Ligand functionalized polymers

Patent metadata

Field	Value
Publication number	US-9296847-B2
Application number	US-201514600117-A
Country	US
Kind code	B2
Filing date	Jan 20, 2015
Priority date	Feb 18, 2010
Publication date	Mar 29, 2016
Grant date	Mar 29, 2016

Abstract

Ligand functionalized substrates, methods of making ligand functionalized substrates, and methods of using functionalized substrates are disclosed.

First claim

The invention claimed is:

1. A guanidinyl functional copolymer of the formula:
-(M Lig ) y -(M Hydrophil ) x -(M hydrophob ) z -(M CO ) w *-,
where
-(M CO ) w * are carbonyl functional monomer units having “w*” polymerized monomer units,
-(M Hydrophil ) x - are positively charged hydrophilic ionic monomer units having “x” polymerized monomer units; said hydrophilic ionic monomers selected from positively charged amino (meth)acrylates, amino (meth)acrylamides dialkylaminoalkylamine adducts of alkenylazlactones, 3-(dimethylamino)propylamine adducts of vinyldimethylazlactone) and diallylamine monomers,
-(M hydrophob ) z - are hydrophobic monomer units having “z” polymerized monomer units;
(M Lig ) y are guanidinyl ligand functional monomer units having “y” polymerized monomer units wherein the pendent guanidinyl groups of the guanidinyl ligand functional monomer units are of the of the formula:

R 9 is C 2 to C 12 alkylene or C 5 -C 12 (hetero)arylene,
each R 3 is independently H, —OH, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl, preferably H or C 1 -C 4 alkyl,
R 4 is H, C 1 -C 12 alkyl, C 5 -C 12 (hetero)aryl, or —N(R 3 ) 2 , preferably H, or C 1 -C 4 alkyl,
where y is 10 to less than 100 wt. % of the monomer units;
x is 1 wt. % to 90 wt. % of the monomer units; and
w* may be comprise 0 to 90 wt. % of the monomer units, and
z is 0 to 20 wt. %, based on 100 wt. % total monomers.

2. The copolymer of claim 1 wherein x is at least 5 wt. %.

3. The copolymer of claim 1 wherein the pendent guanidinyl groups of the guanidinyl ligand functional monomer units are of the formula:

wherein
R 1 is H, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl,
R 2 is a covalent bond, a C 2 to C 12 alkylene, or a C 5 -C 12 (hetero)arylene,

R 9 is C 2 to C 12 alkylene or C 5 -C 12 (hetero)arylene,
each R 3 is independently H, —OH, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl,
each R 4 is H, C 1 -C 12 alkyl, C 5 -C 12 (hetero)aryl, or —N(R 3 ) 2 .

4. The copolymer of claim 1 derived from a carbonyl-functional (co)polymer selected from the group consisting of; acrolein, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, diacetone (meth)acrylamide, acetonyl acrylate, carbon monoxide copolymer, and diacetone (meth)acrylate(co)polymers.

5. The copolymer of claim 1 wherein the ionic monomers are positively charged monomers derived from compounds of the formula

where X is —O— or —NR 3 —;
R 7 is independently H or CH 3 ,
R 6 is a C 2 to C 10 alkylene, preferably C 2 -C 6 ,
each R 8 is independently hydrogen, alkyl, or hydroxyalkyl.

6. The copolymer of claim 1 further comprising monomers selected from acrylic acid; methacrylic acid; 2-acrylamido-2-methyl-1-propanesulfonic acid.

7. The copolymer of claim 1 further comprising a neutral hydrophilic monomer.

8. The copolymer of claim 7 wherein the neutral hydrophilic monomer is of the formula:
R 3 —O—(CH(R 3 )—CH 2 —O) n —C(O)—C(R 3 )═CH 2 ,

wherein each R 3 is independently H or C 1 -C 4 alkyl, and n is at least 2.

9. The copolymer of claim 1 further comprising a hydrophobic monomer.

10. The copolymer of claim 1 wherein the copolymer comprises 1 to 20 wt. % of hydrophobic monomer units based on 100 wt. % total monomer.

11. The copolymer of claim 1 prepared by condensation of a carbonyl functional (co)polymer with a ligand compound of Formula I:

wherein
R 2 is a covalent bond, a C 2 to C 12 alkylene, a C 5 -C 12 (hetero)arylene,

R 9 is C 2 to C 12 alkylene or C 5 -C 12 (hetero)arylene,
each R 3 is independently H, —OH, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl, preferably H or C 1 -C 4 alkyl,
R 4 is H, C 1 -C 12 alkyl, C 5 -C 12 (hetero)aryl, or —N(R 3 ) 2 , preferably H, or C 1 -C 4 alkyl.

12. The copolymer of claim 1 prepared by copolymerizing a monomer of the formula:

wherein
R 1 is H, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl,
R 2 is a covalent bond, a C 2 to C 12 alkylene, a C 5 -C 12 (hetero)arylene,

R 9 is C 2 to C 12 alkylene or C 5 -C 12 (hetero)arylene,
each R 3 is independently H, —OH, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl, preferably H or C 1 -C 4 alkyl,
R 4 is H, C 1 -C 12 alkyl, C 5 -C 12 (hetero)aryl, or —N(R 3 ) 2 , preferably H, or C 1 -C 4 alkyl,
X is —O— or —NR 3 —
R 6 is a C 2 to C 12 alkylene, and
R 7 is H or CH 3 ;
with an ionic hydrophilic monomer.

13. The copolymer of claim 1 prepared by copolymerizing a monomer of the formula:

wherein
R 1 is H, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl,
R 2 is a covalent bond, a C 2 to C 12 alkylene, a C 5 -C 12 (hetero)arylene,

R 9 is C 1 to C 12 alkylene or C 5 -C 12 (hetero)arylene,
each R 3 is independently H, —OH, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl,
R 4 is H, C 1 -C 12 alkyl, C 5 -C 12 (hetero)aryl, or —N(R 3 ) 2 ,
with an ionic hydrophilic monomer.

Assignees

• 3M Innovative Properties Co

Inventors

• Rasmussen Jerald K
• Bothof Catherine A
• Seshadri Kannan
• Satterwhite Erin A
• Fitzsimons Jr Robert T
• Hembre James L
• Ali Mahfuza B

Classifications

• Y10T428/249991

  Synthetic resin or natural rubbers · CPC title

• G01N33/54393

  Improving reaction conditions or stability, e.g. by coating or irradiation of surface, by reduction of non-specific binding, by promotion of specific binding · CPC title

• Y10T428/12264

  having outward flange, gripping means or interlocking feature · CPC title

• C08F26/02

  by a single or double bond to nitrogen · CPC title

• C08G73/00

  Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00 {(polycarbodiimides prepared from isocyanates C08G18/025, C08G18/797)} · CPC title