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CN-122011382-A - Composite resin and preparation method and application thereof, gas separation membrane and preparation method and application thereof

CN122011382ACN 122011382 ACN122011382 ACN 122011382ACN-122011382-A

Abstract

The invention relates to the field of high polymer materials, in particular to a composite resin, a preparation method and application thereof, a gas separation membrane, and a preparation method and application thereof. The composite resin comprises polyimide and zeolite molecular sieve with amino chemically bonded to the surface. The polyimide composite resin with the composition has high gas permeability coefficient, is not easy to plasticize, and relieves Trade-off effect to a certain extent. Is especially suitable for preparing gas separation membranes.

Inventors

  • ZHOU HUI
  • TAO RUOYUAN
  • YANG JIMING
  • Guo Jiacong
  • LI ZEQIU
  • TONG HUA

Assignees

  • 中石油(上海)新材料研究院有限公司
  • 中国石油天然气股份有限公司

Dates

Publication Date
20260512
Application Date
20241111

Claims (16)

  1. 1. A composite resin, characterized in that the composite resin comprises: polyimide having the following structure: Wherein 500≥m+n≥20, 0.5≥m/(m+n). Ltoreq.1, m, n are natural numbers, ar is dianhydride and is not a residue of 6FDA, B is a residue of diamine, the diamine comprises fluoroalkyl-substituted diamine, and the molar ratio of fluoroalkyl-substituted diamine in the diamine is not less than 50%, and Zeolite molecular sieve with amino groups chemically bonded to the surface.
  2. 2. The composite resin according to claim 1, wherein, In the structure, 300 is more than or equal to m+n is more than or equal to 20, 0.5 is less than or equal to m/(m+n) is less than or equal to 0.8, The dianhydride includes pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, 3', at least one of 4,4' -benzophenone tetracarboxylic dianhydride, 4' -terephthaloyl diphthalic anhydride, bisphenol A type diether dianhydride, 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, and 1,2,4, 5-cyclohexane tetracarboxylic dianhydride.
  3. 3. The composite resin according to claim 1 or 2, wherein, In the fluoroalkyl-substituted diamine, fluoroalkyl is a fluorinated C1-C5 alkyl, preferably a trifluoroC 1-C5 alkyl, more preferably a trifluoromethyl; the fluoroalkyl-substituted diamine comprises 2,2' -bis (trifluoromethyl) diaminobiphenyl and/or 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, and/or The diamine also contains other diamine, comprises p-phenylenediamine, m-phenylenediamine, benzidine, 4 '-diaminoanilide, 4' -diamino-2, 2 '-dimethyl-1, 1' -biphenyl, 4 '-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4 '-diaminodiphenyl methane, 4' -diaminodiphenyl ketone, and at least one of 4,4 '-diaminodiphenyl sulfone, 4' -bis (3-aminophenoxy) diphenyl sulfone, 1, 3-bis (4 '-aminophenoxy) benzene, 2' -bis [4- (4-aminophenoxy) phenyl ] propane, 1, 4-cyclohexanediamine, 1, 6-hexamethylenediamine, polyetheramine D-2000, preferably at least two.
  4. 4. A composite resin according to any one of claims 1 to 3, wherein the molar ratio of fluoroalkyl substituted diamine in the diamine is 60 to 100%.
  5. 5. The composite resin according to any one of claim 1 to 4, wherein, The distribution density of the amino groups on the surface of the zeolite molecular sieve on the surface of the molecular sieve is 0.001-0.02 mmol/g, preferably 0.01-0.02 mmol/g, and/or The zeolite molecular sieve has a main pore diameter of 0.3-1.0 nm, and/or The zeolite molecular sieve has a molecular sieve particle size of 0.5 to 2.0 um, and/or The specific surface area of the zeolite molecular sieve is 400-1000 m 2 /g.
  6. 6. The composite resin of any one of claims 1-5, wherein the zeolite molecular sieve comprises at least one of a type a zeolite, an X type zeolite, a Y type zeolite, a mordenite, a ZSM-5 zeolite, a ZSM-11 zeolite, a ZSM-8 zeolite, a ZSM-48 zeolite, a ZSM-35 zeolite, a beta molecular sieve, a 13X molecular sieve, a Silicalite-1 molecular sieve, a SSZ-23 zeolite.
  7. 7. The composite resin of any one of claims 1-6, wherein the zeolite molecular sieve is 0.5-5.0% by weight of the composite resin and the polyimide is 95-99.5% by weight of the composite resin.
  8. 8. The method for producing a composite resin according to any one of claims 1 to 7, characterized in that the method comprises the steps of: (1) The preparation of the polyamic acid solution comprises dispersing zeolite molecular sieve and diamine compound in solvent under inert atmosphere, adding dianhydride compound into the solution for polymerization reaction; (2) The heat treatment comprises the steps of removing part of solvent from the polyamic acid solution and then performing heat treatment in a nitrogen atmosphere.
  9. 9. The method according to claim 8, wherein, The polymerization reaction conditions include a temperature of 5-45 ℃ and/or a reaction time of 4-48 h; And/or The solid content of the polyamic acid solution is 10 to 25 weight percent; And/or The solvent is a strong polar solvent, preferably at least one of N, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and m-cresol.
  10. 10. The method of preparation according to claim 8 or 9, wherein the temperature of the heat treatment is 280-350 ℃.
  11. 11. The process according to any one of claims 8 to 10, wherein the zeolite molecular sieve is prepared by contacting a zeolite molecular sieve of the H + type with aminopropyl trimethoxysilane in the presence of a solvent and a catalyst, preferably, The contact conditions include reflux conditions, and reaction at 110-120 deg.C for 12-24 hr.
  12. 12. Use of a composite resin according to any one of claims 1 to 7 and/or a composite resin prepared by a method according to any one of claims 8 to 11 in the preparation of a gas separation membrane.
  13. 13. A gas separation membrane comprising the composite resin according to any one of claims 1 to 7 and/or the composite resin produced by the production method according to any one of claims 8 to 11.
  14. 14. The gas separation membrane of claim 13, wherein the gas separation membrane has a thickness of 10 to 30um.
  15. 15. A method for producing a gas separation membrane according to claim 13 or 14, characterized in that the method comprises the steps of: (1) The preparation of the polyamic acid solution comprises dispersing zeolite molecular sieve and diamine compound in solvent under nitrogen atmosphere, adding dianhydride compound into the solution for polymerization reaction; (2) Coating and film-forming, comprising the steps of coating the polyamic acid solution in the step (1) on a carrier, and removing the solvent until the solvent content is 15-25wt% to obtain a dry film; (3) The heat treatment comprises the step of heat treating the dry film in a nitrogen atmosphere.
  16. 16. Use of a gas separation membrane according to claim 13 in CH 4 /CO 2 mixed gas separation.

Description

Composite resin and preparation method and application thereof, gas separation membrane and preparation method and application thereof Technical Field The invention relates to the field of high polymer materials, in particular to a composite resin, a preparation method and application thereof, a gas separation membrane, and a preparation method and application thereof. Background Polyimide is a high-performance polymer which is formed by stacking linear molecular main chains containing imide rings, the molecular chain distance is generally 0.3-0.5nm, and the polyimide can be applied to the field of gas separation membranes according to the membrane material characteristics, wherein (1) the polyimide has high thermal stability and high glass transition temperature (Tg), is suitable for gas separation at a certain high temperature, simultaneously maintains high permeability and high selectivity, has good film forming property and high mechanical property, is convenient for manufacturing a membrane assembly, enables the membrane assembly to bear higher working pressure, has high chemical resistance and high tolerance to acid gas, can avoid damage to a membrane structure by impurity gas, influences the separation effect of the membrane, and (4) has easy regulation and control of the molecular chain, multiple structures, can design different membrane materials of a synthetic molecular chain aiming at different separation objects, and has high permeability and high selectivity. In the 80 s of the 20 th century, the company of the department of japan developed a biphenyl type polyimide hollow fiber gas membrane separator for separating H 2/N2、H2/CH4 first. The separation of the gas mixture and the purification of the gas are the essential steps when the gas product meets the application requirements. The membrane separation method does not need additional energy transmission such as refrigeration of the cryogenic method, gas pressurization of the pressure swing adsorption method and the like, does not need other raw materials consumed by the chemical reaction separation method, has low energy consumption and simple process, and is called a green technology. In 1979, monsanto developed a hollow fiber N 2/H2 separation membrane and successfully applied it to the recovery of hydrogen from ammonia synthesis off-gas, after which gas separation membranes were developed on a great scale. At present, the gas separation membrane has great application potential in the fields of hydrogen recovery, natural gas purification, carbon dioxide capture, gas separation and the like. The gas separation membranes currently used are mainly classified into the following ones. (1) an inorganic porous film. The porous membrane is divided into a macroporous membrane, a mesoporous membrane and a microporous membrane, and can comprise a zeolite membrane, a carbon molecular sieve membrane, a Metal Organic Framework (MOF) membrane and the like. In the separation process, the difference between the dynamic diameter of the gas and the pore diameter of the membrane determines the transmission mode of the gas in the membrane, when the pore diameter of the membrane is smaller than the average free path of the gas, gas molecules follow Knudsen diffusion in the membrane, the smaller the molecular mass is, the faster the diffusion speed is, when the gas molecules are adsorbed on the surface of the pore wall, the gas molecules are diffused through the membrane along the surface, the concentration gradient and the bonding strength with the surface determine the diffusion speed and the separation effect, when the condensable gas is adsorbed on the surface of the pore wall and fills the pore channel, the passage of non-condensable gas is limited, capillary condensation occurs, and when the pore diameter of the membrane is between the diameters of two gas components to be separated, the gas with smaller diameter can pass through the pore channel of the membrane, and the gas with larger diameter can be intercepted, so that molecular screening is realized. (2) an organic polymer film. The polymer films are classified into glassy polymer films and rubbery polymer films, and polymer materials such as Cellulose Acetate (CA), polysulfone (PSF) and Polyimide (PI) are used. The organic polymer film separates the gas mixture through a dissolution-diffusion-desorption mechanism, and the gas which is easy to dissolve in the organic matrix in the component to be separated is preferentially adsorbed on the surface of the film, then diffuses in the film under the action of concentration gradient and is desorbed at the downstream side. (3) mixing the matrix film (MMMs). MMMs is a gas separation membrane having both separation performance and mechanical stability, which is produced by adding an inorganic material as a dispersed phase to a polymer matrix. The inorganic material provides gas transport channels to reduce diffusion resistance, and increasing the chain spacing