Monolithic organic porous body, monolithic organic porous ion exchanger, and process for producing the monolithic organic porous body and the monolithic organic porous ion exchanger

Patent metadata

Field	Value
Publication number	US-9346895-B2
Application number	US-200813140650-A
Country	US
Kind code	B2
Filing date	Dec 18, 2008
Priority date	Dec 18, 2008
Publication date	May 24, 2016
Grant date	May 24, 2016

Abstract

A monolithic organic porous body includes a continuous macropore structure that includes cellular macropores that overlap to form openings having an average diameter of 20 to 200 μm, the monolithic organic porous body having a thickness of 1 mm or more and a total pore volume of 0.5 to 5 ml/g, an area of a skeleton observed within an SEM image of a section of the continuous macropore structure (in a dry state) being 25 to 50%. A monolithic ion exchanger is produced by introducing an ion-exchange group into the monolithic organic porous body. The monolithic organic porous body and the monolithic ion exchanger are chemically stable, have high mechanical strength, and ensure a low pressure loss when fluid passes through. The monolithic organic porous body and the monolithic ion exchanger may be used as an adsorbent having a large adsorption capacity or an ion exchanger having a large ion-exchange capacity.

First claim

The invention claimed is:

1. A monolithic organic porous body comprising:
a monolithic organic porous intermediate body which comprises a skeleton comprising a first polymer material, and which has a continuous macropore structure comprising cellular macropores that overlap to form openings having an average diameter of 20 to 200 μm, and
a second polymer material which adheres to portions of a surface of the skeleton throughout the monolithic organic porous intermediate body, so as to thicken the skeleton throughout the monolithic organic porous intermediate body,
wherein the monolithic organic porous body has a thickness of 1 mm or more and a total pore volume of 0.5 to 5 ml/g, and
wherein in an SEM image of a cross-section of the continuous macropore structure in a dry state, a cross-sectional area of a skeleton is 25 to 50% of a total area of the SEM image,
the monolithic organic porous body being produced by performing:
a first step comprising stirring a mixture of an oil-soluble monomer that does not include an ion-exchange group, a surfactant, and water to prepare a water-in-oil emulsion, and polymerizing the water-in-oil emulsion, so as to obtain the monolithic organic porous intermediate body that has a total pore volume of 5 to 16 ml/g,
a second step comprising mixing a vinyl monomer, a crosslinking agent that includes at least two vinyl groups in one molecule, an organic solvent that dissolves the vinyl monomer and the crosslinking agent, but does not dissolve a polymer produced by polymerizing the vinyl monomer, and an initiator, and
a third step comprising polymerizing the mixture obtained by the second step in a stationary state in a presence of the monolithic organic porous intermediate body,
so as to obtain the monolithic organic porous body having a skeleton thicker than the skeleton of the monolithic organic porous intermediate body.

2. A monolithic organic porous body comprising:
a monolithic organic porous intermediate body which comprises a skeleton comprising a first polymer material, and
a second polymer material which adheres to portions of a surface of the skeleton throughout the monolithic organic porous intermediate body, so as to thicken the skeleton throughout the monolithic organic porous intermediate body,
wherein the first polymer material comprises oil-soluble monomers that do not include an ion exchange group, the oil-soluble monomers being polymerized in a water-in-oil emulsion with a surfactant and water,
wherein the second polymer material comprises a vinyl monomer and a crosslinking agent that includes at least two vinyl groups in one molecule,
wherein the monolithic organic porous intermediate body has a continuous macropore structure comprising cellular macropores that overlap to form openings having an average diameter of 20 to 200 μm,
wherein the monolithic organic porous intermediate body has a total pore volume of 5 to 16 ml/g, and
wherein the monolithic organic porous body has a thickness of 1 mm or more and a total pore volume of 0.5 to 5 ml/g,
the monolithic organic porous body being produced by performing:
a first step comprising stirring a mixture of the oil-soluble monomers, the surfactant, and the water to prepare the water-in-oil emulsion, and polymerizing the water-in-oil emulsion, so as to obtain the monolithic organic porous intermediate body,
a second step comprising mixing the vinyl monomer, the crosslinking agent, an organic solvent that dissolves the vinyl monomer and the crosslinking agent, but does not dissolve a polymer produced by polymerizing the vinyl monomer, and an initiator, and
a third step comprising polymerizing the mixture obtained by the second step in a stationary state in a presence of the monolithic organic porous intermediate body,
so as to obtain the monolithic organic porous body having a skeleton thicker than the skeleton of the monolithic organic porous intermediate body.

3. A monolithic organic porous ion exchanger comprising a continuous macropore structure, the continuous macropore structure including cellular macropores that overlap to form openings having an average diameter of 30 to 300 μm in water-wet conditions, the monolithic organic porous ion exchanger having a thickness of 1 mm or more, a total pore volume of 0.5 to 5 ml/g, and an ion-exchange capacity per unit volume of 0.4 mg equivalent/ml or more when in water-wet conditions, ion-exchange groups being uniformly distributed in the monolithic organic porous ion exchanger, and an area of a skeleton observed within an SEM image of a section of the continuous macropore structure (in a dry state) being 25 to 50%,
the monolithic organic porous ion exchanger being produced by performing:
a first step comprising stirring a mixture of an oil-soluble monomer that does not include an ion-exchange group, a surfactant, and water to prepare a water-in-oil emulsion, and polymerizing the water-in-oil emulsion, so as to obtain a monolithic organic porous intermediate body that has a total pore volume of 5 to 16 ml/g,
a second step comprising mixing a vinyl monomer, a crosslinking agent that includes at least two vinyl groups in one molecule, an organic solvent that dissolves the vinyl monomer and the crosslinking agent, but does not dissolve a polymer produced by polymerizing the vinyl monomer, and an initiator,
a third step comprising polymerizing the mixture obtained by the second step in a stationary state in a presence of the monolithic organic porous intermediate body, so as to obtain a monolithic organic porous body having a skeleton thicker than the skeleton of the monolithic organic porous intermediate body, and
a fourth step comprising introducing an ion-exchange group into the monolithic organic porous body.

4. A monolithic organic porous ion exchanger comprising the monolithic organic porous body according to claim 2 , and ion-exchange groups introduced into the monolithic organic porous body, the monolithic organic porous ion exchanger having an ion-exchange capacity per unit volume of 0.4 mg equivalent/ml or more in water-wet conditions, the ion-exchange groups being uniformly distributed in the monolithic organic porous ion exchanger.

5. A method of producing a monolithic organic porous body comprising a step I that includes stirring a mixture of an oil-soluble monomer that does not include an ion-exchange group, a surfactant, and water to prepare a water-in-oil emulsion, and polymerizing the water-in-oil emulsion to obtain a monolithic organic porous intermediate body that has a continuous macropore structure and has a total pore volume of 5 to 16 ml/g, a step II that includes mixing a vinyl monomer, a crosslinking agent that includes at least two vinyl groups in one molecule, an organic solvent that dissolves the vinyl monomer and the crosslinking agent, but does not dissolve a polymer produced by polymerizing the vinyl monomer, and an initiator, and a step III that includes polymerizing the mixture obtained by the step II in a stationary state in the presence of the monolithic organic porous intermediate body obtained by the step I to obtain a monolithic organic porous body having a skeleton thicker than that of the monolithic organic porous intermediate body.

6. The method according to claim 5 , wherein the monolithic organic porous intermediate body obtained by the step I includes a continuous macropore structure that includes cellular macropores that overlap to form openings having an average diameter of 20 to 200 μm, and has a total pore volume of 5 to 16 ml/g.

7. A method of producing a monolithic organic porous ion exchanger comprising a step I that includes stirring a mixture of an oil-soluble monomer that does not include an ion-exchange group, a surfactant, and water to prepare a water-in-oil emulsion, and pol

Assignees

• Inoue Hiroshi
• Nakamura Akira
• Takada Hitoshi
• Kondo Satoru
• Organo Corp

Inventors

• Inoue Hiroshi
• Nakamura Akira
• Takada Hitoshi
• Kondo Satoru

Classifications

• C08J9/28

  by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum · CPC title

• B01J47/00

  Ion-exchange processes in general; Apparatus therefor (ion-exchange chromatography processes or apparatus B01D15/08) · CPC title

• C08J2325/08

  Copolymers of styrene (C08J2329/08, C08J2335/06, C08J2355/02 take precedence) · CPC title

• C02F1/42

  by ion-exchange (ion-exchange in general B01J) · CPC title

• B01J41/20

  Anion exchangers for chromatographic processes · CPC title