CN101844039A - Preparation method of surface grafting PEG (Polyethylene Glycol)-modified asymmetric PVA (Polyvinyl Alcohol) membrane - Google Patents
Preparation method of surface grafting PEG (Polyethylene Glycol)-modified asymmetric PVA (Polyvinyl Alcohol) membrane Download PDFInfo
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- CN101844039A CN101844039A CN201010100356A CN201010100356A CN101844039A CN 101844039 A CN101844039 A CN 101844039A CN 201010100356 A CN201010100356 A CN 201010100356A CN 201010100356 A CN201010100356 A CN 201010100356A CN 101844039 A CN101844039 A CN 101844039A
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Abstract
The invention relates to a preparation method of a surface grafting PEG (Polyethylene Glycol)-modified asymmetric PVA (Polyvinyl Alcohol) membrane, providing a preparation method of a hydrophilic pollution-resistant membrane. The preparation method comprises the following steps of: adding a pore-forming agent and a crosslinking agent in polyvinyl alcohol (PVA) as a membrane material, wherein the mass ratio of a membrane casting solution is 6:94-14:86; solidifying the mixture into a membrane in a gelatinizing agent solution, reacting the surface of the membrane with ethylene oxide, and chemically combining with polyethylene glycol graft modification to prepare a separation membrane with the advantages of adjustable pore diameter, higher capacity of pollution resistance and larger flux and a slowly controlled release membrane with higher stability.
Description
Background technology
Polyvinyl alcohol (PVA) is that a kind of chemical stability is good, traditional macromolecular material that mechanical strength is high, in China stable industrialization product is arranged, especially it has wide resource, cheap, have characteristics such as very strong hydrophily, resistance to acids and bases, resistance tocrocking and make it obtain development widely in the polymeric membrane for separation technical field.PVA film commonly used at present has:
1) PVA film surface chemistry graft modification film such as patent: the preparation method (Peng Yuelian of soiling resistant modified PVA film; The merchant is full of. patent publication No.: CN1973971, China national Patent Office).The soiling resistant modified PVA of this invention is at its surface grafting isocyanates, but comes off owing to ester bond is easy to hydrolysis under the Acidity of Aikalinity condition, influences the stability and the durability of film, and the possible carcinogenicity of the hexichol isocyanic acid of Yin Jining is causing that people pay close attention to simultaneously.Shen Fei, Lu Xiaofeng, Shi Liuqing. the formation of asymmetric Pioloform, polyvinyl acetal milipore filter (membrane science and technology, 2006,26 (2): 33-38).This film is greatly improved by the performance of surface modification to film, but all contains acetal radical in the group of surface grafting, and acetal radical is unfavorable for the long-term utilization of film in acid or alkali condition instability, and certain limitation is arranged in actual applications.Zhi Bei butyral film only is used for adsorbing the report of heavy metal and enzyme still more, is not applied to the report of other ultrafiltration aspect, so for practical application certain limitation is arranged.
The present invention be on asymmetric PVA film surface with ehter bond in conjunction with polyethylene glycol, ehter bond has resistance to acids and bases preferably, and polyethylene glycol has no side effect, and is well suited for medicinal film.
2) membrane surface applies PVA film such as Bian Xiao mistake, Shi Liuqing, Liang Guoming etc. the preparation of composite membrane of polyvinyl alcohol (membrane science and technology, 2004,24 (2): 12-15).The method is to be raw material with the polyvinyl alcohol, adopts the mechanical application method, and PVA solution is coated on the basement membrane uniformly, prepares composite nanometer filtering film.
3) blending and modifying PVA film such as Zhang Leyang, Xu Haisheng, Shen Qundong. the preparation of polyvinyl alcohol perforated membrane (functional polymer journal, 2006,14 (2): 174-176).Zhu Dan, Xu Haisheng, Shen Qundong, etc. the auxiliary phase inversion method of macromolecule prepares the polyvinyl alcohol perforated membrane.(functional polymer journal, 1999,12 (1): 31-34).Both all adopt auxiliary phase inversion method by PVAc and the partially grafted copolymer of PVA that emulsion polymerisation generates, go out the PVAc of not grafting with the acetone extracting, obtain the PVA-PVAc perforated membrane.The PVA that this film is actually with grafting PVAc is the perforated membrane of film material preparation, and there is the ester group of facile hydrolysis simultaneously in non-surface graft modification.
On the preparation method of film, Qiu Yunren, Zhang Qixiu, Wu Zhendong. the preparation of modified PVA milipore filter and performance study (membrane science and technology, 2001,21 (5): 25-28) and preparation and performance study (modern chemical industry, 2001 of polyvinyl alcohol one acetyl cellulose blend milipore filter, 21 (10): all are dry method system films 28-31), what obtain is the homogeneous membrane of symmetrical structure.Be different from method of the present invention fully.Wang Yanli, Yang Hu, Xu Zhenliang. gel is to PVA-PEG-H
2The influence of O system gelling kinetics and film properties (East China University of Science's journal, 2006,32 (10): 1169-1182).The preparation of this PVA film is the preparation method who adopts inversion of phases, but its coagulating bath is to utilize organic solvent-acetone, IPA, THF etc., and the present invention adopts the inorganic salt solution of variable concentrations or ethanol water as coagulating bath, greatly reduces the cost and the condition of film preparation.He uses PEG in casting solution in addition, is pore-foaming agent only, is not and the PVA chemical graft.
The asymmetric PVA diffusion barrier of anti-pollution, the high-throughout surface graft modification characteristics different with patent with each document of the present invention's preparation are:
1) only use single PVA to be the film material;
2) mainly use inorganic salts and a small amount of or do not have ethanol to be coagulating agent;
3) only on the surface of film with the performance of very stable ehter bond grafting modification PVA film, ehter bond is difficult to disconnected row under the Acidity of Aikalinity condition, stable performance, and PEG itself has good solubility, anti-pollution, nontoxic, odorless, oil resistant, ageing-resistant, high-low temperature resistant, function admirable, this just lays a good foundation in the extensive use of reality for the anti-pollution milipore filter of the present invention's preparation.
The content of invention
The present invention mainly prepares the PVA film of dissymmetrical structure by phase transition method, utilize PVA film surface to have a large amount of hydroxyls then, with oxirane under certain conditions with its hydroxyl generation ring-opening polymerisation, thereby at PVA film surface grafting ethylene oxide polymer molecule is PEG, reach purpose, prepare resistant to pollution high-throughout PVA milipore filter its surface modification.
Different aperture provided by the invention, different high-throughout surface graft modification PVA milipore filter, it is characterized in that: it is to be 6 by adopting homogenous material polyvinyl alcohol (PVA) casting solution mass ratio: 94-14: 86, add pore-foaming agent and crosslinking agent again, after the blend, slaking is solidified in shop film, the gelling agent solution.Film after solidifying is dry under constant environment, again film is carried out the reaction of PVA film surface grafting at the organic saturated solution of the NaOH that contains oxirane, after reaction finishes, dry, in 110 ℃ air dry oven, heat-treat, promptly get different aperture of the present invention, the asymmetric PVA milipore filter of different high-throughout surface graft modification.1. the preparation of the asymmetric PVA milipore filter of surface graft modification is characterized in that following two steps:
1) adopt homogenous material polyvinyl alcohol (PVA) as the film material, its casting solution mass ratio is 6: 94-14: 86, add mass fraction again and be 10%～40% pore-foaming agent and 10%～15% crosslinking agent, after the blend, slaking, the system film solidifies in gelling agent solution, takes out the back and becomes the unsymmetric structure film at air drying;
2) dried film was put into the saturated sodium hydroxide solution of dimethyl sulfoxide (DMSO) 1 hour, put into the dimethyl sulphoxide solution that contains oxirane, at pressure is that 0.3～0.8Mpa temperature is under 90 ℃～150 ℃ conditions, reacted 6～12 hours, carry out the reaction of PVA film surface grafting, after reaction finishes, drying, in 110 ℃ air dry oven, heat-treat 2h, promptly get different aperture of the present invention, the asymmetric anti-pollution PVA milipore filter of high-throughout surface graft modification;
2. according to the method that claim 1 provided, it is characterized in that:
Pore-foaming agent comprises nano silicon described in the step 1), nano aluminium oxide, nano-emulsion and micella; Crosslinking agent comprises that alchlor, ferric trichloride, phosphoric acid, sulfuric acid, glycerine, polyethylene glycol, citric acid, succinic acid etc. contain one or more mixtures in the difunctional organic reagent; Gelling agent comprises one or more mixtures in ethanol, ethyl acetate, acetic acid and salt thereof, sulfate, phosphate, the perchlorate;
3. according to the method that claim 1 provided, the film that the present invention obtained is characterised in that the PVA film of surface chemistry in conjunction with the unsymmetric structure of polyethylene glycol ehter bond.
4. PVA membrane technology of the present invention can be used for medicine (pharmaceutically active ingredient or active component in comprising) separation and purification film, the slow release-controlled film of sewage disposal film, various active components etc.
The present invention adopts ehter bond that PEG and PVA film surface are carried out chemical bond, and therefore this PVA film is nontoxic, odorless, oil resistant, ageing-resistant, low temperature resistant, high temperature, function admirable.By graft reaction to the PVA membrane surface modification, improved the stain resistance of film greatly, improved its hydrophily, contact angle is reduced to 48 ° from original 63 °, and makes the high flux surface graft modification PVA milipore filter of molecular cut off from 6000 to 100000.
The present invention compared with prior art under identical rejection condition, can obtain bigger flux, surface graft modification PVA film that the anti-pollution ability is stronger.
Specific embodiment:
Embodiment one, the preparation of the surface graft modification PVA film of low catching molecular
Get 2.4gPVA swelling 1h in 17.6ml distilled water, in 90 ℃ water bath with thermostatic control, fully dissolve 2-3h. then and be cooled to room temperature, add pore-foaming agent 0.2mlOP, crosslinking agent 1mol/LH
2SO
40.6ml, stir 30min at normal temperatures, leave standstill, the about 4-5h of deaeration, promptly get casting solution.At constant environment lower berth film, air dry 30min in air puts into concentration and is 60% coagulating bath and solidifies 30min with casting solution, take out, and air dry in air, stand-by.Again film and glass plate are put into together the organic saturated solution of the NaOH that contains oxirane PEG and carried out the reaction of PVA film surface grafting, under 110 ℃, heat-treat 2h then.
Be under 60% condition in 25 ℃ of room temperatures, humidity then, pressure is under the 0.15Mpa, and the pure water flux of mensuration is W=60L/M
2Mpah.Similarity condition is measured rejection down, utilizes ultraviolet specrophotometer, and the rejection that records PEG6000 is 95%, and the molecular cut off of film is 6000.
Implement example two. the preparation of the surface graft modification PVA film of medium molecular cut off
Get 2.2gPVA swelling 1h in 17.8ml distilled water, in 90 ℃ water bath with thermostatic control, fully dissolve 2-3h. then and be cooled to room temperature, add pore-foaming agent 0.5ml nanometer micro emulsion, crosslinking agent 1mol/LH
2SO
40.6ml, stir 30min at normal temperatures, leave standstill, the about 4-5h of deaeration, promptly get casting solution.With casting solution at constant environment lower berth film, air dry 30min in air, putting into concentration is that 30min is solidified in coagulating bath 40% and that contain 0.4%PEG20000, take out, air dry in air, stand-by.Again film and glass plate are put into together the organic saturated solution of the NaOH that contains oxirane PEG and are carried out the reaction of PVA film surface grafting,, under 110 ℃, heat-treat 2h then.
Be under 60% condition in 25 ℃ of room temperatures, humidity then, pressure is under the 0.15Mpa, and the pure water flux of mensuration is W=80L/M
2Mpah.Similarity condition is measured rejection down, utilizes ultraviolet specrophotometer, and the rejection that records PEG20000 is 95%, and the molecular cut off of film is 20000.
Implement example three. the preparation of the surface graft modification PVA film of high molecular cut off
Get 1.6gPVA swelling 1h in 18.4ml distilled water, in 90 ℃ water bath with thermostatic control, fully dissolve 2-3h. then and be cooled to room temperature, add the H of pore-foaming agent 1.0ml nano silicon, crosslinking agent 1mol/L
2SO
40.6ml, stir 30min at normal temperatures, leave standstill, the about 4-5h of deaeration, promptly get casting solution.With casting solution at constant environment lower berth film, air dry 30min in air, putting into concentration is that 30min is solidified in coagulating bath 10% and that contain 0.4%PEG20000, take out, air dry in air, stand-by.Again film and glass plate are put into together the organic saturated solution of the NaOH that contains oxirane PEG and are carried out the reaction of PVA film surface grafting,, under 100 ℃, heat-treat 2h then.
Be under 60% condition in 25 ℃ of room temperatures, humidity then, pressure is under the 0.15Mpa, and the pure water flux of mensuration is W=110L/M
2Mpah.Similarity condition is measured rejection down, utilizes ultraviolet specrophotometer, and the rejection that records glucan 70,000 is 91%, and the molecular cut off of film is 70000.
Claims (4)
1. the preparation of the asymmetric PVA film of surface grafting PEG modification is characterized in that following two steps:
1) adopt homogenous material polyvinyl alcohol (PVA) as the film material, its casting solution mass ratio is 6: 94-14: 86, add mass fraction again and be 10%～40% pore-foaming agent and 10%～15% crosslinking agent, after the blend, slaking, the system film solidifies in gelling agent solution, takes out the back and becomes the unsymmetric structure film at air drying;
2) dried film was put into the saturated sodium hydroxide solution of dimethyl sulfoxide (DMSO) 1 hour, put into the dimethyl sulphoxide solution that contains oxirane, at pressure is that 0.3～0.8Mpa temperature is under 90 ℃～150 ℃ conditions, reacted 6～12 hours, carry out the reaction of PVA film surface grafting, after reaction finishes, drying, in 110 ℃ air dry oven, heat-treat 2h, promptly get different aperture of the present invention, the asymmetric anti-pollution PVA milipore filter of high-throughout surface graft modification;
2. according to the method that claim 1 provided, it is characterized in that:
Pore-foaming agent comprises nano silicon described in the step 1), nano aluminium oxide, nano-emulsion and micella; Crosslinking agent comprises that alchlor, ferric trichloride, phosphoric acid, sulfuric acid, glycerine, polyethylene glycol, citric acid, succinic acid etc. contain one or more mixtures in the difunctional organic reagent; Gelling agent comprises one or more mixtures in ethanol, ethyl acetate, acetic acid and salt thereof, sulfate, phosphate, the perchlorate;
3. according to the method that claim 1 provided, the film that the present invention obtained is characterised in that the PVA film of surface chemistry in conjunction with the unsymmetric structure of polyethylene glycol ehter bond.
4. PVA membrane technology of the present invention can be used for the separation and purification film of medicine isoreactivity composition or active site, the slow release-controlled film of various active components, sewage disposal film etc.
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| CN201010100356A CN101844039A (en) | 2010-01-22 | 2010-01-22 | Preparation method of surface grafting PEG (Polyethylene Glycol)-modified asymmetric PVA (Polyvinyl Alcohol) membrane |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974238A (en) * | 2012-11-02 | 2013-03-20 | 东华大学 | Film surface hydrophilicity modifying method through PVA grafting by utilizing biological preparation |
| CN104548949A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of polymer porous membrane for removing water pollutants |
| CN105854623A (en) * | 2016-05-26 | 2016-08-17 | 长春工业大学 | Preparation method of latticed microporous film formed by macromolecule crosslinking |
| CN110270236A (en) * | 2019-06-26 | 2019-09-24 | 惠州学院 | A kind of preparation method and applications of grease proofing anti-swelling water-oil separationg film |
| CN113024978A (en) * | 2021-02-26 | 2021-06-25 | 贵州省材料产业技术研究院 | Microporous PVA composite material and preparation method thereof |
-
2010
- 2010-01-22 CN CN201010100356A patent/CN101844039A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974238A (en) * | 2012-11-02 | 2013-03-20 | 东华大学 | Film surface hydrophilicity modifying method through PVA grafting by utilizing biological preparation |
| CN104548949A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of polymer porous membrane for removing water pollutants |
| CN105854623A (en) * | 2016-05-26 | 2016-08-17 | 长春工业大学 | Preparation method of latticed microporous film formed by macromolecule crosslinking |
| CN105854623B (en) * | 2016-05-26 | 2018-05-22 | 长春工业大学 | A kind of preparation method of the latticed microporous barrier formed by high molecular crosslink |
| CN110270236A (en) * | 2019-06-26 | 2019-09-24 | 惠州学院 | A kind of preparation method and applications of grease proofing anti-swelling water-oil separationg film |
| CN110270236B (en) * | 2019-06-26 | 2021-10-01 | 惠州学院 | Preparation method and application of oil-proof swelling-resistant oil-water separation membrane |
| CN113024978A (en) * | 2021-02-26 | 2021-06-25 | 贵州省材料产业技术研究院 | Microporous PVA composite material and preparation method thereof |
| CN113024978B (en) * | 2021-02-26 | 2022-08-12 | 贵州省材料产业技术研究院 | Microporous PVA composite material and preparation method thereof |
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Open date: 20100929 |