# US 11,306,190 B2 · Method for providing a modification to a polymeric surface

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,306,190 B2
- Document ID: US11306190B2
- Status: Granted
- Kind: B2
- Application number: 16/331,338
- Filed: 2017-09-08
- Published: 2019-11-14
- Granted: 2022-04-19
- Earliest claimed: 2016-09-08
- Assignees: Rensselaer Polytechnic Institute
- Applicants: Rensselaer Polytechnic Institute
- Inventors: John Joseph Keating; Georges Belfort; Istvan Zsolt Kocsis; Mirco Sorci; Alexander Kenneth Lee
- Web page: https://patentgrep.com/patent/US11306190B2

## CPC

- B05D 1/36: Successively applying liquids or other fluent materials, e.g. without intermediate treatment
- C08J 7/16: with polymerisable compounds
- B05D 3/144: {of polymeric substrates}
- B05D 7/02: to macromolecular substances, e.g. rubber (treatment or coating of shaped articles made of macromolecular substances C08J7/00)
- B32B 7/10: at least one layer having inter-reactive properties
- B32B 27/08: of synthetic resin
- B32B 27/16: specially treated, e.g. irradiated
- B32B 27/24: using solvents or swelling agents
- B32B 27/28: comprising synthetic resins not wholly covered by any one of the sub-groups {B32B27/30 - B32B27/42}
- B32B 27/281: {comprising polyimides}
- B32B 27/283: {comprising polysiloxanes}
- B32B 27/285: {comprising polyethers}
- B32B 27/286: {comprising polysulphones; polysulfides}
- B32B 27/288: {comprising polyketones}
- B32B 27/30: comprising vinyl {(co)polymers; comprising acrylic (co)polymers}
- B32B 27/302: {comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers}
- B32B 27/304: {comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF}
- B32B 27/32: comprising polyolefins {(comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30)}
- B32B 27/322: {comprising halogenated polyolefins, e.g. PTFE}
- B32B 27/34: comprising polyamides
- B32B 27/36: comprising polyesters
- B32B 27/365: {comprising polycarbonates}
- C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16}
- C09D 7/20: Diluents or solvents
- C09D 125/04: Homopolymers or copolymers of styrene
- C09D 133/06: of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D 133/08: Homopolymers or copolymers of acrylic acid esters
- C09D 133/10: Homopolymers or copolymers of methacrylic acid esters
- C09D 133/14: of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- B32B 2250/244: All polymers belonging to those covered by group B32B27/36
- B32B 2270/00: Resin or rubber layer containing a blend of at least two different polymers
- B32B 2307/726: Permeability to liquids, absorption
- B32B 2307/728: Hydrophilic
- B32B 2307/732: Dimensional properties
- B32B 2535/00: Medical equipment, e.g. bandage, prostheses or catheter
- B32B 2605/12: Ships
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

A method for modifying a polymeric surface is disclosed. The polymeric surface is activated utilizing atmospheric pressure plasma. An atom transfer radical polymerization initiator is then coupled to the activated surface. A monomer is then polymerized on the activated surface utilizing an activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) process. The method enables brush-modification of the polymeric surface, even if the polymeric surface is substantially chemically inert. By way of example, the method enables a chemically inert, substantially hydrophobic polymer surface to be functionalized with substantially hydrophilic polymer brushes. The methods of the present disclosure have general applicability to a myriad of implementations where tunable surface chemistry is advantageous, such as filtration membranes, marine surfaces, and medical devices seeking a biocompatible coating.

## Claims

### Claim 1

A method of modifying a polymeric surface comprising:
providing a polymeric substrate having a surface;
treating said polymeric substrate surface with helium and oxygen atmospheric pressure plasma at a power of 120 W to form an activated polymeric substrate surface;
contacting said activated polymeric substrate surface with atom transfer radical polymerization initiator in the presence of a scavenger compound;
providing a monomer to said activated polymeric substrate surface; and
polymerizing said monomer in the presence of a catalyst and a ligand,
wherein said polymeric substrate surface is composed of poly(ether sulfone).

### Claim 2 (depends on 1)

The method according to claim 1, further comprising providing a reducing agent.

### Claim 3 (depends on 2)

The method according to claim 2, wherein said reducing agent is composed of ascorbic acid, sodium ascorbate, tin (II) 2-ethylhexanoate, or combinations thereof.

### Claim 4 (depends on 1)

The method according to claim 1, further comprising providing a solvent.

### Claim 5 (depends on 4)

The method according to claim 4, wherein said solvent is composed of toluene, anisole, ethanol, or combinations thereof.

### Claim 6 (depends on 1)

The method according to claim 1, wherein said initiator is composed of alpha-bromoisobutyryl bromide, ethyl alpha-bromoisobutyrate, (3-trimethoxysilyl)propyl 2-bromo-2-methylpropionate, halogenated silanes, or combinations thereof.

### Claim 7 (depends on 1)

The method according to claim 1, wherein said catalyst is a copper catalyst.

### Claim 8 (depends on 1)

The method according to claim 1, wherein said copper catalyst is copper bromide or copper chloride.

### Claim 9 (depends on 1)

The method according to claim 1, wherein said ligand is N,N,N′,N″,N″ pentamethyldiethylenetriamine, tris(2-pyridylmethyl)amine, or tris[2-(dimethylamino)ethyl]amine.

### Claim 10 (depends on 1)

The method according to claim 1, wherein said monomer is an alkyl methacrylate, styrene, glycidyl methacrylate, or combinations thereof.

### Claim 11 (depends on 1)

The method according to claim 1, wherein said monomer and said atom transfer radical polymerization initiator are provided at a molar ratio of at least about 400:1.

### Claim 12 (depends on 1)

The method according to claim 1, wherein said catalyst and said atom transfer radical polymerization initiator are provided at a molar ratio of about 0.1:1.

### Claim 13 (depends on 1)

The method according to claim 1, wherein said reducing agent and said catalyst are provided at a molar ratio of about 10:1.

### Claim 14 (depends on 1)

The method according to claim 1, wherein said catalyst and said ligand are provided at a molar ratio of about 1:1 to about 1:10.

### Claim 15 (depends on 1)

The method according to claim 1, wherein polymerizing said monomer occurs at a reaction temperature above about 273 K.

### Claim 16 (depends on 1)

The method according to claim 1, wherein the scavenger compound includes trimethylamine, triethylamine, or combinations thereof.

### Claim 17

A method of modifying a polymeric surface comprising:
providing a polymer substrate having a hydrophobic surface;
treating said hydrophobic polymer substrate surface with helium and oxygen atmospheric pressure plasma at a power of 120 W to form an activated hydrophobic polymer substrate surface;
providing the activated hydrophobic polymer substrate surface to a solution including a scavenger compound;
providing atom transfer radical polymerization initiator to the solution to couple atom transfer radical polymerization initiator to said activated hydrophobic polymer substrate surface; and
polymerizing hydrophilic monomers on said activated hydrophobic polymer substrate surface in the presence of a catalyst, a ligand, and a reducing agent,
wherein said polymeric substrate surface is composed of poly(ether sulfone).

### Claim 18 (depends on 17)

The method according to claim 17, wherein said monomer is ethylene glycol methyl ether methacrylate, diethyleneglycol methyl ether methacrylate, or combinations thereof.

### Claim 19 (depends on 17)

The method according to claim 17, wherein said atom transfer radical polymerization initiator is composed of an alkyl bromide or halogenated silane compound and wherein said catalyst is composed of a copper catalyst.

### Claim 20 (depends on 17)

The method according to claim 17, wherein the scavenger compound includes trimethylamine, triethylamine, or combinations thereof.