Amphiphilic copolymer with zwitterionic and fluorinated moieties

Patent metadata

Field	Value
Publication number	US-12522683-B2
Application number	US-202117454763-A
Country	US
Kind code	B2
Filing date	Nov 12, 2021
Priority date	Nov 16, 2020
Publication date	Jan 13, 2026
Grant date	Jan 13, 2026

Abstract

Provided are amphiphilic copolymers that include repeat units of formulas [Z] m and [P] n , wherein Z is a zwitterionic structural unit including at least one pendant heteroaromatic moiety, the heteroaromatic moiety containing a positively charged quaternary nitrogen atom (e.g., a pyridine ring), and wherein at least one negatively charged functional moiety is linked to the heteroaromatic moiety directly or through a linker, wherein the linker, where present, is an optionally substituted alkyl linker; P is a structural unit including a hydrophobic moiety, the hydrophobic moiety being a linear, branched, or cyclic fluorine-substituted C 1 -C 20 moiety; m is an integer that is ≥1; and n is an integer that is ≥1.

First claim

The invention claimed is:

1 . An amphiphilic copolymer comprising two or more structures of formula (i)-(vi):

wherein
Z is a hydrophilic zwitterionic structural unit comprising at least one pendant heteroaromatic moiety, wherein the heteroaromatic moiety comprises a positively charged quaternary nitrogen atom, and wherein at least one negatively charged functional moiety is linked to the heteroaromatic moiety directly or through a linker, wherein the linker, where present, is an optionally substituted alkylene linker;
P is a hydrophobic structural unit comprising a hydrophobic moiety, said hydrophobic moiety being or comprising a linear, branched, or cyclic fluorine-substituted C 1 -C 20 alkyl moiety;
X is a crosslinking moiety;
m is an integer that is ≥1;
n is an integer that is ≥1;
o is an integer selected from 1 to 10,000;
wherein the amphiphilic copolymer has hydrophilic zwitterionic structural units and hydrophobic structural units randomly distributed therein, and wherein the comonomer residues are located randomly in the copolymer molecule and are configured to have reversible surface chain reorientation in response to surface wetting and/or drying to switch between a first surface energy state and a second surface energy state;
wherein the amphiphilic copolymer comprises a plurality of domains having hydrophilic units and hydrophobic units, and wherein each of the domains has a size smaller than 2 nm 2 ; and
wherein the crosslinking moiety X is selected from a unit of polymerized monomer selected from arylene, alkylene, phenylene, 1,4-phenylene, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, vinyl methacrylate, allyl methacrylate, maleic anhydride, 1,3,5-trivinyltrimethylcyclotrisiloxane glycidyl methacrylate, and di(ethylene glycol)divinyl ether, or any combination thereof.

2 . The copolymer according to claim 1 , wherein the at least one negatively charged functional moiety is an oxygen atom.

3 . The copolymer according to claim 1 , comprising a repeat unit of formula

wherein
S is a heteroaryl ring having a positively charged quaternary nitrogen atom;
G is a moiety comprising the at least one negatively charged functional moiety that is linked to the heteroaromatic moiety; and
R 1a , R 1b , and R 1c are each individually selected from hydrogen, alkyl, phenyl, halo, hydroxyl, amino, nitro, and cyano.

4 . The copolymer according to claim 3 , wherein R 1a , R 1b , and R 1c are each independently selected from hydrogen and alkyl.

5 . The copolymer according to claim 1 , comprising a repeat unit of formula

wherein
Q is the hydrophobic moiety;
L is not present or is a linking moiety; and
R 2a , R 2b , and R 2c are each individually selected from hydrogen, alkyl, phenyl, halo, hydroxyl, amino, nitro, and cyano.

6 . The copolymer according to claim 5 , wherein L is a linker selected from a bond, alkylene, amide, ester, ether, and disulfide moiety, or any combination thereof.

7 . The copolymer according to claim 5 , wherein R 2a , R 2b , and R 2c are each independently selected from hydrogen and alkyl.

8 . The copolymer according to claim 1 comprising a first repeat unit of formula (I) and a second repeat unit of formula (II):

wherein:
G is a moiety comprising the at least one negatively charged functional moiety that is linked to the pyridine ring;
R 1a , R 1b , and R 1c are each individually selected from hydrogen, alkyl, phenyl, halo, hydroxyl, amino, nitro, and cyano;
R 2a , R 2b , and R 2c are each individually selected from hydrogen, alkyl, phenyl, halo, hydroxyl, amino, nitro, and cyano;
q is 0-4;
r≤20; and
s≤41.

9 . The copolymer according to claim 8 , wherein the at least one negatively charged functional moiety comprises a carboxylate anion, a sulfonate anion, a phosphonate anion, or is an oxygen atom.

10 . The copolymer according to claim 8 , wherein the first repeat unit of formula (I) is of formula (IA):

11 . The copolymer according to claim 10 , wherein G is —(CH 2 ) 1-6 SO 3 − .

12 . The copolymer according to claim 11 , wherein R 1a , R 1b , and R 1c are each individually selected from hydrogen and methyl.

13 . A film comprising a layer of the copolymer according to claim 1 , wherein the thickness of the layer is 5 nm to 100 microns.

14 . A composition comprising:
a coating material comprising a copolymer according to claim 1 ; and a substrate;
wherein the substrate is coated with a layer of the coating material on at least one side.

15 . An article comprising the composition of claim 14 .

16 . A method of:
decreasing, reducing, or inhibiting microorganism growth, or killing or denaturing a microorganism, or inhibiting biofilm formation; or controlling bacteria growth on a substrate;
said method comprising applying a layer of the copolymer according to claim 1 on a substrate.

17 . The method according to claim 16 , wherein applying the layer of the copolymer on the substrate comprises:
placing the substrate in an iCVD reactor under vacuum condition; flowing into the reactor in parallel or in sequence a plurality of materials comprising:
an inert carrier gas;
an initiator;
a first monomer that is the source of the at least one pendant heteroaromatic moiety in the

repeat units;
a second monomer that is the source of the

repeat units; and
a crosslinker,

thereby forming a polymeric layer on at least one side of the substrate via iCVD; and
exposing the polymeric layer to a negatively charged functional moiety, thereby forming the layer of the copolymer on the substrate.

18 . The amphiphilic copolymer of claim 1 , wherein the amphiphilic copolymer has a contrast in comonomer surface energies of at least 48 mN m −1 as between hydrophilic and hydrophobic components therein.

19 . The amphiphilic copolymer of claim 1 , wherein the amphiphilic copolymer has a contrast in comonomer surface energies of at least 58 mN m −1 as between hydrophilic and hydrophobic components therein.

20 . The amphiphilic copolymer of claim 1 , wherein the amphiphilic copolymer has a receding contact angle of less than 40 degrees.

21 . The amphiphilic copolymer of claim 1 , wherein a static contact angle of the amphiphilic copolymer is configured to change over time during the reversible surface chain reorientation.

22 . A layer of the copolymer according to claim 1 , wherein the layer has an RMS surface roughness of 35 nm or less.

Assignees

• Univ Cornell

Inventors

• Yang Rong
• Franklin Trevor

Classifications

• C08F222/18

  Esters containing halogen · CPC title

• C08F26/06

  by a heterocyclic ring containing nitrogen · CPC title

• C08F22/18

  Esters containing halogen · CPC title

• C08F20/22

  Esters containing halogen · CPC title

• C08F20/24

  containing perhaloalkyl radicals · CPC title