Method for manufacturing gas separation membrane

Patent metadata

Field	Value
Publication number	US-10906009-B2
Application number	US-201716093877-A
Country	US
Kind code	B2
Filing date	Apr 17, 2017
Priority date	Apr 15, 2016
Publication date	Feb 2, 2021
Grant date	Feb 2, 2021

Abstract

A method for producing a gas separation membrane, including the following steps: step (a): treating the surfaces of silica nanoparticles dispersed in a first solvent with a reactive functional group-containing compound, while nanoparticles are being dispersed in the solvent, to thereby prepare a first solvent dispersion of reactive functional group-modified silica nanoparticles; step (b): replacing the first solvent dispersion's dispersion medium of reactive functional group-modified silica nanoparticles prepared in step (a) with a second solvent without drying of dispersion medium, and then reacting functional group-modified silica nanoparticles with dendrimer-forming monomer or hyperbranched polymer-forming monomer in the second solvent's presence so that dendrimer or hyperbranched polymer is added to reactive functional group, to thereby prepare dendrimer- or hyperbranched polymer-bound silica nanoparticles; step (c): mixing dendrimer- or hyperbranched polymer-bound silica nanoparticles prepared in step (b) with a matrix resin; and step (d): applying mixture prepared in step (c) to a substrate, and then removing the solvent.

First claim

The invention claimed is:

1. A method for producing a gas separation membrane, the method comprising:
treating surfaces of silica nanoparticles dispersed in a first solvent with a reactive functional group-containing compound, while the silica nanoparticles are being dispersed in the first solvent, to thereby prepare a first solvent dispersion including reactive functional group-modified silica nanoparticles, wherein the first solvent is at least one solvent selected from among water and C1 to C4 alcohols;
replacing the dispersion medium of the first solvent dispersion including the reactive functional group-modified silica nanoparticles with a second solvent without drying of the dispersion medium, and then reacting the reactive functional group-modified silica nanoparticles with a dendrimer-forming monomer or a hyperbranched polymer-forming monomer in the presence of the second solvent so that a dendrimer or a hyperbranched polymer is bound to the reactive functional group, to thereby prepare dendrimer-bound or hyperbranched polymer-bound silica nanoparticles;
mixing the dendrimer-bound or hyperbranched polymer-bound silica nanoparticles with a matrix resin to form a mixture; and
applying the mixture to a substrate, and then removing the second solvent.

2. The method for producing the gas separation membrane according to claim 1 , wherein the second solvent is at least one solvent selected from among tetrahydrofuran, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and γ-butyrolactone.

3. The method for producing the gas separation membrane according to claim 1 , wherein the reactive functional group-containing compound is a silane coupling agent.

4. The method for producing the gas separation membrane according to claim 1 , wherein the reactive functional group-containing compound is a compound represented by the following formula (1):

wherein
R 1 represents a methyl group or an ethyl group, and
R 2 represents a C1 to C5 alkylene group.

5. The method for producing the gas separation membrane according to claim 4 , wherein,
in the treating the surfaces of silica nanoparticles, the surfaces of silica nanoparticles are treated with the reactive functional group-containing compound represented by the formula (1) and then treated with another reactive functional group-containing compound, which is a compound represented by the following formula (2) or an acid anhydride thereof, while the silica nanoparticles are being dispersed in the first solvent, to thereby prepare the first solvent dispersion including reactive functional group-modified silica nanoparticles,
the formula (2) is:
[F2]
HOOC—R 3 —COOH  (2)

where R 3 represents a C1 to C20 alkylene group or an aromatic group.

6. The method for producing the gas separation membrane according to claim 1 , wherein
the reactive functional group-modified silica nanoparticles include amino group-modified silica nanoparticles,
the dendrimer-forming monomer includes a combination of a compound having three or more carboxyl groups and a compound having two or more amino groups, and
the reacting the reactive functional group-modified silica nanoparticles includes sequentially adding the compound having three or more carboxyl groups and the compound having two or more amino groups.

7. The method for producing the gas separation membrane according to claim 6 , wherein
the reactive functional group-modified silica nanoparticles include carboxyl group-modified silica nanoparticles,
the dendrimer-forming monomer includes a combination of a compound having three or more amino groups and a compound having two or more carboxyl groups, and
the reacting the reactive functional group-modified silica nanoparticles includes sequentially adding the compound having three or more amino groups and the compound having two or more carboxyl groups.

8. The method for producing the gas separation membrane according to claim 1 , wherein the hyperbranched polymer-forming monomer is a compound having one carboxyl group and two or more amino groups or halogen atoms.

9. The method for producing the gas separation membrane according to claim 1 , wherein the hyperbranched polymer-forming monomer is a compound having one amino group and two or more carboxyl groups or halogen atoms.

10. The method for producing the gas separation membrane according to claim 1 , wherein the matrix resin is at least one species selected from the group consisting of polyimide, polysulfone, polydimethylsiloxane, poly(substituted acetylene), poly-4-methylpentene, and natural rubber.

11. The method for producing the gas separation membrane according to claim 1 , wherein, in the mixing the dendrimer-bound or hyperbranched polymer-bound silica nanoparticles with the matrix resin to form the mixture, the dendrimer-bound or hyperbranched polymer-bound silica nanoparticles are present in the mixture in an amount of 1 mass % to 70 mass %.

12. The method for producing the gas separation membrane according to claim 1 , wherein, in the removing the second solvent, the second solvent is removed by heating.

13. The method for producing the gas separation membrane according to claim 1 , wherein, in the removing the second solvent, the solvent is removed under vacuum.

Assignees

• Nissan Chemical Corp
• Univ Tokyo Metropolitan

Inventors

• Kawakami Hiroyoshi
• Tanaka Manabu
• Kameyama Yuri
• Osawa Azusa
• Isaji Tadayuki
• Kikuchi Takamasa

Classifications

• B01D71/701

  Polydimethylsiloxane · CPC title

• B01D67/00793

  Dispersing a component, e.g. as particles or powder, in another component · CPC title

• B01D71/64

  Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors · CPC title

• B01D71/82

  characterised by the presence of specified groups, e.g. introduced by chemical after-treatment · CPC title

• B01D71/78

  Graft polymers · CPC title