CN115010697A - Preparation of cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane - Google Patents
Preparation of cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 130
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 76
- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 73
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 29
- 150000001768 cations Chemical class 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000004440 column chromatography Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006266 etherification reaction Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 125000002091 cationic group Chemical group 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
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- 239000007787 solid Substances 0.000 claims description 21
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- 239000002904 solvent Substances 0.000 claims description 9
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 8
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
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- 238000012545 processing Methods 0.000 claims description 7
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- HARITLZHGNEHDS-UHFFFAOYSA-N 1-[4-(bromomethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=C(CBr)C=C1 HARITLZHGNEHDS-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 6
- 244000005700 microbiome Species 0.000 abstract description 4
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- 239000001913 cellulose Substances 0.000 abstract 2
- 208000029422 Hypernatremia Diseases 0.000 abstract 1
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 230000036211 photosensitivity Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- 230000000844 anti-bacterial effect Effects 0.000 description 10
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 9
- 239000000047 product Substances 0.000 description 9
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- 238000005286 illumination Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
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- 239000012466 permeate Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000008223 sterile water Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- 239000013535 sea water Substances 0.000 description 2
- UBOKASXZHPZFRZ-UHFFFAOYSA-N 2-phenyl-1h-indole-4,6-diamine Chemical compound N1C2=CC(N)=CC(N)=C2C=C1C1=CC=CC=C1 UBOKASXZHPZFRZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003214 anti-biofilm Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000007853 buffer solution Substances 0.000 description 1
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- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000011534 incubation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
-
- 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
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane, which is obtained by immersing a saponified cellulose acetate reverse osmosis membrane into a brominated 3T-DMAEMA solution for etherification. 3T-DMAEMA has the following structure:
Description
Technical Field
The invention belongs to the technical field of reverse osmosis membrane functionalized grafting, and particularly relates to a preparation method of a cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane.
Background
The rapid growth of population and the development of industrialization have brought about the serious problems of shortage of fresh water resources and environmental pollution. Pollution of fresh water resources and shortage of safe drinking water are major causes of shortage of fresh water resources. Desalination of sea water is considered a major solution to alleviate water shortage in this century. Two techniques, multi-stage flash evaporation and reverse osmosis, are commonly used to recover fresh water from seawater and brackish water in an economical manner. However, compared with multi-stage flash evaporation, the reverse osmosis technology is simpler, lower in energy consumption and higher in efficiency. Currently, most synthetic reverse osmosis membranes are composed of polyamide or cellulose acetate. Cellulose acetate is used as an environment-friendly material with wide source and strong biodegradability, and has the characteristics of rich resources, good hydrophilicity, high desalination rate, good film forming property and the like. Importantly, cellulose acetate has excellent chlorine resistance. The cellulose acetate reverse osmosis membrane can be stably applied to 1mg/L active chlorine aqueous solution for a long time, and the separation performance of the cellulose acetate reverse osmosis membrane is not obviously changed. Recent research has produced cellulose acetate reverse osmosis membranes with good potential for use in water treatment.
However, bio-fouling is the greatest threat to cellulose acetate reverse osmosis membranes due to the inherent surface structure and physicochemical properties of the membrane. Achieving 100% bacteria removal requires more stringent conditions and ongoing maintenance, which is not acceptable in terms of cost. Even if the bacteria removal rate after pretreatment reaches 99.99 percent, the residual viable bacteria can grow and propagate, and even form a biological membrane on the cellulose acetate reverse osmosis membrane. Once formed, biofilms result in higher transmembrane pressures (TMP), resulting in increased operating costs and poor performance of cellulose acetate reverse osmosis membranes. In addition, the membranes may be degraded and destroyed by acidic byproducts produced by microorganisms from the biofouling layer, shortening the useful life of the membranes.
The antimicrobial mechanism of the photosensitizer quaternary ammonium salt is very special. It has the antibacterial performance of quaternary ammonium salt and the photosensitive antibacterial function of photosensitizer. Trithiophene methanol is a good photosensitizer, but synthesis of quaternary ammonium salts from trithiophene methanol has rarely been reported. Quaternary ammonium salts have been reported to prevent microorganisms from adhering to cellulose acetate reverse osmosis membranes by blending techniques, but the combination of a terthiophene quaternary ammonium salt with a cellulose acetate reverse osmosis membrane has not been mentioned. The quaternized trithiophene methanol retains the photosensitive activity, generates singlet oxygen under the irradiation of light, and greatly improves the sterilization efficiency. In addition, the quaternary ammonium salt of the trithiophene methanol has low toxicity, no skin irritation, low corrosivity, good environmental stability and excellent cell membrane penetrating property, and is a promising antibacterial agent.
Disclosure of Invention
The invention aims to provide a preparation method of a cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane, which enables the cellulose acetate reverse osmosis membrane to have photosensitive and antibacterial characteristics, reduces and inhibits the growth and reproduction of microorganisms on the surface of the membrane, and prolongs the service life of the cellulose acetate reverse osmosis membrane.
The technical scheme adopted by the invention is as follows:
the compound 3T-DMAEMA has the following structural formula:
the preparation method of the compound 3T-DMAEMA comprises the following steps:
(1) preparation of intermediate 3T-Br: adding 0.1g of 2,2', 5' -2 ' -trithiophene-5-formaldehyde and 0.1g of 1- (4- (bromomethyl) phenyl) ethanone into a three-neck flask, filling nitrogen into the three-neck flask for protection, adding 10-20ml of absolute ethyl alcohol or anhydrous acetonitrile into the three-neck flask, slowly dropwise adding 0.5ml of piperidine or 0.5ml of 1mol/L KOH solution or 0.5ml of 20% sodium ethoxide solution into the three-neck flask, and reacting for 12-48h at 45-60 ℃; after the reaction, the mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrousNa 2 SO 4 After drying, carrying out column chromatography separation to obtain orange yellow solid 3T-Br;
(2) preparation of 3T-DMAEMA: adding 0.1g of 3T-Br and 500 mu L of dimethylaminoethyl methacrylate into a flask, adding 10-20ml of absolute ethyl alcohol or absolute acetonitrile serving as a solvent, and carrying out reflux reaction at 80-120 ℃ for 12-48 h; after the reaction, the mixture was extracted with ethyl acetate, and the organic layer was extracted with anhydrous Na 2 SO 4 And (4) after drying, carrying out column chromatography separation to obtain orange solid 3T-DMAEMA.
The proportion of the 3T-Br added to the dimethylaminoethyl methacrylate is 0.1 g: 500 μ L.
The reflux reaction is carried out at 80-120 ℃ for 12-48 h.
The compound 3T-DMAEMA is applied to a reverse osmosis membrane.
A preparation method of a cation photosensitizer quaternary ammonium salt reverse osmosis membrane comprises the step of immersing a cellulose acetate reverse osmosis membrane subjected to saponification reaction into a brominated 3T-DMAEMA solution for etherification to obtain a cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane.
The saponification reaction is that a cellulose acetate reverse osmosis membrane is placed in 0.05-0.1% NaOH solution, saponification reaction is carried out for 0.5-2h at 25 ℃, and then the membrane is washed by deionized water until the solution is neutral.
And the bromination is to hydrolyze 3T-DMAEMA in 0.05-0.1% NaOH solution, and bromize the hydrolyzed product by phosphorus tribromide to obtain the brominated 3T-DMAEMA.
The cellulose acetate reverse osmosis membrane is prepared by the following method: putting 1.56g of cellulose acetate and 0.576g of maleic acid into a beaker, and adding 10ml of a mixed solvent of 1, 4-dioxane, acetone and methanol to fully dissolve the solid; sealing and storing after dissolving, and statically defoaming overnight to obtain a transparent and clear casting solution; then slowly pouring the casting film liquid on a clean and smooth glass surface, and uniformly processing the glass surface by using a film scraper to form a film; and then putting the membrane into deionized water for soaking, washing to remove the solvent, and finally washing with a large amount of deionized water to obtain the cellulose acetate reverse osmosis membrane.
The etherification condition is that the pH value is kept between 9 and 11, and the reaction is carried out for 1 to 4 hours at the temperature of 30 ℃; the 1, 4-dioxane, acetone and methanol are mixed according to the following proportion: 6-6.75: 2.7-3: 0.5-1.
Compared with the prior art, the invention has the following advantages and technical effects:
1. the cellulose acetate reverse osmosis membrane prepared by the invention has higher membrane surface roughness on the microstructure, but has better hydrophilicity, which is related to the high hydrophilicity of the grafted cationic photosensitizer quaternary ammonium salt compound;
2. after the compound is grafted, the permeation flux and the salt rejection rate of the reverse osmosis membrane are slightly reduced, but the biological pollution resistance of the membrane is greatly improved, and particularly the photosensitive antibacterial property is endowed to the membrane, so that the service life of the membrane is greatly prolonged.
3. The compound 3T-DMAEMA has excellent antibacterial performance and the capability of eliminating mature biofilm, thereby greatly enhancing the capability of attaching the biofilm-resistant biofilm and indirectly prolonging the service life.
Drawings
FIG. 1 is SEM electron micrographs of cellulose acetate reverse osmosis membranes grafted with a cationic photosensitizer quaternary ammonium salt at different times. a1-e1 is a section electron microscope picture of the film; a2-e2 is a top electron micrograph of the film; a3-e3 is a bottom electron micrograph of the film; a1-a3 is CA-RO membrane; b1-b3 is QCA-RO-1 membrane; c1-c3 is QCA-RO-2 membrane; d1-d3 is QCA-RO-3 membrane; e1-e3 is QCA-RO-4 membrane.
FIG. 2 is a graph of the contact angle of a reverse osmosis membrane of cellulose acetate grafted with a quaternary ammonium salt of a cationic photosensitizer over time.
FIG. 3 is a graph of salt rejection and permeation flux of a cellulose acetate reverse osmosis membrane grafted with a cationic photosensitizer quaternary ammonium salt for different times.
FIG. 4 is a confocal microscope image of the laser scanning of the cellulose acetate reverse osmosis membrane grafted with the cationic photosensitizer quaternary ammonium salt at different times. a is a CA-RO membrane; b is QCA-RO-1 membrane; c is QCA-RO-2 membrane; d is QCA-RO-3 membrane; e is QCA-RO-4 membrane; a1-e1 is a dark group; a2-e2 is a light group.
FIG. 5 is a graph showing the antibacterial effect of a cellulose acetate reverse osmosis membrane grafted with a cationic photosensitizer quaternary ammonium salt on Pseudomonas aeruginosa under light and dark conditions at different times. a is a CA-RO membrane; b is QCA-RO-1 membrane; c is QCA-RO-2 membrane; d is a QCA-RO-3 membrane; e is QCA-RO-4 membrane; a1-e1 is a dark group; a2-e2 is a light group.
FIG. 6 shows the performance of detecting active oxygen generation of 3T-DMAEMA under xenon irradiation with 9, 10-anthracenediyl-bis (methylene) dipropanedioic acid (ABDA) as a probe.
FIG. 7 is a graph showing the antibacterial performance of 3T-DMAEMA at different concentrations on Pseudomonas aeruginosa in light and dark.
FIG. 8 shows the biofilm resistance of 3T-DMAEMA (0.8mg ml-1) under different lighting times, biofilm being exemplified by a Pseudomonas aeruginosa membrane. a is a dark group, b is an illumination group, and the illumination interval is 1 h.
FIG. 9 shows the NMR spectrum of 3T-Br.
FIG. 10 is a high resolution mass spectrum of 3T-Br.
FIG. 11 is a nuclear magnetic resonance hydrogen spectrum of 3T-DMAEMA.
FIG. 12 is a high resolution mass spectrum of 3T-DMAEMA.
Detailed Description
The present invention is further illustrated by the following specific examples. The following are examples of the present invention, and are not intended to limit the present invention, and any modifications, substitutions, and improvements made on the basis of the present invention are included in the scope of the present invention.
For convenience of comparison, a cellulose acetate reverse osmosis membrane was prepared as a comparative example in the following manner: placing 1.56g of cellulose acetate and 0.576g of maleic acid in a beaker, adding 6.75ml of 1, 4-dioxane, 2.7ml of acetone and 0.55ml to dissolve the solid fully; sealing and storing after dissolving, and statically defoaming overnight to obtain a transparent and clear casting solution; then slowly pouring the casting film liquid on a clean and smooth glass surface, and uniformly processing the glass surface by using a film scraper to form a film; then putting the membrane into deionized water for soaking and washing to remove the solvent, and finally washing with a large amount of deionized water to obtain the cellulose acetate reverse osmosis membrane which is marked as a CA-RO membrane.
Example 1
A preparation method of a cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane comprises the following steps:
(1) preparation of intermediate 3T-Br
Adding 0.1g of 2,2', 5', 2' -trithiophene-5-formaldehyde and 0.1g of 1- (4- (bromomethyl) phenyl) ethanone into a three-neck flask, filling nitrogen into the three-neck flask for protection, adding 20ml of anhydrous acetonitrile, slowly dripping 0.5ml of piperidine into the three-neck flask, and reacting for 24 hours at 60 ℃; after the reaction, the mixture was extracted with ethyl acetate, and the organic layer was extracted with anhydrous Na 2 SO 4 After drying, carrying out column chromatography separation to obtain orange yellow solid 3T-Br;
(2) preparation of product 3T-DMAEMA
Adding 0.1g of 3T-Br and 500 mu L of dimethylaminoethyl methacrylate into a flask, adding 20ml of anhydrous acetonitrile serving as a solvent, and carrying out reflux reaction at 120 ℃ for 12 hours; after the reaction, the mixture was extracted with ethyl acetate, and the organic layer was extracted with anhydrous Na 2 SO 4 Carrying out column chromatography separation after drying to obtain orange solid 3T-DMAEMA;
(3) preparation of reverse osmosis membrane of cellulose acetate
Putting 1.56g of cellulose acetate and 0.576g of maleic acid into a beaker, and adding 6.75ml of 1, 4-dioxane, 2.7ml of acetone and 0.55ml of methanol to fully dissolve the solid; sealing and storing after dissolving, and statically defoaming for 12h to obtain a transparent and clear casting solution; then slowly pouring the casting film liquid on a clean and smooth glass surface, and uniformly processing the glass surface by using a film scraper to form a film; then placing the glass plate into a deionized water coagulating bath at 0 ℃, soaking for 15min to separate the film from the glass plate, then placing the glass plate into deionized water at 4 ℃ for soaking for 2h, then transferring the glass plate into deionized water at 85 ℃ for soaking for 10min, finally washing the glass plate by using a large amount of deionized water, and storing the glass plate in the deionized water for later use;
(4) saponification of cellulose acetate reverse osmosis membrane and bromination of 3T-DMAEMA
Placing a cellulose acetate reverse osmosis membrane in 0.08% NaOH solution, performing saponification reaction for 1h at 25 ℃, and washing the membrane with deionized water until the solution is neutral; hydrolyzing 3T-DMAEMA in 0.08% NaOH solution, and brominating the hydrolyzed product with phosphorus tribromide at 0 ℃ for 4h to obtain brominated 3T-DMAEMA;
(5) etherification of cellulose acetate reverse osmosis membranes
The saponified membrane was immersed in 0.05mol/L of brominated 3T-DMAEMA solution, the pH was adjusted and maintained at 11, and the reaction was carried out at 30 ℃ for 1h, and the resulting membrane was labeled QCA-RO-1 according to the reaction time.
Example 2
The preparation method of the cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane comprises the following steps:
(1) preparation of intermediate 3T-Br
Adding 0.1g of 2,2', 5', 2' -trithiophene-5-formaldehyde and 0.1g of 1- (4- (bromomethyl) phenyl) ethanone into a three-neck flask, filling nitrogen into the three-neck flask for protection, adding 20ml of absolute ethyl alcohol, then slowly dropwise adding 0.5ml of 1mol/L KOH solution into the three-neck flask, and reacting for 24 hours at the temperature of 60 ℃; after the reaction, the mixture was extracted with ethyl acetate, and the organic layer was extracted with anhydrous Na 2 SO 4 After drying, carrying out column chromatography separation to obtain orange yellow solid 3T-Br;
(2) preparation of product 3T-DMAEMA
Adding 0.1g of 3T-Br and 500 mu L of dimethylaminoethyl methacrylate into a flask, adding 20ml of absolute ethyl alcohol as a solvent, and carrying out reflux reaction at 80 ℃ for 48 hours; after the reaction, the mixture was extracted with ethyl acetate, and the organic layer was extracted with anhydrous Na 2 SO 4 Carrying out column chromatography separation after drying to obtain orange solid 3T-DMAEMA;
(3) preparation of reverse osmosis membrane of cellulose acetate
Putting 1.56g of cellulose acetate and 0.576g of maleic acid into a beaker, and adding 6ml of 1, 4-dioxane, 3ml of acetone and 1ml of methanol to fully dissolve the solid; sealing and storing after dissolving, and statically defoaming for 12h to obtain a transparent and clear casting solution; then slowly pouring the casting film liquid on a clean and smooth glass surface, and uniformly processing the glass surface by using a film scraper to form a film; then placing the glass plate into a deionized water coagulating bath at 0 ℃, soaking for 15min to separate the film from the glass plate, then placing the glass plate into deionized water at 4 ℃ for soaking for 2h, then transferring the glass plate into deionized water at 60 ℃ for soaking for 30min, finally washing the glass plate by using a large amount of deionized water, and storing the glass plate in the deionized water for later use;
(4) saponification of cellulose acetate reverse osmosis membrane and bromination of 3T-DMAEMA
Placing a cellulose acetate reverse osmosis membrane in 0.05% NaOH solution, performing saponification reaction for 2 hours at 25 ℃, and washing the membrane with deionized water until the solution is neutral; hydrolyzing 3T-DMAEMA in 0.05% NaOH solution, and brominating the hydrolyzed product with phosphorus tribromide for 1h to obtain brominated 3T-DMAEMA; phosphorus tribromide was added dropwise to the reaction vessel over 2h using a peristaltic pump.
(5) Etherification of cellulose acetate reverse osmosis membranes
The saponified membrane was immersed in 0.05mol/L of brominated 3T-DMAEMA solution, the pH was adjusted and maintained at 10, 30 ℃ for 2h, and the resulting membrane was labeled QCA-RO-2 according to the reaction time.
Example 3
The preparation method of the cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane comprises the following steps:
(1) preparation of intermediate 3T-Br
Adding 0.1g of 2,2', 5', 2' -trithiophene-5-formaldehyde and 0.1g of 1- (4- (bromomethyl) phenyl) ethanone into a three-neck flask, filling nitrogen into the three-neck flask for protection, adding 10ml of absolute ethyl alcohol, then slowly dropwise adding 0.5ml of 20% sodium ethoxide solution into the three-neck flask, and reacting for 48 hours at 45 ℃; after the reaction, the mixture was extracted with ethyl acetate, and the organic layer was extracted with anhydrous Na 2 SO 4 After drying, carrying out column chromatography separation to obtain orange yellow solid 3T-Br;
(2) preparation of product 3T-DMAEMA
Adding 0.1g of 3T-Br and 500 mu L of dimethylaminoethyl methacrylate into a flask, adding 10ml of absolute ethyl alcohol as a solvent, and carrying out reflux reaction at 100 ℃ for 48 hours; after the reaction, the mixture was extracted with ethyl acetate, and the organic layer was extracted with anhydrous Na 2 SO 4 Carrying out column chromatography separation after drying to obtain orange solid 3T-DMAEMA;
(3) preparation of reverse osmosis membrane of cellulose acetate
Putting 1.56g of cellulose acetate and 0.576g of maleic acid into a beaker, and adding 6.5ml of 1, 4-dioxane, 3ml of acetone and 0.5ml of methanol to fully dissolve the solid; sealing and storing after dissolving, and statically defoaming for 12h to obtain a transparent and clear casting solution; then slowly pouring the casting film liquid on a clean and smooth glass surface, and uniformly processing the glass surface by using a film scraper to form a film; standing in air for 1min, soaking in 0 deg.C deionized water coagulation bath for 15min to separate the film from the glass plate, soaking in 4 deg.C deionized water for 2 hr, soaking in 85 deg.C deionized water for 10min, washing with large amount of deionized water, and storing in deionized water;
(4) saponification of cellulose acetate reverse osmosis membrane and bromination of 3T-DMAEMA
Placing a cellulose acetate reverse osmosis membrane in 0.1% NaOH solution, performing saponification reaction at 25 ℃ for 30min, and washing the membrane with deionized water until the solution is neutral; hydrolyzing 3T-DMAEMA in 0.1% NaOH solution, and brominating the hydrolyzed product with phosphorus tribromide for 1h to obtain brominated 3T-DMAEMA; phosphorus tribromide was added dropwise to the reaction vessel over 2h using a peristaltic pump.
(5) Etherification of cellulose acetate reverse osmosis membranes
The saponified membrane was immersed in 0.05mol/L of brominated 3T-DMAEMA solution, the pH was adjusted and maintained at 10, 30 ℃ for 3h, and the resulting membrane was labeled QCA-RO-3 according to the reaction time.
Example 4
The preparation method of the cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane comprises the following steps:
(1) preparation of intermediate 3T-Br
Adding 0.1g of 2,2', 5', 2' -trithiophene-5-formaldehyde and 0.1g of 1- (4- (bromomethyl) phenyl) ethanone into a three-neck flask, filling nitrogen into the three-neck flask for protection, adding 10ml of absolute ethyl alcohol, then slowly dropwise adding 0.5ml of 20% sodium ethoxide solution into the three-neck flask, and reacting for 48 hours at 45 ℃; after the reaction is finished, extracting with ethyl acetate, drying an organic layer with anhydrous Na2SO4, and then performing column chromatography separation to obtain orange yellow solid 3T-Br;
(2) preparation of product 3T-DMAEMA
0.1g of 3T-Br was added to the flask together with 500. mu.L of dimethylaminoethyl methacrylate, and 10ml of absolute ethanol was addedAs a solvent, carrying out reflux reaction at 100 ℃ for 48 h; after the reaction, the mixture was extracted with ethyl acetate, and the organic layer was extracted with anhydrous Na 2 SO 4 Carrying out column chromatography separation after drying to obtain orange solid 3T-DMAEMA;
(3) preparation of reverse osmosis membrane of cellulose acetate
Putting 1.56g of cellulose acetate and 0.576g of maleic acid into a beaker, and adding 6.75ml of 1, 4-dioxane, 2.7ml of acetone and 0.55ml of methanol to fully dissolve the solid; sealing and storing after dissolving, and statically defoaming for 12h to obtain a transparent and clear casting solution; then slowly pouring the casting film liquid on a clean and smooth glass surface, and uniformly processing the glass surface by using a film scraper to form a film; then placing the glass plate into a deionized water coagulating bath at 0 ℃, soaking for 15min to separate the film from the glass plate, then placing the glass plate into deionized water at 4 ℃ for soaking for 2h, then transferring the glass plate into deionized water at 85 ℃ for 10min, finally washing the glass plate with a large amount of deionized water, and storing the glass plate in the deionized water for later use;
(4) saponification of cellulose acetate reverse osmosis membrane and bromination of 3T-DMAEMA
Placing a cellulose acetate reverse osmosis membrane in 0.08% NaOH solution, performing saponification reaction at 25 ℃ for 30min, and washing the membrane with deionized water until the solution is neutral; hydrolyzing 3T-DMAEMA in 0.08% NaOH solution, and reacting the hydrolyzed product with phosphorus tribromide at 0 ℃ for 4h to obtain brominated 3T-DMAEMA;
(5) etherification of cellulose acetate reverse osmosis membranes
Immersing a reverse osmosis membrane of the cellulose acetate which is subjected to saponification reaction into a 3T-DMAEMA solution after 0.05mol/L bromination, adjusting the pH value, keeping the pH value at 9, reacting for 4 hours at 30 ℃, and marking the obtained membrane as QCA-RO-4 according to the reaction time.
Evaluation of ability of 3T-DMAEMA to produce singlet oxygen
And (3) detecting the singlet oxygen generating capacity of 3T-DMAEMA by using 9, 10-anthracenediyl-bis (methylene) dipropanedioic acid (ABDA) as a probe. The characteristic absorption peak of ABDA is reduced after being oxidized by singlet oxygen, so that the singlet oxygen generating capacity of 3T-DMAEMA can be evaluated by the reduction degree of the characteristic absorption peak of ABDA. mu.L ABDA (10mM) to 3ml 3T-DMAEMA (20 mu M) PBS solution is taken, mixed uniformly, irradiated by a xenon lamp, and the absorbance value is measured by an ultraviolet spectrophotometer every 60 s. As shown in fig. 6, the absorbance of ABDA continued to decrease with the increase of the illumination time, demonstrating that 3T-DMAEMA can efficiently generate singlet oxygen.
Evaluation of antibacterial Activity of 3T-DMAEMA
Taking pseudomonas aeruginosa as an example, diluting the overnight cultured pseudomonas aeruginosa suspension to OD (optical density) 0.01, mixing the membrane with the diluted bacterial liquid, and setting a dark group and an illumination group. Culturing in 37 deg.C constant temperature incubator for 1 hr, diluting with PBS 10 4 Carrying out flat plate coating after doubling; irradiating the illumination group with xenon lamp for 30min after the culture, and diluting with PBS buffer solution 10 after the irradiation 4 After doubling, the plate was coated. The coated plate is continuously put into a constant temperature incubator at 37 ℃ for overnight culture, and then the antibacterial performance of the micromolecules is judged according to the colony count. As shown in FIG. 5, the antibacterial performance exhibited by the membrane was better and better in either light or dark as the reaction time of the small molecule compound with the membrane was prolonged, which proved that the small molecule compound was successfully loaded on the membrane.
Evaluation of anti-biofilm Capacity of 3T-DMAEMA
By taking pseudomonas aeruginosa as an example, the treatment effect of 3T-DMAEMA on the biomembrane damage and the bacterial activity of the pseudomonas aeruginosa biomembrane is researched. The concentration of the test chemical was fixed at 0.8 mg/mL. Culturing the pseudomonas aeruginosa in a TSB culture medium for 6-8 h, and diluting to 0.02 OD600 as an initial solution. Then, 200. mu.L of the initial solution was added to each well and incubated at 37 ℃ for 36h in a thermostatted incubator, and Pseudomonas aeruginosa will form biofilms in 96 wells under static conditions. After incubation, the biofilm was rinsed with sterile water to remove adherent bacteria. The obtained biofilm was mixed with 200. mu.L of sterile water and 0.8mg m/L of a drug, and different light irradiation times were set. After the illumination is finished, the biological membrane is washed by sterile water, then is stained by 4, 6-diamino-2-phenylindole (DAPI), and is observed by a laser confocal scanning microscope (CLSM) at an excitation wavelength of 461 nm.
Permeate flux and salt rejection evaluation of membranes
Permeate flux (J, L h) -1 m -2 ) And salt rejection (R,%) are key factors in evaluating membrane separation performance. The permeation flux refers to the volume of water passing through a unit time and a unit area under a constant pressure, and is calculated by the formula (1).
The salt rejection is the capacity and efficiency of removing salt from the brine, and is calculated according to equation (2). The experimental conditions were: the concentration of the raw material solution (aqueous sodium chloride solution) was 2000mg/L, and the effective area of the membrane was 30.25cm 2 The testing pressure is 1.5MPa, the constant temperature of the aqueous solution is 25 ℃, and the pH value is 7.0. Five tests were performed on each sample and the results averaged.
J＝V/(A×t), (1)
R(％)＝(1－C p /C f )×100％, (2)
Wherein V (L) is the volume of permeated water, A (cm) -2 ) Is the effective area, t (h) is the penetration time, C p And C f The conductivity (μ Sm) of the permeate and the original solution, respectively -1 )。
Contact Angle testing of films
Contact angle is an important parameter for measuring the wettability of a liquid on the surface of a material. When θ <90 °, the solid surface is hydrophilic, and when θ >90 °, the solid surface is hydrophobic. The contact angle of water and a reverse osmosis membrane of cellulose acetate or a reverse osmosis membrane of quaternized cellulose acetate is measured by a sitting drop method, and the contact angles of CA-RO, QCA-RO-1, QCA-RO-2, QCA-RO-3 and QCA-RO-4 membranes and water are determined by an DATATHICHICAL OCA20 instrument through experimental research. A2. mu.L drop of distilled water was placed on the membrane surface (3 cm. times.4 cm) until a constant water contact angle was reached. The average contact angle was obtained by measuring each film 5 times in succession.
The cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane prepared by using the compound 3T-DMAEMA of the invention loads the 3T-DMAEMA on the cellulose acetate reverse osmosis membrane in a grafting mode, and the cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane not only has the dual characteristics of quaternary ammonium salt antibiosis and photosensitive antibiosis, but also has the capability of resisting mature biofilms; meanwhile, due to the grafting loading mode, the phenomenon that the membrane structure is changed due to leakage of a loading agent, so that the membrane performance is reduced is avoided; in a word, the cation photosensitizer quaternary ammonium salt grafted cellulose acetate reverse osmosis membrane prepared by the invention makes up the short plate on the market, which can not prevent biological pollution, and greatly prolongs the service life of the cellulose acetate reverse osmosis membrane.
Claims (10)
1. A compound 3T-DMAEMA having the formula:
2. a process for the preparation of the compound 3T-DMAEMA of claim 1, comprising the steps of:
(1) preparation of intermediate 3T-Br: adding 0.1g of 2,2', 5' -2 ' -trithiophene-5-formaldehyde and 0.1g of 1- (4- (bromomethyl) phenyl) ethanone into a three-neck flask, filling nitrogen into the three-neck flask for protection, adding 10-20ml of absolute ethyl alcohol or anhydrous acetonitrile into the three-neck flask, slowly dropwise adding 0.5ml of piperidine or 0.5ml of 1mol/L KOH solution or 0.5ml of 20% sodium ethoxide solution into the three-neck flask, and reacting for 12-48h at 45-60 ℃; after the reaction, the mixture was extracted with ethyl acetate, and the organic layer was extracted with anhydrous Na 2 SO 4 After drying, carrying out column chromatography separation to obtain orange yellow solid 3T-Br;
(2) preparation of 3T-DMAEMA: adding the 3T-Br and dimethylaminoethyl methacrylate into a flask, adding 10-20ml of absolute ethyl alcohol or absolute acetonitrile as a solvent, and carrying out reflux reaction; after the reaction, the mixture was extracted with ethyl acetate, and the organic layer was extracted with anhydrous Na 2 SO 4 And (4) after drying, carrying out column chromatography separation to obtain orange solid 3T-DMAEMA.
3. The method of claim 2, wherein 3T-Br is added in an amount of 0.1 g: dimethylaminoethyl methacrylate was added in an amount of 500. mu.L.
4. The method for preparing compound 3T-DMAEMA according to claim 2, wherein the reflux reaction is carried out at 80-120 ℃ for 24-48 h.
5. Use of the compound 3T-DMAEMA of claim 1 on a reverse osmosis membrane.
6. A preparation method of a cation photosensitizer quaternary ammonium salt reverse osmosis membrane is characterized in that a saponified cellulose acetate reverse osmosis membrane is immersed into a brominated 3T-DMAEMA solution for etherification to obtain a cation photosensitizer quaternary ammonium salt graft cellulose acetate reverse osmosis membrane.
7. The method for preparing a cationic photosensitizer quaternary ammonium salt reverse osmosis membrane according to claim 6, characterized in that the saponification reaction is carried out by placing a cellulose acetate reverse osmosis membrane in 0.05% -0.1% NaOH solution, carrying out saponification reaction for 0.5-2h at 25 ℃, and then washing the membrane with deionized water until the solution is neutral.
8. The method for preparing the cation photosensitizer quaternary ammonium salt reverse osmosis membrane according to claim 6, characterized in that the bromination is carried out by hydrolyzing 3T-DMAEMA in 0.05-0.1% NaOH solution, and brominating the hydrolyzed product with phosphorus tribromide to obtain brominated 3T-DMAEMA.
9. The method of claim 6 wherein said cellulose acetate reverse osmosis membrane is prepared by the following steps: putting 1.56g of cellulose acetate and 0.576g of maleic acid into a beaker, and adding 10ml of a mixed solvent of 1, 4-dioxane, acetone and methanol to fully dissolve the solid; sealing and storing after dissolving, and statically defoaming overnight to obtain a transparent and clear casting solution; then slowly pouring the casting film liquid on a clean and smooth glass surface, and uniformly processing the glass surface by using a film scraper to form a film; and then putting the membrane into deionized water for soaking, washing to remove the solvent, and finally washing with a large amount of deionized water to obtain the cellulose acetate reverse osmosis membrane.
10. The preparation method of the cation photosensitizer quaternary ammonium salt reverse osmosis membrane according to claim 6, characterized in that the etherification condition is that the pH value is kept between 9 and 11, and the reaction is carried out for 1 to 4 hours at 30 ℃; the 1, 4-dioxane, acetone and methanol are mixed according to the following proportion: 6-6.75: 2.7-3: 0.5-1.
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Application publication date: 20220906 |