Fluorochemical water and oil repellents

• US 6,479,612 B1
• Filed: 06/19/2000
• Issued: 11/12/2002
• Est. Priority Date: 08/10/1999
• Status: Expired due to Fees

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Liu, Andrew H., Del Pesco, Thomas Wayne, Kirchner, Jack
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): Bissett, Melanie
• Application Number:
  US09/596,322
• Time in Patent Office: 876 Days
• Field of Search: 528/70, 528/71, 428/423.4, 428/425.1, 428/425.5, 428/423.5, 428/423.7, 524/840, 442/80, 442/82
• US Class Current: 528/70
• CPC Class Codes: C08G 18/0828 containing sulfonate groups or groups forming them
• CPC Class Codes: C08G 18/3812 having fluorine atoms
• CPC Class Codes: C14C 9/00 Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
• CPC Class Codes: Y10T 428/31558 Next to animal skin or membrane
• CPC Class Codes: Y10T 428/31562 Next to polyamide [nylon, etc.]
• CPC Class Codes: Y10T 428/31565 Next to polyester [polyethylene terephthalate, etc.]
• CPC Class Codes: Y10T 428/31598 Next to silicon-containing [silicone, cement, etc.] layer
• CPC Class Codes: Y10T 442/2172 Also specified as oil repellent
• CPC Class Codes: Y10T 442/2189 Fluorocarbon containing

Abstract

A polymer having at least one urea linkage derived by contacting (1) at least one polyisocyanate, or mixture of polyisocyanates, (2) at least one fluorocarbon alcohol, fluorocarbon thiol or fluorocarbon amine, (3) at least one straight or branched chain alcohol, amine or thiol, and (4) at least one alcohol containing a sulfonic acid group or its salt, and then (5) optionally at least one linking agent useful for imparting oil repellency and water repellency to substrates.

Claims

1. A polymer having at least one urea linkage derived by contacting (1) at least one polyisocyanate, or mixture of polyisocyanates, (2) at least one fluorocarbon alcohol, fluorocarbon thiol or fluorocarbon amine, (3) a straight and branched chain mixture of at least one alcohol, amine or thiol, and (4) at least one alcohol containing a sulfonic acid group or its salt, and then (5) optionally at least one linking agent.

2. The polymer of claim 1 dispersed in water.

3. The polymer of claim 1 wherein the polyisocyanate contains at least three isocyanate groups or is a diisocyanate precursor of a polyisocyanate containing at least three isocyanate groups.

4. The polymer of claim 1 wherein the polyisocyanate is a hexamethylene diisocyanate homopolymer.

5. The polymer of claim 1 wherein the fluorocarbon alcohol, fluorocarbon thiol or fluorocarbon amine is of formula

6. The polymer of claim 5 wherein R_f—

X—

is F(CF₂)_q(CH₂)_n—

wherein n is 1 to about 20 and q is from about 4 to about 20.

7. The polymer of claim 1 wherein the straight chain alcohol, amine or thiol of component (3) is a formula selected from the group consisting of H(CH₂)_x—

OH, H(CH₂)_x—

NH₂, and H(CH₂)₄—

SH, and a mixture thereof, wherein x is from about 12 to about 20, and the branched chain alcohol, amine or thiol of component (3) is a formula selected from the group consisting of C_yH_(2y+1)CH₂OH, C_yH_(2y+1)CH₂NH₂, and C_yH_(2y+1)CH₂SH, and a mixture thereof, wherein y is from about 15 to about 19.

8. The polymer of claim 1 wherein the alcohol containing a sulfonic acid is of the formula MO₃S—

Y—

OH wherein M is an alkali metal;

ammonium;

alkyl, dialkyl, trialkyl or tetraalkyl ammonium;

or hydrogen; and

Y is a straight or branched chain alkyl group containing 2 to 10 carbon atoms or an aryl or aralkyl group containing an aromatic ring and 6 to 11 carbon atoms.

9. The polymer of claim 1 wherein the linking agent is water, glycol, or a fluorinated diol.

10. The polymer of claim 1 wherein the molar ratio of reactants per 100 isocyanate groups is from about 28 to about 48 for reactant (2), from about 28 to about 48 for reactant (3), from 1 to about 20 for reactant (4), and from about 4 to about 30 for reactant (5).

11. A method of imparting oil repellency and water repellency to a wood, masonry or leather substrate or a fibrous substrate comprising contacting said substrate with a dispersion of a polymer having at least one urea linkage derived by reacting (1) at least one polyisocyanate, or mixture of polyisocyanates, (2) at least one fluorocarbon alcohol, fluorocarbon thiol, or fluorocarbon amine (3) a straight and branched chain mixture of at least one alcohol, amine or thiol, and (4) at least one alcohol containing a sulfonic acid group or its salt, and then (5) optionally at least one linking agent.

12. The method of claim 11 wherein the amount of fluorine contacted with the wood, masonry or leather substrate is from about 0.2 g fluorine/m2 to about 2.3 g fluorine/m2.

13. The method of claim 12 wherein no curing step is employed.

14. The method of claim 11 wherein the amount of polymer contacted with the fibrous substrate is sufficient to provide a fluorine content of at least about 200 μ

g/g by weight of the dry substrate.

15. A wood, masonry or leather substrate treated to provide oil repellency and water repellency by contacting said substrate with a dispersion of a polymer having at least one urea linkage derived by reacting (1) at least one polyisocyanate, or mixture of polyisocyanates, (2) at least one fluorocarbon alcohol, fluorocarbon thiol, or fluorocarbon amine (3) a straight and branched chain mixture of at least one alcohol, amine or thiol, and (4) at least one alcohol containing a sulfonic acid group or its salt, and then (5) optionally at least one linking agent.

16. The substrate of claim 15 treated to provide oil repellency and water repellency which has a fluorine content of at least about 0.2 g fluorine/m2 in the dry substrate.

17. A fibrous substrate treated to provide oil repellency and water repellency by contacting said substrate with a dispersion of a-polymer having at least one urea linkage derived by reacting (1) at least one polyisocyanate, or mixture of polyisocyanates, (2) at least one fluorocarbon alcohol, fluorocarbon thiol, or fluorocarbon amine (3) a straight and branched chain mixture of at least one alcohol, amine or thiol, and (4) at least one alcohol containing a sulfonic acid group or its salt, and then (5) optionally at least one linking agent.

18. The substrate of claim 17 treated to provide oil and water repellency which has a fluorine content of at least about 200 μ

g/g by weight of the dry fibrous substrate.

19. The substrate of claim 18 wherein the oil and water repellency is retained after laundering without a subsequent heat treatment.