CN106139936B - Polyimide gas separating film and its preparation method and application - Google Patents

Polyimide gas separating film and its preparation method and application Download PDF

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CN106139936B
CN106139936B CN201610495759.0A CN201610495759A CN106139936B CN 106139936 B CN106139936 B CN 106139936B CN 201610495759 A CN201610495759 A CN 201610495759A CN 106139936 B CN106139936 B CN 106139936B
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polyimide
gas separating
separating film
polyimide gas
bia
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CN106139936A (en
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庄永兵
胡锦平
胡国宜
蒋志强
李成章
张培峰
黄磊
吴建华
奚小金
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CHANGZHOU SUNLIGHT PHARMACEUTICAL Co Ltd
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CHANGZHOU SUNLIGHT PHARMACEUTICAL Co Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The invention discloses a kind of polyimide gas separating films and its preparation method and application, the polyimide gas separating film is made of equimolar dianhydride monomer with diamine monomer, dianhydride monomer is made of 6FDA and TTD according to 1: 1~4: 1 molar ratio, diamine monomer is made of a kind of diamine monomer containing spirane structure and BIA according to 1: 1~1: 9 molar ratio, and the diamine monomer containing spirane structure is SBF either CSBF or BSBF；Recycling of the polyimide gas separating film for carbon dioxide in the separation of carbon dioxide and methane, the removing of carbon dioxide in natural and oil extraction in oil field in the separation and recycling, including biogas of carbon dioxide.

Description

Polyimide gas separating film and its preparation method and application
Technical field
The present invention relates to a kind of polyimide gas separating films and its preparation method and application.
Background technology
Polyimides is the ideal material of heat safe gas separation membrane because of high-fire resistance and good comprehensive performance. Currently, minimal amount of polyimides varities practice is used for various gases pair in high-temperature-resistant gas separation membrane material（As hydrogen/nitrogen, Nitrogen/oxygen, carbon dioxide/nitrogen, carbon dioxide/methane etc.）Separation, remove moisture from air, hydrocarbon raw material gas and alcohols, It can be used as osmotic evaporation film and ultrafiltration membrane.But conventional polyimide resin indissoluble solution and infusibility melt, thus limit its work Widely applied possibility in industry.
Currently, the commercialized polyimide resin for gas separation membrane only has two kinds of Matrimid 5218 and P84, Wherein Matrimid 5218 is by 3,3', 4,4'- benzophenone tetracid dianhydride and 5（6）Amino -1-（4- aminophenyls）-1,3, 3- trimethyl indanes are made, and P84 is then BTDA-TDI/MDI copolymers, is by 3,3', 4,4'- benzophenone tetracid dianhydrides （BTDA）, diphenylmethane diisocyanate ester（MDI）And toluene-2,4-diisocyanate（TDI）Three kinds of monomer copolycondensations are made.
The typical air permeability performance of both commercialization polyimide gas separating films is as shown in table 1【Data source is in document “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 relatively low, less than 50；CO simultaneously2It oozes Permeability is relatively low, to CO2Infiltration coefficient less than 10Barrer.
Currently, also there are many patent documents to disclose polyimide gas separating film, but what these gas separation membranes had There are CO2/CH4The relatively low and/or CO of selectivity2The relatively low problem of permeability, some presence can not be dissolved in asking in Conventional solvents Topic, also there are problems that heat resistance is poor, can not be applied to high temperature resistant occasion.
Invention content
It is an object of the invention to solve the above problems, a kind of CO is provided2/CH4Selectivity and CO2Permeability is higher, And the polyimide gas separating film and its preparation method and application with preferable heat resistance.
Realizing the technical solution of 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；The dianhydride monomer is made of 6FDA and TTD；The diamine monomer is by a kind of knot containing loop coil The diamine monomer of structure is formed with BIA；The diamine monomer containing spirane structure is SBF either CSBF or BSBF.
The molar ratio of the 6FDA and TTD is 1: 1~4: 1.
The chemical name of the 6FDA is that 2,2'- is bis-（Bis- carboxy phenyls of 3,4-）Hexafluoropropane tetracid dianhydride, abbreviation hexafluoro two Acid anhydride；The chemical name of the TTD is triptycene -2,3,6,7- tetracarboxylic acid dianhydrides；Their chemical structural formula is as follows：
。
The molar ratio of the diamine monomer containing spirane structure and the BIA are 1: 1~1: 9.
The chemical name of the SBF is 9,9'- spiral shells two [9H- fluorenes] -2,2'- diamines；The chemical name of CSBF is 3,3'- Dimethyl -9,9'- spiral shells two [9H- fluorenes] -2,2'- diamines；The chemical name of BSBF is bis- bromo- 9,9'- spiral shells two [9H- fluorenes] of 3,3'-- 2,2'- diamines；Their chemical structural formula is as follows：
。
The chemical name of the BIA is 6- amino -2-（3- aminobenzenes）Benzimidazole, chemical structural formula are as follows：
。
The preparation method of above-mentioned polyimide gas separating film has steps of：
1. being first dissolved in the diamine monomer containing spirane structure in aprotic polar solvent with BIA, 6FDA is then successively added And TTD, it is stirred to react 4~50h at a temperature of 0~50 DEG C, obtains polyamic acid solution；
2. 1. polyamic acid solution that step obtains is carried out hot-imide to handle to obtain polyimide powder；
3. 2. polyimide powder that step obtains is dissolved in aprotic polar solvent, be configured to solid content be 10~ 25% polyimide solution；
4. polyimide gas separating film is made in 3. polyimide solution that step obtains.
Above-mentioned steps 1. described in aprotic polar solvent be -2 pyrrolidones of N- methyl（NMP）Or N, N'- diformazan Base formamide（DMF）.
Above-mentioned steps 1. in reaction temperature be preferably 5~30 DEG C, be stirred to react the time be preferably 8~for 24 hours.
Above-mentioned steps 2. described in hot-imide processing the specific method is as follows：It is added into the polyamic acid solution Water entrainer, 7~48h of return stirring obtain homogeneous polyimide solution；Then water entrainer is steamed completely, is stopped heating, is waited for it Cooled to room temperature（15~25 DEG C, similarly hereinafter）Afterwards, reaction solution is poured into the methanol of high-speed stirred, obtains sediment；By institute After sediment successively fully washs through methanol and absolute methanol, filters, spontaneously dry, continue drying at 120 DEG C of vacuum For 24 hours, polyimide powder is obtained.
The water entrainer is toluene, dimethylbenzene or chlorobenzene.
Above-mentioned steps 3. described in aprotic polar solvent be -2 pyrrolidones of N- methyl（NMP）, N, N'- dimethyl methyls Amide（DMF）, N, N'- dimethylacetylamides（DMAc）One or both of.
4. the specific method is as follows for above-mentioned steps：Gained polyimide solution is coated on substrate, control liquid film is molten Thickness after agent volatilization is 5~70 μm, solvent is removed in high temperature drying tunnel, then cooled to room temperature, demoulding is to get polyamides Imines gas separation membrane.
It is described removing solvent processing mode be：Use gradient within the scope of 80 DEG C~300 DEG C respectively under nitrogen protection The mode of heating removes solvent.
The substrate is glass plate or steel plate.
Above-mentioned polyimide gas separating film is for carbon dioxide in the separation and recycling, including biogas of carbon dioxide The recycling of carbon dioxide in the removing of separation, carbon dioxide in natural with methane and oil extraction in oil field.
The good effect that the present invention has：The present invention using 6FDA and TTD as dianhydride monomer, with BIA and contain spirane structure SBF/CSB/BSBF polyimides is made as diamine monomer and according to certain molar ratio, the gas made of the polyimides Body seperation film not only has higher CO2/CH4Selective and higher CO2Permeability, and with preferable heat resistance and Solubility is especially adapted for use in heat safe occasion so as to the separation and recycling for carbon dioxide.
Specific implementation mode
（Embodiment 1）
1. equipped with N2In the 500mL four-hole boiling flasks of snorkel, thermometer and mechanical agitator, in N2In atmosphere, first it is added SBF（3.4642g、0.0100mol）And BIA（8.9706g、0.0400mol）, add NMP（300g）, wait for that diamines is completely dissolved Afterwards, 6FDA is successively added（13.3273g、0.0300mol）And TTD（7.8866g、0.0200mol）, 8h is reacted at 30 DEG C, is obtained To corresponding polyamic acid solution.
2. 75g toluene is added in the polyamic acid solution 1. obtained to step, at a reflux temperature lasting agitating and heating 48h Homogeneous polyimide solution is obtained afterwards；Then toluene is steamed completely, stops heating, it, will be anti-after its cooled to room temperature It answers liquid to pour into the methanol of high-speed stirred, obtains sediment；Gained sediment is successively fully washed through methanol and absolute methanol, Filtering, after spontaneously drying, continue at 120 DEG C of vacuum it is dry for 24 hours, obtain polyimide powder.
Using NMP as mobile phase, its number-average molecular weight is measured with gel permeation chromatograph（Mn）It is 58654, Weight-average molecular Amount（Mw）It is 185490.
3. at room temperature, 2. polyimide powder that step obtains is dissolved in DMAc, be configured to solid content be 15% it is poly- Imide solution.
4. 3. polyimide solution coating that step is obtained is on a glass, the thickness of control liquid film after evaporation of the solvent It is 20~25 μm, it is each at 80 DEG C, 140 DEG C, 190 DEG C, 250 DEG C and 300 DEG C respectively under nitrogen protection in high temperature drying tunnel 0.5h removes solvent, and then cooled 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 flasks of snorkel, thermometer and mechanical agitator, in N2In atmosphere, first it is added CSBF（5.6172g、0.0150mol）And BIA（7.8493g、0.0350mol）, add DMF（310g）, wait for that diamines is completely molten 6FDA is successively added in Xie Hou（11.1061g、0.0250mol）And TTD（9.8583g、0.0250mol）, reacted at 15 DEG C 12h obtains corresponding polyamic acid solution.
2. 70g chlorobenzenes are added in the polyamic acid solution 1. obtained to step, at a reflux temperature lasting agitating and heating 36h Homogeneous polyimide solution is obtained afterwards；Then chlorobenzene is steamed completely, stops heating, it, will be anti-after its cooled to room temperature It answers liquid to pour into the methanol of high-speed stirred, obtains sediment；Gained sediment is successively fully washed through methanol and absolute methanol, Filtering, after spontaneously drying, continue at 120 DEG C of vacuum it is dry for 24 hours, obtain polyimide powder.
Using NMP as mobile phase, its number-average molecular weight is measured with gel permeation chromatograph（Mn）It is 66754, Weight-average molecular Amount（Mw）It is 167354.
3. at room temperature, 2. polyimide powder that step obtains is dissolved in DMAc, be configured to solid content be 25% it is poly- Imide solution.
4. 3. polyimide solution coating that step is obtained is on a glass, the thickness of control liquid film after evaporation of the solvent It is 40~45 μm, it is each at 80 DEG C, 140 DEG C, 190 DEG C, 250 DEG C and 300 DEG C respectively under nitrogen protection in high temperature drying tunnel 0.5h removes solvent, and then cooled 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 flasks of snorkel, thermometer and mechanical agitator, in N2In atmosphere, first it is added BSBF（2.0169g、0.0040mol）And BIA（7.1765g、0.0320mol）, add NMP（260g）, wait for that diamines is completely molten 6FDA is successively added in Xie Hou（10.6618g、0.0240mol）And TTD（4.7320g、0.0120mol）, it reacts at 5 DEG C for 24 hours, Obtain corresponding polyamic acid solution.
2. 75g chlorobenzenes are added in the polyamic acid solution 1. obtained to step, at a reflux temperature lasting agitating and heating 36h Homogeneous polyimide solution is obtained afterwards；Then chlorobenzene is steamed completely, stops heating, it, will be anti-after its cooled to room temperature It answers liquid to pour into the methanol of high-speed stirred, obtains sediment；Gained sediment is successively fully washed through methanol and absolute methanol, Filtering, after spontaneously drying, continue at 120 DEG C of vacuum it is dry for 24 hours, obtain polyimide powder.
Using NMP as mobile phase, its number-average molecular weight is measured with gel permeation chromatograph（Mn）It is 56754, Weight-average molecular Amount（Mw）It is 145784.
3. at room temperature, 2. polyimide powder that step obtains is dissolved in NMP, be configured to solid content be 15% it is poly- Imide solution.
4. 3. polyimide solution coating that step is obtained is on a glass, the thickness of control liquid film after evaporation of the solvent It is 40~45 μm, it is each at 80 DEG C, 140 DEG C, 190 DEG C of C, 250 DEG C and 300 DEG C respectively under nitrogen protection in high temperature drying tunnel 0.5h removes solvent, and then cooled 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 flasks of snorkel, thermometer and mechanical agitator, in N2In atmosphere, first it is added SBF（3.4642g、0.0100mol）And BIA（3.3640g、0.0150mol）, add NMP（200g）, wait for that diamines is completely dissolved Afterwards, 6FDA is successively added（8.8848g、0.0200mol）And TTD（1.9717g、0.0050mol）, 12h is reacted at 18 DEG C, is obtained To corresponding polyamic acid solution.
2. 50g toluene is added in the polyamic acid solution 1. obtained to step, at a reflux temperature lasting agitating and heating 36h Homogeneous polyimide solution is obtained afterwards；Then toluene is steamed completely, stops heating, it, will be anti-after its cooled to room temperature It answers liquid to pour into the methanol of high-speed stirred, obtains sediment；Gained sediment is successively fully washed through methanol and absolute methanol, Filtering, after spontaneously drying, continue at 120 DEG C of vacuum it is dry for 24 hours, obtain polyimide powder.
Using NMP as mobile phase, its number-average molecular weight is measured with gel permeation chromatograph（Mn）It is 57682, Weight-average molecular Amount（Mw）It is 134678.
3. at room temperature, 2. polyimide powder that step obtains is dissolved in NMP, be configured to solid content be 15% it is poly- Imide solution.
4. 3. polyimide solution coating that step is obtained is on stainless steel, the thickness of control liquid film after evaporation of the solvent Degree is 60~70 μm, each at 80 DEG C, 140 DEG C, 190 DEG C, 250 DEG C and 300 DEG C respectively under nitrogen protection in high temperature drying tunnel 0.5h removes solvent, and then cooled 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 flasks of snorkel, thermometer and mechanical agitator, in N2In atmosphere, first add Enter CSBF（7.4896g、0.0200mol）And BIA（6.7280g、0.0300mol）, add NMP（500g）, wait for that diamines is complete After dissolving, 6FDA is successively added（16.8812g、0.0380mol）And TTD（4.7320g、0.0120mol）, reacted at 25 DEG C 15h obtains corresponding polyamic acid solution.
2. 125g dimethylbenzene is added in the polyamic acid solution 1. obtained to step, at a reflux temperature lasting agitating and heating Homogeneous polyimide solution is obtained after 18h；Then dimethylbenzene is steamed completely, stops heating, after its cooled to room temperature, Reaction solution is poured into the methanol of high-speed stirred, obtains sediment；Gained sediment is successively abundant through methanol and anhydrous ether Washing, filtering, after spontaneously drying, continue at 120 DEG C of vacuum it is dry for 24 hours, obtain polyimide powder.
Using NMP as mobile phase, its number-average molecular weight is measured with gel permeation chromatograph（Mn）It is 50998, Weight-average molecular Amount（Mw）It is 164530.
3. at room temperature, 2. polyimide powder that step obtains is dissolved in DMF, be configured to solid content be 14% it is poly- Imide solution.
4. 3. polyimide solution coating that step is obtained is on a glass, the thickness of control liquid film after evaporation of the solvent It is 5~10 μm, it is each at 80 DEG C, 140 DEG C, 190 DEG C, 250 DEG C and 300 DEG C respectively under nitrogen protection in high temperature drying tunnel 0.5h removes solvent, and then cooled to room temperature, is finally putting into demoulding in water, obtains polyimide gas separating film.
（Test case）
According to ISO15105-1 standards made from 1~embodiment of VAC-V2 pressure differential gas permeameter testing example 5 The permeability of polyimide gas separating film, the results are shown in Table 2.
In addition, using dynamic thermomechanical analysis apparatus（DMA）Glass transition temperature is tested in a nitrogen atmosphere（Heating rate For 20 DEG C/min）；Simultaneously according to JISC2318 standard testing mechanical performances；As a result 2 are still shown in Table.
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 preferably ventilative separating property.Glass transition simultaneously Temperature is also far above Matrimid 5218（323℃）With P84 resins（315℃）, while there is better heat resistance.

Claims (10)

1. a kind of polyimide gas separating film, it is made of equimolar dianhydride monomer with diamine monomer；It is characterized in that： The dianhydride monomer is made of 6FDA and TTD；The diamine monomer is made of a kind of diamine monomer containing spirane structure with BIA； The diamine monomer containing spirane structure is SBF either CSBF or BSBF；
The chemical name of the 6FDA is that 2,2'- is bis-（Bis- carboxy phenyls of 3,4-）Hexafluoropropane tetracid dianhydride；
The chemical name of the TTD is triptycene -2,3,6,7- tetracarboxylic acid dianhydrides；
The chemical name of the SBF is 9,9'- spiral shells two [9H- fluorenes] -2,2'- diamines；
The chemical name of the CSBF is 3,3'- dimethyl -9,9'- spiral shells two [9H- fluorenes] -2,2'- diamines；
The chemical name of the BSBF is 3,3'- bis- bromo- 9,9'- spiral shells two [9H- fluorenes] -2,2'- diamines；
The chemical name of the BIA is 6- amino -2-（3- aminobenzenes）Benzimidazole.
2. polyimide gas separating film according to claim 1, it is characterised in that：The 6FDA rubs with the TTD's You are than being 1: 1~4: 1.
3. polyimide gas separating film according to claim 1, it is characterised in that：The diamines list containing spirane structure The molar ratio of body and the BIA are 1: 1~1: 9.
4. polyimide gas separating film according to claim 2, it is characterised in that：The diamines list containing spirane structure The molar ratio of body and the BIA are 1: 1~1: 9.
5. the preparation method of the polyimide gas separating film described in one of Claims 1-4, has steps of：
1. first diamine monomer and BIA containing spirane structure are dissolved in aprotic polar solvent, be then successively added 6FDA and TTD is stirred to react 4~50h at a temperature of 0~50 DEG C, obtains polyamic acid solution；
2. 1. polyamic acid solution that step obtains is carried out hot-imide to handle to obtain polyimide powder；
3. 2. polyimide powder that step obtains is dissolved in aprotic polar solvent, it is 10~25% to be configured to solid content Polyimide solution；
4. polyimide gas separating film is made in 3. polyimide solution that step obtains.
6. the preparation method of polyimide gas separating film according to claim 5, it is characterised in that：Step 1. described in Aprotic polar solvent be -2 pyrrolidones of N- methyl or N, N'- dimethylformamide.
7. the preparation method of polyimide gas separating film according to claim 5, it is characterised in that：Step 2. described in Hot-imide processing the specific method is as follows：Water entrainer is added into the polyamic acid solution, 7~48h of return stirring is obtained To homogeneous polyimide solution；Then water entrainer is steamed completely, is stopped heating, after its cooled to room temperature, will be reacted Liquid pours into the methanol of high-speed stirred, obtains sediment；Gained sediment is successively fully washed through methanol and absolute methanol, mistake Filter, after spontaneously drying, continue at 120 DEG C of vacuum it is dry for 24 hours, obtain polyimide powder.
8. the preparation method of polyimide gas separating film according to claim 5, it is characterised in that：Step 3. described in Aprotic polar solvent be -2 pyrrolidones of N- methyl, N, N'- dimethylformamides, N, one in N'- dimethylacetylamides Kind or two kinds.
9. the preparation method of polyimide gas separating film according to claim 5, it is characterised in that：Step 4. specific Method is as follows：Gained polyimide solution is coated on substrate, the thickness of control liquid film after evaporation of the solvent is 5~70 μm, Solvent is removed in high temperature drying tunnel, then cooled to room temperature, demoulding is to get polyimide gas separating film.
10. the polyimide gas separating film described in one of Claims 1-4 is used for the separation and recycling of carbon dioxide, including Carbon dioxide in the separation of carbon dioxide and methane, the removing of carbon dioxide in natural and oil extraction in oil field in biogas Recycling.
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