Sulfonic acid-containing polymeric materials as amine sorbents

Patent metadata

Field	Value
Publication number	US-10220370-B2
Application number	US-201515312712-A
Country	US
Kind code	B2
Filing date	May 28, 2015
Priority date	Jun 13, 2014
Publication date	Mar 5, 2019
Grant date	Mar 5, 2019

Abstract

A method of capturing a basic, nitrogen-containing compound is provided. The basic, nitrogen-containing compound is captured by sorption (e.g., adsorption) on a sulfonic-acid containing polymeric material. The sulfonic acid-containing polymeric material is formed from a polymerizable composition that contains a free-radically polymerizable spirobisindane monomer. Additionally, a polymeric material is provided that is a reaction product of a sulfonic acid-containing polymeric material having at least one —SO3H group and a basic, nitrogen-containing compound of formula Q. This polymeric material has at least one group of formula —SO 3 − (QH + ).

First claim

I claim:

1. A method of capturing a nitrogen-containing compound, the method comprising:
a) providing a sulfonic acid-containing polymeric material having at least one —SO 2 OH group, the sulfonic acid-containing polymeric material comprising a first reaction product of a first reaction mixture comprising:
i) a 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 R1 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
ii) a sulfonyl-containing compound; and

b) sorbing vapors of a basic, nitrogen-containing compound on the sulfonic acid-containing polymeric material to form a nitrogen containing polymeric material.

2. The method of claim 1 , wherein the basic, nitrogen-containing compound has a molecular weight (weight average molecular weight) no greater than 150 grams/mole.

3. The method of claim 1 , wherein the basic, nitrogen-containing compound is ammonia, a hydrazine compound, amine compound, or a nitrogen-containing heterocyclic compound.

4. A nitrogen containing polymeric material comprising an acid-base reaction product of an acid-base reaction mixture comprising:
a) a sulfonic acid-containing polymeric material having at least one —SO 3 H group, the sulfonic acid-containing polymeric material comprising a first reaction product of a first reaction mixture comprising:
i) a 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 R1 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
ii) a sulfonyl-containing compound; and

b) a basic, nitrogen-containing compound.

5. The nitrogen containing polymeric material of claim 4 , wherein each R 2 and each R 3 are alkyl.

6. The nitrogen containing polymeric material of claim 4 , wherein R 4 is hydrogen.

7. The nitrogen containing polymeric material of claim 4 , wherein the compound of Formula (I) is 3,3,3′,3′-tetramethyl-1,1′-spirobisindan-6,6′-divinyl.

8. The nitrogen containing polymeric material of claim 4 , wherein the polymerizable composition further comprises a polyvinyl aromatic monomer or a polyvinyl aromatic monomer substituted with one or more alkyl groups.

9. The nitrogen containing polymeric material of claim 4 , wherein the polymerizable composition optionally further comprises up to 25 weight percent of a monovinyl 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.

10. The nitrogen containing polymeric material of claim 9 , wherein the polymerizable composition comprises the 1 to 99 weight percent monomer of Formula (I), 0 to 25 weight percent monovinyl 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.

11. The nitrogen containing polymeric material of claim 4 , wherein the sulfonic acid-containing polymeric material is in a form of particles or beads.

12. The nitrogen containing polymeric material of claim 4 is porous.

13. The nitrogen containing polymeric material of claim 4 , wherein the sulfonic acid-containing polymeric material has the BET surface area equal to at least 50 m 2 /gram.

14. The nitrogen containing polymeric material of claim 4 , wherein the basic, nitrogen-containing compound has a molecular weight (weight average molecular weight) no greater than 150 grams/mole.

15. The nitrogen containing polymeric material of claim 4 , wherein the basic, nitrogen-containing compound is ammonia, a hydrazine compound, amine compound, or a nitrogen-containing heterocyclic compound.

Assignees

• 3M Innovative Properties Co

Inventors

• Wendland Michael S

Classifications

• B01D2253/202

  Polymeric adsorbents · CPC title

• B01J39/05 Primary

  in the strongly acidic form · CPC title

• C08F212/36

  Divinylbenzene · CPC title

• C08F8/36

  Sulfonation; Sulfation · CPC title

• B01D2253/308

  Pore size · CPC title