CN103316598A - Preparation method of dry-type preserved polyacrylonitrile membrane - Google Patents
Preparation method of dry-type preserved polyacrylonitrile membrane Download PDFInfo
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- CN103316598A CN103316598A CN2013102801743A CN201310280174A CN103316598A CN 103316598 A CN103316598 A CN 103316598A CN 2013102801743 A CN2013102801743 A CN 2013102801743A CN 201310280174 A CN201310280174 A CN 201310280174A CN 103316598 A CN103316598 A CN 103316598A
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- polyacrylonitrile
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- phthalic acid
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Abstract
The invention discloses a preparation method of a dry-type preserved polyacrylonitrile membrane. The preparation method is characterized in that polyacrylonitrile is used as a main high polymer material for membrane preparation, phthalic acid ester is added to film casting liquid containing the polyacrylonitrile, an organic solvent and additives, and a phase inversion method is used for preparing the polyacrylonitrile membrane. The method provided by the invention is used for the preparing the polyacrylonitrile membrane, so that a complicated aftertreatment process is omitted, thus the cost reduction is facilitated; the prepared membrane has toughness through dry-type preservation, is suitable for serving as supporting base membranes of composite membranes such as pervaporation membranes, gas separation membranes and reverse osmosis membranes and has wide application prospect.
Description
Technical field
The present invention relates to a kind of membrane material technology, be specifically related to the preparation method that a kind of dry type is preserved polyacrylonitrile film.
Background technology
Polyacrylonitrile has good chemical stability and acidproof, alkali resistance.Its abundant raw material, cheap is a kind of well behaved membrane material.Polyacrylonitrile film has been widely used in the aspects such as chemical industry, food, beverage, bioengineering, medical material at present, yet polyacrylonitrile contains the very strong cyano group of polarity, active force is strong between macromolecular chain, pliability is little, the symmetry of chain is poor, be in amorphous state, thus the polyacrylonitrile film of making of conventional method, if very crisp without post processing.
When the making of polyacrylonitrile film, the casting solution that normally organic solvent solution of membrane material and additive is formed is made by phase inversion, and film is moist after finally by water rinse, preserves under hygrometric state, is called wet film.But wet film is unsuitable for making composite membrane as counterdie, because the solution of separating layer material is generally polymer organic solution, chance water will produce gelation and separate out, be difficult to form uniform ultra-thin parting absciss layer at wet film, and separating layer and counterdie can not fitted because of the existence of moisture content and caused intermediate peeling.And dry type film matters are made composite membrane support counterdie.The making of dry type film, a kind of is after wet film is dipped in approximately 10% glycerine water solution, dries to form in air.Yet this method is complicated, Expenses Cost, and the difficult making that is applicable to composite membrane.
Summary of the invention
The object of the present invention is to provide a kind of aftertreatment technology that need not complexity, and obtain the preparation method of pliable and tough dry type polyacrylonitrile film.Technological core of the present invention is to add the phthalic acid ester masking in resulting casting solution, again with its water-bath rinsing, dry and namely get the dry type polyacrylonitrile film with high mechanical properties, the method technique is simple, effectively solution prepared the technological problems that the dry type polyacrylonitrile film will pass through the post processing of complexity, high energy consumption in the past, save a large amount of artificial and energy consumptions, cost is low, is suitable for suitability for industrialized production.
In order to realize that purpose of the present invention adopts following technical scheme:
A kind of dry type of the present invention is preserved the preparation method of polyacrylonitrile film, comprises the steps:
(1) polyacrylonitrile resin is dissolved in the organic solvent, being mixed with polyacrylonitrile resin quality percentage composition is the solution of 10%-20%;
(2) additive is dissolved in the solution of step (1), is mixed with the casting solution I that additive quality percentage composition is 0%-10%;
(3) phthalic acid ester is dissolved in the casting solution I, being mixed with phthalic acid ester quality percentage composition is 2%-10% casting solution II;
(4) it is 100-250 μ m planar film that the casting solution II striking that step (3) is made forms a layer thickness at glass plate, behind the volatilization 2-20s, soaks 10-30min in the deionized water with 5-35 ℃ of its immersion in air, gets the wet type polyacrylonitrile film;
(5) with wet type polyacrylonitrile film rinsing in 5-35 ℃ of water-bath of step (4), room temperature was dried and is namely got the dry type polyacrylonitrile film after it was taken out;
Wherein, the described organic solvent of step (1) is a kind of in dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, lactic acid nitrile, nitrobenzene, ethylene carbonate, the dimethyl sulfoxide (DMSO); The described additive of step (2) is one or more the mixture in polyethylene glycol, PVP, n-butanol, ethylene glycol monoemethyl ether, lithium nitrate, lithium chloride, the water; The described phthalic acid ester of step (3) is a kind of in o-phthalic acid dibutyl ester, dibutyl phthalate, the diisooctyl phthalate.
The preferred 60000-100000 of the mean molecule quantity of polyacrylonitrile resin of the present invention.
The adding purpose of additive of the present invention is the properties that changes film, such as structure and water flux etc.In the technical scheme of the present invention, can add additive and also can not add additive.Usually such as polyethylene glycol (PEG), the addition of PVP (PVP) is higher, accounts for the 4%-8% of solution (casting solution I) gross mass, other additives such as water, and n-butanol, the additions such as salt are generally less than 4%.
Among the present invention, the preferred 4%-10% of concentration of phthalic acid ester described in the step (3), more preferably 6%-8%.When the concentration of phthalic acid less than 4% the time, the film of preparation is more crisp, toughness drop, and its concentration is greater than 10% time, near the solution cloud point.
The present invention also provides the dry type polyacrylonitrile for preparing with said method film.With the polyacrylonitrile film that method of the present invention prepares, 20-80 μ m, toughness are 80-100%, have the characteristics of high mechanical properties.
Compared with prior art, beneficial effect of the present invention is:
1. the present invention adopts the method that adds masking behind the phthalic acid ester in the casting solution that contains polyacrylonitrile and additive, obtains the dry type polypropylene screen of high tenacity.Add phthalic acid ester in the casting solution, reduced the degree of crystallinity of polymer molecule, improve the toughness of polyacrylonitrile film.
The present invention at normal temperatures stirring and dissolving obtain casting solution, and with its simple method masking after coagulation that applies, water rinse, naturally dry and to obtain the dry type polyacrylonitrile film, whole preparation process does not need special equipment, method of operating is simple, can directly preserve or use after the masking, do not need to carry out to be kept at after the masking in the prior art the loaded down with trivial details postprocessing working procedures such as glycerine, significantly reduce cost, be conducive to industrialization promotion.
3. the dry type polyacrylonitrile film of method of the present invention preparation is applicable to the support counterdie of the composite membranes such as infiltrating and vaporizing membrane, gas separation membrane and counter-infiltration, is with a wide range of applications.
The specific embodiment
The average thickness of the polyacrylonitrile film of embodiment of the invention preparation is measured with feeler (or micrometer caliper), and concrete grammar is:
Polyacrylonitrile film is made into the rectangular of 20mm * 200mm,, records thickness value, and calculate every average thickness values every 50mm feeler (or micrometer caliper) Thickness Measurement by Microwave with ruler.Do 3 parallel tests, and get the average thickness that its mean value is film.
The toughness of the polyacrylonitrile film of embodiment of the invention preparation is measured with the doubling method, and concrete grammar is:
Polyacrylonitrile film is made into the rectangular of 20mm * 200mm, in 23-27 ℃, the environment of humidity 50-65%, places more than one hour,, observe film and whether rupture every 180 ° of doublings of 20mm parallel membrane bar with ruler, the record breaks.
Each membrane sample is prepared the rectangular of 5 20mm * 200mm, does above-mentioned doubling experiment, calculates the rate that fractures of every film, and gets its mean value as the toughness of film, and computational methods are as follows:
The rate that fractures (%)=[(doubling number of times-breaks)/doubling number of times] * 100%;
Toughness (%)=∑ rate/5 that fracture
Embodiment 1
16g polyacrylonitrile (molecular weight is 90,000) is dissolved in the 72g dimethyl formamide, add again the 8g molecular weight after the stirring and dissolving and be 400 polyethylene glycol, add again the 4g dioctyl phthalate after the stirring and dissolving, stirring and dissolving gets casting solution, the casting solution striking is formed one deck planar film at glass plate, thickness is 200 μ m, it is placed 10 seconds in air after, to immerse in 15 ℃ the deionized water with the glass plate of polyacrylonitrile rete, soak after 30 minutes and take out, in room-temperature water bath, after the rinsing it is dried in air at room temperature, can obtain the dry type polyacrylonitrile film, the average thickness of film is 80 μ m, and its toughness is 90%.
Embodiment 2
15g polyacrylonitrile (molecular weight is 90,000) is dissolved in the 72g dimethylacetylamide, add again the 5g molecular weight after the stirring and dissolving and be 200 polyethylene glycol, add again the 8g dioctyl phthalate after the molten stirring solution, stirring and dissolving gets casting solution, the casting solution striking is formed one deck planar film at glass plate, thickness is 150 μ m, it is placed 5 seconds in air after, to immerse in 10 ℃ the deionized water with the glass plate of polyacrylonitrile rete, soak after 20 minutes and take out, in room-temperature water bath, after the rinsing it is dried in air at room temperature, can obtain the dry type polyacrylonitrile film, the average thickness of film is 50 μ m, and its toughness is 100%.
Embodiment 3
12g polyacrylonitrile (molecular weight is 90,000) is dissolved in the 78g 1-METHYLPYRROLIDONE, add again 4g PVP K30 after the stirring and dissolving, add again the 6g dioctyl phthalate after the stirring and dissolving, stirring and dissolving gets casting solution, the casting solution striking forms one deck planar film at glass plate, thickness is 200 μ m, it is placed 5 seconds in air after, to immerse in 20 ℃ the deionized water with the glass plate of polyacrylonitrile rete, soak after 30 minutes and take out, it is dried it after rinsing in 20 ℃ of water-baths in air at room temperature, can obtain the dry type polyacrylonitrile film, the average thickness of film is 70 μ m, and its toughness is 90%.
Embodiment 4
16g polyacrylonitrile (molecular weight is 90,000) is dissolved in the 72g dimethyl formamide, add again the 6g molecular weight after the stirring and dissolving and be 1000 polyethylene glycol, add again the 6g dibutyl phthalate after the molten stirring solution, stirring and dissolving gets casting solution, the casting solution striking forms one deck planar film at glass plate, thickness is 200 μ m, it is placed 5 seconds in air after, to immerse in 15 ℃ the deionized water with the glass plate of polyacrylonitrile rete, take out after 20 minutes, in 20 ℃ of water-baths, after the rinsing it is dried in air at room temperature, can obtain the dry type polyacrylonitrile film, the average thickness of film is 60 μ m, and its toughness is 100%.
Embodiment 5
16g polyacrylonitrile (molecular weight is 90,000) is dissolved in the 76g dimethyl formamide, adds again 1g LiNO after the stirring and dissolving
3With 2g H
2O, add the 5g dibutyl phthalate after the molten stirring solution, stirring and dissolving gets casting solution again, and the casting solution striking forms one deck planar film at glass plate, thickness is 150 μ m, it is placed 10 seconds in air after, will immerse with the glass plate of polyacrylonitrile rete in 15 ℃ the deionized water, take out after 30 minutes, in 20 ℃ of water-baths, after the rinsing it is dried in air at room temperature, can obtain the dry type polyacrylonitrile film, the average thickness of film is 40 μ m, and its toughness is 100%.
Claims (4)
1. the preparation method that dry type is preserved polyacrylonitrile film is characterized in that, comprises the steps:
(1) polyacrylonitrile resin is dissolved in the organic solvent, being mixed with polyacrylonitrile resin quality percentage composition is the solution of 10%-20%;
(2) additive is dissolved in the solution of step (1), is mixed with the casting solution I that additive quality percentage composition is 0%-10%;
(3) phthalic acid ester is dissolved in the casting solution I, being mixed with phthalic acid ester quality percentage composition is 2%-10% casting solution II;
(4) it is 100-250 μ m planar film that the casting solution II striking that step (3) is made forms a layer thickness at glass plate, behind the volatilization 2-20s, soaks 10-30min in the deionized water with 5-35 ℃ of its immersion in air, gets the wet type polyacrylonitrile film;
(5) with wet type polyacrylonitrile film rinsing in 5-35 ℃ of water-bath of step (4), room temperature was dried and is namely got the dry type polyacrylonitrile film after it was taken out;
Wherein, the described organic solvent of step (1) is that organic solvent is a kind of in dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, lactic acid nitrile, nitrobenzene, ethylene carbonate, the dimethyl sulfoxide (DMSO); The described additive of step (2) is one or more the mixture in polyethylene glycol, PVP, n-butanol, ethylene glycol monoemethyl ether, lithium nitrate, lithium chloride, the water; The described phthalic acid ester of step (3) is a kind of in o-phthalic acid dibutyl ester, dibutyl phthalate, the diisooctyl phthalate.
2. preparation method according to claim 1 is characterized in that, the mean molecule quantity of the polyacrylonitrile resin described in the step (1) is 60000-100000.
3. the dry type for preparing of claim 1 or 2 described methods is preserved polyacrylonitrile film.
4. dry type according to claim 3 is preserved polyacrylonitrile film, it is characterized in that, described dry type polyacrylonitrile film thickness is that 20-80 μ m, toughness are 80-100%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032215A (en) * | 2015-07-11 | 2015-11-11 | 河南工程学院 | Preparation method for high-strength high-flux aromatic polyamide porous membrane |
| CN110684233A (en) * | 2019-10-11 | 2020-01-14 | 海南大学 | Porous hydrogel film for extracting uranium from seawater and preparation method thereof |
| CN111905572A (en) * | 2020-07-14 | 2020-11-10 | 江苏千里膜业科技有限公司 | Preparation method of MBR (membrane bioreactor) flat dry film for domestic sewage treatment |
| CN111905571A (en) * | 2020-07-14 | 2020-11-10 | 江苏千里膜业科技有限公司 | Preparation method of MBR (membrane bioreactor) flat dry film for industrial sewage treatment |
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| US4143092A (en) * | 1976-01-26 | 1979-03-06 | Samuel Bingham Company | Polyurethane-derived plasticizer for polyacrylonitrile printing rolls |
| CN1237475A (en) * | 1998-05-29 | 1999-12-08 | 中国科学院大连化学物理研究所 | Prepartion of composite gas separation membrane its application |
| CN1380131A (en) * | 2002-01-25 | 2002-11-20 | 中国科学院化学研究所 | Preparation method of dry type polyacrylointrile ultrafiltration membrane |
| CN101195082A (en) * | 2007-06-18 | 2008-06-11 | 海南立昇净水科技实业有限公司 | Modified polyvinyl chloride hollow fiber microporous memebrane and method for providing the same |
| CN103143266A (en) * | 2013-03-05 | 2013-06-12 | 中国科学院生态环境研究中心 | Preparation method of hollow fiber membrane with spiral reinforcing ribs and spinning nozzle |
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| US4143092A (en) * | 1976-01-26 | 1979-03-06 | Samuel Bingham Company | Polyurethane-derived plasticizer for polyacrylonitrile printing rolls |
| CN1237475A (en) * | 1998-05-29 | 1999-12-08 | 中国科学院大连化学物理研究所 | Prepartion of composite gas separation membrane its application |
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| CN101195082A (en) * | 2007-06-18 | 2008-06-11 | 海南立昇净水科技实业有限公司 | Modified polyvinyl chloride hollow fiber microporous memebrane and method for providing the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032215A (en) * | 2015-07-11 | 2015-11-11 | 河南工程学院 | Preparation method for high-strength high-flux aromatic polyamide porous membrane |
| CN105032215B (en) * | 2015-07-11 | 2017-03-08 | 河南工程学院 | The preparation method of high-intensity high-throughput aromatic polyamides perforated membrane |
| CN110684233A (en) * | 2019-10-11 | 2020-01-14 | 海南大学 | Porous hydrogel film for extracting uranium from seawater and preparation method thereof |
| CN111905572A (en) * | 2020-07-14 | 2020-11-10 | 江苏千里膜业科技有限公司 | Preparation method of MBR (membrane bioreactor) flat dry film for domestic sewage treatment |
| CN111905571A (en) * | 2020-07-14 | 2020-11-10 | 江苏千里膜业科技有限公司 | Preparation method of MBR (membrane bioreactor) flat dry film for industrial sewage treatment |
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Application publication date: 20130925 |