CN103736406B - Polyamide reverse osmosis composite film of a kind of antipollution easy cleaning and preparation method thereof - Google Patents
Polyamide reverse osmosis composite film of a kind of antipollution easy cleaning and preparation method thereof Download PDFInfo
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Abstract
The invention discloses polyamide reverse osmosis composite film of a kind of antipollution easy cleaning and preparation method thereof, method of the present invention comprises: (1) polyamide reverse osmosis composite film is used successively isopropyl alcohol and washed with de-ionized water clean; (2) polyamide reverse osmosis composite film after cleaning, 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine, potassium thiosulfate, sodium hydrogensulfite and deionized water are joined in container, pass into the oxygen in nitrogen eliminating container; (3) airtight container, water-bath.The inventive method is easy, mild condition, environmental friendliness, and the polyamide reverse osmosis composite film contamination resistance of the antipollution easy cleaning prepared is strong, physical cleaning can be carried out by the salinity changing water inlet to film surface after pollution, without the need for chemical machine cleaning agent, improve the durability of film, reduce expense, extend the service life of film.
Description
Technical field
The present invention relates to polyamide reverse osmosis composite film of a kind of antipollution easy cleaning and preparation method thereof.
Background technology
Along with quickening and the population growth of social industrialization paces, shortage of fresh water becomes one of facing mankind to be threatened greatly, and desalinization becomes the critical path of head it off.Conventional bio-chemistry separation technology separation product purity is not high, energy consumption large, is difficult to effectively carry out Selective Separation, and often causes comparatively serious secondary pollution.Membrane separation technique is the separation technology developed rapidly after the sixties in 20th century, the effect have separation, concentrating, purify.Reverse osmosis technology is a kind of reliable separation method of economy solving water crisis, has been widely used in seawater and brackish water desalination, Sewage treatment and pure water manufacture.Film, as the core component of membrane separation technique, has Selective Separation function, but fouling membrane affects the performance and used life of film greatly, adds the use cost of film.
Commercial polyamide reverse osmosis composite film is with porous polysulfones for supporting layer, and p-phenylenediamine (PPD) and pyromellitic trimethylsilyl chloride interfacial polymerization form composite bed.Polyamide reverse osmosis composite film has that excellent chemical stability, high water flux and salt retain, high temperature resistant, withstand voltage and acid and alkali-resistance.But fouling membrane becomes the subject matter affecting film and can better apply.The surface roughness of reverse osmosis composite membrane, surface hydrophilicity and surface charge are the principal elements affecting membrane separating property.At present, polyamide reverse osmosis composite film modification is mainly to following three performances improving film: (1) surface roughness; (2) parent/hydrophobic performance; (3) surface charge.Coarse film surface has larger effective infiltrating area, can improve the infiltration of film, but increase film surface roughness can aggravate colloid and the biological pollution to film; The film surface of good hydrophilic property is conducive to the permeation flux and the antifouling property that improve film; The charging characteristic on film surface can affect the separating property of film to charge species, and film properties affects comparatively large by pH, and usual neutral-surface can resist various charged contaminants, has good antifouling property.
Membrane modifying comprises carry out surface modification to film again after being prepared film forming after substrate modifications and first being adopted by base material certain film-forming method to prepare film forming.The stuctures and properties that the preparation of membrane surface modification intention is a kind of does not change body substantially also has the NEW TYPE OF COMPOSITE membrane material of functionalized surface, and membrane surface modification has consequence in film industry.Membrane surface modification mainly comprises the methods such as coating, irradiation grafting modification, plasma graft and ATRP.Surface coating belongs to the category of physical modification, and the method is simple, but surface coating layer is easy to come off, therefore very restricted in the application; Irradiation grafting modification is a kind of important surface graft modification method, have the advantages such as safe, pollution-free and easy and simple to handle, but irradiation can cause homopolymerization and the degraded of monomer; Plasma modification technology has lot of advantages, fast and effeciently can give material new performance, and only change the character of material surface, body is not affected substantially, but plasma treatment can decay along with time variations, make modified effect unstable.ATRP is the method for extensive use the most in activity/controllable free radical polymerization, have easy and simple to handle, monomeric species is many, mild condition, advantages of environment protection, is successfully applied to the modification of material in recent years.
Amphoteric ion polymer has hydrophilic anions and canons group, as-OH ,-COOH, and-SO
3deng and be not subject to solution ph impact thus make it have unique stable against biological contamination performance, namely can the absorption of impedance nonspecific proteins matter, bacterial adhesion and biomembranous formation, this characteristic makes this type of material more and more be applied in association areas such as biomedicines.Up to now, people have synthesized the amphoteric ion polymer of a lot of novel functionalization and have been applied to the every field such as petroleum industry, bio-medical material, pharmaceutical synthesis and sewage disposal.
Summary of the invention
The object of this invention is to provide a kind of polyamide reverse osmosis composite film of antipollution easy cleaning.
Second object of the present invention is to provide the preparation method of a kind of mild condition, antipollution easy cleaning polyamide reverse osmosis composite film simple to operate.
Technical scheme of the present invention is summarized as follows:
A polyamide reverse osmosis composite film for antipollution easy cleaning, gathers 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine at polyamide reverse osmosis composite film surface grafting.
A preparation method for the polyamide reverse osmosis composite film of antipollution easy cleaning, comprises the steps:
(1) polyamide reverse osmosis composite film is used successively isopropyl alcohol and washed with de-ionized water clean;
(2) polyamide reverse osmosis composite film after cleaning, 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine, potassium thiosulfate, sodium hydrogensulfite and deionized water are joined in container, obtain 50-300 ml water solution, make 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine concentration be 1-2mmolL
-1, thiosulfuric acid potassium concn is 1-2mmolL
-1, concentration of sodium bisulphite is 1-2mmolL
-1, continue to pass into the oxygen in nitrogen 15-20min eliminating container;
(3) airtight container, 20-70 DEG C of water-bath 1-24h, namely obtains a kind of polyamide reverse osmosis composite film of antipollution easy cleaning.
The present invention gathers (4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine) (PSVBP) by the method for Redox Initiator radical polymerization at polyamide reverse osmosis composite film surface grafting amphoteric ion polymer, the method has easy and simple to handle, mild condition, advantages of environment protection, and the polyamide reverse osmosis composite film contamination resistance of the antipollution easy cleaning prepared is strong, physical cleaning can be carried out by the salinity changing water inlet to film surface after pollution, without the need for chemical machine cleaning agent, improve the durability of film, this expense that Chemical cleaning greatly reduced needed for usual film is brought and ambient influnence, extend the service life of film.
Accompanying drawing explanation
Fig. 1 is monomer 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine (SVBP) nuclear-magnetism figure.
Fig. 2 is the FTIR figure of the polyamide reverse osmosis composite film of the antipollution easy cleaning of polyamide reverse osmosis composite film, embodiment 2, embodiment 3 and embodiment 4 preparation, wherein: a is polyamide reverse osmosis composite film; B is the polyamide reverse osmosis composite film of antipollution easy cleaning prepared by embodiment 2, and c is the polyamide reverse osmosis composite film of antipollution easy cleaning prepared by embodiment 3, and d is the polyamide reverse osmosis composite film of antipollution easy cleaning prepared by embodiment 4.
Fig. 3 is the XPS figure of the polyamide reverse osmosis composite film of the antipollution easy cleaning of polyamide reverse osmosis composite film, embodiment 2, embodiment 3 and embodiment 4 preparation, wherein: a is polyamide reverse osmosis composite film; B is the polyamide reverse osmosis composite film of antipollution easy cleaning prepared by embodiment 2, and c is the polyamide reverse osmosis composite film of antipollution easy cleaning prepared by embodiment 3, and d is the polyamide reverse osmosis composite film of antipollution easy cleaning prepared by embodiment 4.
Fig. 4 is the pollution-self-cleaning flux pattern of polyamide reverse osmosis composite film.
Fig. 5 is the pollution-self-cleaning flux pattern of a kind of antipollution easy cleaning polyamide reverse osmosis composite film prepared by embodiment 2.
Fig. 6 is the pollution-self-cleaning flux pattern of a kind of antipollution easy cleaning polyamide reverse osmosis composite film prepared by embodiment 3.
Fig. 7 is the pollution-self-cleaning flux pattern of a kind of antipollution easy cleaning polyamide reverse osmosis composite film prepared by embodiment 4.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
The preparation of ampholytic monomer 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine (SVBP), comprises the steps:
(1) get 18.72g(0.1mol) 2-(4-pyridine) ethyl sulfonic acid and 4g(0.1mol) NaOH at room temperature together be dissolved in 120ml formamide;
(2) by 15.26g(0.1mol) 4-1-chloro-4-methyl-benzene and a nitrobenzene slowly instills in formamide solution under nitrogen protection;
(3) stirred at ambient temperature 65h;
(4) reacted solution is cooled to 4 DEG C in refrigerator, and is deposited in ice acetone;
(5) filter, much filtrate vacuum drying in vacuum drying oven is obtained thick product;
(6) finally in ice absolute ethyl alcohol, crystallization obtains salt-free pure SVBP monomer.See Fig. 1.
Embodiment 2
A preparation method for the polyamide reverse osmosis composite film of antipollution easy cleaning, comprises the steps:
(1) polyamide reverse osmosis composite film is used successively isopropyl alcohol and washed with de-ionized water clean;
(2) 20cm × 5cm polyamide reverse osmosis composite film after cleaning, 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine, potassium thiosulfate, sodium hydrogensulfite and deionized water are joined in container, obtain 100 ml water solution, make 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine concentration be 1mmolL
-1, thiosulfuric acid potassium concn is 2mmolL
-1, concentration of sodium bisulphite is 2mmolL
-1, continue to pass into the oxygen in nitrogen 20min eliminating container;
(3) airtight container, 60 DEG C of water-bath 24h, take out film, and pure water cleans, and namely obtains a kind of polyamide reverse osmosis composite film of antipollution easy cleaning.Being successfully prepared of film is confirmed by FTIR and XPS test.See Fig. 2, Fig. 3.
Embodiment 3
A preparation method for the polyamide reverse osmosis composite film of antipollution easy cleaning, comprises the steps:
(1) polyamide reverse osmosis composite film is used successively isopropyl alcohol and washed with de-ionized water clean;
(2) 20cm × 5cm polyamide reverse osmosis composite film after cleaning, 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine, potassium thiosulfate, sodium hydrogensulfite and deionized water are joined in container, obtain 50 ml water solution, make 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine concentration be 2mmolL
-1, thiosulfuric acid potassium concn is 1mmolL
-1, concentration of sodium bisulphite is 1mmolL
-1, continue to pass into the oxygen in nitrogen 15min eliminating container;
(3) airtight container, 20 DEG C of water-bath 24h, take out film, and pure water cleans, and namely obtains a kind of polyamide reverse osmosis composite film of antipollution easy cleaning.Being successfully prepared of film is confirmed by FTIR and XPS test.See Fig. 2, Fig. 3.
Embodiment 4
A preparation method for the polyamide reverse osmosis composite film of antipollution easy cleaning, comprises the steps:
(1) polyamide reverse osmosis composite film is used successively isopropyl alcohol and washed with de-ionized water clean;
(2) 20cm × 5cm polyamide reverse osmosis composite film after cleaning, 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine, potassium thiosulfate, sodium hydrogensulfite and deionized water are joined in container, obtain 300 ml water solution, make 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine concentration be 2mmolL
-1, thiosulfuric acid potassium concn is 2mmolL
-1, concentration of sodium bisulphite is 2mmolL
-1, continue to pass into the oxygen in nitrogen 20min eliminating container;
(3) airtight container, 70 DEG C of water-bath 1h, take out film, and pure water cleans, and namely obtains a kind of polyamide reverse osmosis composite film of antipollution easy cleaning.Being successfully prepared of film is confirmed by FTIR and XPS test.See Fig. 2, Fig. 3.
Embodiment 5
Fouling membrane is tested:
(1) weighing 100mg bovine serum albumin and 500mgNaCl are in beaker, are settled to 1L volumetric flask in after dissolving with 50mL pure water;
(2) antipollution easy cleaning polyamide reverse osmosis composite film polyamide reverse osmosis composite film and embodiment 2-4 prepared respectively is fixed in laboratory self-control cross-flow devices, with NaCl solution precompressed 12h under pressure is 1.6Mpa of 500mg/L, until flux stabilized.
(3) water flux of the BSA/NaCl solution testing film using (1) to configure, interval collection permeate at regular intervals.
Salt response Membrane cleaning step:
(1) Membrane cleaning uses 2g/LNaCl measured in solution membrane flux and rejection baseline before carrying out.
(2) with pure water, cleaning 30min is carried out to film;
(3) with the NaCl solution of 2mol/L, cleaning 30min is carried out to film;
(4) step (2), (3) are repeated;
(5) with 2g/LNaCl measured in solution membrane flux.
(6) flux computing formula is as follows:
J-water flux (L/m
2h), Q-through volume (L), A-film effective area (m
2), △ t-time (h).
The results are shown in Figure 4-Fig. 7.
As can be seen from Fig. 4-Fig. 7, increase in time, former polyamide reverse osmosis composite film and antipollution easy cleaning polyamide reverse osmosis composite film flux all reduce, but the contaminated degree of antipollution easy cleaning polyamide reverse osmosis composite film is less than former polyamide reverse osmosis composite film, and after supersalt is washed, flux recovery obtains more, illustrates that antipollution easy cleaning polyamide reverse osmosis composite film resistance tocrocking and easy cleaning are all better than former polyamide reverse osmosis composite film.
Claims (1)
1. a preparation method for the polyamide reverse osmosis composite film of antipollution easy cleaning, is characterized in that comprising the steps:
(1) polyamide reverse osmosis composite film is used successively isopropyl alcohol and washed with de-ionized water clean;
(2) polyamide reverse osmosis composite film after cleaning, 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine, potassium thiosulfate, sodium hydrogensulfite and deionized water are joined in container, obtain 50-300 ml water solution, make 4-(2-sulfoethyl)-1-(4-vinyl benzyl) pyridine betaine concentration be 1-2mmolL
-1, thiosulfuric acid potassium concn is 1-2mmolL
-1, concentration of sodium bisulphite is 1-2mmolL
-1, continue to pass into the oxygen in nitrogen 15-20min eliminating container;
(3) airtight container, 20-70 DEG C of water-bath 1-24h, namely obtains a kind of polyamide reverse osmosis composite film of antipollution easy cleaning.
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| CN106731867A (en) * | 2016-12-08 | 2017-05-31 | 厦门建霖工业有限公司 | The preparation method and preparation facilities of a kind of efficient anti-pollution reverse osmosis membrane |
| CN113390865B (en) * | 2021-06-07 | 2022-11-18 | 浙江工业大学 | Acid-base indicating test paper and preparation method and application thereof |
| CN114984782B (en) * | 2022-08-02 | 2022-12-09 | 湖南沁森高科新材料有限公司 | Anti-pollution polyamide reverse osmosis membrane with high flux and high desalination rate and preparation method thereof |
Citations (3)
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| CN1257747A (en) * | 1998-12-24 | 2000-06-28 | 中国科学院长春应用化学研究所 | Process for modifying reverse osmosis composite membrane by inner interface adsorption of surfactant |
| CN101439271A (en) * | 2008-12-04 | 2009-05-27 | 宁波灏钻科技有限公司 | Method for preparing hydrophilic anti-pollution reverse osmosis membrane |
| CN103331110A (en) * | 2013-05-27 | 2013-10-02 | 天津工业大学 | Pollution-resistant chlorine polyamide-resistant reverse osmosis composite membrane and preparation method thereof |
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2013
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Patent Citations (3)
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| CN1257747A (en) * | 1998-12-24 | 2000-06-28 | 中国科学院长春应用化学研究所 | Process for modifying reverse osmosis composite membrane by inner interface adsorption of surfactant |
| CN101439271A (en) * | 2008-12-04 | 2009-05-27 | 宁波灏钻科技有限公司 | Method for preparing hydrophilic anti-pollution reverse osmosis membrane |
| CN103331110A (en) * | 2013-05-27 | 2013-10-02 | 天津工业大学 | Pollution-resistant chlorine polyamide-resistant reverse osmosis composite membrane and preparation method thereof |
Non-Patent Citations (3)
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| Improved biocompatibility and antifouling property of polypropylene;Jie Zhao et al.;《Journal of Membrane Science》;20110301;第369卷;全文 * |
| Stimuli responsive amphiphilic block copolymers for aqueous media;Murat Mertoglu et al.;《Polymer》;20051212;第46卷;第7728页第2.2.3节以及第7730页图1 * |
| Surface hydrophilization of microporous polypropylene membrane by grafting;Yun-Feng Yang et al.;《Journal of Membrane Science》;20101015;第362卷;第255页的摘要，第256页2.1 * |
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