CN1760236A - A kind of polyimide polymer and preparation method and application - Google Patents
A kind of polyimide polymer and preparation method and application Download PDFInfo
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- CN1760236A CN1760236A CN 200410083621 CN200410083621A CN1760236A CN 1760236 A CN1760236 A CN 1760236A CN 200410083621 CN200410083621 CN 200410083621 CN 200410083621 A CN200410083621 A CN 200410083621A CN 1760236 A CN1760236 A CN 1760236A
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Abstract
The invention provides a kind of polyimide polymer, this polymkeric substance is with (A) 4, two kinds of tetracarboxylic dianhydrides that 4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride, (B) pyromellitic acid dianhydride are formed, (C) 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate or 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate salt is starting monomer.The present invention also provides the method with above-mentioned polymer manufacture gas separation membrane, the separatory membrane of preparation can be used for multiple gases and separates, include but not limited to, oxygen/nitrogen separates, from the air-flow of hydrogen separating hydrogen gas, from carbonated air-flow separating carbon dioxide etc.Polyimide provided by the invention has very high gas-premeable and selectivity, also has advantages such as cost is moderate, solvability is good simultaneously.
Description
Technical field
The present invention relates to a kind of polyimide polymer, but relate in particular to the film forming polyimide polymer of a kind of shape.
The invention still further relates to the preparation method of above-mentioned polymkeric substance.
The invention still further relates to and utilize above-mentioned polymer manufacture gas separation membrane.
The invention still further relates to the application of above-mentioned gas separatory membrane.
Background technology
The application of polymkeric substance in gas delivery is known in the art, concern between the existing lot of documents report polymer architecture characteristic separated from the gas, the accumulation of clearly having put down in writing the hardening polymer main chain in the prior art and having suppressed chain simultaneously can improve gas permeability, and increases the selectivity to some mixed gas.Studies show that polyimide is exactly a kind of rigid rod polymkeric substance with ideal gas delivery characteristic, referring to Chinese patent CN1293081A.If the dianhydride of structure rigidity is used in combination with the diamines of replacement, then gas-premeable obviously increases, this is because the polynary substituting group of amine functional group adjacent has spatially hindered polymkeric substance rotating freely around the imines chain, and then it is caused to have high free volume, referring to Chinese patent CN1036964A.
K.Tanaka Kazuhiro Tanaka, membrane science magazine (Journal of Membrane Science), Part B, the 30th volume, 1992, has reported that 6FDA-TMPDA type polyimide film has high gas permeability, H by the 907th page
2Permeability coefficient is 516Barrer (1Barrer=10
-10Cm
3(STP) cm/cm
2ScmHg), CO
2Permeability coefficient is 431Barrer, but institute's permselective property is low, H
2/ N
2Ideal separation factor is 16.3, CO
2/ N
2Ideal separation factor is 13.6, and cost is very high, and the way of solution is exactly on the basis that reduces the polymkeric substance cost, the preparation composite film material.
Found in recent years that some polyimide that contain sulphonate-base had good permselective property such as F.Piroux, membrane science magazine (Journal of Membrane Science), 209 volumes, the 241st page, 2002, reported the H of NTDA-BDSA type sulphonate-base polyimide film
2/ N
2Ideal separation factor is 236, CO
2/ N
2Ideal separation factor is 86.7, but gas permeability is low, H
2Permeability coefficient is 7.1Barrer, CO
2Permeability coefficient is 2.6Barrer.
Although polyimide is in gas delivery Application for Field prospect, commercial at present polyimide gas separating film has only three kinds: Ultem
, Matrimid
Reach polyimide based on BPDA and ODA.This mainly is because the cost of polyimide is very high, has limited it and has used, and the way of solution is exactly on the basis that reduces the polymkeric substance cost, the preparation composite membrane.Polyimide does not often dissolve in a large amount of solvents as a base polymer, makes the aromatic polyimide material be difficult to secondary processing and becomes many products.Though dissolving in non-protonic solvent, some polyimide (is generally N-Methyl pyrrolidone, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) equal solvent), can prepare homogeneous membrane by methods such as phase transformations, but because non-protonic solvent is generally the responsive solvent of substrate material, so be difficult to prepare the coating of composite membrane, and the polyimide that is dissolved in the more weak easy volatile solvent of solvability (such as ethanol, acetone etc.) will have better coatings applications.
In sum, the existing polyimide mould material is difficult to have simultaneously higher gas permeability and gas-selectively; When the system film, also be difficult to find good solvent, perhaps can not be dissolved in weak deliquescent easy volatile solvent, be difficult to as the composite membrane coating.
Summary of the invention
But the object of the present invention is to provide the film forming polyimide polymer of a kind of shape.
Another object of the present invention is to provide the method for the above-mentioned polymkeric substance of preparation.
For achieving the above object, polyimide polymer provided by the invention has the structure shown in the following formula
Wherein, the structure of Ar is:
The method of the above-mentioned polymkeric substance of preparation provided by the invention, with (A) 4, two kinds of tetracarboxylic dianhydrides that 4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride, (B) pyromellitic acid dianhydride are formed, (C) 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate or 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate salt is starting monomer.
Wherein: (A) ratio of composition in tetracarboxylic dianhydride's monomer is 0～100 mole of %, (B) 100～0 moles of % of the ratio of composition in tetracarboxylic dianhydride's monomer, (A) composition and (B) summation of composition be 100 moles of %.
The concrete grammar of its preparation polymkeric substance is: with A composition and/or B composition, be dissolved in non-protonic solvent with the C composition, under 20～30 ℃, nitrogen atmosphere stirred 1～3 hour, with acid anhydrides and tertiary amine is that dewatering agent carries out imidization, wherein the acid anhydrides mole dosage is 2～6 times of C composition consumption, and the tertiary amine consumption is mole dosage such as C composition; React after 2～4 hours, sedimentation in the easy volatile organic solvent, filtration, washing, drying at room temperature 2～4 hours, 150～170 ℃ of dryings 18～24 hours, target product.
A composition among the present invention, B composition and C composition its structural formula of compound is as follows separately:
C composition among the present invention can be: 3, and 5-diamino-2,4,6-tri-methyl p-toluenesulfonate, 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate lithium salts, 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate sodium salt or 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate sylvite.
Easy volatile organic solvent among the present invention can be: methyl alcohol, ethanol or acetone.
The polyimide polymer of the present invention's preparation can be used for preparing gas separation membrane, and its preparation method is:
Polyimide polymer is dissolved in the mixed solvent of non-protonic solvent or water and weak solvability solvent, be mixed with mass content and be 10%～15% solution,, solution is poured on flat board (as sheet glass) goes up knifing after 0.5～2 hour through 100～150 order double-layer nylon net filtrations, vacuum defoamation; Be placed on together with flat board on 100～110 ℃ the hot plate and make solvent evaporation, after 1～2 hour film is taken off, put into vacuum drying oven in 40～50 ℃ handle 1～2 hour down after, under 120 ℃ and 200 ℃, handled respectively 10～12 hours, obtain gas separation membrane.
Non-protonic solvent among the present invention can be: N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO).
The mixed solvent of water among the present invention and weak solvability solvent is meant that water-content is 5～95 weight %, and weak solvability solvent is the mixed solvent of 95～5 weight %, and the summation of water and weak solvability solvent is 100 weight %.Weak solvability solvent can be: methyl alcohol, ethanol or acetone.
The present invention can be used for multiple gases with the gas separation membrane of polyimide preparation and separates, and includes but not limited to, oxygen/nitrogen separates, from the air-flow of hydrogen separating hydrogen gas, from carbonated air-flow separating carbon dioxide etc.
Description of drawings
Fig. 1 is TGA (thermo-gravimetric analysis) curve of polymkeric substance 6FDA-MLi, and wherein 6FDA is 4,4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride, and MLi is 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate lithium salts.
Fig. 2 is DSC (the differential scanning formula calorimetry) curve of polymkeric substance 6FDA-MLi, and wherein 6FDA is 4,4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride, and MLi is 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate lithium salts.
Embodiment
Following examples are used for illustrating practicality of the present invention, but should not be seen as qualification the present invention.As long as meet the present invention summary of the invention partly illustrate condition, all can realize the present invention.
Embodiment 1
4.724g 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate lithium salts (MLi), 41.226g dimethyl sulfoxide (DMSO) and 9.018g 4,4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride (6FDA) powder will be added in the 100ml three neck round-bottomed flasks of band stirring.Reaction mixture was stirred 3 hours down and under the nitrogen protection at 20～30 ℃; form very heavy-gravity solution; add the 10g acetic anhydride then and the 2g triethylamine carries out imidization; react after 4 hours; sedimentation in acetone; filtration, washing with acetone three times, drying at room temperature 170 ℃ of dryings 24 hours, obtained 6FDA-MLi type polyimide after 3 hours.Fig. 1 is the TGA curve of polymkeric substance 6FDA-MLi.As we know from the figure, the second-order transition temperature of 6FDA-MLi type polyimide is 244.09 ℃; Fig. 2 is the DSC curve of polymkeric substance 6FDA-MLi.As we know from the figure, 5% thermal weight loss temperature of 6FDA-MLi type polyimide is 286.07 ℃.
4.724g 3 will be added in the 100ml three neck round-bottomed flasks of band stirring, 5-diamino-2,4,6-tri-methyl p-toluenesulfonate lithium salts (MLi), 34.341g dimethyl sulfoxide (DMSO) and 4.509g 4,4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride (6FDA) and 2.214g pyromellitic acid dianhydride (PMDA) powder.Reaction mixture was stirred 3 hours down at 20～30 ℃, form very heavy-gravity solution, add the 10g acetic anhydride then and the 2g triethylamine carries out imidization, react after 4 hours, sedimentation in acetone, filtration, washing with acetone three times, drying at room temperature 170 ℃ of dryings 24 hours, obtained faint yellow 6FDA/PMDA (50/50)-MLi type polyimide powder after 3 hours.
Embodiment 3
4.724g 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate lithium salts (MLi), 27.457g dimethyl sulfoxide (DMSO) and 4.428g pyromellitic acid dianhydride (PMDA) powder will be added in the 100ml three neck round-bottomed flasks of band stirring.Reaction mixture was stirred 3 hours down and under the nitrogen protection at 20～30 ℃; form very heavy-gravity solution; add the 10g acetic anhydride then and the 2g triethylamine carries out imidization; react after 4 hours; sedimentation in acetone; filtration, washing with acetone three times, drying at room temperature 170 ℃ of dryings 24 hours, obtained 6FDA-MLi type polyimide after 3 hours.
Embodiment 4
The polyimide powder 0.498g that embodiment 1 is obtained joins in the mixing solutions of 9.61g dehydrated alcohol and 1.010g distilled water, and stirring at room is after 2 hours, and polyimide dissolves fully, obtains colourless transparent solution.
Embodiment 5
The polyimide that embodiment 1,2 or 3 is obtained dissolves in the N-Methyl pyrrolidone, is mixed with mass content and is 10%～15% solution,, after 1 hour solution is poured on the clean sheet glass through 100 order double-layer nylon net filtrations, vacuum defoamation, uses the scraper knifing; Be placed on 100～110 ℃ the hot plate together with sheet glass then and make solvent evaporation, after 2 hours film is taken off, put into vacuum drying oven and heat-treat.Heat treatment mode is: handle after 2 hours down for 50 ℃, handled respectively under 120 ℃ and 200 ℃ 12 hours, obtain sulfonic acid lithium salts base polyimide homogeneous membrane 6FDA-MLi, 6FDA/PMDA (50/50)-MLi and PMDA-MLi, its thickness is 25～80 μ m.The gas permeation property of this measured film is listed in the table 1.
The gas permeation property of table 1, polymkeric substance
| Polyimide | Permeability coefficient (Barrer *) | Separation factor | ||||||
| H 2 | CO 2 | O 2 | N 2 | CH 4 | H 2/N 2 | O 2/N 2 | CO 2/CH 4 | |
| 6FDA-Mli | 21.2 | 0.540 | 2.54 | 0.484 | 17.2 | 39.3 | 4.70 | 35.5 |
| 6FDA/PMDA(50/50)- MLi | 12.2 | 0.743 | 0.479 | 0.0484 | 1.67 | 164 | 6.45 | 34.5 |
| PMDA-MLi | 3.92 | 0.0181 | 0.125 | 0.019 | 0.598 | 217 | 6.90 | 31.5 |
*1Barrer=10
-10Cm
3(STP) cm/cm
2ScmHg, probe temperature are 35 ℃, and test pressure is 0.2MPa.
Claims (12)
1. a polyimide polymer has the structure shown in the following formula
Wherein, the structure of Ar is:
M＝H(Li，Na，K)
2. the method for preparing the described polymkeric substance of claim 1, with (A) 4, two kinds of tetracarboxylic dianhydrides that 4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride, (B) pyromellitic acid dianhydride are formed, (C) 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate or 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate salt is starting monomer.
Wherein: (A) ratio of composition in tetracarboxylic dianhydride's monomer is 0～100 mole of %, (B) 100～0 moles of % of the ratio of composition in tetracarboxylic dianhydride's monomer, (A) composition and (B) summation of composition be 100 moles of %;
This preparation method is:
With A composition and/or B composition, be dissolved in non-protonic solvent with the C composition, under 20～30 ℃, nitrogen atmosphere stirred 1～3 hour, with acid anhydrides and tertiary amine is that dewatering agent carries out imidization, and wherein the acid anhydrides mole dosage is 2～6 times of C composition consumption, and the tertiary amine consumption is mole dosage such as C composition; React after 2～4 hours, sedimentation in the easy volatile organic solvent, filtration, washing, drying at room temperature 2～4 hours, 150～170 ℃ of dryings 18～24 hours, polyimide polymer.
3. the preparation method of the described polymkeric substance of claim 2 is characterized in that, the C composition is: 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate, 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate lithium salts, 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate sodium salt or 3,5-diamino-2,4,6-tri-methyl p-toluenesulfonate sylvite.
4. the preparation method of the described polymkeric substance of claim 2 is characterized in that, non-protonic solvent is: N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO).
5. the preparation method of the described polymkeric substance of claim 2 is characterized in that, the acid anhydrides in the dewatering agent is an acetic anhydride, and tertiary amine is triethylamine, Trimethylamine 99 or pyridine.
6. the preparation method of the described polymkeric substance of claim 2 is characterized in that, the easy volatile organic solvent is: methyl alcohol, ethanol or acetone.
7. the described polymkeric substance of claim 1 is used to prepare the method for gas separation membrane, polyimide polymer is dissolved in the mixed solvent of non-protonic solvent or water and weak solvability solvent, be mixed with mass content and be 10%～15% solution, filtration, deaeration were poured on the dull and stereotyped knifing of going up with solution after 0.5～2 hour; Be placed on together with flat board on 100～110 ℃ the hot plate and make solvent evaporation, after 1～2 hour film is taken off, put into vacuum drying oven in 40～50 ℃ handle 1～2 hour down after, under 120 ℃ and 200 ℃, handled respectively 10～12 hours, obtain gas separation membrane;
Wherein in the mixed solvent of water and weak solvability solvent, water-content is 5～95 weight %, and weak solvability solvent is 95～5 weight %, and the summation of water and weak solvability solvent is 100 weight %.
8. the described method for preparing gas separation membrane of claim 7 is characterized in that non-protonic solvent is: N-Methyl pyrrolidone, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO).
9. the method for claim 7 is characterized in that, weak solvability solvent is: methyl alcohol, ethanol or acetone.
10. the described method for preparing gas separation membrane of claim 7 is characterized in that, filtration is with 100～150 order double-layer nylon nets.
11. the described method for preparing gas separation membrane of claim 7 is characterized in that, flat board is a sheet glass.
12. the gas separation membrane of claim 7 preparation separates in oxygen/nitrogen, separating hydrogen gas and the application on the separating carbon dioxide gas from carbonated air-flow from the air-flow of hydrogen.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100593520C (en) * | 2006-05-26 | 2010-03-10 | 中国科学院化学研究所 | Polyimide copolymer infiltration vaporization separation film for treating phenols-containing waste water and preparing method thereof |
| CN101100511B (en) * | 2006-07-05 | 2011-06-29 | 达兴材料股份有限公司 | Polyimide resin polymer and liquid crystal alignment layer material containing the same |
| CN103930966A (en) * | 2011-11-03 | 2014-07-16 | 工程吸气公司 | Improved composite getters |
| JP2016030760A (en) * | 2014-07-25 | 2016-03-07 | 富士ゼロックス株式会社 | Polyimide precursor composition, method for producing polyimide precursor, polyimide molded article and method for producing polyimide molded article |
| WO2017002407A1 (en) * | 2015-06-30 | 2017-01-05 | 富士フイルム株式会社 | Gas separation membrane, gas separation module, gas separation device, gas separation method, and polyimide compound |
| CN108114615A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of polyimide gas separating film material and preparation and application |
| CN110404423A (en) * | 2019-08-16 | 2019-11-05 | 中国科学院大连化学物理研究所 | A kind of high-performance polyimide hollow-fibre membrane and the preparation method and application thereof |
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2004
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100593520C (en) * | 2006-05-26 | 2010-03-10 | 中国科学院化学研究所 | Polyimide copolymer infiltration vaporization separation film for treating phenols-containing waste water and preparing method thereof |
| CN101100511B (en) * | 2006-07-05 | 2011-06-29 | 达兴材料股份有限公司 | Polyimide resin polymer and liquid crystal alignment layer material containing the same |
| CN103930966A (en) * | 2011-11-03 | 2014-07-16 | 工程吸气公司 | Improved composite getters |
| JP2016030760A (en) * | 2014-07-25 | 2016-03-07 | 富士ゼロックス株式会社 | Polyimide precursor composition, method for producing polyimide precursor, polyimide molded article and method for producing polyimide molded article |
| WO2017002407A1 (en) * | 2015-06-30 | 2017-01-05 | 富士フイルム株式会社 | Gas separation membrane, gas separation module, gas separation device, gas separation method, and polyimide compound |
| JPWO2017002407A1 (en) * | 2015-06-30 | 2018-01-11 | 富士フイルム株式会社 | Gas separation membrane, gas separation module, gas separation device, gas separation method and polyimide compound |
| US10537859B2 (en) | 2015-06-30 | 2020-01-21 | Fujifilm Corporation | Gas separation membrane, gas separation module, gas separation device, gas separation method, and polyimide compound |
| CN108114615A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of polyimide gas separating film material and preparation and application |
| CN110404423A (en) * | 2019-08-16 | 2019-11-05 | 中国科学院大连化学物理研究所 | A kind of high-performance polyimide hollow-fibre membrane and the preparation method and application thereof |
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