CN106345308B - A kind of chlorine resistance is strong and the preparation method of resistant to pollution polyesteramide composite nanometer filtering film - Google Patents
A kind of chlorine resistance is strong and the preparation method of resistant to pollution polyesteramide composite nanometer filtering film Download PDFInfo
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- CN106345308B CN106345308B CN201610892897.2A CN201610892897A CN106345308B CN 106345308 B CN106345308 B CN 106345308B CN 201610892897 A CN201610892897 A CN 201610892897A CN 106345308 B CN106345308 B CN 106345308B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—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
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
Abstract
The preparation method of strong and resistant to pollution polyesteramide composite nanometer filtering film the invention discloses a kind of chlorine resistance; the method is using serinol as aqueous phase reactions monomer; water phase is added as phase transfer catalyst and acylation catalyst in 4-dimethylaminopyridine simultaneously, new polyester amide composite nanometer filtering film is prepared by serinol and interface polymerization reaction of the polynary acyl chlorides on porous support layer.The present invention is by serinol and polynary acyl chlorides in carrying out interface polymerization reaction on porous support layer under the catalytic action of 4-dimethylaminopyridine, to obtain a kind of novel polyesteramide composite nanometer filtering film, the nanofiltration membrane has the characteristics that chlorine resistance is good, hydrophily is strong, contamination resistance is strong and solute retention ability is strong, and preparation process is easy to be mild, is suitable for industrialized production.
Description
Technical field
The invention belongs to technical field of membrane separation, and it is compound to be related to the polyesteramide that a kind of chlorine resistance is strong, contamination resistance is strong
The preparation method of nanofiltration membrane.
Background technique
With the development of economy, the aggravation of the increase of population and water pollution, the world is multinational to be faced with shortage of water resources
Problem.Therefore, in the case where extra clean water resource can not supplement, carrying out purified treatment to existing water resource is reply water
The important measure of crisis of resource.Nanofiltration membrane (NF) is a kind of special membrane material between ultrafiltration membrane and reverse osmosis membrane, its energy
Small organic molecule is enough retained, there is partially desalted ability, while having the characteristics that flux is high, low energy consumption, has been applied at present
In the softening of water, bitter desalination, advanced treatment of wastewater, drug and the various fields such as biology purification and food processing.
The polyamide composite nanofiltration membrane prepared on supporting layer by interface polymerization reaction by polyamine and polynary acyl chlorides
Leading position has been occupied in the market share of nanofiltration membrane at present.However, more serious membrane pollution problem and chlorine resistance
Difference is to limit the major obstacle of its further genralrlization application.Therefore, exploitation has contamination resistance and the strong Performances of Novel Nano-Porous of chlorine resistance
Filter membrane is the focus of numerous researchers.It is existing studies have shown that the polyamide prepared by polyamine and polynary acyl chlorides is compound
Nanofiltration membrane contaminant removal capacity usually with higher and desalting ability, but its contamination resistance and chlorine resistance are poor；And by
Crosslinked hyperbranched polyalcohol composite nano filter membrance prepared by polyphenol or polyalcohol and polynary acyl chlorides or polyacid usually has stronger contamination resistance
And chlorine resistance, but its fenestra is larger, and pollutant interception capacity and salt rejection rate are lower.How by polyamide nanofiltration membrane and polyester nanofiltration
The advantages of film, combines, to prepare the composite nanometer filter that a kind of contamination resistance is strong, chlorine resistance is strong and contaminant removal capacity is strong
Film is our goal in research.
Summary of the invention
The preparation of strong and resistant to pollution polyesteramide composite nanometer filtering film the object of the present invention is to provide a kind of novel chlorine resistance
Method combines the advantages of polyamide nanofiltration membrane and polyester nanofiltration membrane, solves that existing commercial nanofiltration membrane is easy to pollute, chlorine resistance
The problem of difference.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of chlorine resistance is strong and the preparation method of resistant to pollution polyesteramide composite nanometer filtering film, using serinol as aqueous phase reactions
Monomer, at the same using 4-dimethylaminopyridine be added water phase be used as phase transfer catalyst and acylation catalyst, by serinol with it is more
Interface polymerization reaction of first acyl chlorides on porous support layer prepares new polyester amide composite nanometer filtering film, the specific steps are as follows:
One, prepare aqueous phase solution: into pure water be added 0.5 ~ 5%(w/v) serinol, while be added 0.05 ~ 0.5%(w/
V) 4-dimethylaminopyridine uses triethylamine by the pH of solution as phase transfer and acylation catalyst after being sufficiently stirred and dissolving
Value is adjusted to 11.3 ~ 12.0；
Two, it prepares organic phase solution: with one of n-hexane, hexamethylene, toluene, normal heptane or normal octane or a variety of being
Organic solvent, into organic solvent be added 0.01 ~ 0.5%(w/v) polynary acyl chlorides；
Three, using polysulfones, polyether sulfone, sulfonated polyether sulfone or the porous ultrafiltration membrane of polypropylene as supporting course, first by aqueous phase solution
It swings to support layer surface and impregnates 1 ~ 10 minute, then outwell aqueous phase solution and remove film surface excessive moisture, then by organic phase
Solution swings to film surface, and reacts 10 ~ 120 seconds, and organic solvent is used sufficiently rinse to remove not to film surface after reaction
Reaction monomers；
Four, film of the organic solvent after flushed is placed at 20 ~ 80 DEG C and is heat-treated 5 ~ 20 minutes；
Five, finally film is sufficiently cleaned with pure water, thus to obtain polyesteramide composite nanometer filtering film.
The present invention is by serinol and polynary acyl chlorides on porous support layer under the catalytic action of 4-dimethylaminopyridine
Interface polymerization reaction is carried out, to obtain a kind of novel polyesteramide composite nanometer filtering film, which has chlorine resistance good, close
Aqueous feature strong, contamination resistance is strong and solute retention ability is strong, and preparation process is easy to be mild, is suitable for industrialized production.
Detailed description of the invention
Fig. 1 is serinol molecular structural formula；
Fig. 2 is new polyester amide composite nanometer filtering film atomic force microscope pattern；
Fig. 3 is new polyester amide composite nanometer filtering film scanning electron microscope pattern；
Fig. 4 is new polyester amide composite nanometer filtering film infrared spectroscopy.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawing, and however, it is not limited to this, all to this
Inventive technique scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered
Within the protection scope of the present invention.
Specific embodiment 1: the strong and resistant to pollution polyesteramide composite nanometer filter present embodiments provide for a kind of chlorine resistance
The preparation method of film, the specific steps are as follows:
One, prepare aqueous phase solution: 2%(w/v is added into pure water) serinol (its structural formula is as shown in Figure 1), simultaneously plus
Enter 0.2%(w/v) 4-dimethylaminopyridine as phase transfer and acylation catalyst, after being sufficiently stirred and dissolving use triethylamine
The pH value of solution is adjusted to 11.5；
Two, prepare organic phase solution: using n-hexane as organic solvent, 0.1%(w/v is added into organic solvent) it is polynary
Acyl chlorides；
Three, using the porous ultrafiltration membrane of polyether sulfone as supporting course, aqueous phase solution is swung into support layer surface first and impregnates 2 points
Then clock outwells aqueous phase solution and removes film surface excessive moisture, organic phase solution is then swung to film surface, and reaction 60 seconds, instead
Organic solvent is used sufficiently rinse to remove unreacted monomer to film surface after answering；
Four, film of the organic solvent after flushed is placed at 50 DEG C and is heat-treated 10 minutes；
Five, finally film is sufficiently cleaned with pure water, thus to obtain polyesteramide composite nanometer filtering film.
Fig. 2A gives the porous support layers atomic force microscope shape appearance figure not reacted, and it is poly- that Fig. 2 B then gives interface
Obtained polyesteramide composite nanometer filtering film shape appearance figure after the completion of closing, as shown in Figure 2, by the above reaction step, successfully compared with
To form concavo-convex polyesteramide active layer on smooth supporting course.
Fig. 3 A and B are respectively the scanning electron microscope shape appearance figure of porous support layers and polyesteramide composite nanometer filtering film, and two
The comparison of person equally confirms the generation of polyesteramide active layer.It is received in addition, Fig. 3 B also clearly illustrates that the polyesteramide is compound
Filter membrane surface has the shape characteristic similar to particle packing, this is significantly different with traditional polyamide composite nanofiltration membrane.
Fig. 4 then confirms the generation of ester bond and amido bond after reaction using the angle of infrared spectroscopy chemically key, thus into
One step confirms the generation of polyesteramide active layer.
Specific embodiment 2: the strong and resistant to pollution polyesteramide composite nanometer filter present embodiments provide for a kind of chlorine resistance
The preparation method of film, the specific steps are as follows:
One, prepare aqueous phase solution: 1%(w/v is added into pure water) serinol (its structural formula is as shown in Figure 1), simultaneously plus
Enter 0.2%(w/v) 4-dimethylaminopyridine as phase transfer and acylation catalyst, after being sufficiently stirred and dissolving use triethylamine
The pH value of solution is adjusted to 11.5；
Two, prepare organic phase solution: using normal octane as organic solvent, 0.05%(w/v is added into organic solvent) it is polynary
Acyl chlorides；
Three, using polysulfone porous ultrafiltration membrane as supporting course, aqueous phase solution is swung into support layer surface first and is impregnated 2 minutes,
Then it outwells aqueous phase solution and removes film surface excessive moisture, organic phase solution is then swung into film surface, and react 50 seconds, reaction knot
Organic solvent is used sufficiently rinse to remove unreacted monomer to film surface after beam；
Four, film of the organic solvent after flushed is placed at 60 DEG C and is heat-treated 15 minutes；
Five, finally film is sufficiently cleaned with pure water, thus to obtain polyesteramide composite nanometer filtering film.
Specific embodiment 3: the strong and resistant to pollution polyesteramide composite nanometer filter present embodiments provide for a kind of chlorine resistance
The preparation method of film, the specific steps are as follows:
One, prepare aqueous phase solution: 0.5%(w/v is added into pure water) serinol (its structural formula is as shown in Figure 1), simultaneously
0.05%(w/v is added) 4-dimethylaminopyridine as phase transfer and acylation catalyst, using three second after being sufficiently stirred and dissolving
The pH value of solution is adjusted to 11.5 by amine；
Two, prepare organic phase solution: using toluene and hexamethylene as organic solvent, the two volume ratio is 1:1, to organic solvent
Middle addition 0.05%(w/v) polynary acyl chlorides；
Three, using the porous ultrafiltration membrane of polypropylene as supporting course, aqueous phase solution is swung into support layer surface first and impregnates 4 points
Then clock outwells aqueous phase solution and removes film surface excessive moisture, organic phase solution is then swung to film surface, and reaction 70 seconds, instead
Organic solvent is used sufficiently rinse to remove unreacted monomer to film surface after answering；
Four, film of the organic solvent after flushed is placed at 70 DEG C and is heat-treated 15 minutes；
Five, finally film is sufficiently cleaned with pure water, thus to obtain polyesteramide composite nanometer filtering film.
Specific embodiment 4: the strong and resistant to pollution polyesteramide composite nanometer filter present embodiments provide for a kind of chlorine resistance
The preparation method of film, the specific steps are as follows:
One, prepare aqueous phase solution: 1.5%(w/v is added into pure water) serinol (its structural formula is as shown in Figure 1), simultaneously
0.15%(w/v is added) 4-dimethylaminopyridine as phase transfer and acylation catalyst, using three second after being sufficiently stirred and dissolving
The pH value of solution is adjusted to 11.5 by amine；
Two, prepare organic phase solution: using normal octane as organic solvent, 0.07%(w/v is added into organic solvent) it is polynary
Acyl chlorides；
Three, using the porous ultrafiltration membrane of sulfonated polyether sulfone as supporting course, aqueous phase solution is swung into support layer surface first and impregnates 3
Minute, it then outwells aqueous phase solution and removes film surface excessive moisture, organic phase solution is then swung into film surface, and react 60 seconds,
Organic solvent is used sufficiently rinse to remove unreacted monomer to film surface after reaction；
Four, film of the organic solvent after flushed is placed at 80 DEG C and is heat-treated 15 minutes；
Five, finally film is sufficiently cleaned with pure water, thus to obtain polyesteramide composite nanometer filtering film.
Claims (5)
1. a kind of chlorine resistance is strong and the preparation method of resistant to pollution polyesteramide composite nanometer filtering film, it is characterised in that the method step
It is rapid as follows:
One, prepare aqueous phase solution: into pure water be added 0.5 ~ 5%(w/v) serinol, while be added 0.05 ~ 0.5%(w/v)
The pH value of solution is adjusted to 11.3 ~ 12.0 after being sufficiently stirred and dissolving by 4-dimethylaminopyridine；
Two, prepare organic phase solution: into organic solvent be added 0.01 ~ 0.5%(w/v) polynary acyl chlorides；
Three, aqueous phase solution is swung into support layer surface first and impregnated 1 ~ 10 minute, then outwelled aqueous phase solution and remove film surface
Organic phase solution is then swung to film surface by excessive moisture, and is reacted 10 ~ 120 seconds, after reaction using organic solvent to film
Face is sufficiently rinsed；
Four, film of the organic solvent after flushed is heat-treated；
Five, finally heat treated film is sufficiently cleaned with pure water, thus to obtain polyesteramide composite nanometer filtering film.
2. chlorine resistance according to claim 1 is strong and the preparation method of resistant to pollution polyesteramide composite nanometer filtering film, special
Sign is in the step 1 that the pH value of solution is adjusted to 11.3 ~ 12.0 using triethylamine.
3. chlorine resistance according to claim 1 is strong and the preparation method of resistant to pollution polyesteramide composite nanometer filtering film, special
Sign is that the organic solvent is one of n-hexane, hexamethylene, toluene, normal heptane or normal octane or a variety of.
4. chlorine resistance according to claim 1 is strong and the preparation method of resistant to pollution polyesteramide composite nanometer filtering film, special
Sign is that the supporting layer is polysulfones, polyether sulfone, sulfonated polyether sulfone or the porous ultrafiltration membrane of polypropylene.
5. chlorine resistance according to claim 1 is strong and the preparation method of resistant to pollution polyesteramide composite nanometer filtering film, special
Sign is that the heat treatment temperature is 20 ~ 80 DEG C, and the time is 5 ~ 20 minutes.
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| CN201610892897.2A CN106345308B (en) | 2016-10-13 | 2016-10-13 | A kind of chlorine resistance is strong and the preparation method of resistant to pollution polyesteramide composite nanometer filtering film |
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Citations (6)
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| CN102500244A (en) * | 2011-11-30 | 2012-06-20 | 杭州水处理技术研究开发中心有限公司 | Preparation method of reverse osmosis composite membrane for sea water desalinization |
| CN102698620A (en) * | 2012-06-12 | 2012-10-03 | 浙江大学 | Method for preparing reverse osmosis composite membrane by taking hyperbranched polymer as monomer |
| WO2013176524A1 (en) * | 2012-05-24 | 2013-11-28 | 주식회사 엘지화학 | Reverse osmosis membrane |
| CN103477227A (en) * | 2011-03-28 | 2013-12-25 | 3M创新有限公司 | Ligand functional substrates |
| CN104667759A (en) * | 2013-11-29 | 2015-06-03 | 贵阳时代沃顿科技有限公司 | Preparation method of high-throughput anti-pollution composite nanofiltration membrane |
| CN105983348A (en) * | 2015-03-06 | 2016-10-05 | 南京理工大学 | Preparation method for polyesteramide composite nanofiltration membrane |
-
2016
- 2016-10-13 CN CN201610892897.2A patent/CN106345308B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103477227A (en) * | 2011-03-28 | 2013-12-25 | 3M创新有限公司 | Ligand functional substrates |
| CN102500244A (en) * | 2011-11-30 | 2012-06-20 | 杭州水处理技术研究开发中心有限公司 | Preparation method of reverse osmosis composite membrane for sea water desalinization |
| WO2013176524A1 (en) * | 2012-05-24 | 2013-11-28 | 주식회사 엘지화학 | Reverse osmosis membrane |
| CN102698620A (en) * | 2012-06-12 | 2012-10-03 | 浙江大学 | Method for preparing reverse osmosis composite membrane by taking hyperbranched polymer as monomer |
| CN104667759A (en) * | 2013-11-29 | 2015-06-03 | 贵阳时代沃顿科技有限公司 | Preparation method of high-throughput anti-pollution composite nanofiltration membrane |
| CN105983348A (en) * | 2015-03-06 | 2016-10-05 | 南京理工大学 | Preparation method for polyesteramide composite nanofiltration membrane |
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