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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- 239000004642 Polyimide Substances 0.000 title claims abstract description 24
- 229920001721 polyimide Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000835 fiber Substances 0.000 title claims abstract 9
- 239000012528 membrane Substances 0.000 title claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005266 casting Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 239000000701 coagulant Substances 0.000 claims 1
- 230000015271 coagulation Effects 0.000 claims 1
- 238000005345 coagulation Methods 0.000 claims 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 238000009472 formulation Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 108010010803 Gelatin Proteins 0.000 abstract 2
- 229920000159 gelatin Polymers 0.000 abstract 2
- 239000008273 gelatin Substances 0.000 abstract 2
- 235000019322 gelatine Nutrition 0.000 abstract 2
- 235000011852 gelatine desserts Nutrition 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000012510 hollow fiber Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000007872 degassing Methods 0.000 description 3
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000614 phase inversion technique Methods 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
Description
本发明属于高分子气体分离膜的制备技术,具体地讲是指以聚酰亚胺粉末为制膜材料,以N-甲基吡咯烷酮、无水乙醇等极性有机溶剂和丙酮等低沸点溶剂配成混合溶剂,溶解聚酰亚胺,配制铸膜液,然后静置脱泡,采用相转化法于湿纺丝工艺纺丝,制得聚酰亚胺中空纤维气体分离膜。The invention belongs to the preparation technology of polymer gas separation membranes, specifically refers to the use of polyimide powder as the membrane material, and the preparation of polar organic solvents such as N-methylpyrrolidone and absolute ethanol and low boiling point solvents such as acetone. into a mixed solvent, dissolve polyimide, prepare a casting solution, and then stand for defoaming, and use a phase inversion method to spin in a wet spinning process to prepare a polyimide hollow fiber gas separation membrane.
和其他制膜材料如聚砜、聚丙烯、醋酸纤维素相比,聚酰亚胺具有很高的玻璃化转变温度Tg,其机械性能、热稳定性和耐化学性等非常优秀,是一种良好的制膜材料,同时采用相转化法可一步制备出具有致密分离层、能直接用于气体分离的膜。目前已在气体分离、起滤、反渗透等领域得到广泛应用,有关以聚酰亚胺为制膜材料的专利很多,如H本公开特许公报85-125204,85-125205,85-150806,85-125209,85-125210等,报道了以聚酰亚胺为制膜材料制备出的不对称中空纤维气体分离膜,虽然有关键制备工艺未透露,但其膜分离系数偏低,表明没有形成足够的致密皮层。中国发明专利91105349.2也报道了以聚酰亚胺为制膜材料,制备平板气体分离膜;但其步骤繁琐复杂,后处理耗用有机溶剂甚多,不易处理;同时平板膜装填面积小,用于气体分离有占地面积大,投资费用高等缺点。Compared with other membrane materials such as polysulfone, polypropylene, and cellulose acetate, polyimide has a high glass transition temperature Tg, and its mechanical properties, thermal stability, and chemical resistance are excellent. It is a good membrane material, and the phase inversion method can be used to prepare a membrane with a dense separation layer and can be directly used for gas separation in one step. At present, it has been widely used in the fields of gas separation, filtration, reverse osmosis, etc., and there are many patents related to polyimide as membrane material, such as the H patent publication 85-125204, 85-125205, 85-150806, 85 -125209, 85-125210, etc., reported the asymmetric hollow fiber gas separation membrane prepared from polyimide as the membrane material. of dense cortex. Chinese invention patent 91105349.2 has also reported that polyimide is used as the membrane material to prepare a flat gas separation membrane; but its steps are tedious and complicated, and the post-treatment consumes a lot of organic solvents, which is not easy to handle; at the same time, the flat membrane has a small filling area and is used for Gas separation has the disadvantages of large floor space and high investment costs.
本发明的目的在于提供一种聚酰亚胺不对称中空纤维膜的制备技术,其操作简单容易,成本低,且用其制得的产品稳定性高,性能稳定。The purpose of the present invention is to provide a preparation technology of polyimide asymmetric hollow fiber membrane, which is simple and easy to operate, low in cost, and the product made by it has high stability and stable performance.
本发明提供了一种聚酰亚胺不对称中空纤维膜的制备方法,包括铸膜液配制及成丝过程,其特征在于:The invention provides a method for preparing a polyimide asymmetric hollow fiber membrane, which includes the preparation of the casting solution and the silk-forming process, and is characterized in that:
(1)铸膜液配方如下(重量百分比)(1) The formulation of the casting solution is as follows (percentage by weight)
聚酰亚胺 15~35%Polyimide 15~35%
低沸点有机溶剂 25~45%Organic solvent with low boiling point 25~45%
极性有机溶剂 30~60%Polar organic solvent 30~60%
其中低沸点有机溶剂选自丙酮、乙醚、正戊烷、氯仿之一到二种;极性有机溶剂选自N-甲基吡咯烷酮、无水乙醇、N,N-二甲基酰胺、N,N-二甲基乙酰胺、二甲基亚砜、甲酰呱啶之一到二种;Wherein the low-boiling point organic solvent is selected from one or two of acetone, ether, n-pentane, and chloroform; the polar organic solvent is selected from N-methylpyrrolidone, dehydrated alcohol, N, N-dimethylamide, N, N - one or two of dimethylacetamide, dimethyl sulfoxide, and piperidine;
(2)成丝(2) into silk
铸膜液经纺丝喷头成丝后,用相对湿度在30~80%的氮气吹扫,时间0.5~15秒,使溶剂挥发;再进行凝胶浴完成相转化,凝胶液为水,水浴时间12~84小时。After the casting solution is formed into filaments through the spinning nozzle, it is purged with nitrogen at a relative humidity of 30-80% for 0.5-15 seconds to evaporate the solvent; then a gel bath is carried out to complete the phase inversion. Time 12-84 hours.
此外,本发明中所述聚酰亚胺最好为:和 其中,A为-O-、-SO2-、-CO-、-S-、-C(CF3)3或 ;Z为-CH2-、-CO-或 In addition, polyimide described in the present invention is preferably: and Wherein, A is -O-, -SO 2 -, -CO-, -S-, -C(CF 3 ) 3 or ; Z is -CH 2 -, -CO- or
本发明中所述极性有机溶剂最好为N-甲基吡咯烷酮、无水乙醇;低沸点有机溶剂最好为丙酮、正戊烷、氯仿;前者与后者比例为2~3∶1。The polar organic solvent described in the present invention is preferably N-methylpyrrolidone and absolute ethanol; the low boiling point organic solvent is preferably acetone, n-pentane, and chloroform; the ratio of the former to the latter is 2 to 3:1.
本发明步骤简单易行,已经成功地纺制出聚酰亚胺不对称中空纤维膜,其性能良好稳定,寿命长,尤其气体透量比中国发明专利91105349.2要高得多。同时采用水浴代替有机溶剂浴作为凝胶浴,节约资金;在铸膜液配方上,采用三元替代91105349.2的四元,并且加入沸点相对低一些的极性有机溶剂,如无水乙醇代替一部分低沸点有机溶剂;在工艺上采用不同比例的干湿氮气为吹扫气,加上套筒调节溶剂挥发时间,使溶剂挥发时间和速度更易控制,易于得到更致密更薄的分离皮层。The steps of the invention are simple and easy, and the asymmetric hollow fiber membrane of polyimide has been spun successfully. The performance is good and stable, and the service life is long, especially the gas permeability is much higher than that of the Chinese invention patent 91105349.2. At the same time, a water bath is used instead of an organic solvent bath as a gel bath to save money; in the formulation of the casting solution, a ternary is used to replace the quaternary of 91105349.2, and a polar organic solvent with a relatively low boiling point is added, such as anhydrous ethanol instead of a part of low Boiling point organic solvent; in the process, different proportions of dry and wet nitrogen are used as the purge gas, and the sleeve is added to adjust the solvent volatilization time, so that the solvent volatilization time and speed are easier to control, and it is easier to obtain a denser and thinner separation skin.
下面的实施例进一步阐述了本发明。The following examples further illustrate the invention.
附图1为设备结构原理示意图。Accompanying drawing 1 is the schematic diagram of equipment structure principle.
实施例1Example 1
结构为 的聚酰亚胺粉末15g,加入27.2gN-甲基吡咯烷酮+16.6g丙酮的混合溶剂中,在45℃下加热搅拌50小时,成为均匀溶液,加入如图1所示装置的料罐(1)中,静置72小时脱泡。经喷头(2)成丝状流出后,用于、湿氮气吹扫,套上2个套筒(3),使铸膜液挥发时间约为4秒,于湿氮气比例为2.4∶1,进入凝胶槽(4)初步成丝(6),丝(6)用导向管(5)导出成卷,放入水储进行完全凝胶。水浴凝胶72小时,自然晾得到的中空纤维膜氢气透过速率为4.35×10-5cm3(STP)/cm2.sec.cmHg,αH2/N2=45.8。structured as 15g of polyimide powder, add 27.2g N-methylpyrrolidone + 16.6g acetone in the mixed solvent, heat and stir at 45 ℃ for 50 hours, become a uniform solution, add the feed tank (1) of the device as shown in Figure 1 In, let stand for 72 hours to defoam. After flowing out in filament form from the nozzle (2), it is used for purging with wet nitrogen, and two sleeves (3) are put on, so that the casting liquid volatilizes for about 4 seconds, and the ratio of wet nitrogen is 2.4:1. The gel tank (4) is preliminarily formed into filaments (6), and the filaments (6) are exported into rolls with a guide tube (5), and put into water storage for complete gelation. After gelling in a water bath for 72 hours, the hydrogen permeation rate of the hollow fiber membrane obtained by air drying was 4.35×10 -5 cm 3 (STP)/cm 2 .sec.cmHg, and α H2/N2 = 45.8.
实施例2Example 2
结构为 的聚酰亚胺粉末15g,加入27.2g N-甲基吡咯烷酮+16.6g丙酮的混合溶剂中,在45℃下加热搅拌50小时,成为均匀溶液,加入如图1所示装置的料罐中,静置72小时脱泡,套上2个套筒,使铸膜液挥发时间约为4秒,干湿氮气比例为2.4∶1,纺丝,水浴凝胶72小时,自然晾干,在烘箱中干燥,温度100℃,得到的膜的氢气透过速率为4.25×10-5cm3(STP)/cm2.sec.cmHg,αH2/N2=62。structured as Add 15g of polyimide powder to a mixed solvent of 27.2g N-methylpyrrolidone + 16.6g acetone, heat and stir at 45°C for 50 hours to form a uniform solution, add it to the material tank of the device shown in Figure 1, Stand still for 72 hours for degassing, put on 2 sleeves, make the casting liquid evaporate for about 4 seconds, the ratio of dry and wet nitrogen is 2.4:1, spin, gel in water bath for 72 hours, dry naturally, in an oven After drying at 100°C, the hydrogen permeation rate of the obtained film was 4.25×10 -5 cm 3 (STP)/cm 2 .sec.cmHg, and α H2/N2 =62.
实施例3Example 3
结构为 的聚酰亚胺粉末15g,加入27.2g N-甲基吡咯烷酮+16.6g丙酮的混合溶剂中,在45℃下加热搅拌50小时,成为均匀溶液,加入如图1所示装置的料罐中,静置72小时脱泡,套上2个套筒,使铸膜液挥发时间约为4秒,干湿氮气比例为2.4∶1,纺丝,水浴凝胶72小时,自然晾干,在真空烘箱中干燥,温度100℃,得到的膜的氢气透过速率为4.7×10-5cm3(STP)/cm2.sec.cmHg,αH2/N2=35。structured as Add 15g of polyimide powder to a mixed solvent of 27.2g N-methylpyrrolidone + 16.6g acetone, heat and stir at 45°C for 50 hours to form a uniform solution, add it to the material tank of the device shown in Figure 1, Stand still for 72 hours for degassing, put on 2 sleeves, make the casting liquid evaporate for about 4 seconds, the ratio of dry and wet nitrogen is 2.4:1, spin, gel in a water bath for 72 hours, dry naturally, and place in a vacuum oven Drying in medium temperature at 100°C, the hydrogen permeation rate of the obtained film was 4.7×10 -5 cm 3 (STP)/cm 2 .sec.cmHg, and α H2/N2 =35.
实施例4Example 4
结构为 的聚酰亚胺粉末20g,加入44.7g N-甲基吡咯烷酮+10.1g丙酮+3.1g无水乙醇所配成的混合溶剂中,在40℃下加热搅拌60小时,成为均匀溶液,加于图1所示装置的料罐中,静置56小时脱泡,套上3个套筒,使铸膜液挥发时间约为6秒,干湿氮气比例为2.5∶1,纺丝,水浴凝胶72小时,自然晾干,所制得的膜的氢气透过速率为1.1×10-4cm3(STP)/cm2.sec.cmHg,αH2/N2=60。structured as Add 20g of polyimide powder into a mixed solvent composed of 44.7g N-methylpyrrolidone + 10.1g acetone + 3.1g absolute ethanol, heat and stir at 40°C for 60 hours to form a homogeneous solution, and add it to Fig. In the material tank of the device shown in 1, let it stand for 56 hours for degassing, put on 3 sleeves, make the casting liquid volatilize for about 6 seconds, and the ratio of dry and wet nitrogen is 2.5:1, spinning, water bath gel 72 Hours, air-dried naturally, the hydrogen permeation rate of the prepared membrane was 1.1×10 -4 cm 3 (STP)/cm 2 .sec.cmHg, α H2/N2 =60.
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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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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 |
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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 |
WO2015016228A1 (en) * | 2013-07-29 | 2015-02-05 | 三菱レイヨン株式会社 | Device and method for producing hollow porous membrane |
CN110694495B (en) * | 2013-09-30 | 2022-09-16 | 佐治亚科技研究公司 | Asymmetric modified carbon molecular sieve hollow fiber membranes with improved permeability |
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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 |
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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 |
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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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