CN101700474A - Polyimide gas separation membrane with high molecular weight and preparation method thereof - Google Patents
Polyimide gas separation membrane with high molecular weight and preparation method thereof Download PDFInfo
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- CN101700474A CN101700474A CN200910238789A CN200910238789A CN101700474A CN 101700474 A CN101700474 A CN 101700474A CN 200910238789 A CN200910238789 A CN 200910238789A CN 200910238789 A CN200910238789 A CN 200910238789A CN 101700474 A CN101700474 A CN 101700474A
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Abstract
The invention discloses a polyimide gas separation membrane with high molecular weight and a preparation method thereof, the polyimide gas separation membrane consists of aromatic diamine and aromatic dianhydride, a polar solvent is used for matching, and the polyimide gas separation membrane with the high molecular weight is prepared by the technological steps of preparing polyamic acid solution, preparing a polyimide membrane and stripping the polyimide membrane, thereby preparing the polyimide gas separation membrane with the high molecular weight. The polyimide gas separation membrane has the advantages of strong solubility, high molecular weight, good permeability, stable performances, good membrane-forming property, easy processing and molding, simple preparation technology, low cost and easy industrialization, and can be extensively applied in CO2/CH4 and CO2/H2 separation in petroleum and natural gas and be suitable for popularization.
Description
Affiliated technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of polyimide gas separation membrane with high molecular weight and preparation method.
Technical background
In technical field of polymer materials, polyimide material is a kind of high-performance polymer material with imide ring architectural characteristic, have excellent hear resistance, anti-irradiation, excellent mechanical performance and electric property etc., be widely used in technical fields such as Aeronautics and Astronautics, automobile, petrochemical industry.Wherein polyimide gas separating film is one of widely used material of polyimides.It is a kind of " green technology " that the polyimides gas film separates, and owing to advantages such as it have low energy consumption, environmental friendliness, process is simple, easy to operate, separation property is strong, with the competition of traditional isolation technics (absorption, absorption, cryogenic separation etc.) in demonstrate special advantages, its research and application development are very rapid.Yet, polyimides has good separation selectivity usually, but most of polyimides chain rigiditys are big, gas permeability is poor, while is owing to the rigidity of polyimide molecule chain itself, and intermolecular strong interaction, makes medium-sized polyimides until neither fusion of decomposition temperature, also do not dissolve, the result is difficult to process film forming.Improve dissolubility and machinability, and to keep its excellent properties be one of focus of research at present.Discover, the molecular weight that increases polyimide gas separating film can make performances such as its intensity and malleable be improved, though what use now is that molecular weight has reached 50000 polyimides, molecular weight greater than 50000 polyimide gas separating film will tool application prospect widely.Therefore, how to prepare a kind of resolvability that has, the molecular weight height, film forming and permeance property are good, and preparation technology is simple, and cost is low, is easy to industrialization, and polyimide gas separating film easy to utilize then is the current problem of being badly in need of solution in the art.
Summary of the invention
It is strong to the purpose of this invention is to provide a kind of dissolubility, the molecular weight height, and film forming and permeance property are good, preparation technology is simple, cost is low, be easy to industrialization polyimide gas separation membrane with high molecular weight easy to utilize and preparation method.
In order to achieve the above object, the present invention is by the following technical solutions: a kind of polyimide gas separation membrane with high molecular weight, be characterized in: by aromatic diamines and aromatic dianhydride example 1: 1.0-1 in molar ratio: 1.3, be dissolved in the polar solvent, forming mass concentration is the solution of 1%-40%, at first the prepared in reaction polyamic acid solution is made polyimide gas separation membrane with high molecular weight again behind system film and demoulding.
Above-mentioned described polyimide gas separation membrane with high molecular weight has weight average molecular weight and is higher than 80000.
Above-mentioned described aromatic diamines comprises: 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fas (Bis-AP-AF), 3 of 2-, 3 '-dimethyl-4,4 '-diphenylmethane diamine (DMMDA), 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas (BAHFP), 4 of 2-, 4 '-diaminodiphenyl ether (ODA) etc.
Above-mentioned described aromatic dianhydride comprises: 3,3 ', 4, and 4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride (HQDPA), 4,4 '-hexafluoroisopropyli,ene-phthalic anhydride (6FDA), 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride (ODPA), 3,3 ', 4,4 '-BPDA (BPDA), 1,2 ', 4,5 '-pyromellitic dianhydride (PMDA), 3,3 ', 4,4 '-diphenyl sulphone (DPS) tetracarboxylic dianhydride (DSDA) etc.
Above-mentioned described polar solvent comprises: N-methyl pyrrolidone, N, N-dimethylacetylamide, N, dinethylformamide, phenol, cresols, parachlorophenol, 1,2,4-trichloro-benzene, o-dichlorohenzene, DAA and oxolane and carbinol mixture etc.
The preparation method of above-mentioned described polyimide gas separation membrane with high molecular weight comprises following processing step:
A. prepare polyamic acid solution
Under nitrogen or argon shield, described aromatic diamine monomers under agitation is dissolved in the described polar solvent, after dissolving finishes, under-20 ℃-23 ℃, add described aromatic dianhydride again, be reflected at lasting 2-24h under the continuous stirring, obtain polyamic acid solution;
B. prepare polyimide film
The hot-imide film forming, after will going up polyamic acid solution and being diluted to mass fraction and being 1-15%,, and the film forming glass plate placed fill the nitrogen baking oven and carry out hot-imide in glass plate top casting film forming, the hot-imide temperature is 60 ℃-400 ℃, and the time of hot-imide is 2h-48h;
Chemistry imidizate film forming, adding dehydrating agent and catalyst carry out chemical imidizate in above-mentioned polyamic acid solution, react 12-48h down at-20 ℃-23 ℃, after after reaction finishes it being diluted to mass fraction and being 1-15%, in glass plate top casting film forming, and the film forming glass plate placed fill the nitrogen baking oven, under 100 ℃ of-400 ℃ of temperature, the dry 4-48h that handles;
C. polyimide film demoulding
The glass plate that will have polyimide film is cooled to room temperature, carries out the poach demoulding then, and the film of taking off from glass plate becomes the polyimide gas separation membrane with high molecular weight that thickness is 20-100 μ m.
The above-mentioned described aromatic dianhydride that adds again is the aromatic dianhydride monomer or is dissolved in aromatic dianhydride solution in the described polar solvent.
Above-mentioned described dehydrating agent comprises: acetic anhydride, propionic andydride, valeric anhydride etc., consumption are 0.1-6 times of diamine monomer molal quantity; Described catalyst comprises: pyridine, triethylamine, isoquinolin etc., consumption are 0.1-8 times of diamine monomer molal quantity.
Because having adopted above-mentioned aromatic diamines, aromatic dianhydride is that raw material at first prepares polyamic acid, adopt hot-imide film forming or chemical imidizate film forming principle to prepare the process of polyimide gas separating film then, it is strong to make that the present invention has dissolubility, the molecular weight height, good penetrability, stable performance, film forming is good, and machine-shaping is easy, preparation technology is simple, cost is low, is easy to industrialization, can be widely used in CO in oil, the natural gas
2/ CH
4, CO
2/ H
2Separation, reached the purpose of invention.
The specific embodiment:
Below in conjunction with specific embodiment the present invention is described in further detail:
Embodiment 1:
The N that in mechanical agitator, thermometer, nitrogen are housed derive the dry four-hole boiling flask of pipe, adds 60mL, the N-dimethylacetylamide, logical nitrogen protection, under strong mechanical agitation, add 2 of 21.98g (0.06mol), two (the 3-amino-4-hydroxy phenyl) HFC-236fas (Bis-AP-AF) of 2-are stirred to fully and are cooled to after the dissolving-5-0 ℃; Then, with 19.62g (1.015 * 0.06mol) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) is dissolved in the N of 60mL, in the N-dimethylacetylamide, fully slowly join again in the above-mentioned four-hole boiling flask reactor after the dissolving ,-5-0 ℃ following reaction 2-6h, obtain polyamic acid solution; With the polyamic acid that is synthesized N, the N-dimethylacetylamide directly is diluted to the solution that mass fraction is 5-10%, is tiled in equably then on the clean glass plate; Filling the heating rate of nitrogen baking oven, carrying out hot-imide at 60 ℃ of constant temperature 8h, 120 ℃ of constant temperature 1h, 150 ℃ of constant temperature 1h, 200 ℃ of constant temperature 2h, 250 ℃ of constant temperature 1-3h, 275 ℃ of constant temperature 1-3h successively with 1 ℃/min; The glass plate that has polyimide film after hot-imide handled is cooled to room temperature, poach demoulding then, and promptly making thickness is that 60 μ m weight average molecular weight are 110600 polyimide gas separation membrane with high molecular weight.
Embodiment 2:
Present embodiment and specific embodiment 1 are different is that the reaction temperature of synthesizing polyamides acid is 0-5 ℃.Other is identical with specific embodiment 1; Finally making thickness is that 43 μ m weight average molecular weight are 109800 polyimide gas separation membrane with high molecular weight.
Embodiment 3:
That present embodiment and specific embodiment 1 are different is the N that adds 50mL in four-hole boiling flask, N-dimethylacetylamide and with 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) is dissolved in the N of 50mL, in the N-dimethylacetylamide.Other is identical with specific embodiment 1; Finally making thickness is that 57 μ m weight average molecular weight are 98300 polyimide gas separation membrane with high molecular weight.
Embodiment 4:
The N that in mechanical agitator, thermometer, argon gas are housed derive the dry four-hole boiling flask of pipe, adds 150mL, the N-dimethylacetylamide, logical argon shield, under strong mechanical agitation, add 2 of 21.98g (0.06mol), two (the 3-amino-4-hydroxy phenyl) HFC-236fas (Bis-AP-AF) of 2-are stirred to fully and are cooled to 0-5 ℃ after the dissolving; Then with 19.62g (1.015 * 0.06mol) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) slowly joins in the above-mentioned four-hole boiling flask reactor, at 0-5 ℃ of following reaction 3-8h, obtains polyamic acid solution; Add 10.21g (0.10mol) acetic anhydride more respectively and 2.37g (0.03mol) pyridine carries out chemical imidizate, obtain polyimide solution behind the reaction 12-24h under the room temperature, with prepared polyimide solution N, the N-dimethylacetylamide directly is diluted to the solution that mass fraction is 5-10%, is tiled in equably then on the clean glass plate; With the heating rate of 1 ℃/min, successively at 140-150 ℃ of following constant temperature 4-6h, 270-280 ℃ of following constant temperature 12-24h carries out drying to be handled in filling the nitrogen baking oven; The glass plate that has polyimide film after drying handled is cooled to room temperature, poach demoulding then, and promptly making thickness is that 45 μ m weight average molecular weight are 101300 polyimide gas separation membrane with high molecular weight.
Embodiment 5:
What present embodiment and specific embodiment 4 were different is logical nitrogen protection.Other is identical with specific embodiment 1; Finally making thickness is that 38 μ m weight average molecular weight are 100200 polyimide gas separation membrane with high molecular weight.
Embodiment 6:
The N-methyl pyrrolidone that in mechanical agitator, thermometer, nitrogen are housed derive the dry four-hole boiling flask of pipe, adds 50mL, logical nitrogen protection, under strong mechanical agitation, add 3 of 11.30g (0.05mol), 3 '-dimethyl-4,4 '-diphenylmethane diamine (DMMDA) is stirred to fully and is cooled to 0-5 ℃ after the dissolving; Then, with 20.40g (1.015 * 0.05mol) 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride (HQDPA) is dissolved in the N-methyl pyrrolidone of 50mL, fully slowly joins in the above-mentioned four-hole boiling flask reactor after the dissolving again, react 12-18h down at 0-5 ℃, obtain polyamic acid solution; Add 25.5g (0.25mol) acetic anhydride more respectively and 23.3g (0.23mol) triethylamine carries out chemical imidizate, obtain polyimide solution behind the reaction 12-36h under the room temperature, it is 10% solution that prepared polyimide solution directly is diluted to mass fraction with the N-methyl pyrrolidone, is tiled in equably then on the clean glass plate; With the heating rate of 1 ℃/min, successively at 120-150 ℃ of following constant temperature 4-8h, 250-400 ℃ of following constant temperature 1-24h carries out drying to be handled in filling the nitrogen baking oven; The glass plate that has polyimide film after drying handled is cooled to room temperature, poach demoulding then, and promptly making thickness is that 62 μ m weight average molecular weight are 91500 polyimide gas separation membrane with high molecular weight.
Claims (7)
1. polyimide gas separation membrane with high molecular weight, it is characterized in that: by aromatic diamines and aromatic dianhydride example 1: 1.0-1 in molar ratio: 1.3, be dissolved in the polar solvent, forming mass concentration is the solution of 1%-40%, at first the prepared in reaction polyamic acid solution is made weight average molecular weight again and is higher than 80000 polyimide gas separation membrane with high molecular weight behind system film and demoulding.
2. according to the described polyimide gas separating film of claim 1, it is characterized in that: described aromatic diamines comprises: 2, two [the 3 amino-4-hydroxy phenyl] fluoro-propanes, 3 of 2-, 3 '-dimethyl-4,4 '-diphenylmethane diamine, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas, 4 of 2-, 4 '-diaminodiphenyl ether.
3. according to the described polyimide gas separating film of claim 1, it is characterized in that: described aromatic dianhydride comprises: 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-triphen diether tetracarboxylic dianhydride, 4,4 '-hexafluoroisopropyli,ene-phthalic anhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA, 1,2 ', 4,5 '-pyromellitic dianhydride, 3,3 ', 4,4 '-diphenyl sulphone (DPS) tetracarboxylic dianhydride.
4. according to the described polyimide gas separating film of claim 1, it is characterized in that: described polar solvent comprises: N-methyl pyrrolidone, N, N-dimethylacetylamide, N, dinethylformamide, phenol, cresols, parachlorophenol, 1,2,4-trichloro-benzene, o-dichlorohenzene, DAA and oxolane and carbinol mixture.
5. according to the preparation method of the described polyimide gas separating film of claim 1, its processing step is as follows:
A. prepare polyamic acid solution
Under nitrogen or argon shield, described aromatic diamine monomers under agitation is dissolved in the described polar solvent, after dissolving finishes, under-20 ℃-23 ℃, add described aromatic dianhydride again, be reflected at lasting 2-24h under the continuous stirring, obtain polyamic acid solution;
B. prepare polyimide film
The hot-imide film forming, after will going up polyamic acid solution and being diluted to mass fraction and being 1-15%,, and the film forming glass plate placed fill the nitrogen baking oven and carry out hot-imide in glass plate top casting film forming, the hot-imide temperature is 60 ℃-400 ℃, and the time of hot-imide is 2h-48h;
Chemistry imidizate film forming, adding dehydrating agent and catalyst carry out chemical imidizate in above-mentioned polyamic acid solution, react 12-48h down at-20 ℃-23 ℃, after after reaction finishes it being diluted to mass fraction and being 1-15%, in glass plate top casting film forming, and the film forming glass plate placed fill the nitrogen baking oven, under 100 ℃ of-400 ℃ of temperature, the dry 4-48h that handles;
C. polyimide film demoulding
The glass plate that will have polyimide film is cooled to room temperature, carries out the poach demoulding then, and the film of taking off from glass plate becomes the polyimide gas separation membrane with high molecular weight that thickness is 20-100 μ m.
6. according to the preparation method of the described polyimide gas separating film of claim 5, it is characterized in that: the described aromatic dianhydride that adds again is the aromatic dianhydride monomer or is dissolved in aromatic dianhydride solution in the described polar solvent.
7. according to the preparation method of the described polyimide gas separating film of claim 5, it is characterized in that: above-mentioned described dehydrating agent comprises: acetic anhydride, propionic andydride, valeric anhydride etc., consumption are 0.1-6 times of diamine monomer molal quantity; Described catalyst comprises: pyridine, triethylamine, isoquinolin etc., consumption are 0.1-8 times of diamine monomer molal quantity.
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