Polymeric materials for capturing formaldehyde

Patent metadata

Field	Value
Publication number	US-10391471-B2
Application number	US-201515520163-A
Country	US
Kind code	B2
Filing date	Nov 10, 2015
Priority date	Nov 17, 2014
Publication date	Aug 27, 2019
Grant date	Aug 27, 2019

Abstract

Sorbent polymeric material suitable for capturing formaldehyde, polymeric material resulting from the capture of formaldehyde by the sorbent polymeric material, and methods for capturing formaldehyde are provided. The sorbent polymeric material has multiple aromatic rings and can be formed by initially preparing a precursor polymeric material from a polymerizable composition that contains a free-radically polymerizable spirobisindane monomer. The precursor polymeric material is subsequently treated with a sulfonyl-containing compound to form groups of formula —SO2R5 where each R5 is independently —NH2 or —NR6-Q-NR6R7. Each R6 is hydrogen or an alkyl. Each R7 is hydrogen or —C(═NH)—NH2. Each Q is a single bond, alkylene, or a group of formula -(Q1-NR6)x-Q2- where each Q1 is an alkylene, each Q2 is an alkylene, and x is in an integer in a range of 1 to 4.

First claim

I claim:

1. A method of capturing formaldehyde, the method comprising:
a) providing a sorbent polymeric material having multiple aromatic rings and having at least one group of formula —SO 2 R 5 and up to one group of formula —SO 2 R 5 for each aromatic ring in the sorbent polymeric material, wherein providing the sorbent polymeric material comprises reacting a precursor polymeric material with a sulfonyl-containing compound, the precursor polymeric material comprising a polymerized product of a polymerizable composition comprising a monomer of Formula (I)

wherein
each R 1 is hydrogen, halo, alkyl, aryl, alkaryl, or aralkyl, wherein at least one R 1 is hydrogen;
each R 2 is independently hydrogen, alkyl, aryl, alkaryl, aralkyl, combines with a R 3 connected to a same carbon atom to form a cyclic alkyl, or combines with a R 3 connected to the same carbon atom to form a cyclic alkyl that is fused to one or more carbocyclic rings;
each R 3 is independently hydrogen, alkyl, aryl, alkaryl, aralkyl, combines with a R 2 connected to a same carbon atom to form a cyclic alkyl, combines with a R 2 connected to the same carbon atom to form a cyclic alkyl that is fused to one or more carbocyclic rings, or combines with R 4 connected to an adjacent carbon atom to form a carbon-carbon bond; and
each R 4 is independently hydrogen or combines with R 3 connected to the adjacent carbon atom to form a carbon-carbon bond; and
each R 5 is independently —NH 2 or —NR 6 -Q-NR 6 R 7 ;
each R 6 is independently hydrogen or an alkyl;
each R 7 is hydrogen or —C(═NH)—NH 2 ;
Q is a single bond, alkylene, or a group of formula -(Q 1 -NR 6 ) x -Q 2 -;
each Q 1 is an alkylene;
each Q 2 is an alkylene; and
x is in an integer in a range of 1 to 4; and

b) sorbing formaldehyde on the sorbent polymeric material.

2. The method of claim 1 , wherein the group of formula —SO 2 R 5 is a —SO 2 NH 2 group and wherein sorbing formaldehyde on the sorbent polymeric material converts the at least one SO 2 NH 2 group to a SO 2 —N═CH 2 group, —SO 2 —NH—CH 2 OH group, or —SO 2 —N(CH 2 OH) 2 group.

3. The method of claim 1 , wherein the group of formula —SO 2 R 5 is a —SO 2 NH—NH 2 group and wherein sorbing formaldehyde on the sorbent polymeric material converts the at least one —SO 2 NH—NH 2 group to a group of formula —SO 2 —NH—N═CH 2 , —SO 2 —NH—NH—CH 2 OH, or —SO 2 —NH—N(CH 2 OH) 2 .

4. The method of claim 1 , wherein the group of formula —SO 2 R 5 is of formula —SO 2 —NR 6 -Q-NR 6 R 7 where R 7 is hydrogen and wherein sorbing formaldehyde on the sorbent polymeric material converts the at least one group of formula —SO 2 —NR 6 -Q-NR 6 R 7 to a group of formula —SO 2 —NR 8 -Q-NR 9 R 10 that is different from —SO 2 —NR 6 -Q-NR 6 R 7 ,
wherein
each R 8 is hydrogen, alkyl, or —CH 2 OH;
each R 9 is hydrogen, alkyl, —CH 2 OH, or combines with a R 10 group attached to the same nitrogen atom to form ═CH 2 ; and
each R 10 is hydrogen, —CH 2 OH, or combines with a R 9 group attached to the same nitrogen atom to form ═CH 2 .

5. The method of claim 1 , wherein the group of formula —SO 2 R 5 is of formula —SO 2 —NR 6 -Q-NR 6 R 7 where R 7 is —C(═NH)—NH 2 and wherein sorbing formaldehyde on the sorbent polymeric material converts the at least one group of formula —SO 2 —NR 6 -Q-NR 6 R 7 to a group of formula —SO 2 —NR 8 -Q-NR 8 —C(═NR 8 )—N(R 11 ) 2 that is different from —SO 2 —NR 6 -Q-NR 6 R 7 ,
wherein
each R 8 is independently hydrogen, alkyl, or —CH 2 OH; and
each R 11 is independently hydrogen, —CH 2 OH or two R 11 groups attached to the same nitrogen atom combine to form ═CH 2 .

6. The method of claim 1 , wherein the compound of Formula (I) is 3,3,3′,3′-tetramethyl-1,1′-spirobisindan-6,6′-divinyl.

7. The method of claim 1 , wherein the polymerizable composition further comprises a polyvinyl aromatic monomer or a polyvinyl aromatic monomer substituted with one or more alkyl groups.

8. The method of claim 1 , wherein the polymerizable composition further comprises up to 25 weight percent of a mono-vinyl aromatic monomer or a mono-vinyl aromatic monomer substituted with one or more alkyl groups, wherein the weight percent is based on a total weight of monomers in the polymerizable composition.

9. The method of claim 1 , wherein the polymerizable composition comprises the 1 to 99 weight percent monomer of Formula (I), 0 to 25 weight percent mono-vinyl aromatic monomer, and 1 to 99 weight percent polyvinyl aromatic monomer, wherein the weight percents are based on a total weight of monomers in the polymerizable composition.

10. The method of claim 1 , wherein the sorbent polymeric material has the BET surface area equal to at least 100 m 2 /gram and is porous.

11. A polymeric material comprising a reaction product of a mixture comprising:
a) a sorbent polymeric material having multiple aromatic rings and having at least one group of formula —SO 2 R 5 and up to one group of formula —SO 2 R 5 for each aromatic ring in the sorbent polymeric material, wherein the sorbent polymeric material comprises a reaction product of a precursor polymeric material and a sulfonyl-containing compound, the precursor polymeric material comprising a polymerized product of a polymerizable composition comprising a monomer of Formula (I)

wherein
each R 1 is hydrogen, halo, alkyl, aryl, alkaryl, or aralkyl, wherein at least one R 1 is hydrogen;
each R 2 is independently hydrogen, alkyl, aryl, alkaryl, aralkyl, combines with a R 3 connected to a same carbon atom to form a cyclic alkyl, or combines with a R 3 connected to the same carbon atom to form a cyclic alkyl that is fused to one or more carbocyclic rings;
each R 3 is independently hydrogen, alkyl, aryl, alkaryl, aralkyl, combines with a R 2 connected to a same carbon atom to form a cyclic alkyl, combines with a R 2 connected to the same carbon atom to form a cyclic alkyl that is fused to one or more carbocyclic rings, or combines with R 4 connected to an adjacent carbon atom to form a carbon-carbon bond; and
each R 4 is independently hydrogen or combines with R 3 connected to the adjacent carbon atom to form a carbon-carbon bond; and
each R 5 is independently —NH 2 or —NR 6 -Q-NR 6 R 7 ;
each R 6 is independently hydrogen or an alkyl;
each R 7 is hydrogen or —C(═NH)—NH 2 ;
Q is a single bond, alkylene, or a group of formula -(Q 1 -NR 6 ) x -Q 2 -;
each Q 1 is an alkylene;
each Q 2 is an alkylene; and
x is in an integer in a range of 1 to 4; and

b) formaldehyde.

12. The polymeric material of claim 11 , wherein the group of formula —SO 2 R 5 is a —SO 2 NH 2 group and wherein sorbing formaldehyde on the sorbent polymeric material converts the at least one —SO 2 NH 2 group to a —SO 2 —N═CH 2 group, —SO 2 —NH—CH 2 OH group, or —SO 2 —N(CH 2 OH) 2 group.

13. The polymeric material of claim 11 , wherein the group of formula —SO 2 R 5 is a —SO 2 NH—NH 2 group and wherein sorbing formaldehyde on the sorbent polymeric material converts the at least one —SO 2 NH—NH 2 group to a group of formula —SO 2 —NH—N═CH 2 , —SO 2 —NH—NH—CH 2 OH, or —SO 2 —NH—N(CH 2 OH) 2 .

14. The polymeric material of claim 11 , wherein the group of formula —SO 2 R 5 is of formula —SO 2 —NR 6 -Q-NR 6 R 7 where R 7 is hydrogen and wherein sorbing formaldehyde on the sorbent polymeric material converts the at least one group of formula —SO 2 —NR 6 -Q-

Assignees

• 3M Innovative Properties Co

Inventors

• Wendland Michael S

Classifications

• C08F2800/10

  as molar percentages · CPC title

• B01J20/28057

  Surface area, e.g. B.E.T specific surface area · CPC title

• B01D2253/306

  Surface area, e.g. BET-specific surface · 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

• B01J20/264

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