CN1099310C - Preparation of asymmetrical hollow polyimide fibre membrane - Google Patents
Preparation of asymmetrical hollow polyimide fibre membrane Download PDFInfo
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- CN1099310C CN1099310C CN98113914A CN98113914A CN1099310C CN 1099310 C CN1099310 C CN 1099310C CN 98113914 A CN98113914 A CN 98113914A CN 98113914 A CN98113914 A CN 98113914A CN 1099310 C CN1099310 C CN 1099310C
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- organic solvent
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- polyimides
- fibre membrane
- casting solution
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Abstract
The present invention relates to preparation of asymmetrical hollow polyimide fiber films, which comprises the preparation of a film casting solution and a fiber forming process. The present invention is characterized in that (1) a film casting solution has the following formulation (weight percentage): 15 to 35% of polyimide, 25 to 45% of organic solvent with a low boiling point and 30 to 60% of polar organic solvent; (2) fiber formulation: the film casting solution is prepared into fiber yarns through a spinning nozzle, and then the fiber yarns are swept by nitrogen of which the relative moisture is from 30 to 80% for 0.5 to 15 seconds to make the solvent volatilized; then a gelatin bath is carried out to complete phase inversion; the gelatin solution is water, and the water bath time is from 12 to 84 hours; the present invention has simple and easy operation and low cost. The product prepared by the present invention has high stability and stable performance.
Description
The invention belongs to the technology of preparing of macromolecule gas separation membrane, be meant with the polyimide powder to be material of preparing specifically, be made into mixed solvent with low boiling point solvents such as N-methyl pyrrolidone, absolute ethyl alcohol isopolarity organic solvent and acetone, the dissolving polyimides, the preparation casting solution, standing and defoaming adopts phase inversion in the spinning of wet spinning silk technology then, makes polyimides doughnut gas separation membrane.
Compare with other material of preparing such as polysulfones, polypropylene, cellulose acetate, polyimides has very high glass transition temperature Tg, its mechanical performance, heat endurance and chemical resistance etc. are very outstanding, be a kind of good material of preparing, adopt phase inversion a step to prepare the film that has fine and close separating layer, can be directly used in the gas separation simultaneously.Separated, risen fields such as filter, counter-infiltration at present is used widely at gas, relevant is that the patent of material of preparing is a lot of with the polyimides, as H disclosure special permission communique 85-125204,85-125205,85-150806,85-125209,85-125210 etc. have reported to be the asymmetric doughnut gas separation membrane that material of preparing is prepared with the polyimides, though there is crucial preparation technology not reveal, but its film separation is on the low side, shows not form enough dense layer surfaces.Chinese invention patent 91105349.2 has also reported with the polyimides to be material of preparing, prepares dull and stereotyped gas separation membrane; But its complex steps complexity, it is a lot of that post processing consumes organic solvent, is difficult for handling; The area of flat sheet membrane filling simultaneously is little, and being used for the gas separation has floor space big, shortcomings such as investment cost height.
The object of the present invention is to provide the technology of preparing of the asymmetric hollow-fibre membrane of a kind of polyimides, it is simple to operate easily, and cost is low, and with its product stability height that makes, stable performance.
The invention provides the preparation method of the asymmetric hollow-fibre membrane of a kind of polyimides, comprise the casting solution preparation and become the silk process, it is characterized in that:
(1) formula of casting following (percentage by weight)
Polyimides 15～35%
Low boiling point organic solvent 25～45%
Polar organic solvent 30～60%
Wherein low boiling point organic solvent is selected from one of acetone, ether, pentane, chloroform to two kinds; Polar organic solvent is selected from N-methyl pyrrolidone, absolute ethyl alcohol, N, N-dimethylformamide, N, and one of N-dimethylacetylamide, dimethyl sulfoxide (DMSO), the pyridine of formyl croak are to two kinds;
(2) become silk
Casting solution is through spinning nozzle Cheng Sihou, and usefulness relative humidity purges at 30～80% nitrogen, 0.5～15 second time, makes solvent evaporates; Carry out coagulation bath again and finish inversion of phases, coagulant liquid is a water, 12～84 hours water-bath time.
In addition, polyimides is preferably described in the present invention:
With
Wherein, A be-O-,-SO
2-,-CO-,-S-,-C (CF
3)
3Or
Z is
-CH
2-,-CO-or
Polar organic solvent described in the present invention is preferably N-methyl pyrrolidone, absolute ethyl alcohol; Low boiling point organic solvent is preferably acetone, pentane, chloroform; The former with the latter ratio is 2～3: 1.
Step of the present invention is simple, has successfully spun out the asymmetric hollow-fibre membrane of polyimides, and it is functional stable, and the life-span is long, and especially the saturating amount of gas is more much higher than Chinese invention patent 91105349.2.Adopt the water-bath replace organic solvent to bathe simultaneously, economize on the use of funds as coagulation bath; On formula of casting, adopt ternary to substitute 91105349.2 quaternary, and add lower relatively the polar organic solvent of boiling point, replace a part of low boiling point organic solvent as absolute ethyl alcohol; Adopting the wet nitrogen of doing of different proportion on technology is sweep gas, adds upper bush and regulates the solvent evaporates time, makes solvent evaporates time and speed more easy to control, is easy to obtain finer and close thinner selective separating.
The following examples have further been set forth the present invention.
Accompanying drawing 1 is the unit construction principle schematic diagram.
Embodiment 1
Structure is
Polyimide powder 15g, add in the mixed solvent of 27.2gN-methyl pyrrolidone+16.6g acetone, under 45 ℃, added thermal agitation 50 hours, become homogeneous solution, add in the batch can (1) of device as shown in Figure 1, leave standstill deaeration in 72 hours.After shower nozzle (2) became thread outflow, the nitrogen that is used for, wets purged, and puts 2 sleeves (3), making the casting solution volatilization time be about 4 seconds, is 2.4: 1 in wet nitrogen ratios, enters the preliminary one-tenth silk of gel groove (4) (6), silk (6) is derived rolling with guide pipe (5), puts into the complete gel of water storage carrying out.Water-bath gel 72 hours, the hollow-fibre membrane hydrogen transmission rates that obtains that dries in the air naturally is 4.35 * 10
-5Cm
3(STP)/cm
2.sec.cmHg, α
H2/N2=45.8.
Embodiment 2
Structure is
Polyimide powder 15g, add in the mixed solvent of 27.2g N-methyl pyrrolidone+16.6g acetone, under 45 ℃, added thermal agitation 50 hours, become homogeneous solution, add in the batch can that installs as shown in Figure 1, leave standstill deaeration in 72 hours, put 2 sleeves, make the casting solution volatilization time be about 4 seconds, doing wet nitrogen ratios is 2.4: 1, spinning, water-bath gel 72 hours dries naturally, and is dry in baking oven, 100 ℃ of temperature, the hydrogen transmission rates of the film that obtains is 4.25 * 10
-5Cm
3(STP)/cm
2.sec.cmHg, α
H2/N2=62.
Embodiment 3
Structure is
Polyimide powder 15g, add in the mixed solvent of 27.2g N-methyl pyrrolidone+16.6g acetone, under 45 ℃, added thermal agitation 50 hours, become homogeneous solution, add in the batch can that installs as shown in Figure 1, leave standstill deaeration in 72 hours, put 2 sleeves, make the casting solution volatilization time be about 4 seconds, doing wet nitrogen ratios is 2.4: 1, spinning, water-bath gel 72 hours dries naturally, and is dry in vacuum drying oven, 100 ℃ of temperature, the hydrogen transmission rates of the film that obtains is 4.7 * 10
-5Cm
3(STP)/cm
2.sec.cmHg, α
H2/N2=35.
Embodiment 4
Structure is
Polyimide powder 20g, add in the 44.7g N-mixed solvent that methyl pyrrolidone+10.1g acetone+the 3.1g absolute ethyl alcohol is made into, under 40 ℃, added thermal agitation 60 hours, become homogeneous solution, be added in the batch can of device shown in Figure 1, leave standstill deaeration in 56 hours, put 3 sleeves, make the casting solution volatilization time be about 6 seconds, doing wet nitrogen ratios is 2.5: 1, spinning, water-bath gel 72 hours, naturally dry, the hydrogen transmission rates of prepared film is 1.1 * 10
-4Cm
3(STP)/cm
2.sec.cmHg, α
H2/N2=60.
Claims (3)
1. the preparation method of the asymmetric hollow-fibre membrane of polyimides comprises the casting solution preparation and becomes the silk process, it is characterized in that:
(1) formula of casting following (percentage by weight)
Polyimides 15～35%
Low boiling point organic solvent 25～45%
Polar organic solvent 30～60%
Wherein low boiling point organic solvent is selected from one of acetone, ether, pentane, chloroform to two kinds; Polar organic solvent is selected from N-methyl pyrrolidone, absolute ethyl alcohol, N, N-dimethylformamide, N, and one of N-dimethylacetylamide, dimethyl sulfoxide (DMSO), the pyridine of formyl croak are to two kinds;
(2) become silk
Casting solution is through spinning nozzle Cheng Sihou, and usefulness relative humidity purges at 30～80% nitrogen, 0.5～15 second time, makes solvent evaporates; Carry out coagulation bath again and finish inversion of phases, coagulant liquid is a water, 12～84 hours water-bath time.
2. the preparation method of the asymmetric hollow-fibre membrane of polyimides as claimed in claim 1 is characterized in that: described polyimides is:
With
Wherein, A be-O-,-SO
2-,-CO-,-S-,-C (CF
3)
3Or
Z is
-CH
2-,-CO-or
3. the preparation method of the asymmetric hollow-fibre membrane of polyimides as claimed in claim 1 or 2 is characterized in that: described polar organic solvent is N-methyl pyrrolidone or absolute ethyl alcohol; Low boiling point organic solvent is acetone, pentane or chloroform; The former with the latter ratio is 2～3: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113914A CN1099310C (en) | 1998-04-16 | 1998-04-16 | Preparation of asymmetrical hollow polyimide fibre membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113914A CN1099310C (en) | 1998-04-16 | 1998-04-16 | Preparation of asymmetrical hollow polyimide fibre membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1231941A CN1231941A (en) | 1999-10-20 |
| CN1099310C true CN1099310C (en) | 2003-01-22 |
Family
ID=5223606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113914A Expired - Fee Related CN1099310C (en) | 1998-04-16 | 1998-04-16 | Preparation of asymmetrical hollow polyimide fibre membrane |
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| Country | Link |
|---|---|
| CN (1) | CN1099310C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314478C (en) * | 2005-01-20 | 2007-05-09 | 石油大学(华东) | Preparation of sodium polyimide filtering membranes for concentrated extracted liquid of antibionic solvent |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100646312B1 (en) * | 2005-06-10 | 2006-11-23 | (주)에어레인 | Hollow fiber membrane for oxygen separation and preparation method thereof |
| CN101992033A (en) * | 2009-08-28 | 2011-03-30 | 陈克 | Method for preparing polyimide hollow fiber pervaporation membrane and application thereof |
| CN102121173B (en) * | 2011-02-22 | 2012-05-30 | 天津工业大学 | Method for preparing sound-absorbing and heat-insulating materials formed by superfine fiber nonwovens |
| CN102071542B (en) * | 2011-02-22 | 2012-08-29 | 天津工业大学 | Method for preparing polymeric nano-micro fiber non-woven fabric |
| CN102974235B (en) * | 2012-11-22 | 2015-07-15 | 云南云天化股份有限公司 | Preparation method of thermoplastic polyimide microporous film |
| CN105579627B (en) * | 2013-07-29 | 2017-09-29 | 三菱化学株式会社 | The manufacture device and manufacture method of hollow form multiple aperture plasma membrane |
| BR112016007089A2 (en) * | 2013-09-30 | 2020-05-12 | Georgia Tech Res Inst | ASYMMETRIC MODIFIED CARBON MOLECULAR SIEVE FIBER MEMBRANES WITH IMPROVED PERMEABILITY |
| CN105670015B (en) * | 2016-01-27 | 2021-06-04 | 江苏巨贤合成材料有限公司 | Gaseous poor solvent induced forming preparation method of polyimide three-dimensional porous membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4512893A (en) * | 1981-04-14 | 1985-04-23 | Ube Industries, Ltd. | Porous aromatic imide polymer membrane and a process for its manufacture |
| CN1068974A (en) * | 1991-07-31 | 1993-02-17 | 中国科学院长春应用化学研究所 | Preparation of asymmetric polyimide gas separation membrane |
-
1998
- 1998-04-16 CN CN98113914A patent/CN1099310C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4512893A (en) * | 1981-04-14 | 1985-04-23 | Ube Industries, Ltd. | Porous aromatic imide polymer membrane and a process for its manufacture |
| CN1068974A (en) * | 1991-07-31 | 1993-02-17 | 中国科学院长春应用化学研究所 | Preparation of asymmetric polyimide gas separation membrane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314478C (en) * | 2005-01-20 | 2007-05-09 | 石油大学(华东) | Preparation of sodium polyimide filtering membranes for concentrated extracted liquid of antibionic solvent |
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|---|---|
| CN1231941A (en) | 1999-10-20 |
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