# US 2014/0154420 A1 · Partially fluorinated copolymers

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- Number: US 2014/0154420 A1
- Document ID: US20140154420A1
- Status: Published application
- Kind: A1
- Application number: 14/071,718
- Filed: 2013-11-05
- Published: 2014-06-05
- Earliest claimed: 2012-12-05
- Assignees: E. I. Du Pont de Nemours and Company
- Applicants: E I Du Pont De Nemours and Company
- Inventors: JOHN CHRISTOPHER SWOREN
- Web page: https://patentgrep.com/patent/US20140154420A1

## CPC

- C09D 139/00: Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C08F 220/24: containing perhaloalkyl radicals
- C09D 133/16: Homopolymers or copolymers of esters containing halogen atoms
- 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)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

This invention is directed to a copolymer comprising fluorinated (met)acrylates, alkyl methacrylates, ethoxylates (meth)acrylates, and alkyl amino (meth)acrylates. These copolymers are capable of providing improved oil and water repellency to hard substrates while also maintaining its stability in a mixture of organic solvents.

## Claims

### Claim 1

A partially fluorinated copolymer comprising the reaction product of monomers copolymerized in the following percentages by weight:
a) from about 45% to about 75% of one or more monomers of Formula (I):
Rf-L-Q-C(O)—CR1═CH2 (I);
b) from about 25% to about 30% of one or more monomers of Formula (II):
RH-Q-C(O)—CR2═CH2 (II);
c) from about 0.5% to about 15% of one or more monomers of Formula (III):
R—(OCH2CH2)n—(OCH2CH(CH3))pQ-C(O)—CR3═CH2 (III);
d) from about 0.1% to about 4% of one or more monomers of Formula (IV):
e) from about 0% to about 2% of one or more monomers of Formula (V):
HO—C(O)—CR8═CH2 (V);
f) from about from about 0% to about 2% of one or more monomers of Formula (VI):
HO—CH2CH2-Q-C(O)—CR9═CH2 (VI);
g) from about from about 0% to about 2% of one or more monomers of Formula (VII):
CH2═CR10C(O)O(CH2CH2O)x(CH2CH(CH3)O)yC(O)CR11═CH2 (VII);
wherein
Rf is a linear or branch fluoroalkyl of 2 to 10 carbons optionally interrupted by 1 to 4 interrupting groups —O—, —CH2—, and/or —CHF— groups;
RH is a linear, branched, or cyclic alkyl chain of 7 to 22 carbons;
each Q is independently —O— or —S—;
L is —R12—, —SO2—N(R13)—R15—, —CO—N(R14)—R15—, —CH2CH(OR14)CH2—, —R6—SO2—N(R14)—R15—, or —R15—O—C(O)—N(R14)—R15—;
R1, R3, R7, R8, R9, R10, R11 are each independently H or —CH3;
R is —H or a linear, branched, or cyclic alkyl chain of 1 to 20 carbons;
R2 is —CH3;
R4 and R5 are each independently methyl or ethyl;
R6, R12 and R15 are each independently a linear or branched divalent alkyl chain of 2 to 10 carbons;
R13 and R14 are each independently —H, —CH3, C2 to C10 alkylene, or C1 to C4 acyl;
n is 0 to 10 and p is 0 to 10 provided that when p is 0, n is at least 2
and n+p is greater than 0; and
x is 0 to 10 and y is 0 to 10 provided that x+y is at least 1;
wherein the concentration of monomers of a), b), c), d), e), f), and g) is equal to 100% by weight.

### Claim 2 (depends on 1)

The partially fluorinated copolymer of claim 1 wherein Rf is a fluoroalkyl of 2 to 6 carbons, L is R12, R1 is H or CH3.

### Claim 3 (depends on 2)

The partially fluorinated copolymer of claim 2, wherein Rf is a fluoroalkyl of 4 to 6 carbons, and R1 is CH3.

### Claim 4 (depends on 1)

The partially fluorinated copolymer of claim 1 wherein RH is linear or branched alkyl chain of 7 to 22 carbons and Q is O.

### Claim 5 (depends on 4)

The partially fluorinated copolymer of claim 4 wherein RH is an octyl, 2-ethylhexyl, decyl, isodecyl, lauryl, cetyl, or stearyl.

### Claim 6 (depends on 1)

The partially fluorinated copolymer of claim 1 wherein p is 0.

### Claim 7 (depends on 1)

The partially fluorinated copolymer of claim 1 wherein p and n are both greater than 0.

### Claim 8 (depends on 1)

The partially fluorinated copolymer of claim 1 wherein the repeat unit of monomer e) is present.

### Claim 9 (depends on 1)

The partially fluorinated copolymer of claim 1 wherein the repeat unit of monomers e) and f) are present.

### Claim 10 (depends on 1)

The partially fluorinated copolymer of claim 1 wherein the repeat unit of monomers e), f), and g) are present.

### Claim 11 (depends on 1)

The partially fluorinated copolymer of claim 1 wherein the repeat unit of monomer f) is present.

### Claim 12 (depends on 1)

The partially fluorinated copolymer of claim 1 wherein the repeat unit of monomers f) and g) are present.

### Claim 13 (depends on 1)

The partially fluorinated copolymer of claim 1 wherein the repeat unit of monomers g) is present.

### Claim 14 (depends on 1)

The partially fluorinated copolymer of claim 1 wherein the repeat unit of monomers e) and g) are present.

### Claim 15

A method for treating a hard surface substrate comprises contacting the hard surface substrate with a partially fluorinated copolymer comprising the reaction product of monomers copolymerized in the following percentages by weight:
a) from about 45% to about 75% of one or more monomers of Formula (I):
Rf-L-Q-C(O)—CR1═CH2 (I);
b) from about 25% to about 30% of one or more monomers of Formula (II):
RH-Q-C(O)—CR2═CH2 (II);
c) from about 0.5% to about 15% of one or more monomers of Formula (III):
R—(OCH2CH2)n—(OCH2CH(CH3))pQ-C(O)—CR3═CH2 (III);
d) from about 0.1% to about 4% of one or more monomers of Formula (IV):
e) from about 0% to about 2% of one or more monomers of Formula (V):
HO—C(O)—CR8═CH2 (V);
f) from about from about 0% to about 2% of one or more monomers of Formula (VI):
HO—CH2CH2-Q-C(O)—CR9═CH2 (VI);
g) from about from about 0% to about 2% of one or more monomers of Formula (VII):
CH2═CR10C(O)O(CH2CH2O)x(CH2CH(CH3)O)yC(O)CR11═CH2 (VII);
wherein
Rf is a linear or branch fluoroalkyl of 2 to 10 carbons optionally interrupted by 1 to 4 interrupting groups —O—, —CH2—, and/or —CHF— groups;
RH is a linear, branched, or cyclic alkyl chain of 7 to 22 carbons;
each Q is independently —O— or —S—;
L is —R12—, —SO2—N(R13)—R15—, —CO—N(R14)—R15—, —CH2CH(OR14)CH2—, —R6—SO2—N(R14)—R15—, or —R15—O—C(O)—N(R14)—R15—;
R1, R3, R7, R8, R9, R10, R11 are each independently H or —CH3;
R is —H or a linear, branched, or cyclic alkyl chain of 1 to 20 carbons;
R2 is —CH3;
R4 and R5 are each independently methyl or ethyl;
R6, R12 and R15 are each independently a linear or branched divalent alkyl chain of 2 to 10 carbons;
R13 and R14 are each independently —H, —CH3, C2 to C10 alkylene, or C1 to C4 acyl;
n is 0 to 10 and p is 0 to 10 provided that when p is 0, n is at least 2
and n+p is greater than 0; and
x is 0 to 10 and y is 0 to 10 provided that x+y is at least 1;
wherein the concentration of monomers of a), b), c), d), e), f), and g) is equal to 100% by weight.

### Claim 16 (depends on 15)

The method of claim 15 wherein the contacting is by brush, spray, roller, doctor blade, wipe and dip techniques.

### Claim 17 (depends on 15)

The method of claim 15 wherein the hard surface substrate is unglazed concrete, brick, tile, stone, granite, limestone, grout, mortar, composite materials, terrazzo, gypsum board, marble, statuary, monuments, or wood.

### Claim 18 (depends on 16)

A substrate treated with the method of claim 16 which is unglazed concrete, brick, tile, stone, granite, limestone, grout, mortar, composite materials, terrazzo, gypsum board, marble, statuary, monuments, or wood.

### Claim 19

A method for treating leather substrates comprises contacting the leather substrate with a partially fluorinated copolymer comprising the reaction product of monomers copolymerized in the following percentages by weight:
a) from about 45% to about 75% of one or more monomers of Formula (I):
Rf-L-Q-C(O)—CR1═CH2 (I);
b) from about 25% to about 30% of one or more monomers of Formula (II):
RH-Q-C(O)—CR2═CH2 (II);
c) from about 0.5% to about 15% of one or more monomers of Formula (III):
R—(OCH2CH2)n—(OCH2CH(CH3))pQ-C(O)—CR3═CH2 (III);
d) from about 0.1% to about 4% of one or more monomers of Formula (IV):
e) from about 0% to about 2% of one or more monomers of Formula (V):
HO—C(O)—CR8═CH2 (V);
f) from about from about 0% to about 2% of one or more monomers of Formula (VI):
HO—CH2CH2-Q-C(O)—CR9═CH2 (VI);
g) from about from about 0% to about 2% of one or more monomers of Formula (VII):
CH2═CR10C(O)O(CH2CH2O)x(CH2CH(CH3)O)yC(O)CR11═CH2 (VII);
wherein
Rf is a linear or branch fluoroalkyl of 2 to 10 carbons optionally interrupted by 1 to 4 interrupting groups —O—, —CH2—, and/or —CHF— groups;
RH is a linear, branched, or cyclic alkyl chain of 7 to 22 carbons;
each Q is independently —O— or —S—;
L is —R12—, —SO2—N(R13)—R15—, —CO—N(R14)—R15—, —CH2CH(OR14)CH2—, —R6—SO2—N(R14)—R15—, or —R15—O—C(O)—N(R14)—R15—;
R1, R3, R7, R8, R9, R10, R11 are each independently H or —CH3;
R is —H or a linear, branched, or cyclic alkyl chain of 1 to 20 carbons;
R2 is —CH3;
R4 and R5 are each independently methyl or ethyl;
R6, R12 and R15 are each independently a linear or branched divalent alkyl chain of 2 to 10 carbons;
R13 and R14 are each independently —H, —CH3, C2 to C10 alkylene, or C1 to C4 acyl;
n is 0 to 10 and p is 0 to 10 provided that when p is 0, n is at least 2
and n+p is greater than 0; and
x is 0 to 10 and y is 0 to 10 provided that x+y is at least 1;
wherein the concentration of monomers of a), b), c), d), e), f), and g) is equal to 100% by weight.

### Claim 20 (depends on 19)

The method of claim 19 wherein the contacting is by spray, dipping, foam, nip, immersion, brush, roller, sponge, mat techniques.