Polymeric sorbents for aldehydes

Patent metadata

Field	Value
Publication number	US-10654026-B1
Application number	US-201816619347-A
Country	US
Kind code	B1
Filing date	Jun 13, 2018
Priority date	Jun 16, 2017
Publication date	May 19, 2020
Grant date	May 19, 2020

Abstract

Polymeric sorbents for aldehydes including formaldehyde are provided. More particularly, the polymeric sorbents are a reaction product of a hydrolyzed divinylbenzene/maleic anhydride polymeric material having carboxylic acid groups with a nitrogen-containing compound having at least two primary amino groups and/or secondary amino groups. The nitrogen-containing compound is ionically attached to the hydrolyzed divinylbenzene/maleic anhydride within the polymeric sorbent and has at least one primary amino and/or secondary amino group available for reacting with an aldehyde. Additionally, methods of making the polymeric sorbents, methods of sorbing aldehydes (i.e., aldehydes that are volatile under use conditions) on the polymeric sorbents, compositions resulting from the sorption of aldehydes on the polymeric sorbents, composite granules containing the polymeric sorbents, methods of making the composite granules, and methods of sorbing aldehydes on the composite granules are provided.

First claim

What is claimed is:

1. A composition comprising:
(a) a polymeric sorbent comprising a reaction product of
a hydrolyzed divinylbenzene/maleic anhydride polymeric material having carboxylic acid groups; and
a nitrogen-containing compound having at least two amino groups of formula —NHR wherein R is hydrogen or alkyl and wherein the nitrogen-containing compound is attached to the hydrolyzed divinylbenzene/maleic anhydride polymeric material with an ionic bond; and

(b) an aldehyde sorbed on the polymeric sorbent, the aldehyde being of Formula (I)
R 2 —(CO)—H  (I)

wherein R 2 is hydrogen, alkyl, vinyl, or aryl and wherein the molecular weight of the aldehyde of Formula (I) is no greater than 200 grams/mole.

2. The composition of claim 1 , wherein the hydrolyzed divinylbenzene/maleic anhydride polymeric material is a hydrolyzed product of a divinylbenzene/maleic anhydride precursor material, the divinylbenzene/maleic anhydride precursor material being formed from a polymerizable composition comprising
1) 8 to 65 weight percent maleic anhydride based on the total weight of monomers in the polymerizable composition;
2) 30 to 85 weight percent divinylbenzene based on the total weight of monomers in the polymerizable composition; and
3) 0 to 40 weight percent of a styrene-type monomer based on the total weight of monomers in the polymerizable composition, wherein the styrene-type monomer is styrene, an alkyl-substituted styrene, or a combination thereof.

3. The composition of claim 2 , wherein the polymerizable composition comprises 15 to 65 weight percent maleic anhydride, 30 to 85 weight percent divinylbenzene, and 0 to 40 weight percent styrene-type monomer.

4. The composition of claim 2 , wherein the polymerizable composition comprises 25 to 65 weight percent maleic anhydride, 30 to 75 weight percent divinylbenzene, and 1 to 20 weight percent styrene-type monomer.

5. The composition of claim 1 , wherein the nitrogen-containing compound is of Formula (V)
R 4 NHR 1   (V)

wherein
R 1 is hydrogen or an alkyl;
R 4 is a group of formula —R 5 —NHR 6 , or —(C═NH)—NH 2 ;
R 5 is an alkylene, (hetero)arylene, (hetero)aralkylene, heteroalkylene having one or more oxy (—O—) groups, or heteroalkylene having one or more —NH— groups, wherein the (hetero)arylene and (hetero)aralkylene are optionally substituted with a primary amino group and/or a secondary amino group; and

R 6 is hydrogen, alkyl, or —(C═NH)—NH 2 .

6. The composition of claim 1 , wherein the nitrogen-containing compound is of Formula (VI)
R 7 —(NHR 1 ) z   (VI)

wherein
R 1 is hydrogen or alkyl;
R 7 is a z-valent radical of an alkane or a z-valent radical of a heteroalkane; and
z is an integer in a range of 3 to 10.

7. The composition of claim 1 , wherein the nitrogen-containing compound has a molecular weight no greater than 2000 Daltons.

8. The composition of claim 1 , wherein the polymeric sorbent further comprises an acid-base dye.

9. The composition of claim 1 , wherein the polymeric sorbent is in a composite granule that comprises the polymeric sorbent and a binder.

10. A method of sorbing an aldehyde on a polymeric sorbent, the method comprising:
providing a polymeric sorbent comprising a reaction product of
a) a hydrolyzed divinylbenzene/maleic anhydride polymeric material having carboxylic acid groups; and
b) a nitrogen-containing compound having at least two amino groups of formula —NHR wherein R is hydrogen or alkyl and wherein the nitrogen-containing compound is attached to the hydrolyzed divinylbenzene/maleic anhydride polymeric material with an ionic bond;
sorbing the aldehyde on the polymeric sorbent, the aldehyde being of Formula (I)
R 2 —(CO)—H  (I)

wherein R 2 is hydrogen, alkyl, vinyl, or aryl and wherein the molecular weight of the aldehyde of Formula (I) is no greater than 200 grams/mole.

11. The method of claim 10 , wherein R 2 is hydrogen or methyl.

12. The method of claim 10 , wherein the polymeric sorbent sorbs an amount of aldehyde in a range of 0.5 to 15 millimoles per gram based on a weight of the polymeric sorbent.

13. The method of claim 10 , wherein the polymeric sorbent comprises an acid-base dye and wherein the acid-base dye changes color when the aldehyde sorption capacity of the polymeric sorbent is reached or is close to being reached.

14. The method of claim 10 , wherein the polymeric sorbent is in a composite granule that comprises the polymeric sorbent and a binder.

Assignees

• 3M Innovative Properties Co

Inventors

• Wendland Michael S
• Kobe Michael W

Classifications

• B01J20/265 Primary

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

• B01D53/02

  by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)} · CPC title

• B01J20/28069

  Pore volume, e.g. total pore volume, mesopore volume, micropore volume · CPC title

• B01J20/264 Primary

  derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers · CPC title

• B01D2257/70

  Organic compounds not provided for in groups B01D2257/00 - B01D2257/602 · CPC title