Adsorbent for organic fluoro-compound comprising cyclodextrin-supported polymer

Patent metadata

Field	Value
Publication number	US-9308519-B2
Application number	US-201314646511-A
Country	US
Kind code	B2
Filing date	Nov 19, 2013
Priority date	Dec 7, 2012
Publication date	Apr 12, 2016
Grant date	Apr 12, 2016

Abstract

The present invention is to provide a material that is capable of selectively adsorbing organic fluoro-compounds such as perfluorooctane sulfonic acid, allows the adsorbed organic fluoro-compounds to be recovered, and is reusable as an adsorbent, specifically to provide a polymer in which cyclodextrin is supported on the surface of a water-insoluble polymer, and an adsorbent containing the same, and a method of use of the same as a selective adsorbent of, in particular, an organic fluoro-compound.

First claim

The invention claimed is:

1. An adsorbent for an organic fluoro-compound, wherein cyclodextrin is supported on the surface of a water-insoluble polymer,
wherein the water-insoluble polymer comprises polystyrene particles,
wherein the polystyrene particles and the cyclodextrin are chemically bonded via a divalent linking group —X— in which
X is N, O, S, O(CH 2 ) n O, with n being 1 to 6, or
X is O(CH 2 CH 2 O) n , with n being 2 to 6, and
the hyphen “-” is a single bond; and

wherein the organic fluoro-compound is selected from the group consisting of fluoroalkane carboxylic acids (R—COOH), fluoroalkane sulfonic acids (R—SO 3 H), fluoroalkyl alcohols (R—(CH 2 ) n OH, with n being 1 to 6, and a mixture thereof, in which R is selected from the group consisting of CF 3 (CF 2 ) n , with n 0 to 11; HCF 2 (CF 2 ) n with n being 0 to 11; CF 3 (CF 2 ) n O[CF(CF 3 )CF 2 O] m CF(CF 3 ), with n being 0 to 5 and m being 0 to 5; and (CF 3 ) 2 CF(CF 2 ) n , with n being 0 to 10.

2. The adsorbent of claim 1 , wherein X is N.

3. The adsorbent of claim 2 , wherein synthesis is carried out by reacting cyclodextrin having an amino group substituted for at least one hydroxyl groups is reacted with the polystyrene particles having a chloromethyl group.

4. The adsorbent of claim 1 , wherein the cyclodextrin is β-cyclodextrin.

5. A method for removal of an organic fluoro-compound, which comprises:
adsorbing the organic fluoro-compound with an adsorbent from an aqueous solution containing the organic fluoro-compound, wherein the adsorbent comprises cyclodextrin supported on the surface of a water-insoluble polymer,
wherein the water-insoluble polymer comprises polystyrene particles,
wherein the polystyrene particles and the cyclodextrin are chemically bonded via a divalent linking group —X— in which
X is N, O, S, O(CH 2 ) n O, with n being 1 to 6, or
X is O(CH 2 CH 2 O) n , with n being 2 to 6, and
the hyphen “-” is a single bond; and

wherein the organic fluoro-compound is selected from the group consisting of fluoroalkane carboxylic acids (R—COOH), fluoroalkane sulfonic acids (R—SO 3 H), fluoroalkyl alcohols (R—(CH 2 ) n OH, with n being 1 to 6, and a mixture thereof, in which R is selected from the group consisting of CF 3 (CF 2 ) n , with n being 0 to 11; HCF 2 (CF 2 ) n with n being 0 to 11; CF 3 (CF 2 ) n O[CF(CF 3 )CF 2 O] m CF(CF 3 ), with n being 0 to 5 and m being 0 to 5; and (CF 3 ) 2 CF(CF 2 ) n , with n being 0 to 10.

6. A method for recovery of an organic fluoro-compound, which comprises:
adsorbing the organic fluoro-compound with an adsorbent from an aqueous solution containing the organic fluoro-compound; and
washing the adsorbed organic fluoro-compound with an organic solvent,
wherein the adsorbent comprises cyclodextrin supported on the surface of a water-insoluble polymer,
wherein the water-insoluble polymer comprises polystyrene particles,
wherein the polystyrene particles and the cyclodextrin are chemically bonded via a divalent linking group —X— in which
X is N, O, S, O(CH 2 ) n O, with n being 1 to 6, or
X is O(CH 2 CH 2 O) n , with n being 2 to 6, and
the hyphen “-” is a single bond; and

wherein the organic fluoro-compound is selected from the group consisting of fluoroalkane carboxylic acids (R—COOH), fluoroalkane sulfonic acids (R—SO 3 H), fluoroalkyl alcohols (R—(CH 2 ) n OH, with n being 1 to 6, and a mixture thereof, in which R is selected from the group consisting of CF 3 (CF 2 ) n , with n being 0 to 11; HCF 2 (CF 2 ) n with n being 0 to 11; CF 3 (CF 2 ) n O[CF(CF 3 )CF 2 O] m CF(CF 3 ), with n being 0 to 5 and m being 0 to 5; and (CF 3 ) 2 CF(CF 2 ) n , with n being 0 to 10.

Assignees

• Daikin Ind Ltd
• Univ Osaka

Inventors

• Adachi Kenji
• Kuramitsu Masaki
• Akashi Mitsuru
• Kida Toshiyuki

Classifications

• B01J20/3475 Primary

  in the liquid phase · CPC title

• C02F2303/16

  Regeneration of sorbents, filters · CPC title

• B01J20/261

  obtained by reactions only involving carbon to carbon unsaturated bonds (macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds per se C08F) · CPC title

• B01J20/265 Primary

  modified or post-treated polymers (polymer carriers or substrates subjected to further impregnating or coating B01J20/3208) · CPC title

• C02F1/285

  using synthetic organic sorbents · CPC title