CN106139936A - Polyimide gas separating film and its preparation method and application - Google Patents
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- CN106139936A CN106139936A CN201610495759.0A CN201610495759A CN106139936A CN 106139936 A CN106139936 A CN 106139936A CN 201610495759 A CN201610495759 A CN 201610495759A CN 106139936 A CN106139936 A CN 106139936A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention discloses a kind of polyimide gas separating film and its preparation method and application, this polyimide gas separating film is made up with diamine monomer of equimolar dianhydride monomer, dianhydride monomer is made up of according to the mol ratio of 1: 1~4: 1 6FDA Yu TTD, diamine monomer is made up of according to the mol ratio of 1: 1~1: 9 with BIA a kind of diamine monomer containing spirane structure, and the diamine monomer containing spirane structure is SBF or CSBF or BSBF;This polyimide gas separating film for the separation of carbon dioxide and recovery, separates with methane including carbon dioxide in biogas, the recovery of carbon dioxide in the removing of carbon dioxide in natural and oil extraction in oil field.
Description
Technical field
The present invention relates to a kind of polyimide gas separating film and its preparation method and application.
Background technology
Polyimides, because high-fire resistance and good combination property, is the preferable material of resistant to elevated temperatures gas separation membrane.
At present, minimal amount of polyimides varities practice in high-temperature-resistant gas separation membrane material, for various gases to (as hydrogen/nitrogen,
Nitrogen/oxygen, carbon dioxide/nitrogen, carbon dioxide/methane etc.) separation, from air, hydrocarbon raw material gas and alcohol apoplexy due to endogenous wind remove moisture, also
Can be as osmotic evaporation film and ultrafilter membrane.But, conventional polyimide resin indissoluble solution and infusibility melt, thus limit its work
Wide variety of probability in industry.
At present, the business-like polyimide resin for gas separation membrane only has Matrimid 5218 and P84 two kinds,
Wherein Matrimid 5218 is by 3,3', 4,4'-benzophenone tetracarboxylic dianhydride and 5(6)-amino-1-(4-aminophenyl)-1,3,
3-trimethyl indane prepares, and P84 is then BTDA-TDI/MDI copolymer, is by 3,3', 4,4'-benzophenone tetracarboxylic dianhydrides
(BTDA), diphenylmethane diisocyanate ester (MDI) and three kinds of monomer copolycondensations of toluene-2,4-diisocyanate (TDI) prepare.
[Data Source is in document as shown in table 1 for the typical air permeability performance of both commercialization polyimide gas separating films
“Carbon membranes from blends of PBI and polyimides for N2/CH4 and CO2/CH4
Separation and hydrogen purification ", S.S. Hosseini, T.S.Chung, Journal of
Membrane Science 328(2009) 174-185].
Table 1
As can be seen from Table 1: the CO of Matrimid 5218 and P842/CH4Selectivity is the most relatively low, less than 50;CO simultaneously2Ooze
Property is relatively low, to CO thoroughly2Infiltration coefficient less than 10Barrer.
At present, a lot of patent documentation is also had to disclose polyimide gas separating film, but what these gas separation membranes had
There is CO2/CH4Selectivity is relatively low and/or CO2The problem that permeability is relatively low, some existence cannot be dissolved in asking in Conventional solvents
Topic, the existence heat resistance also having is poor, the problem that cannot be applied to high temperature resistant occasion.
Summary of the invention
It is an object of the invention to solve the problems referred to above, it is provided that a kind of CO2/CH4Selectivity and CO2Permeability is the highest,
And there is the polyimide gas separating film of preferable heat resistance and its preparation method and application.
The technical scheme realizing above-mentioned purpose of the present invention is: a kind of polyimide gas separating film, it is by equimolar
Dianhydride monomer is made with diamine monomer;Described dianhydride monomer is made up of 6FDA with TTD;Described diamine monomer is tied containing volution by one
The diamine monomer of structure forms with BIA;The described diamine monomer containing spirane structure is SBF or CSBF or BSBF.
The mol ratio of described 6FDA and described TTD is 1: 1~4: 1.
The chemical name of described 6FDA is 2, double (3,4-bis-carboxy phenyl) the HFC-236fa tetracarboxylic dianhydride of 2'-, is called for short hexafluoro two
Acid anhydride;The chemical name of described TTD is triptycene-2,3,6,7-tetracarboxylic acid dianhydride;Their chemical structural formula is as follows:
。
The described diamine monomer containing spirane structure is 1: 1~1: 9 with the mol ratio of described BIA.
The chemical name of described SBF is 9,9'-spiral shell two [9H-fluorenes]-2,2'-diamidogen;The chemical name of CSBF is 3,3'-
Dimethyl-9,9'-spiral shell two [9H-fluorenes]-2,2'-diamidogen;The chemical name of BSBF be 3,3'-bis-bromo-9,9'-spiral shell two [9H-fluorenes]-
2,2'-diamidogen;Their chemical structural formula is as follows:
。
The chemical name of described BIA is 6-amino-2-(3-aminobenzene) benzimidazole, its chemical structural formula is as follows:
。
The preparation method of above-mentioned polyimide gas separating film has steps of:
The most first the diamine monomer containing spirane structure and BIA are dissolved in aprotic polar solvent, then successively add 6FDA and
TTD, at a temperature of 0~50 DEG C, stirring reaction 4~50h, obtains polyamic acid solution;
2. polyamic acid solution step 1. obtained carries out hot-imide process and obtains polyimide powder;
3. being dissolved in aprotic polar solvent by the polyimide powder that 2. step obtains, being configured to solid content is 10~25%
Polyimide solution;
4. the polyimide solution that 3. step obtains is made polyimide gas separating film.
Above-mentioned steps 1. described in aprotic polar solvent be N-methyl-2 ketopyrrolidine (NMP) or N, N'-diformazan
Base Methanamide (DMF).
Above-mentioned steps 1. middle reaction temperature is preferably 5~30 DEG C, and the stirring response time is preferably 8~24h.
Above-mentioned steps 2. described in hot-imide process concrete grammar as follows: in described polyamic acid solution add
Water entrainer, return stirring 7~48h, obtain homogeneous polyimide solution;Steam water entrainer the most completely, stop heating, treat it
After naturally cooling to room temperature (15~25 DEG C, lower same), reactant liquor is poured in the methanol of high-speed stirred, be precipitated thing;By institute
Precipitate fully washs through methanol and absolute methanol after first, filters, after natural drying, continues to be dried at 120 DEG C of vacuum
24h, obtains polyimide powder.
Described water entrainer is toluene, dimethylbenzene or chlorobenzene.
Above-mentioned steps 3. described in aprotic polar solvent be N-methyl-2 ketopyrrolidine (NMP), N, N'-dimethyl methyl
One or both in amide (DMF), N, N'-dimethyl acetylamide (DMAc).
Above-mentioned steps concrete grammar 4. is as follows: be coated on substrate by gained polyimide solution, controls liquid film molten
Thickness after agent volatilization is 5~70 μm, and then desolvation in high temperature drying tunnel naturally cools to room temperature, demoulding, obtain polyamides
Imines gas separation membrane.
The processing mode of described desolvation is: use gradient the most respectively in the range of 80 DEG C~300 DEG C
The mode heated up removes solvent.
Described substrate is glass plate or steel plate.
Above-mentioned polyimide gas separating film is used for separation and the recovery of carbon dioxide, including carbon dioxide in biogas
Separate with methane, the recovery of carbon dioxide in the removing of carbon dioxide in natural and oil extraction in oil field.
The good effect that the present invention has: the present invention is using 6FDA and TTD as dianhydride monomer, with BIA with containing spirane structure
SBF/CSB/BSBF make polyimides as diamine monomer and according to certain mol ratio, the gas being made up of this polyimides
Body separation film not only has higher CO2/CH4Selectivity and higher CO2Permeability, and have preferable heat resistance and
Solubility such that it is able to for separation and the recovery of carbon dioxide, be especially adapted for use in resistant to elevated temperatures occasion.
Detailed description of the invention
(embodiment 1)
1. equipped with N2In the 500mL four-hole boiling flask of breather, thermometer and mechanical agitator, at N2In atmosphere, it is initially charged SBF
(3.4642g, 0.0100mol) and BIA(8.9706g, 0.0400mol), add NMP(300g), after diamidogen is completely dissolved,
Successively add 6FDA(13.3273g, 0.0300mol) and TTD(7.8866g, 0.0200mol), at 30 DEG C, react 8h, obtain
Corresponding polyamic acid solution.
2. in the polyamic acid solution that 1. step obtains, add 75g toluene, the most continuously stirred heating 48h
After obtain homogeneous polyimide solution;Steam toluene the most completely, stop heating, after it naturally cools to room temperature, will be anti-
Answer liquid to pour in the methanol of high-speed stirred, be precipitated thing;Gained precipitate is fully washed through methanol and absolute methanol after first,
After filtration, natural drying, continue to be dried 24h at 120 DEG C of vacuum, obtain polyimide powder.
Using NMP as flowing phase, recording its number-average molecular weight (Mn) with chromatograph of gel permeation is 58654, Weight-average molecular
Amount (Mw) is 185490.
3., under room temperature, polyimide powder step 2. obtained is dissolved in DMAc, be configured to solid content be 15% poly-
Imide solution.
4. polyimide solution step 3. obtained coats on a glass, controls liquid film thickness after evaporation of the solvent
It is 20~25 μm, in high temperature drying tunnel, each at 80 DEG C, 140 DEG C, 190 DEG C, 250 DEG C and 300 DEG C the most respectively
0.5h removes solvent, then naturally cools to room temperature, is finally putting into demoulding in water, obtains polyimide gas separating film.
(embodiment 2)
1. equipped with N2In the 500mL four-hole boiling flask of breather, thermometer and mechanical agitator, at N2In atmosphere, it is initially charged
CSBF(5.6172g, 0.0150mol) and BIA(7.8493g, 0.0350mol), add DMF(310g), treat that diamidogen is the most molten
Xie Hou, successively adds 6FDA(11.1061g, 0.0250mol) and TTD(9.8583g, 0.0250mol), react at 15 DEG C
12h, obtains the polyamic acid solution of correspondence.
2. in the polyamic acid solution that 1. step obtains, add 70g chlorobenzene, the most continuously stirred heating 36h
After obtain homogeneous polyimide solution;Steam chlorobenzene the most completely, stop heating, after it naturally cools to room temperature, will be anti-
Answer liquid to pour in the methanol of high-speed stirred, be precipitated thing;Gained precipitate is fully washed through methanol and absolute methanol after first,
After filtration, natural drying, continue to be dried 24h at 120 DEG C of vacuum, obtain polyimide powder.
Using NMP as flowing phase, recording its number-average molecular weight (Mn) with chromatograph of gel permeation is 66754, Weight-average molecular
Amount (Mw) is 167354.
3., under room temperature, polyimide powder step 2. obtained is dissolved in DMAc, be configured to solid content be 25% poly-
Imide solution.
4. polyimide solution step 3. obtained coats on a glass, controls liquid film thickness after evaporation of the solvent
It is 40~45 μm, in high temperature drying tunnel, each at 80 DEG C, 140 DEG C, 190 DEG C, 250 DEG C and 300 DEG C the most respectively
0.5h removes solvent, then naturally cools to room temperature, is finally putting into demoulding in water, obtains polyimide gas separating film.
(embodiment 3)
1. equipped with N2In the 500mL four-hole boiling flask of breather, thermometer and mechanical agitator, at N2In atmosphere, it is initially charged
BSBF(2.0169g, 0.0040mol) and BIA(7.1765g, 0.0320mol), add NMP(260g), treat that diamidogen is the most molten
Xie Hou, successively adds 6FDA(10.6618g, 0.0240mol) and TTD(4.7320g, 0.0120mol), at 5 DEG C, react 24h,
Obtain the polyamic acid solution of correspondence.
2. in the polyamic acid solution that 1. step obtains, add 75g chlorobenzene, the most continuously stirred heating 36h
After obtain homogeneous polyimide solution;Steam chlorobenzene the most completely, stop heating, after it naturally cools to room temperature, will be anti-
Answer liquid to pour in the methanol of high-speed stirred, be precipitated thing;Gained precipitate is fully washed through methanol and absolute methanol after first,
After filtration, natural drying, continue to be dried 24h at 120 DEG C of vacuum, obtain polyimide powder.
Using NMP as flowing phase, recording its number-average molecular weight (Mn) with chromatograph of gel permeation is 56754, Weight-average molecular
Amount (Mw) is 145784.
3., under room temperature, polyimide powder step 2. obtained is dissolved in NMP, be configured to solid content be 15% poly-
Imide solution.
4. polyimide solution step 3. obtained coats on a glass, controls liquid film thickness after evaporation of the solvent
It is 40~45 μm, in high temperature drying tunnel, each at 80 DEG C, 140 DEG C, 190 DEG C of C, 250 DEG C and 300 DEG C the most respectively
0.5h removes solvent, then naturally cools to room temperature, is finally putting into demoulding in water, obtains polyimide gas separating film.
(embodiment 4)
1. equipped with N2In the 500mL four-hole boiling flask of breather, thermometer and mechanical agitator, at N2In atmosphere, it is initially charged SBF
(3.4642g, 0.0100mol) and BIA(3.3640g, 0.0150mol), add NMP(200g), after diamidogen is completely dissolved,
Successively add 6FDA(8.8848g, 0.0200mol) and TTD(1.9717g, 0.0050mol), at 18 DEG C, react 12h, obtain
Corresponding polyamic acid solution.
2. in the polyamic acid solution that 1. step obtains, add 50g toluene, the most continuously stirred heating 36h
After obtain homogeneous polyimide solution;Steam toluene the most completely, stop heating, after it naturally cools to room temperature, will be anti-
Answer liquid to pour in the methanol of high-speed stirred, be precipitated thing;Gained precipitate is fully washed through methanol and absolute methanol after first,
After filtration, natural drying, continue to be dried 24h at 120 DEG C of vacuum, obtain polyimide powder.
Using NMP as flowing phase, recording its number-average molecular weight (Mn) with chromatograph of gel permeation is 57682, Weight-average molecular
Amount (Mw) is 134678.
3., under room temperature, polyimide powder step 2. obtained is dissolved in NMP, be configured to solid content be 15% poly-
Imide solution.
4. polyimide solution step 3. obtained coats on stainless steel, controls liquid film thickness after evaporation of the solvent
Degree is 60~70 μm, in high temperature drying tunnel, each at 80 DEG C, 140 DEG C, 190 DEG C, 250 DEG C and 300 DEG C the most respectively
0.5h removes solvent, then naturally cools to room temperature, is finally putting into demoulding in water, obtains polyimide gas separating film.
(embodiment 5)
1. equipped with N2In the 1000mL four-hole boiling flask of breather, thermometer and mechanical agitator, at N2In atmosphere, it is initially charged
CSBF(7.4896g, 0.0200mol) and BIA(6.7280g, 0.0300mol), add NMP(500g), treat that diamidogen is the most molten
Xie Hou, successively adds 6FDA(16.8812g, 0.0380mol) and TTD(4.7320g, 0.0120mol), react at 25 DEG C
15h, obtains the polyamic acid solution of correspondence.
2. in the polyamic acid solution that 1. step obtains, add 125g dimethylbenzene, the most continuously stirred heating
Homogeneous polyimide solution is obtained after 18h;Steam dimethylbenzene the most completely, stop heating, after it naturally cools to room temperature,
Reactant liquor is poured in the methanol of high-speed stirred, be precipitated thing;By abundant through methanol and absolute ether after gained precipitate elder generation
After washing, filtration, natural drying, continue to be dried 24h at 120 DEG C of vacuum, obtain polyimide powder.
Using NMP as flowing phase, recording its number-average molecular weight (Mn) with chromatograph of gel permeation is 50998, Weight-average molecular
Amount (Mw) is 164530.
3., under room temperature, polyimide powder step 2. obtained is dissolved in DMF, be configured to solid content be 14% poly-
Imide solution.
4. polyimide solution step 3. obtained coats on a glass, controls liquid film thickness after evaporation of the solvent
It is 5~10 μm, in high temperature drying tunnel, each at 80 DEG C, 140 DEG C, 190 DEG C, 250 DEG C and 300 DEG C the most respectively
0.5h removes solvent, then naturally cools to room temperature, is finally putting into demoulding in water, obtains polyimide gas separating film.
(test case)
The polyamides prepared by VAC-V2 pressure differential gas permeameter testing example 1~embodiment 5 according to ISO15105-1 standard
The permeability of imines gas separation membrane, the results are shown in Table 2.
It addition, use dynamic thermomechanical analysis apparatus (DMA) tested glass transition temperature (heating rate in a nitrogen atmosphere
It is 20 DEG C/min);Simultaneously according to JISC2318 standard testing mechanical performance;Result is still shown in Table 2.
Table 2
As can be seen from Table 2: the polyimide gas separating film of the present invention is to CO2Gas permeability coefficient and CO2/CH4
The selectivity of gas pair is far above Matrimid 5218 and P84, has the most ventilative separating property.Glass transition simultaneously
Temperature is also far above Matrimid 5218(323 DEG C) and P84 resin (315 DEG C), there is more preferable heat resistance simultaneously.
Claims (10)
1. a polyimide gas separating film, it is made up with diamine monomer of equimolar dianhydride monomer;It is characterized in that:
Described dianhydride monomer is made up of 6FDA with TTD;Described diamine monomer is made up of with BIA a kind of diamine monomer containing spirane structure;
The described diamine monomer containing spirane structure is SBF or CSBF or BSBF.
Polyimide gas separating film the most according to claim 1, it is characterised in that: described 6FDA rubs with described TTD's
Your ratio is 1: 1~4: 1.
Polyimide gas separating film the most according to claim 1, it is characterised in that: the described diamidogen list containing spirane structure
Body is 1: 1~1: 9 with the mol ratio of described BIA.
Polyimide gas separating film the most according to claim 2, it is characterised in that: the described diamidogen list containing spirane structure
Body is 1: 1~1: 9 with the mol ratio of described BIA.
5. the preparation method of the polyimide gas separating film that one of Claims 1-4 is described, has steps of:
The most first the diamine monomer containing spirane structure and BIA are dissolved in aprotic polar solvent, then successively add 6FDA and
TTD, at a temperature of 0~50 DEG C, stirring reaction 4~50h, obtains polyamic acid solution;
2. polyamic acid solution step 1. obtained carries out hot-imide process and obtains polyimide powder;
3. being dissolved in aprotic polar solvent by the polyimide powder that 2. step obtains, being configured to solid content is 10~25%
Polyimide solution;
4. the polyimide solution that 3. step obtains is made polyimide gas separating film.
The preparation method of polyimide gas separating film the most according to claim 5, it is characterised in that: step 1. described in
Aprotic polar solvent be N-methyl-2 ketopyrrolidine or N, N'-dimethylformamide.
The preparation method of polyimide gas separating film the most according to claim 5, it is characterised in that: step 2. described in
Hot-imide process concrete grammar as follows: in described polyamic acid solution add water entrainer, return stirring 7~48h,
To homogeneous polyimide solution;Steam water entrainer the most completely, stop heating, after it naturally cools to room temperature, will reaction
Liquid is poured in the methanol of high-speed stirred, is precipitated thing;Gained precipitate is fully washed through methanol and absolute methanol after first, mistake
After filter, natural drying, continue to be dried 24h at 120 DEG C of vacuum, obtain polyimide powder.
The preparation method of polyimide gas separating film the most according to claim 5, it is characterised in that: step 3. described in
Aprotic polar solvent be in N-methyl-2 ketopyrrolidine, N, N'-dimethylformamide, N, N'-dimethyl acetylamide
Plant or two kinds.
The preparation method of polyimide gas separating film the most according to claim 5, it is characterised in that: step 4. concrete
Method is as follows: be coated on substrate by gained polyimide solution, and controlling liquid film thickness after evaporation of the solvent is 5~70 μm,
Desolvation in high temperature drying tunnel, then naturally cools to room temperature, demoulding, obtains polyimide gas separating film.
10. the polyimide gas separating film that one of Claims 1-4 is described is used for separation and the recovery of carbon dioxide, including
In biogas carbon dioxide separate with methane, carbon dioxide in the removing of carbon dioxide in natural and oil extraction in oil field
Reclaim.
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