CN110354692B - Preparation method of pressure retardation permeable membrane modified by zwitter-ion random copolymer - Google Patents

Preparation method of pressure retardation permeable membrane modified by zwitter-ion random copolymer Download PDF

Info

Publication number
CN110354692B
CN110354692B CN201810318059.3A CN201810318059A CN110354692B CN 110354692 B CN110354692 B CN 110354692B CN 201810318059 A CN201810318059 A CN 201810318059A CN 110354692 B CN110354692 B CN 110354692B
Authority
CN
China
Prior art keywords
membrane
vinyl
poly
random
polyamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810318059.3A
Other languages
Chinese (zh)
Other versions
CN110354692A (en
Inventor
李雪
蔡韬
黄文刚
李家乐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Research Institute of Wuhan University
Original Assignee
Shenzhen Research Institute of Wuhan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Research Institute of Wuhan University filed Critical Shenzhen Research Institute of Wuhan University
Priority to CN201810318059.3A priority Critical patent/CN110354692B/en
Publication of CN110354692A publication Critical patent/CN110354692A/en
Application granted granted Critical
Publication of CN110354692B publication Critical patent/CN110354692B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a preparation method of a pressure retardation permeable membrane modified by a zwitterionic random copolymer, which comprises the following steps of carrying out random copolymerization on N-vinyl imidazole and an N-vinyl phthalimide monomer containing an amino protecting group by taking methyl-2- [ methyl- (4-pyridine) dithiocarbonate ] propionate as a chain transfer agent and azodiisobutyronitrile as an initiator; respectively quaternizing the poly N-vinyl imidazole chain segment under the action of propane sultone and 4-bromobutyric acid; carrying out amino deprotection on a poly N-vinyl phthalimide chain segment under the action of hydrazine hydrate to prepare a zwitterionic polymer; the zwitterionic polymer is prepared into an aqueous solution to be grafted and modified on a porous supporting layer of the permeable composite membrane. The comonomer used in the invention is simple and easy to obtain, the random copolymer is convenient to synthesize, the condition is mild, and the implementation is easy; the chemical stability and water solubility of the graft polymer are improved, and the cost is greatly reduced; has excellent protein and microbe adhesion resisting effect.

Description

Preparation method of pressure retardation permeable membrane modified by zwitter-ion random copolymer
Technical Field
The invention relates to the technical field of membrane separation, in particular to a preparation method of a pressure retardation permeable membrane modified by a zwitterionic random copolymer.
Background
The functional polymer modified polymer composite membrane can integrate the advantages of stable structural performance of a polymer membrane body and various functions of the surface of a modification layer, and gradually becomes the front edge of the membrane and membrane process field. The application of the polymer composite membrane in the research of pressure-delay permeation power generation is a research hotspot which is internationally raised in recent years.
Pressure-retarded osmosis power generation is a new technology based on membrane separation, essentially utilizes natural osmosis phenomenon to develop energy, has great potential, and becomes a new energy research hotspot in recent years. The two solutions with concentration difference are separated by a permeable membrane, and water can automatically flow from the low-concentration solution to the high-concentration solution, which is a natural osmosis phenomenon; if the osmosis process is controlled, the flow of water into the concentrate solution increases the concentrate pressure, and the increased pressure is used to stroke a turbine generator to generate electricity. Meanwhile, a certain Pressure is added in the high-concentration solution in advance, so that a turbine of the generator can be pushed more easily, the osmotic water flow can be converted into electric power more effectively, the process is called a Pressure retarded osmosis process (or Pressure retarded osmosis), and the osmotic power generation carried out by the process can not generate any pollution and waste gas; the concentration difference of the solution at the two sides of the osmotic membrane is effectively controlled, and stable electric power can be continuously generated.
The polyamide-polyether sulfone composite membrane based on interfacial polymerization of a polyether sulfone porous supporting layer is the most important pressure retardation permeable membrane at present. However, the polyamide-polyethersulfone composite membrane does not have optimal hydrophilicity and bioadhesion resistance, and has the defect of being easily adhered by proteins and microorganisms in pressure retardation osmosis, thereby causing membrane pollution. Membrane fouling is a common problem in membrane separation processes and typically results in reduced membrane flux and reduced stability, greatly compromising membrane performance and life.
The zwitterionic polymer refers to a macromolecule polymerized by micromolecular monomers with positive and negative charge ionic groups; the positive charge groups and the negative charge groups on the polymer enable the zwitterion molecules to form electrostatic interaction with different types of charged molecules; in addition, the zwitterionic molecule has good water molecule adsorption capacity, a stable hydration layer can be formed on the surface of the zwitterionic molecule, and the hydration layer serves as a physical structure and energy barrier to prevent protein and organisms from approaching or adsorbing, so that the surface of the zwitterionic molecule has good anti-bioadhesion capacity. The surface modification of the permeable Membrane with zwitterions has been reported (Journal of Membrane Science,497,2016, 142-; Journal of Membrane Science,449,2014, 50-57; the defects of the preparation method is that various zwitterion small molecule monomers have to be synthesized, the preparation method is complex, the price of the zwitterion small molecule monomers is high, and particularly, the phosphorylcholine monomers are very expensive and have no practicability.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a pressure retardation permeable membrane modified by a zwitterionic random copolymer.
The technical scheme adopted by the invention is as follows: a method for preparing a pressure retardation permeable membrane modified by a zwitterionic random copolymer comprises the following steps:
preparation of S1 zwitterionic random copolymer:
s1.1, carrying out random copolymerization on N-vinylimidazole with the molar fraction of 75-100% and a monomer containing an amino protecting group with the molar fraction of 0-25% under the action of a chain transfer agent and Azobisisobutyronitrile (AIBN) serving as initiators through reversible addition-fragmentation chain transfer free radical polymerization; the monomer with the amino protecting group is as follows: n-vinylphthalimide or
Figure BDA0001624447780000021
Wherein R is1Is one of the following structures or a derivative thereof:
Figure BDA0001624447780000022
Figure BDA0001624447780000031
the chain transfer agent is methyl-2- [ methyl- (4-pyridine) dithiocarbonate ] propionate or one of the following two structures:
Figure BDA0001624447780000032
wherein R is3Is one of the following structures or a derivative thereof:
Figure BDA0001624447780000033
R4is one of the following structures or a derivative thereof:
Figure BDA0001624447780000034
R5is one of the following structures or a derivative thereof:
Figure BDA0001624447780000035
n is any repeating unit number greater than or equal to 1;
s1.2 quaternizing the poly-N-vinylimidazole segment under the action of a quaternizing agent; the quaternizing agent is propane sultone, halogenated sulfonic acid derivative X-R2-SO3H. 4-bromobutyric acid, halocarboxylic acid or halocarboxylic acid derivative X-R2-COOH, wherein X is halogen, R2Is an alkyl group;
s1.3, under the action of hydrazine hydrate, carrying out amino deprotection on a poly N-vinyl phthalimide chain segment to prepare poly [ (N-vinyl-N '-propane sulfonic acid imidazolium salt) -random- (N-vinylamine) ] and poly [ (N-vinyl-N' -butyric acid imidazolium salt) -random- (N-vinylamine) ];
s2 preparing the poly [ (N-vinyl-N '-propanesulfonic acid imidazolium salt) -random- (N-vinylamine) ] or poly [ (N-vinyl-N' -butyric acid imidazolium salt) -random- (N-vinylamine) ] prepared in the step S1 into an aqueous solution to be grafted and modified on the porous support layer of the osmosis composite membrane.
Preferably, the chemical reaction formula of step S1.1 is:
Figure BDA0001624447780000041
preferably, in Propane Sultone (PS), halosulfonic acid or halosulfonic acid derivatives X-R2-SO3Step S1.2 chemical reaction under the action of H is:
Figure BDA0001624447780000042
preferably, in 4-Bromobutyric Acid (BA), a halocarboxylic acid or halocarboxylic acid derivative X-R2The chemical reaction of step S1.3 under the action of-COOH is:
Figure BDA0001624447780000043
preferably, step S2 includes the steps of:
s2.1 dissolving 200 mg dopamine hydrochloride in 1L 0.01mol L-1To the Tris buffer solution at pH 8.5, 0.005mol L was added-1Copper sulfate and 0.025mol L-1Hydrogen peroxide to prepare a solution A; immersing the porous supporting layer penetrating the composite membrane into the solution A in a mold for 30-60 minutes; washing with deionized water for 5 times;
s2.2: preparing 3-15 g/L of aqueous solution B from the poly [ (N-vinyl-N '-propanesulfonic acid imidazolium salt) -random- (N-vinylamine) ] or the poly [ (N-vinyl-N' -butyric acid imidazolium salt) -random- (N-vinylamine) ] prepared in the step S1, wherein the aqueous solution contains 0.5% volume fraction of triethylamine; and (3) immersing the porous supporting layer of the polydopamine-coated permeable composite membrane obtained in the step (S2.1) in the water solution B for 1-6 hours in a mold.
Preferably, the permeation composite membrane in step S2 is a composite membrane formed by interfacial polymerization of a polyamide-polyester membrane, a polyamide-polyethersulfone membrane, a polyamide-polysulfone membrane, a polyamide-polyacrylonitrile membrane, a polyamide-polyvinylidene fluoride membrane, or a polyamide-polyimide membrane.
Preferably, the preparation of the polyamide-polyethersulfone membrane comprises the following steps:
porous supporting layer of spun polyether sulfone membrane
Spinning a polyethersulfone membrane porous supporting layer by a non-solvent induced phase separation method, firstly, carrying out vacuum drying on a polyethersulfone raw material at 90 +/-5 ℃ to remove water, preparing the polyethersulfone raw material into a solution C with the mass fraction of 12-25% by taking N-methylpyrrolidone as a solvent, and removing bubbles; under the conditions of room temperature and 50-90% of relative air humidity, spreading the solution C on a glass plate into a sheet by using a film scraping knife with a gap of 20-300 micrometers, then soaking the glass plate in water for 1-10 minutes, taking purified water for soaking again for 1-10 hours to obtain a polyether sulfone film porous supporting layer, wherein the thickness of the obtained film is 40-350 micrometers, and the pore diameter is 2-15 nanometers;
spun polyamide-polyethersulfone membranes
Immersing a polyether sulfone membrane porous supporting layer into an aqueous solution of aqueous-phase m-phenylenediamine with the mass fraction of 1-3% for 1-3 minutes, and wiping off redundant aqueous-phase solution on the surface of the membrane; then immersing the membrane into a normal hexane solution of oil phase isophthaloyl dichloride for 0.5-5 minutes, and taking out the membrane; rinsing with deionized water for 10 times, and performing heat treatment at 50-90 ℃ for 5-15 minutes to obtain the polyamide-polyether sulfone membrane with pure water flux of 1-5 Lm-2h-1bar-1The rejection rate of sodium chloride is 85-95%.
Compared with the prior art, the invention has the beneficial effects that:
1. the comonomer used in the invention is simple and easy to obtain, the random copolymer is convenient to synthesize, the condition is mild, and the implementation is easy;
2. as the polydopamine layer, a copper sulfate and hydrogen peroxide oxidation system is adopted to replace the original oxygen oxidation system, the reaction time is reduced from the original 24 hours to 0.5-1 hour, the obtained polydopamine layer is uniform and does not agglomerate, the thickness is controllable, and the scheme is simpler and more feasible;
3. the invention adopts the monomer with the amino precursor which can be commercialized to carry out copolymerization, thus improving the chemical stability and water solubility of the graft polymer;
4. the invention prepares the novel monomer, greatly reduces the cost;
5. the pressure retardation permeable membrane prepared by the invention has excellent protein and microorganism adhesion resistance, and the adhesion amount is reduced to 5-7% from 100% compared with that of an unmodified polyamide-polyether sulfone membrane.
Drawings
FIGS. 1a, 1b and 1c are bovine serum albumin adsorption test charts of unmodified polyethersulfone membrane, poly [ (N-vinyl-N '-propanesulfonate imidazolium salt) -random- (N-vinylamine) ] modified polyethersulfone membrane and poly [ (N-vinyl-N' -butyric acid imidazolium salt) -random- (N-vinylamine) ] modified polyethersulfone membrane, respectively;
FIGS. 2a, 2b and 2c are respectively gram negative type Escherichia coli adsorption test charts of unmodified polyethersulfone membrane, poly [ (N-vinyl-N '-propanesulfonate imidazolium salt) -random- (N-vinylamine) ] modified polyethersulfone membrane and poly [ (N-vinyl-N' -butyric acid imidazolium salt) -random- (N-vinylamine) ] modified polyethersulfone membrane;
FIGS. 3a, 3b and 3c are the adsorption test charts of gram positive type Staphylococcus aureus of unmodified polyethersulfone membrane, poly [ (N-vinyl-N '-propanesulfonate imidazolium salt) -random- (N-vinylamine) ] modified polyethersulfone membrane and poly [ (N-vinyl-N' -butyric acid imidazolium salt) -random- (N-vinylamine) ] modified polyethersulfone membrane, respectively;
Detailed Description
In order to facilitate the understanding and implementation of the present invention for those of ordinary skill in the art, the present invention is further described in detail with reference to the accompanying drawings and examples, it is to be understood that the embodiments described herein are merely illustrative and explanatory of the present invention and are not restrictive thereof.
A method for preparing a pressure retardation permeable membrane modified by a zwitterionic random copolymer comprises the following steps:
step S1 preparation of zwitterionic random copolymer:
s1.1, mixing N-vinyl imidazole and N-vinyl phthalimide monomer containing amino protecting group, wherein the mass ratio of the N-vinyl imidazole to the N-vinyl phthalimide monomer is 10.36: random copolymerization is carried out by reversible addition-fragmentation chain transfer radical polymerization under the action of methyl-2- [ methyl- (4-pyridine) dithiocarbonate ] propionate (MMP) as a chain transfer agent and Azobisisobutyronitrile (AIBN) as an initiator. The monomers carrying an amino protecting group may also be:
Figure BDA0001624447780000071
wherein R is1May be one of the following structures or a derivative thereof:
Figure BDA0001624447780000072
Figure BDA0001624447780000081
chain transfer agents other than MMPs may also be one of the following two structures:
Figure BDA0001624447780000082
wherein R is3May be one of the following structures or a derivative thereof:
Figure BDA0001624447780000083
R4may be one of the following structures or a derivative thereof:
Figure BDA0001624447780000084
R5may be one of the following structures or a derivative thereof:
Figure BDA0001624447780000085
n as defined above may be any number of repeating units greater than or equal to 1;
step S1.2, quaternizing the poly N-vinyl imidazole chain segment under the action of propane sultone and 4-bromobutyric acid respectively; the propane sultone can also be replaced by halogenated sulfonic acid or halogenated sulfonic acid derivatives X-R2-SO3H may be replaced by 4-bromobutyric acid, which may be a halocarboxylic acid or a halocarboxylic acid derivative X-R2-COOH substitution; wherein X is halogen, R2Is alkyl)
Step S1.3, carrying out amino deprotection on a poly [ N-vinyl phthalimide ] chain segment under the action of hydrazine hydrate to prepare poly [ (N-vinyl-N '-propane sulfonic acid imidazolium salt) -random- (N-vinylamine) ] and poly [ (N-vinyl-N' -butyric acid imidazolium salt) -random- (N-vinylamine) ];
step S2 is to prepare the poly [ (N-vinyl-N '-imidazolium propanesulfonate) -random- (N-vinylamine) ] or poly [ (N-vinyl-N' -imidazolium butyrate) -random- (N-vinylamine) ] prepared in step S1 as an aqueous solution to graft-modify on the porous support layer of the osmosis composite membrane.
The chemical reaction formula of step S1.1 is:
Figure BDA0001624447780000091
step S1.2 the chemical reaction formula for quaternizing the poly N-vinylimidazole segment under the action of Propane Sultone (PS) is as follows:
Figure BDA0001624447780000092
step S1.3 the chemical reaction formula for quaternizing the poly N-vinylimidazole segment under the action of 4-Bromobutyric Acid (BA) is as follows:
Figure BDA0001624447780000101
in the above technical solution, step S2 includes the following steps:
step S2.1 dissolving 200 mg dopamine hydrochloride in 1L 0.01mol L-1Tris buffer of pH 8.5Adding 0.005mol L into the washing liquid-1Copper sulfate and 0.025mol L-1Hydrogen peroxide to prepare a solution A; immersing the porous supporting layer penetrating the composite membrane into the solution A in a mold for 30-60 minutes; washing with deionized water for 5 times;
step S2.2: preparing 3-15 g/L of aqueous solution B from the poly [ (N-vinyl-N '-propanesulfonic acid imidazolium salt) -random- (N-vinylamine) ] or the poly [ (N-vinyl-N' -butyric acid imidazolium salt) -random- (N-vinylamine) ] prepared in the step S1, wherein the aqueous solution contains 0.5% volume fraction of triethylamine; and (3) immersing the porous supporting layer of the polydopamine-coated permeable composite membrane obtained in the step (S2.1) in the water solution B for 1-6 hours in a mold.
In step S2, the permeation composite membrane is a composite membrane formed by interfacial polymerization of a polyamide-polyester membrane, a polyamide-polyethersulfone membrane, a polyamide-polyacrylonitrile membrane, a polyamide-polyvinylidene fluoride membrane, a polyamide-polyimide membrane, or the like.
Taking the preparation of a polyamide-polyethersulfone membrane as an example, the method comprises the following steps:
porous supporting layer of spun polyether sulfone membrane
Spinning a polyethersulfone membrane porous supporting layer by a non-solvent induced phase separation method, firstly, carrying out vacuum drying on a polyethersulfone raw material at 90 +/-5 ℃ to remove water, preparing the polyethersulfone raw material into a solution C with the mass fraction of 12-25% by taking N-methylpyrrolidone as a solvent, and removing bubbles; under the conditions of room temperature and 50-90% of relative air humidity, spreading the solution C on a glass plate into a sheet by using a film scraping knife with a gap of 20-300 micrometers, then soaking the glass plate in water for 1-10 minutes, taking purified water for soaking again for 1-10 hours to obtain a polyether sulfone film porous supporting layer, wherein the thickness of the obtained film is 40-350 micrometers, and the pore diameter is 2-15 nanometers;
spun polyamide-polyethersulfone membranes
Immersing a polyether sulfone membrane porous supporting layer into an aqueous solution of aqueous-phase m-phenylenediamine with the mass fraction of 1-3% for 1-3 minutes, and wiping off redundant aqueous-phase solution on the surface of the membrane; then immersing the membrane into a normal hexane solution of oil phase isophthaloyl dichloride for 0.5-5 minutes, and taking out the membrane; rinsing with deionized water for 10 times, and heat treating at 50-90 deg.C for 5-15 minObtaining the polyamide-polyether sulfone membrane with the pure water flux of 1-5 Lm-2h-1bar-1The rejection rate of sodium chloride is 85-95%.
As shown in FIGS. 1a, 1b and 1c, respectively, the membrane was an unmodified polyethersulfone membrane, poly [ (N-vinyl-N' -propanesulfonate imidazolium salt) -random- (N-vinylamine)]Modified polyethersulfone membrane, poly [ (N-vinyl-N' -imidazolium butyrate) -random- (N-vinylamine)]Modified polyethersulfone membrane bovine serum albumin adsorption test chart, unmodified polyethersulfone membrane and poly [ (N-vinyl-N' -propane sulfonic acid imidazolium salt) -random- (N-vinylamine)]Modified polyethersulfone membrane, poly [ (N-vinyl-N' -imidazolium butyrate) -random- (N-vinylamine)]The modified polyethersulfone membrane was rinsed with phosphate buffer solution 2 times, and immersed in phosphate buffered saline (0.5mg L) solution of fluorescent-labeled bovine serum albumin at room temperature-1) For 1 hour. Fluorescence measurements were performed using a Leica DMLM fluorescence spectrometer. FIGS. 1a, 1b and 1c show the results of fluorescence measurement, respectively. Due to hydrophobic interactions, the unmodified polyethersulfone membrane surface was completely covered by protein, i.e. the unmodified membrane was subject to severe protein adhesion, see fig. 1 a. The membrane surface modified by the zwitterionic polymer has only weak fluorescence, which shows that only a small amount of adhesion exists. From the adhesion strength, poly [ (N-vinyl-N' -propanesulfonic acid imidazolium salt) -random- (N-vinylamine)]The modified polyethersulfone membrane reduced the adhesion strength from 100% to 7.8%, see FIG. 1b, poly [ (N-vinyl-N' -butylimidazolium) -random- (N-vinylamine)]The modified polyethersulfone membrane adhesion strength was reduced from 100% to 8.1%, see figure 1 c.
As shown in FIGS. 2a, 2b and 2c, respectively, an unmodified polyethersulfone membrane, poly [ (N-vinyl-N' -propanesulfonate imidazolium salt) -random- (N-vinylamine)]Modified polyethersulfone membrane, poly [ (N-vinyl-N' -imidazolium butyrate) -random- (N-vinylamine)]Modifying polyether sulfone membrane gram negative type escherichia coli adsorption test chart; an unmodified polyether sulfone membrane, poly [ (N-vinyl-N' -propane sulfonic acid imidazolium salt) -random- (N-vinylamine)]Modified polyethersulfone membrane, poly [ (N-vinyl-N' -imidazolium butyrate) -random- (N-vinylamine)]The modified polyethersulfone membrane is rinsed with phosphate buffer solution for 2 times, and immersed in phosphate buffer solution containing Escherichia coli at room temperatureIn the washing liquid (1X 10)8Total bacterial population per ml) for 4 hours, and measured by scanning electron microscopy, and fig. 2a, 2b, and 2c are scanning electron microscopy results. The unmodified polyethersulfone membrane surface is densely covered by escherichia coli and even has bacterial clusters, and only sporadic escherichia coli adheres to the membrane surface modified by the zwitterionic polymer as shown in fig. 2 a. As can be seen from the quantitative determination of adhesion strength, poly [ (N-vinyl-N' -propanesulfonic acid imidazolium salt) -random- (N-vinylamine)]The modified polyethersulfone membrane reduced the adhesion strength from 100% to 5.2%, see FIG. 2b, poly [ (N-vinyl-N' -butylimidazolium) -random- (N-vinylamine)]The modified polyethersulfone membrane adhesion strength was reduced from 100% to 5.8%, see figure 2 c.
As shown in FIGS. 3a, 3b and 3c, respectively, an unmodified polyethersulfone membrane, poly [ (N-vinyl-N' -propanesulfonate imidazolium salt) -random- (N-vinylamine)]Modified polyethersulfone membrane, poly [ (N-vinyl-N' -imidazolium butyrate) -random- (N-vinylamine)]Modified polyethersulfone membrane gram positive type staphylococcus aureus adsorption test chart, respectively subjecting unmodified polyethersulfone membrane and poly [ (N-vinyl-N' -propanesulfonic acid imidazolium salt) -random- (N-vinylamine)]Modified polyethersulfone membrane, poly [ (N-vinyl-N' -imidazolium butyrate) -random- (N-vinylamine)]The modified polyethersulfone membrane was rinsed 2 times with phosphate buffer and immersed in Staphylococcus aureus-containing phosphate buffer (1X 10)8Total bacterial population per ml) for 4 hours, and measured by scanning electron microscopy, and fig. 3a, 3b, and 3c are scanning electron microscopy results. The unmodified polyethersulfone membrane surface is densely covered by bacteria and has a large number of bacterial clusters, and only a small amount of bacteria are adhered to the membrane surface modified by the zwitterionic polymer as shown in figure 3 a. As can be seen from the quantitative determination of adhesion strength, poly [ (N-vinyl-N' -propanesulfonic acid imidazolium salt) -random- (N-vinylamine)]The modified polyethersulfone membrane reduced the adhesion strength from 100% to 6.8%, see FIG. 3b, poly [ (N-vinyl-N' -butylimidazolium) -random- (N-vinylamine)]The modified polyethersulfone membrane adhesion strength was reduced from 100% to 7.4%, see figure 3 c.
Respectively for unmodified polyethersulfone membrane and poly [ (N-vinyl-N' -propane sulfonic acid imidazolium salt) -random- (N-vinylamine)]Modified polyether sulfone membrane, poly [ (N-vinyl-N' -butyric acid imidazolium salt) -random- (N-ethyl acetate)Enamine)]Modified polyether sulfone membrane is used for pressure retardation permeability measurement and 0.8mol L is used-1The sodium chloride is used as simulated salt water, the deionized water is used as simulated fresh water for measurement, and the sodium chloride and the deionized water are respectively contacted with the polyamide layer and the zwitterionic polymer modified polyether sulfone layer. The water flow flows reversely, and the flow rate is 0.1-0.5 liter per minute. The water flux, rejection and permeation flux of the pressure retarded osmosis membrane are shown in the attached table 1.
Attached table 1
Figure BDA0001624447780000131
The pressure retardation osmotic membrane modified by the zwitterionic random copolymer can be used in different industrial fields, such as drug separation, salt water desalination, sewage treatment, pressure retardation osmotic power generation and the like.
It should be understood that parts of the specification not set forth in detail are well within the prior art.
It should be understood that the above description of the preferred embodiments is given for clarity and not for any purpose of limitation, and that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

1. A preparation method of a pressure retardation permeable membrane modified by a zwitterionic random copolymer is characterized by comprising the following steps:
preparation of S1 zwitterionic random copolymer:
s1.1, carrying out random copolymerization on N-vinylimidazole with the molar fraction of 75-100% and a monomer containing an amino protecting group with the molar fraction of 0-25% under the action of a chain transfer agent and Azobisisobutyronitrile (AIBN) serving as initiators through reversible addition-fragmentation chain transfer free radical polymerization; the monomer containing the amino protecting group is as follows: n-vinyl phthalimide;
s1.2 quaternizing the poly-N-vinylimidazole segment under the action of a quaternizing agent; the quaternizing agent is propane sultone, halogenated sulfonic acid derivative X-R2-SO3H. 4-bromobutyric acid, halocarboxylic acid or halocarboxylic acid derivative X-R2-COOH, wherein X is halogen, R2Is an alkyl group;
s1.3, under the action of hydrazine hydrate, carrying out amino deprotection on a poly N-vinyl phthalimide chain segment to prepare poly [ (N-vinyl-N '-propane sulfonic acid imidazolium salt) -random- (N-vinylamine) ] and poly [ (N-vinyl-N' -butyric acid imidazolium salt) -random- (N-vinylamine) ];
s2 preparing the poly [ (N-vinyl-N '-propanesulfonic acid imidazolium salt) -random- (N-vinylamine) ] or poly [ (N-vinyl-N' -butyric acid imidazolium salt) -random- (N-vinylamine) ] prepared in the step S1 into an aqueous solution to be grafted and modified on the porous support layer of the osmosis composite membrane.
2. The method of claim 1, wherein the chemical reaction formula of step S1.1 is:
Figure FDA0003123301230000021
3. the method of claim 1 wherein said zwitterionic random copolymer is incorporated into a Propane Sultone (PS), a halosulfonic acid, or a halosulfonic acid derivative X-R2-SO3Step S1.2 chemical reaction under the action of H is:
Figure FDA0003123301230000022
4. the zwitterionic random copolymer modified pressure retarded osmosis membrane of claim 1The preparation method is characterized in that 4-Bromobutyric Acid (BA), halogenated carboxylic acid or halogenated carboxylic acid derivative X-R2The chemical reaction formula of step S1.2 under the action of-COOH is:
Figure FDA0003123301230000023
5. the method for preparing a zwitterionic random copolymer-modified pressure retarded osmosis membrane according to any one of claims 1, 2, 3 or 4, wherein step S2 comprises the steps of:
s2.1 dissolving 200 mg of dopamine hydrochloride in 1L of 0.01mol L-1To the Tris buffer solution at pH 8.5, 0.005mol L was added-1Copper sulfate and 0.025mol L-1Hydrogen peroxide to prepare a solution A; immersing the porous supporting layer penetrating the composite membrane into the solution A in a mold for 30-60 minutes; washing with deionized water for 5 times;
s2.2, preparing the poly [ (N-vinyl-N '-imidazolium propanesulfonate) -random- (N-vinylamine) ] or the poly [ (N-vinyl-N' -imidazolium butyrate) -random- (N-vinylamine) ] prepared in the step S1 into an aqueous solution B of 3-15 g/L, wherein the aqueous solution contains triethylamine with the volume fraction of 0.5%; and (3) immersing the porous supporting layer of the polydopamine-coated permeable composite membrane obtained in the step (S2.1) in the water solution B for 1-6 hours in a mold.
6. The method for preparing the pressure retarded osmosis membrane modified by the zwitterionic random copolymer as claimed in claim 5, wherein the osmosis composite membrane in step S2 is a composite membrane formed by interfacial polymerization of a polyamide-polyester membrane, a polyamide-polyethersulfone membrane, a polyamide-polysulfone membrane, a polyamide-polyacrylonitrile membrane, a polyamide-polyvinylidene fluoride membrane or a polyamide-polyimide membrane.
7. The method for preparing the zwitterionic random copolymer modified pressure retarded osmosis membrane according to claim 6, wherein the preparation of the polyamide-polyether sulfone membrane comprises the following steps:
porous supporting layer of spun polyether sulfone membrane
Spinning a polyethersulfone membrane porous supporting layer by a non-solvent induced phase separation method, firstly, carrying out vacuum drying on a polyethersulfone raw material at 90 +/-5 ℃ to remove water, preparing the polyethersulfone raw material into a solution C with the mass fraction of 12-25% by taking N-methylpyrrolidone as a solvent, and removing bubbles; under the conditions of room temperature and 50-90% of relative air humidity, spreading the solution C on a glass plate into a sheet by using a film scraping knife with a gap of 20-300 micrometers, then soaking the glass plate in water for 1-10 minutes, taking purified water for soaking again for 1-10 hours to obtain a polyether sulfone film porous supporting layer, wherein the thickness of the obtained film is 40-350 micrometers, and the pore diameter is 2-15 nanometers;
spun polyamide-polyethersulfone membranes
Immersing a polyether sulfone membrane porous supporting layer into an aqueous solution of aqueous-phase m-phenylenediamine with the mass fraction of 1-3% for 1-3 minutes, and wiping off redundant aqueous-phase solution on the surface of the membrane; then immersing the membrane into a normal hexane solution of oil phase isophthaloyl dichloride for 0.5-5 minutes, and taking out the membrane; rinsing with deionized water for 10 times, and performing heat treatment at 50-90 ℃ for 5-15 minutes to obtain the polyamide-polyether sulfone membrane with pure water flux of 1-5 Lm-2h-1bar-1The rejection rate of sodium chloride is 85-95%.
CN201810318059.3A 2018-04-10 2018-04-10 Preparation method of pressure retardation permeable membrane modified by zwitter-ion random copolymer Active CN110354692B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810318059.3A CN110354692B (en) 2018-04-10 2018-04-10 Preparation method of pressure retardation permeable membrane modified by zwitter-ion random copolymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810318059.3A CN110354692B (en) 2018-04-10 2018-04-10 Preparation method of pressure retardation permeable membrane modified by zwitter-ion random copolymer

Publications (2)

Publication Number Publication Date
CN110354692A CN110354692A (en) 2019-10-22
CN110354692B true CN110354692B (en) 2021-09-14

Family

ID=68214295

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810318059.3A Active CN110354692B (en) 2018-04-10 2018-04-10 Preparation method of pressure retardation permeable membrane modified by zwitter-ion random copolymer

Country Status (1)

Country Link
CN (1) CN110354692B (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2337004C (en) * 1998-07-17 2008-12-23 Biocompatibles Limited Method for providing coated moulded polymeric articles
CN102029117A (en) * 2009-09-29 2011-04-27 中国科学院大连化学物理研究所 Method for modifying surface of ultrafiltration membrane
CN102294176A (en) * 2011-08-17 2011-12-28 浙江大学 High permeability nanofiltration membrane containing zwitterion and preparation method thereof
CN103990385A (en) * 2014-05-20 2014-08-20 中国科学院宁波材料技术与工程研究所 Preparation method of novel polyamide composite separation membrane
CN104028114A (en) * 2014-05-16 2014-09-10 浙江大学 Preparation method of nanofiltration membrane based on nano betaine type carboxymethyl cellulose
CN104028117A (en) * 2014-05-16 2014-09-10 浙江大学 Preparation method of amphoteric polyelectrolyte complex surface-modified polyamide reverse osmosis membrane
CN104226128A (en) * 2014-09-12 2014-12-24 浙江大学 Method for forming amphoteric ion structure on surface of separation membrane and separation membrane
CN105148750A (en) * 2015-08-21 2015-12-16 浙江大学 Method for modifying surface of polyamide composite film
CN105233709A (en) * 2015-10-13 2016-01-13 天津大学 Surface grafting-modified aromatic polyamide composite reverse osmosis membrane and preparation method thereof
WO2016109621A1 (en) * 2014-12-30 2016-07-07 Tufts University Zwitterionic copolymers for fouling resistant filtration membranes
CN107108489A (en) * 2014-10-09 2017-08-29 联邦科学与工业研究组织 general RAFT agent

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2337004C (en) * 1998-07-17 2008-12-23 Biocompatibles Limited Method for providing coated moulded polymeric articles
CN102029117A (en) * 2009-09-29 2011-04-27 中国科学院大连化学物理研究所 Method for modifying surface of ultrafiltration membrane
CN102294176A (en) * 2011-08-17 2011-12-28 浙江大学 High permeability nanofiltration membrane containing zwitterion and preparation method thereof
CN104028114A (en) * 2014-05-16 2014-09-10 浙江大学 Preparation method of nanofiltration membrane based on nano betaine type carboxymethyl cellulose
CN104028117A (en) * 2014-05-16 2014-09-10 浙江大学 Preparation method of amphoteric polyelectrolyte complex surface-modified polyamide reverse osmosis membrane
CN103990385A (en) * 2014-05-20 2014-08-20 中国科学院宁波材料技术与工程研究所 Preparation method of novel polyamide composite separation membrane
CN104226128A (en) * 2014-09-12 2014-12-24 浙江大学 Method for forming amphoteric ion structure on surface of separation membrane and separation membrane
CN107108489A (en) * 2014-10-09 2017-08-29 联邦科学与工业研究组织 general RAFT agent
WO2016109621A1 (en) * 2014-12-30 2016-07-07 Tufts University Zwitterionic copolymers for fouling resistant filtration membranes
CN105148750A (en) * 2015-08-21 2015-12-16 浙江大学 Method for modifying surface of polyamide composite film
CN105233709A (en) * 2015-10-13 2016-01-13 天津大学 Surface grafting-modified aromatic polyamide composite reverse osmosis membrane and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Tailoring macromolecular architecture with imidazole functionality: A;Matthew D. Green 等;《European Polymer Journal》;20101014;486-496 *

Also Published As

Publication number Publication date
CN110354692A (en) 2019-10-22

Similar Documents

Publication Publication Date Title
CN108905624B (en) Polyester-polyamide amphoteric charge composite nanofiltration membrane and preparation method thereof
Li et al. Thermo-responsive polysulfone membranes with good anti-fouling property modified by grafting random copolymers via surface-initiated eATRP
CN110052179B (en) Preparation method of anti-pollution composite nanofiltration membrane
Zhang et al. Silver–PEGylated dendrimer nanocomposite coating for anti-fouling thin film composite membranes for water treatment
Ni et al. Surface coating on the polyamide TFC RO membrane for chlorine resistance and antifouling performance improvement
Wang et al. Surface modification of NF membrane with zwitterionic polymer to improve anti-biofouling property
Zhao et al. Zwitterionic hydrogel thin films as antifouling surface layers of polyethersulfone ultrafiltration membranes anchored via reactive copolymer additive
Tripathi et al. Polyethylene glycol cross-linked sulfonated polyethersulfone based filtration membranes with improved antifouling tendency
CN102755844B (en) Preparation method for surface ionization modified polysulfone ultrafiltration membrane
Ahmadiannamini et al. Influence of polyanion type and cationic counter ion on the SRNF performance of polyelectrolyte membranes
CN109663510B (en) Zwitterionic random copolymer P (MMA)x-r-CBMAy) Modified PVDF antifouling film and preparation method thereof
Kim et al. Polysulfone based ultrafiltration membranes with dopamine and nisin moieties showing antifouling and antimicrobial properties
CN112237853B (en) Antibacterial and anti-pollution microporous membrane and preparation method thereof
CN110773007A (en) Calcium alginate hydrogel filtering membrane containing black phosphorus/graphene oxide and preparation method thereof
CN112426884A (en) Antibacterial composite reverse osmosis membrane and preparation method thereof
CN106632922A (en) Preparation method of block polymer containing hydrophilic segment and method for modifying polyvinylidene fluoride (PVDF) micro-filtration membrane by block polymer
US20230415103A1 (en) Polyamide composite reverse osmosis membrane and preparation method thereof
Wang et al. Cu2+/alginate nanofiltration membranes fabricated at the aqueous contra-diffusion “interface” for salt/dye rejection
JP2016182690A (en) Surface-modified substrate, polymer-coated substrate, and production method of them
US10532328B2 (en) Polyaniline-based chlorine resistant hydrophilic filtration membranes
CN102512997B (en) Hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and preparation method thereof
Su et al. Preparation of thin-film composite membrane with Turing structure by PEO-assisted interfacial polymerization combined with choline chloride modification to improve permeability
CN110354692B (en) Preparation method of pressure retardation permeable membrane modified by zwitter-ion random copolymer
KR20140113113A (en) Positive charged poly(vinylidene fluoride) porous membranes and manufacturing method thereof
Nguyen et al. Immobilization of bio-macromolecules onto membranes via an adsorbed nanolayer: an insight into the mechanism

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant