CN102580580B - Polyimide gas separation membrane and preparation method thereof - Google Patents
Polyimide gas separation membrane and preparation method thereof Download PDFInfo
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- CN102580580B CN102580580B CN201210048356.3A CN201210048356A CN102580580B CN 102580580 B CN102580580 B CN 102580580B CN 201210048356 A CN201210048356 A CN 201210048356A CN 102580580 B CN102580580 B CN 102580580B
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- polyimide
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- gas separating
- polar solvent
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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
- 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
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a polyimide gas separation membrane and a preparation method thereof. The preparation method provided by the invention comprises the following steps that 1, one or more aromatic diamine compounds and one or more aromatic dianhydride compounds undergo a polymerization reaction in the presence of a polar solvent to produce a polyamide acid; and 2, the polyamide acid is subjected to membrane preparation and stripping so that a polyimide membrane is obtained; and the polyimide membrane is subjected to gamma ray radiation to form the polyimide gas separation membrane. The preparation method provided by the invention can realize preparation of the polyimide gas separation membrane which has performances of different gas separation by control of an irradiation degree under the condition of no change of a polyimide membrane, has the advantages of simple processes, convenient operation and good feasibility of industrialization, can be widely utilized for the separation of H2/CH4, CO2/CH4 and CO2/H2 of petroleum and natural gas, and has wide application prospects.
Description
Technical field
The present invention relates to a kind of polyimide gas separating film and preparation method thereof, belong to synthesis of polymer material technical field.
Background technology
In technical field of polymer materials, polyimide material is a kind of high-performance polymer material with imide ring architectural characteristic, there is good chemical stability, heat endurance and mechanical property, more and more be subject to people's attention, in the industries such as aerospace, electrician, microelectronics and chemical industry, be used widely.Wherein polyimide gas separating film is one of widely used material of polyimides.It is a kind of " green technology " that polyimides gas film separates, and due 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 unique advantage, its research and application development are very rapid.But polyimides has good separation selectivity conventionally, but most of polyimides chain rigidity is large, and gas permeability is poor.Therefore, how preparing one, to have permeance property good, and preparation technology is simple, and cost is low, is easy to industrialization, and polyimide gas separating film easy to utilize is the current problem that solves be badly in need of in the art.
Crosslinking with radiation technology, in brief, refers to the ionising radiation utilizing under high-energy ray (gamma-rays and electron beam etc.) effect, and the cross-linking reaction of bringing out is carried out the technology of modification to material.Can at room temperature carry out because radiotechnology has, the advantage such as technique is simple, and environmental pollution is little, makes it be subject to extensive concern as a kind of new technology of polymer modification.
It is reported, existing method of polyimide gas separating film being carried out to radiation modification, mainly in polyimides building-up process, first in its formula, add some functional compounds that are conducive to crosslinking with radiation as sensitising agent, ethylene glycol, dihydroxylic alcohols etc. synthesize, be then coated with film preparation polyimide gas separating film.But the method limitation is large, complicated process of preparation is difficult to suitability for industrialized production, is difficult to apply.
Summary of the invention
The object of this invention is to provide polyimide gas separating film of a kind of applicable suitability for industrialized production and preparation method thereof, a kind of polyimide gas separating film of applicable suitability for industrialized production is provided.
The preparation method of a kind of polyimide gas separating film provided by the present invention, comprises the steps:
(1) aromatic diamine compound and aromatic dianhydride compound carry out polymerisation and obtain polyamic acid in polar solvent;
(2) described polyamic acid obtains polyimide film after masking and demoulding step; Described polyimide film obtains described polyimide gas separating film through gamma Rays.
In above-mentioned preparation method, in step (1), described aromatic diamine compound specifically can be 2, two (3-amino-4-hydroxylphenyl) HFC-236fas (Bis-AP-AF) of 2-and/or two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas (BAHFP) of 2,2-; Described aromatic dianhydride compound specifically can be 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) and/or 4 '-hexafluoroisopropyli,ene-phthalic anhydride (6FDA).
In above-mentioned preparation method, in step (1), described polar solvent can be selected from 1-METHYLPYRROLIDONE, DMA, DMF, phenol, cresols and parachlorophenol any.
In above-mentioned preparation method, in step (1), the quality percentage composition that the gross mass of described aromatic diamine compound and aromatic dianhydride compound accounts for described polar solvent can be 5%～50%, specifically can be 15% or 27%; The molfraction ratio of described aromatic diamine compound and aromatic dianhydride compound can be 1: (0.8～1.3), specifically can be 1: 0.985,1: 1.005 or 1: 1.015.
In above-mentioned preparation method, in step (1), described polymerisation is carried out in inert atmosphere; The temperature of described polymerisation is-20 ℃～23 ℃, specifically can be-20 ℃ ,-10 ℃, 0 or 10 ℃, and the time is 1 hour～20 hours, specifically can be 2 hours, 6 hours, 10 hours or 20 hours.
In above-mentioned preparation method, in step (2), described masking and demoulding step are as follows: with described polar solvent, described polyamic acid being mixed with to quality percentage composition is 1%～15% solution; Then by described solution in glass plate top casting film forming, and the glass plate after film forming is placed in and fills nitrogen baking oven and carry out hot-imide, obtain described polyimide film through demoulding.
In above-mentioned preparation method, the temperature of described hot-imide can be 60 ℃～400 ℃, and the time can be 2 hours～and 48 hours.
In above-mentioned preparation method, in step (2), described gamma-rays is to be produced by radioactive substance; The dosage of described radiation can be 1kGy～400kGy, and as 20kGy, 50kGy or 100kGy, temperature can be 0 ℃～80 ℃, as 23 ℃ or 40 ℃; After the concrete steps of above-mentioned irradiation operations pack polyimides in the container of resistance to irradiation material, send in the radiation chamber of suspension type or pile formula irradiation devices and carry out irradiation.
In above-mentioned preparation method, described radioactive substance can be
60co.
The present invention also further provides the polyimide gas separating film of being prepared by said method.
Preparation method provided by the invention, under the constant condition of polyimide film, by controlling the degree of irradiation, can prepare the polyimide gas separating film of gas with various separating property, have technique simple, easy to operate, easily realize industrialized advantage; Polyimide gas separating film provided by the invention, can be widely used in H in oil, natural gas
2/ CH
4, CO
2/ CH
4, CO
2/ H
2separation, have a extensive future.
The specific embodiment
The experimental technique using in following embodiment if no special instructions, is conventional method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, polyimide gas separating film and application thereof
In the dry four-hole boiling flask that mechanical agitator, thermometer, nitrogen are housed derive pipe, add the N of 60mL, N-dimethylacetylamide, logical nitrogen protection, under strong mechanical agitation, add 2 of 21.98g (0.06mol), two (3-amino-4-hydroxylphenyl) HFC-236fas (Bis-AP-AF) of 2-, are stirred to completely and are cooled to-10～-5 ℃ after dissolving; Then, by 3 of 19.62g (1.015 × 0.06mol), 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) is dissolved in the N of 60mL, in N-dimethylacetylamide, after fully dissolving, slowly join again (in this system, the quality percentage composition that the gross mass of Bis-AP-AF and BTDA accounts for DMA is 27%) in above-mentioned four-hole boiling flask reactor, at-10 ℃, react 10h, obtain polyamic acid solution; It is 5% solution that the polyamic acid of synthesized is directly diluted to mass fraction with DMA, is then laid in equably on clean glass plate; Fill the heating rate of nitrogen baking oven with 1 ℃/min, 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 3h, 275 ℃ of constant temperature 1h successively; Glass plate with polyimide film after treatment hot-imide is cooled to room temperature, then poach demoulding, making thickness is 60 μ m polyimide films; Adopt
60co radiation source, utilizes
60the gamma-rays of Co radiation carries out radiation modification processing to polyimide film, and umber of exposures is for once, and dosage is 20kGy, and irradiation temperature is 23 ℃, can make polyimide gas separating film.
Polyimide gas separating film prepared by the present embodiment separates H
2/ CH
4the ideal separation factor of gas is 1085, separation of C O
2/ CH
4the ideal separation factor of gas is 158.
The preparation of embodiment 2, polyimide gas separating film and application thereof
The method of the present embodiment is identical with embodiment 1, and difference is: Bis-AP-AF is 1: 0.985 with the molfraction ratio of BTDA; The temperature of polymerisation is-20 ℃, and the reaction time is 20 hours; Gamma-ray dose of radiation is 50kGy, and radiation temperature is 40 ℃, makes polyimide gas separating film.
Polyimide gas separating film prepared by the present embodiment separates H
2/ CH
4the ideal separation factor of gas is 2287, separation of C O
2/ CH
4the ideal separation factor of gas is 282.
The preparation of embodiment 3, polyimide gas separating film and application thereof
In the dry four-hole boiling flask that mechanical agitator, thermometer, nitrogen are housed derive pipe, add the N of 60mL, dinethylformamide, logical nitrogen protection, under strong mechanical agitation, add 2 of 9.157g (25mmol), two (3-amino-4-hydroxylphenyl) HFC-236fas (Bis-AP-AF) of 2-, are stirred to completely and are cooled to-5 ℃ after dissolving; Then by 4 of 10.939g (24.625mmol), 4 '-hexafluoro isopropyl phthalic anhydride (6FDA) is dissolved in the N of 60mL, in dinethylformamide, after fully dissolving, slowly join again in above-mentioned four-hole boiling flask reactor (in this system, the gross mass of Bis-AP-AF and 6TDA accounts for N, the quality percentage composition of dinethylformamide is 15%), at 0 ℃, react 6h, obtain polyamic acid solution; Other prepares polyimide film and irradiation polyimide film is in the same manner as in Example 1.
Polyimide gas separating film prepared by the present embodiment separates H
2/ CH
4the ideal separation factor of gas is 652, separation of C O
2/ CH
4the ideal separation factor of gas is 216.
The preparation of embodiment 4, polyimide gas separating film and application thereof
The preparation method of the present embodiment is in the same manner as in Example 3, and difference is: Bis-AP-AF is 1: 1.005 with the molfraction ratio of 6TDA; The temperature of polymerisation is 10 ℃, and the reaction time is 2 hours; Gamma-ray dose of radiation is 100kGy, makes polyimide gas separating film.
Polyimide gas separating film prepared by the present embodiment separates H
2/ CH
4the ideal separation factor of gas is 814, separation of C O
2/ CH
4the ideal separation factor of gas is 241.
Claims (6)
1. a preparation method for polyimide gas separating film, comprises the steps:
(1) aromatic diamine compound and aromatic dianhydride compound carry out polymerisation and obtain polyamic acid in polar solvent;
(2) described polyamic acid obtains polyimide film after masking and demoulding step; Described polyimide film obtains described polyimide gas separating film through gamma Rays;
In step (1), described aromatic diamine compound is two (3-amino-4-hydroxylphenyl) HFC-236fas of 2,2-and/or two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas of 2,2-; Described aromatic dianhydride compound is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and/or 4 '-hexafluoroisopropyli,ene-phthalic anhydride;
In step (1), the quality percentage composition that the gross mass of described aromatic diamine compound and aromatic dianhydride compound accounts for described polar solvent is 5%～50%; The molfraction of described aromatic diamine compound and aromatic dianhydride compound is than being 1:(0.8～1.3);
In step (2), described gamma-rays is to be produced by radioactive substance; The dosage of described radiation is 1kGy～400kGy, and temperature is 0 ℃～80 ℃; Described radioactive substance is
60co.
2. method according to claim 1, is characterized in that: in step (1), described polar solvent is selected from 1-METHYLPYRROLIDONE, DMA, DMF, phenol, cresols and parachlorophenol any.
3. method according to claim 1, is characterized in that: in step (1), described polymerisation is carried out in inert atmosphere; The temperature of described polymerisation is-20 ℃～23 ℃, and the time is 1 hour～20 hours.
4. method according to claim 1, is characterized in that: in step (2), described masking and demoulding step are as follows: with described polar solvent, described polyamic acid being mixed with to quality percentage composition is 1%～15% solution; Then by described solution in glass plate top casting film forming, and the glass plate after film forming is placed in and fills nitrogen baking oven and carry out hot-imide, obtain described polyimide film through demoulding.
5. method according to claim 4, is characterized in that: the temperature of described hot-imide is 60 ℃～400 ℃, and the time is 2 hours～48 hours.
6. the polyimide gas separating film that in claim 1-5 prepared by arbitrary described method.
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| CN103285739B (en) * | 2013-05-16 | 2015-08-19 | 中国科学院过程工程研究所 | A kind of preparation method of hydrophobic porous diffusion barrier |
| CN106390780A (en) * | 2015-07-29 | 2017-02-15 | 北京市射线应用研究中心 | Modified polyimide hollow fiber gas separation membrane, modification method and applications thereof |
| CN105344258B (en) * | 2015-11-02 | 2017-12-19 | 吉林大学 | A kind of polyimides containing trifluoromethyl/carboxyl multi-walled carbon nanotube gas separation mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof |
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| CN1176975C (en) * | 2002-12-27 | 2004-11-24 | 中国科学院长春应用化学研究所 | Preparation of polyimide moulded by casting |
| CN101700474B (en) * | 2009-11-30 | 2012-05-30 | 北京市射线应用研究中心 | Polyimide gas separation membrane with high molecular weight and preparation method thereof |
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Address after: 401, building 201, yard a 10, Jiuxianqiao North Road, Chaoyang District, Beijing 100015 Patentee after: Beijing Ray Application Research Center Co.,Ltd. Address before: Room 502, gate a, building 201, No. 10, Jiuxianqiao North Road, Chaoyang District, Beijing 100015 Patentee before: BEIJING RADIATION APPLICATION RESEARCH CENTER |