Porous polymeric resins

Patent metadata

Field	Value
Publication number	US-9725545-B2
Application number	US-201414204324-A
Country	US
Kind code	B2
Filing date	Mar 11, 2014
Priority date	Nov 9, 2007
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

Porous polymeric resins, reaction mixtures and methods that can be used to prepare the porous polymeric resins, and uses of the porous polymeric resin are described. More specifically, the polymeric resins typically have a hierarchical porous structure plus reactive groups that can be used to interact with or react with a variety of different target compounds. The reactive groups can be selected from an acidic group or a salt thereof, an amino group or salt thereof, a hydroxyl group, an azlactone group, a glycidyl group, or a combination thereof.

First claim

We claim:

1. A porous polymeric resin having a hierarchical porous structure comprising 1) a first porous structure comprising a first set of pores associated with a bulk polymeric matrix and having an average pore diameter less than 200 nanometers and 2) a second porous structure comprising a second set of pores having an average pore diameter greater than 500 nanometers and that are distinct from the first set of pores, the porous polymeric resin comprising the reaction product of a reaction mixture comprising an aqueous phase monomer mixture wherein all or substantially all of the monomers in the monomer mixture have a lipophilicity index no greater than 20, the monomer mixture comprising
a) a crosslinking monomer of Formula (I)

in an amount of 55 to 99 weight percent based on a total weight of the monomer mixture,
wherein
R 1 is hydrogen or methyl;
Q is oxy or —NH—; and
Y is an alkylene or heteroalkylene, wherein Y can be optionally substituted with a hydroxyl group; and
b) a functional monomer having (a) an ethylenically unsaturated group and (b) a first functional group selected from (1) an acidic group or a salt thereof, (2) an amino group or a salt thereof, (3) a hydroxyl group, (4) an azlactone group, (5) a glycidyl group, or (6) a combination thereof.

2. The porous polymeric resin of claim 1 , wherein the porous polymeric resin is a porous polymeric bead.

3. The porous polymeric resin of claim 1 , wherein the porous polymeric resin is a monolith.

4. The porous polymeric resin of claim 1 , wherein the functional monomer has an acidic group or a salt thereof and wherein the polymeric porous resin is a cation exchange resin.

5. The porous polymeric resin of claim 1 , wherein the functional monomer has an amino group or a salt thereof, the polymeric porous resin being an anion exchange resin.

6. The porous polymeric resin of claim 1 , wherein the functional monomer has a hydroxyl group, the polymeric porous resin being a size exclusion resin.

7. A modified polymeric resin comprising the reaction product of a modifying agent and the porous polymeric resin of claim 1 , wherein the modifying agent reacts with the first functional group to covalently attach the modifying agent to the porous polymeric resin.

8. The modified polymeric resin of claim 7 , wherein the modifying agent is a biomolecule.

9. The modified polymeric resin of claim 8 , wherein the biomolecule is a protein, virus, vaccine, antibody, enzyme, nucleic acid, DNA, or RNA.

10. The modified polymeric resin of claim 7 , wherein the functional monomer has a first functional group that is a hydroxyl and the modifying agent has a carboxyl group.

11. The modified polymeric resin of claim 7 , wherein the functional monomer has a first functional group that is an azlactone group and the modifying agent has a nucleophilic group.

12. The modified polymeric resin of claim 7 , wherein the functional monomer has a first functional group that is a glycidyl group and the modifying agent has a nucleophilic group.

13. The modified polymeric resin of claim 8 , wherein the attached biomolecule has functional group that is capable of reacting or interacting with a complementary functional group on another biomolecule, the modified polymeric resin being an affinity resin.

14. The modified polymeric resin of claim 7 , wherein the modifying agent has an ionic group that is capable of reacting or interacting with a target compound having an opposite charge, the modified polymeric resin being an ion exchange resin or a size exclusion resin.

15. The modified polymeric resin of claim 7 , wherein the modifying agent has hydrophobic group that is capable of reacting or interacting with a target compound having a hydrophobic group, the modified polymeric resin being a reverse phase resin or a hydrophobic interaction resin.

16. The modified polymeric resin of claim 7 , wherein the modifying agent has a metal-chelating group that is capable of reacting or interacting with a metal-containing species, the modified polymeric resin being a chelating resin.

17. The modified polymeric resin of claim 7 , wherein the modifying agent is an antibody that is capable of binding with a cell, the modified polymeric resin being a cell selection resin.

18. The modified polymeric resin of claim 7 , wherein the modifying agent is an enzyme, the modified polymeric resin being an enzyme resin.

19. A porous polymeric resin having a hierarchical porous structure comprising 1) a first porous structure comprising a first set of pores associated with a bulk polymeric matrix and having an average pore diameter less than 200 nanometers and 2) a second porous structure comprising a second set of pores having an average pore diameter greater than 500 nanometers and that are distinct from the first set of pores, the porous polymeric resin comprising the reaction product of a reaction mixture comprising an aqueous phase monomer mixture wherein all or substantially all of the monomers in the monomer mixture have a lipophilicity index no greater than 20, the monomer mixture comprising
a) a crosslinking monomer of Formula (I)

in an amount of 55 to 99 weight percent based on a total weight of the monomer mixture,
wherein
R 1 is hydrogen or methyl;
Q is oxy or —NH—; and
Y is an alkylene or heteroalkylene, wherein Y can be optionally substituted with a hydroxyl group; and
b) a functional monomer having (a) an ethylenically unsaturated group and (b) a first functional group selected from (1) an acidic group or a salt thereof, (2) an amino group or a salt thereof, (3) a hydroxyl group, (4) an azlactone group, (5) a glycidyl group, or (6) a combination thereof, wherein a scanning electron micrograph of the porous polymeric resin shows multiple pores corresponding to the first porous structure and multiple pores corresponding to the second porous structure.

Assignees

• 3M Innovative Properties Co

Inventors

• Wickert Peter D
• Shannon Simon K
• Seshadri Kannan
• Rasmussen Jerald K
• Hembre James I
• Fitzsimons Jr Robert T

Classifications

• C08J9/26

  by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out · CPC title

• C08J2201/0462

  using organic solvents · 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

• C08F228/02 Primary

  by a bond to sulfur · CPC title

• C08J2333/04

  esters · CPC title