Liquid complex coacervates, articles derived therefrom, and methods for the manufacture thereof

Patent metadata

Field	Value
Publication number	US-2025026875-A1
Application number	US-202218708368-A
Country	US
Kind code	A1
Filing date	Nov 9, 2022
Priority date	Nov 10, 2021
Publication date	Jan 23, 2025
Grant date	—

Abstract

A cured product of a liquid complex coacervate includes a macroion phase of a polyanion, a polycation, and a salt; wherein the polyanion has repeating units including one or more of a carboxylate group, a sulfonate group, a phosphonate group, a sulfate group, or a phosphate group; and wherein the polycation has repeating units including one or more of a nitrogen-containing cationic group, a phosphorus-containing cationic group, or a sulfur-containing cationic group; provided that when the polycation is poly(diallyldimethyl ammonium), the poly anion is not polystyrene sulfonate, or when the polyanion is polystyrene sulfonate, the polycation is not poly(diallyldimethyl ammonium). Methods of forming coatings are also disclosed.

First claim

1 . A cured product of a liquid complex coacervate, wherein the liquid complex coacervate comprises a macroion phase comprising a polyanion, a polycation, and a salt;
wherein the polyanion comprises repeating units comprising one or more of a carboxylate group, a sulfonate group, a phosphonate group, a sulfate group, or a phosphate group; and wherein the polycation comprises repeating units comprising one or more of a nitrogen-containing cationic group, a phosphorus-containing cationic group, or a sulfur-containing cationic group; provided that when the polycation is poly(diallyldimethyl ammonium), the polyanion is not polystyrene sulfonate, or when the polyanion is polystyrene sulfonate, the polycation is not poly(diallyldimethyl ammonium).

2 . The cured product of claim 1 ,
wherein the polyanion comprises repeating units derived from a monomer having a (meth)acrylate group or a (meth)acrylamide group and the carboxylate group, the sulfonate group, or the phosphonate group; and wherein the polycation comprises repeating units derived from a monomer having a (meth)acrylate group or a (meth)acrylamide group and the nitrogen-containing cationic group, the phosphorus-containing cationic group, or the sulfur-containing cationic group.

3 . The cured product of claim 1 ,
wherein the polyanion comprises repeating units of one or more of formulas (I)—(IV)

wherein in the foregoing Formulas,
R 1 is H or methyl;
L 1 is a divalent linking group; and
Z is independently at each occurrence —O— or —NH— or —NR—, wherein R is a substituted or unsubstituted C 1-12 alkyl group, a substituted or unsubstituted C 3-12 cycloalkyl group, a substituted or unsubstituted C 6-20 aryl group, a C 1-20 alkylene oxide group, or a poly(C 1-6 alkylene oxide) group; and
wherein the polycation comprises repeating units of formula (V)

wherein
R 1 is H or methyl;
L 1 is a divalent linking group;
Z is independently at each occurrence —O— or —NH— or —NR—, wherein R is a substituted or unsubstituted C 1-12 alkyl group, a substituted or unsubstituted C 3-12 cycloalkyl group, a substituted C 6-20 aryl group, a C 1-20 alkylene oxide group, or a poly(C 1-6 alkylene oxide) group; and
R 2 is independently at each occurrence a substituted or unsubstituted C 1-20 alkyl group; and
wherein the salt comprises an alkali metal salt, a transition metal salt, a lanthanide metal salt, an actinide metal salt, a volatile salt, or a combination thereof.

4 . (canceled)

5 . The cured product of claim 1 , wherein the polyanion comprises repeating units of formula (I) or (III)

wherein R 1 is methyl, Z is —O—, and L 1 is a C 1-6 alkylene group.

6 . The cured product of claim 1 , wherein the polyanion, the polycation, or both further comprise repeating units derived from a neutral hydrophilic monomer, repeating units derived from a neutral hydrophobic comonomer, or a combination thereof;
wherein the repeating units derived from a neutral hydrophilic monomer are of formula (VI)

wherein in the forgoing formulas,

R 1 is independently at each occurrence H or methyl;
Z is independently at each occurrence —O— or —NH— or —NR—, wherein R is a substituted or unsubstituted C 1-12 alkyl group, a substituted or unsubstituted C 3-12 cycloalkyl group, a substituted or unsubstituted C 6-20 aryl group, a C 1-20 alkylene oxide group, or a poly(C 1-6 alkylene oxide) group;
R 3 is hydroxy-substituted C 1-6 alkyl group, an oligo(C 1-6 oxyalkylene) group, a poly(C 1-6 oxyalkylene) group, or —NH 2 ; and
R 4 is a substituted or unsubstituted C 1-20 alkyl group, a substituted or unsubstituted C 3-12 cycloalkyl group, a substituted or unsubstituted C 6-20 aryl group.

7 . (canceled)

8 . The cured product of claim 1 , wherein
the polyanion comprises repeating units according to formulas (I), (VI) and (VII), wherein the repeating units of formulas (I), (VI) and (VII) are present in a molar ratio of (I):(VI):(VII) of 10-100:0-90:0-90; or the polyanion comprises repeating units according to formulas (III), (VI) and (VII), wherein the repeating units of formulas (III), (VI) and (VII) are present in a molar ratio of (III):(VI):(VII) of 10-100:0-90:0-90; and the polycation comprises repeating units according to formulas (V), (VI) and (VII), wherein the repeating units of formulas (V), (VI) and (VII) are present in a molar ratio of (V):(VI):(VII) of 10-100:0-90:0-90.

9 . (canceled)

10 . (canceled)

11 . (canceled)

12 . The cured product of claim 1 , wherein the cured product is in the form of a protective coating, a removable coating, a repositionable coating, a replaceable coating, a barrier coating, a paper coating, a water-proof coating, an anti-fouling coating, a protective film, a pressure sensitive adhesive, a laminating adhesive, a protective film for oral care, an ink, a membrane, or nail polish.

13 . An article comprising the cured product of claim 1 , wherein the article is a film, coating, or fiber, or wherein the cured product is disposed on at least a portion of a surface of the article.

14 . (canceled)

15 . (canceled)

16 . A method of forming the cured product of claim 1 , the method comprising:
combining a polyanion, a polycation and a salt to provide a liquid complex coacervate; and curing the liquid complex coacervate to provide the cured product.

17 . A method of forming a coating on a substrate, the method comprising:
combining a polyanion, a polycation and a salt to provide a liquid complex coacervate; depositing the liquid complex coacervate on at least a portion of the substrate; and curing the deposited liquid complex coacervate to provide the coating; wherein the polyanion comprises repeating units comprising one or more of a carboxylate group, a sulfonate group, or a phosphonate group; and wherein the polycation comprises repeating units comprising one or more of a nitrogen-containing cationic group, a phosphorus-containing cationic group, or a sulfur-containing cationic group, provided that when the polycation is poly(diallyldimethyl ammonium), the polyanion is not polystyrene sulfonate, or when the polyanion is polystyrene sulfonate, the polycation is not poly(diallyldimethyl ammonium).

18 . The method of claim 17 ,
wherein the polyanion comprises repeating units of one or more of formulas (I)—(IV)

wherein in the foregoing Formulas,
R 1 is H or methyl;
L 1 is a divalent linking group; and
Z is independently at each occurrence —O— or —NH— or —NR—, wherein R is a substituted or unsubstituted C 1-12 alkyl group, a substituted or unsubstituted C 3-12 cycloalkyl group, a substituted or unsubstituted C 6-20 aryl group, a C 1-20 alkylene oxide group, or a poly(C 1-6 alkylene oxide) group; and
wherein the polycation comprises repeating units of formula (V)

Assignees

• Univ Massachusetts
• Basf Se

Inventors

• Perry Sarah L
• Ramírez Marrero Isaac A
• Konradi Rupert
• Von Vacano Bernhard Ulrich
• Kaiser Nadine
• Gutzler Rainer

Classifications

• C09D133/14

  of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen · CPC title

• C09D133/02

  Homopolymers or copolymers of acids; Metal or ammonium salts thereof · CPC title

• C08F220/56

  Acrylamide; Methacrylamide · CPC title

• C08F220/34

  Esters containing nitrogen {, e.g. N,N-dimethylaminoethyl (meth)acrylate} · CPC title

• C08F220/06 Primary

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title