CN106914155B - A kind of method that chloromethyl polysulphone prepares positively charged nanofiltration membranes - Google Patents

A kind of method that chloromethyl polysulphone prepares positively charged nanofiltration membranes Download PDF

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CN106914155B
CN106914155B CN201710228753.1A CN201710228753A CN106914155B CN 106914155 B CN106914155 B CN 106914155B CN 201710228753 A CN201710228753 A CN 201710228753A CN 106914155 B CN106914155 B CN 106914155B
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positively charged
chloromethyl polysulphone
polysulfones
casting solution
film
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CN106914155A (en
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周勇
余亚伟
高从堦
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • 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
    • 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
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/16—Membrane materials having positively charged functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • 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
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • C02F2101/40—Organic compounds containing sulfur

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a kind of method that chloromethyl polysulphone prepares positively charged nanofiltration membranes, chloromethyl polysulphone is put into trimethylamine solution to obtain positively charged polysulfone material, magnetic agitation is for 24 hours.Then positively charged polysulfone material is put into ethylene glycol monomethyl ether and prepares casting solution, casting solution is coated in the surface of polysulfones ultrafiltration counterdie, then drying is prepared into nanofiltration membrane within the temperature range of 30 DEG C -40 DEG C.Nanofiltration membrane is respectively as follows: 69.3%/52.6 Lm to the rejection and flux of sodium chloride, magnesium chloride under the pressure of 1.2MPa‑2·h‑1、76.8%/40.6 L·m‑2·h‑1.Due to containing charge positive charge group in filmogen, therefore film is to the rejection of positively charged dyestuff 95% or more, therefore salt and positively charged dye separation be can be applied to, simultaneously because it has hydrophilic radical, therefore the nanofiltration membrane prepared also has preferable antifouling property.

Description

A kind of method that chloromethyl polysulphone prepares positively charged nanofiltration membranes
Technical field
The invention belongs to macromolecular filter membrane preparation fields more particularly to a kind of chloromethyl polysulphone to prepare positively charged nanofiltration membranes Method.
Background technique
The separating property of film was continued to optimize in recent years, but either still industrialized in the laboratory research stage Nanofiltration membrane all encounters some problems, as fouling membrane, the problems such as film oxidation and not chlorine-resistant.Therefore it just needs to explore new material of preparing With filming technology.Polysulfones is that the engineering plastics of a kind of high temperature resistant and high mechanical strength have excellent creep resistance, Er Qie Bisphenol-A class polysulfone material becomes after occurring becomes most important material of preparing at this stage after cellulose derivative.Sulfonation is poly- The generally linear macromolecular of sulfone, strand are made of diphenyl sulfone, ether and isopropyl and sulfonic group, and different groups exists Different performances is endowed in strand, the diphenyl sulfone being made of the sulfuryl of the sulphur atom in highest price and phenyl is constituted Height conjugated system increases the stability of strand, provides the high thermo oxidative stability of macromolecular, rigidity, intensity and size Stability, polysulfones strand is based on rigidity, while ether chain imparts the certain toughness of strand, flexibility, processability, dissolution again Property and easy mobility.But polysulfone material has hydrophobicity, and antifouling property is poor, film prepared therefrom not anti-pollution.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of method that chloromethyl polysulphone prepares positively charged nanofiltration membranes, leads to The hydrophily for introducing amino increase film is crossed, and makes the surface of film with positive charge；While with polysulfones excellent performance, make The seperation film of preparation has good rejection to positively charged dyestuff.
It adopts the following technical scheme that thus:
A kind of method that chloromethyl polysulphone prepares positively charged nanofiltration membranes, it is characterised in that the following steps are included:
Step (1): chloromethyl polysulphone being put into the trimethylamine aqueous solution that mass fraction is 5%, and the chloromethylation is poly- The mass ratio that feeds intake of sulfone and trimethylamine aqueous solution is 1:10, under the revolving speed of 800-1500r/min after magnetic agitation 12-36h, very Empty pump filter, removes extra trimethylamine aqueous solution, and lotus positive electricity polysulfones is made in the vacuum drying at 25-45 DEG C；
Step (2): taking lotus positive electricity polysulfones made from excessive step (1) to be dissolved in ethylene glycol monomethyl ether, at normal temperature with The revolving speed of 800-1500r/min, which stirs 24 hours, sufficiently to be dissolved, and after vacuum filtration, takes the mother liquor that upper layer is transparent, mother liquor is dried Measure the solutes content of lotus positive electricity polysulfones in mother liquor；
Step (3): it takes mother liquor made from step (2) to be added in ethylene glycol monomethyl ether, is configured to the different casting solution of concentration, institute Casting solution is stated using lotus positive electricity polysulfones as solute, mass fraction 0.1%-0.9%, casting solution is then coated uniformly on polysulfones ultrafiltration On counterdie, coating number is 1-3 times, and standing 5-15 minutes after coating makes fully reacting, then extra casting solution is removed, finally Film is put into baking oven and is dried within the temperature range of 30 DEG C -40 DEG C, final products film is made.
Further, the magnetic agitation time is 24 hours in the step (1), and vacuum drying temperature is 35 DEG C.
Further, in the step (3), the coating number of casting solution is 2 times, and the time of repose after coating is 10 points Clock.
According to the technical solution of the present invention, chloromethyl polysulphone is put into trimethylamine solution to obtain positively charged gather Sulfone material, magnetic agitation are optimized for 24 hours with ensuring to react.Then positively charged polysulfone material is put into ethylene glycol monomethyl ether and is prepared Casting solution is coated in the surface of polysulfones ultrafiltration counterdie, then dries and be prepared within the temperature range of 30 DEG C -40 DEG C by casting solution Nanofiltration membrane.Nanofiltration membrane is respectively as follows: 69.3%/52.6 to the rejection and flux of sodium chloride, magnesium chloride under the pressure of 1.2MPa L·m-2·h-1、76.8%/40.6 L·m-2·h-1.Due to containing charge positive charge group in filmogen, film is to positively charged The rejection of the dyestuff of lotus can be applied to salt and positively charged dye separation 95% or more, simultaneously because its band There is hydrophilic radical, therefore the nanofiltration membrane prepared also has preferable antifouling property.Casting solution is added by control in the present invention Drying temperature and coating number when the concentration and film forming of middle polysulfones come the structure of adjusting film, rejection.Prepared receives Filter membrane permselective property with higher and stain resistance, film-forming method is simple and easy, has good industrial applications prospect.
Specific embodiment
Below with reference to example, the present invention will be further described, but the scope of protection of the present invention is not limited thereto:
Embodiment 1:
30g chloromethyl polysulphone is put into 300g, mass fraction is in 5% trimethylamine aqueous solution, in 800-1500r/min Revolving speed under magnetic agitation for 24 hours, vacuum filtration, remove extra trimethylamine solution, the vacuum drying at 35 DEG C, be made lotus positive electricity Polysulfones；
The polysulfones of 10g lotus positive electricity is incorporated in 500ml ethylene glycol monomethyl ether, at normal temperature with 800-1500r/min revolving speed Stirring 24 hours, after vacuum filtration, takes the mother liquor that upper layer is transparent, then takes the mother liquor of 20g to dry solute in measurement solution and contains Amount；
It takes mother liquor that ethylene glycol monomethyl ether is added and is configured to 50g casting solution, the casting solution concentration is the matter of the polysulfones of lotus positive electricity Measuring score is 0.85%, and then casting solution is coated uniformly on polysulfones ultrafiltration counterdie, stands 10 minutes, then by extra casting film Liquid remove, finally by film be put into baking oven 30 DEG C at a temperature of carry out drying 10min film forming.
Under the pressure of 1.2MPa, for film to magnesium chloride, the rejection and permeation flux of sodium chloride are as follows:
。
Embodiment 2:
Change the concentration of filmogen in casting solution, other steps are same as Example 1.Under the pressure of 1.2MPa, film To magnesium chloride, the rejection and permeation flux of sodium chloride are as follows:
。
Embodiment 3:
The number coated when changing film, other steps are same as Example 1.Under the pressure of 1.2MPa, film is to chlorination Magnesium, the rejection and permeation flux of sodium chloride are as follows:
。
Embodiment 4:
What is selected is the film for preparing under 30 DEG C of drying conditions of casting solution that concentration is 0.55%, test film to safranine T, in Property red and Nitroso R salt rejection, result is as follows:
。

Claims (3)

1. a kind of method that chloromethyl polysulphone prepares positively charged nanofiltration membranes, it is characterised in that the following steps are included:
Step (1): by chloromethyl polysulphone be put into mass fraction be 5% trimethylamine aqueous solution in, the chloromethyl polysulphone with The mass ratio that feeds intake of trimethylamine aqueous solution is 1:10, and under the revolving speed of 800-1500r/min after magnetic agitation 12-36h, vacuum is taken out Filter, removes extra trimethylamine aqueous solution, the vacuum drying at 25-45 DEG C, and lotus positive electricity polysulfones is made；
Step (2): lotus positive electricity polysulfones made from excessive step (1) is taken to be dissolved in ethylene glycol monomethyl ether, at normal temperature with 800- The revolving speed of 1500r/min, which stirs 24 hours, sufficiently to be dissolved, and after vacuum filtration, takes filtrate, just by lotus in filtrate drying measurement filtrate The solutes content of voltolisation sulfone；
Step (3): it takes filtrate made from step (2) to be added in ethylene glycol monomethyl ether, is configured to the different casting solution of concentration, the casting Then casting solution is coated uniformly on polysulfones ultrafiltration counterdie using lotus positive electricity polysulfones as solute, mass fraction 0.1%-0.9% by film liquid On, coating number is 1-3 times, and standing 5-15 minutes after coating makes fully reacting, then extra casting solution is removed, finally by film It is put into baking oven and is dried within the temperature range of 30 DEG C -40 DEG C, final products film is made.
2. the method that a kind of chloromethyl polysulphone described in accordance with the claim 1 prepares positively charged nanofiltration membranes, which is characterized in that institute Stating the magnetic agitation time in step (1) is 24 hours, and vacuum drying temperature is 35 DEG C.
3. the method that a kind of chloromethyl polysulphone described in accordance with the claim 1 prepares positively charged nanofiltration membranes, which is characterized in that institute It states in step (3), the coating number of casting solution is 2 times, and the time of repose after coating is 10 minutes.
CN201710228753.1A 2017-04-10 2017-04-10 A kind of method that chloromethyl polysulphone prepares positively charged nanofiltration membranes Active CN106914155B (en)

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CN112844079B (en) * 2020-12-29 2023-05-26 宁波日新恒力科技有限公司 Modified polysulfone porous supporting layer for reverse osmosis composite membrane, preparation method of modified polysulfone porous supporting layer and quaternized polysulfone modified reverse osmosis composite membrane

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101766962A (en) * 2010-01-05 2010-07-07 浙江大学 Method for preparing positively charged nanofiltration membranes
CN104524994A (en) * 2015-01-14 2015-04-22 安得膜分离技术工程(北京)有限公司 Ultrafiltration membrane and preparing method thereof
CN105709619A (en) * 2014-08-31 2016-06-29 海南立昇净水科技实业有限公司 Positively charged nanofiltration membrane and preparation method thereof
CN106179002A (en) * 2016-08-09 2016-12-07 中北大学 A kind of polysulfones side chain graft poly-tertiary amine micro-filtration membrane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101766962A (en) * 2010-01-05 2010-07-07 浙江大学 Method for preparing positively charged nanofiltration membranes
CN105709619A (en) * 2014-08-31 2016-06-29 海南立昇净水科技实业有限公司 Positively charged nanofiltration membrane and preparation method thereof
CN104524994A (en) * 2015-01-14 2015-04-22 安得膜分离技术工程(北京)有限公司 Ultrafiltration membrane and preparing method thereof
CN106179002A (en) * 2016-08-09 2016-12-07 中北大学 A kind of polysulfones side chain graft poly-tertiary amine micro-filtration membrane

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