liquid configuring is coated in equably to the surface of silicon rubber infiltrating and vaporizing membrane, heat treatment 16h at 130 ℃, forms a layer thickness on film surface and is about the antipollution rete of 2 microns, thereby prepare resistant to pollution silicone rubber membrane.
Comparative example 8
The infiltrating and vaporizing membrane adopting is the silicone rubber membrane in embodiment 8.
Embodiment 9
Coating solution collocation method is with embodiment 8, the coating liquid configuring is coated in to hydrophobic type molecular screen membrane surface equably, heat treatment 18h at 100 ℃, forms a layer thickness on film surface and is about the antipollution rete of 0.8 micron, thereby prepare resistant to pollution hydrophobic type molecular screen membrane.
Comparative example 9
The infiltrating and vaporizing membrane adopting is the hydrophobic type molecular screen membrane in embodiment 9.
Embodiment 10
Coating solution collocation method is with embodiment 8, the coating liquid configuring is coated in to polyether amide block copolymer film surface equably, at 100 times cross-linking reaction 18h, on film surface, form a layer thickness and be about the antipollution rete of 6 microns, thereby prepare resistant to pollution polyether amide block copolymer film.
Comparative example 10
The infiltrating and vaporizing membrane adopting is the polyether amide block copolymer film in embodiment 10.
Antifouling property experiment: respectively the infiltrating and vaporizing membrane of unmodified infiltrating and vaporizing membrane and antipollution modification is used for to the acetone/butanol fermentation process of 37 ℃, the organic solvents such as the acetone that infiltration evaporation original position separation and fermentation produces and butanols, continued operation 140h, the flux of investigation infiltrating and vaporizing membrane and separation factor are with the variation of operating time.Experimental result is summarised in table 1.As can be seen from Table 1, the infiltrating and vaporizing membrane of antipollution modification is compared with unmodified infiltrating and vaporizing membrane, and antifouling property improves greatly, and the attenuation rate of film properties is reduced to below 10% by original 50～60%.
The antifouling property of table 1 infiltrating and vaporizing membrane in zymotic fluid
Claims (7)
1. a preparation method for anti-pollution permeable vaporization film, its concrete steps are as follows: in container, add organic solvent, polysiloxane, contain CF
3or CF
2the fluorine containing silane of segment and catalyst, wherein the quality that adds of organic solvent is 5～35 times of polysiloxane quality, the quality that adds of fluorine containing silane is 0.05～0.3 times of polysiloxane quality, the quality that adds of catalyst is 0.005～0.01 times of polysiloxane quality, obtains uniform coating solution after stirring; Then coating solution is coated in to infiltrating and vaporizing membrane surface equably, after Overheating Treatment, on infiltrating and vaporizing membrane surface, forms one deck antipollution rete, thereby prepare anti-pollution permeable vaporization film.
2. preparation method according to claim 1, is characterized in that described organic solvent is hexane, heptane, toluene or oxolane.
3. preparation method according to claim 1, is characterized in that described polysiloxane is dihydroxy-PSI, dihydroxy-dimethyl silicone polymer, two chloro-dimethyl silicone polymer or diethoxy-dimethyl silicone polymers.
4. preparation method according to claim 1, it is characterized in that described fluorine containing silane is (3,3,3-trifluoro propyl) trimethoxy silane, (3,3,3-trifluoro propyl) trichlorosilane, 1H, 1H, 2H, 2H-perfluor decyl triethoxysilane or trichlorine (1H, 1H, 2H, 2H-perfluoro capryl) silane.
5. preparation method according to claim 1, is characterized in that described catalyst is dibutyl tin acetate, diethyl two tin laurates, dibutyl tin dilaurate, aniline, dibutylamine or chloroplatinic acid.
6. preparation method according to claim 1, is characterized in that: coating solution is coated in behind infiltrating and vaporizing membrane surface equably, and described heat treated temperature is 80～140 ℃, and heat treatment time is 6～24h.
7. preparation method according to claim 1, is characterized in that: the thickness of the antipollution rete forming on infiltrating and vaporizing membrane surface is 0.2～10 micron.
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| CN201110375074.XA CN102500241B (en) | 2011-11-22 | 2011-11-22 | Preparation method for anti-pollution permeable vaporization film |
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| CN201110375074.XA CN102500241B (en) | 2011-11-22 | 2011-11-22 | Preparation method for anti-pollution permeable vaporization film |
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| CN102500241B true CN102500241B (en) | 2014-02-26 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108201792B (en) * | 2016-12-16 | 2022-02-11 | 大连联和环保技术有限公司 | Preparation method of fluorine-containing silicone rubber composite separation membrane |
| CN106582314B (en) * | 2017-02-26 | 2019-01-25 | 浙江理工大学 | A kind of small-bore hydrophobic composite membrane preparation method for membrane distillation |
| CN108295669A (en) * | 2018-03-05 | 2018-07-20 | 北京清源洁华膜技术有限公司 | A kind of composite membrane and preparation method thereof of separation VOCs |
| CN112933983B (en) * | 2021-01-29 | 2022-06-28 | 三明学院 | Graphene silicon dioxide core-shell structure filled PDMS hybrid membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1310749A (en) * | 1998-06-30 | 2001-08-29 | 罗狄亚化学公司 | Crosslinkable silicone composition useful, in particular for producing water-repellent and/or oil-repellent coating and/or impregnation with low surface energy |
| CN1331260A (en) * | 2000-06-30 | 2002-01-16 | 中国科学院化工冶金研究所 | Process for preparing anti-pollution film |
| CN1724127A (en) * | 2005-06-16 | 2006-01-25 | 南京工业大学 | Organic and inorganic composite hydrophobic film and its preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262287A (en) * | 2006-03-29 | 2007-10-11 | Dainippon Ink & Chem Inc | Coating composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1310749A (en) * | 1998-06-30 | 2001-08-29 | 罗狄亚化学公司 | Crosslinkable silicone composition useful, in particular for producing water-repellent and/or oil-repellent coating and/or impregnation with low surface energy |
| CN1331260A (en) * | 2000-06-30 | 2002-01-16 | 中国科学院化工冶金研究所 | Process for preparing anti-pollution film |
| CN1724127A (en) * | 2005-06-16 | 2006-01-25 | 南京工业大学 | Organic and inorganic composite hydrophobic film and its preparing process |
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| Title |
|---|
| JP特开2007-262287A 2007.10.11 |
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