Amino-containing polymeric material with rigid and contorted divinyl crosslinker

Patent metadata

Field	Value
Publication number	US-9463454-B2
Application number	US-201414889666-A
Country	US
Kind code	B2
Filing date	Apr 22, 2014
Priority date	May 14, 2013
Publication date	Oct 11, 2016
Grant date	Oct 11, 2016

Abstract

Amino-containing polymeric materials and methods of making these materials are provided. More specifically, the amino-containing polymeric materials are prepared by treating a precursor polymeric material with an amine compound. The precursor polymeric materials are formed from a polymerizable composition that contains a rigid and contorted divinyl crosslinker. The amino-containing polymeric materials can be used as anion exchange resins.

First claim

I claim:

1. An amino-containing polymeric material comprising a reaction product of a reaction mixture comprising:
a) a precursor polymeric material comprising a polymerized product of a polymerizable composition comprising
i) a monomer mixture comprising
1) 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
2) a second monomer of Formula (II)

wherein
R 5 is an alkylene; and
X is a halo; and

ii) a free radical initiator; and

b) an amine compound.

2. The amino-containing polymeric material of claim 1 , wherein each R 1 of the first monomer is hydrogen or halo.

3. The amino-containing polymeric material of claim 1 , wherein each R 2 and each R 3 of the first monomer are alkyl.

4. The amino-containing polymeric material of claim 1 , wherein R 4 of the first monomer is hydrogen.

5. The amino-containing polymeric material of claim 1 , wherein the first monomer is 3,3,3′,3′-tetramethyl-1,1′-spirobisindan-6,6′-divinyl.

6. The amino-containing polymeric material of claim 1 , wherein the monomer mixture comprises 1 to 25 mole percent of the first monomer of Formula (I).

7. The amino-containing polymeric material of claim 1 , wherein the monomer mixture further comprises a polyvinyl aromatic monomer that is not of Formula (I).

8. The amino-containing polymeric material of claim 1 , wherein the amino-containing polymer is in a form of particles or beads.

9. The amino-containing polymeric material of claim 1 , wherein the amine compound has at least one primary amino group or secondary amino group.

10. The amino-containing polymeric material of claim 1 , wherein the amine compound is a trialkylamine.

11. The amino-containing polymeric material of claim 1 , wherein the amino-containing polymeric material is an anion exchange resin.

12. A method of preparing an amino-containing polymeric material, the method comprising:
preparing a polymerizable composition comprising
i) a monomer mixture comprising
1) a first 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;
2) a second monomer of Formula (II)

wherein
R 5 is an alkylene; and
X is a halo; and

ii) a free radical initiator; and

forming a precursor polymeric material by reacting the polymerizable composition; and
treating the precursor polymeric material with an amine compound to form the amino-containing polymeric material.

13. The method of claim 12 , wherein the polymerizable composition comprises (1) an organic phase comprising the monomer mixture and the free radical initiator and (2) an aqueous phase comprising water and a suspending agent, wherein the organic phase is suspended as droplets within the aqueous phase and wherein the amino-containing polymeric material is in a form of particles or beads.

Assignees

• 3M Innovative Properties Co

Inventors

• Wendland Michael S

Classifications

• B01J41/14 Primary

  obtained by reactions only involving unsaturated carbon-to-carbon bonds · CPC title

• B01J41/20

  Anion exchangers for chromatographic processes · CPC title

• C08F8/32

  by reaction with amines · CPC title

• C08F212/14

  substituted by heteroatoms or groups containing heteroatoms · CPC title

• C08F212/34

  Monomers containing two or more unsaturated aliphatic radicals · CPC title