Fluoropolymer compositions and treated substrates

• US 7,968,669 B2
• Filed: 05/16/2008
• Issued: 06/28/2011
• Est. Priority Date: 05/16/2008
• 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: Yang, Yun, Qiu, Weiming, Ober, Michael Henry, Raghavanpillai, Anilkumar
• Primary Examiner(s): Cano; Milton I
• Assistant Examiner(s): LEONARD, MICHAEL L
• Application Number:
  US12/152,736
• Publication Number:
  US 20090286949A1
• Time in Patent Office: 1,138 Days
• Field of Search: 528/49, 528/70, 528/45, 528/69, 528/76, 811/56, 811/564, 811/567, 811/551
• US Class Current: 528/49
• CPC Class Codes: C08G 18/2825 having at least 6 carbon atoms
• CPC Class Codes: C08G 18/283 Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• CPC Class Codes: C08G 18/2885 containing halogen atoms
• CPC Class Codes: D06M 15/576 containing fluorine
• CPC Class Codes: D06M 2200/11 Oleophobic properties
• CPC Class Codes: D06M 2200/12 Hydrophobic properties
• CPC Class Codes: Y10T 428/23986 With coating, impregnation, or bond
• CPC Class Codes: Y10T 428/2933 Coated or with bond, impregnation or core
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• 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 428/31569 Next to natural rubber
• CPC Class Codes: Y10T 428/31573 Next to addition polymer of ethylenically unsaturated monomer

Abstract

A polymer having at least one carbamate linkage prepared by: (i) reacting (a) at least one diisocyanate, polyisocyanate, or mixture thereof, and (b) at least one fluorinated compound selected from the formula (I):
R_f(CH₂)_x[(CF₂CF₂)_y(CH₂CH₂)_z]_m(R1)_r-xH  (I)

• • wherein R_f is a perfluoroalkyl group having 1 to about 6 carbon atoms;
  • the total number of carbons in said formula (I) excluding (R1)_r-XH ranges from about 8 to about 22;
  • and (ii) optionally reacting with (c) water, a linking agent, or a mixture thereof.

Claims

1. A polymer having at least one carbamate linkage prepared by:

(i) reacting (a) at least one diisocyanate, polyisocyanate, or mixture thereof, having isocyanate groups, and (b) at least one fluorinated compound selected from the formula (I);

R_f(CH₂)_x[(CF₂CF₂)_y(CH₂CH₂)_z]_m(R¹)_r—

XH 

 

(I)

wherein

R_f is a linear or branched chain perfluoroalkyl group having 1 to about 6 carbon atoms;

subscript x is an integer from 1 to about 6;

subscripts y, z and m are each independently 1, 2 or 3, or a mixture thereof;

subscript r is 0 or 1;

the total number of carbons in said formula (I) excluding (R¹)_rXH ranges from about 8 to about 22;

X is —

O—

, —

NR—

, —

S—

, —

S(CH₂)_tO—

, or —

S(CH₂)_tNR—

;

subscript t is from 1 to about 10;

R is H or C_1-4 alkyl;

R¹ is a divalent radical selected from the group consisting of —

S(CH₂)_n—

,

2. The polymer of claim 1 wherein for the reactant of formula (I), X is O, and subscripts x, y, z, and m are each independently 1 or 2, and subscript r is 0.

3. The polymer of claim 1 wherein R_f has 4 to 6 carbon atoms.

4. The polymer of claim 1 wherein R_f has 4 to 6 carbon atoms, x is 2, y and z are each 1, m is 1 or 2, and r is 0.

5. The polymer of claim 1 wherein said fluorinated compound reacts with about 5 mol % to about 90 mol % of said isocyanate groups.

6. The composition of claim 1 wherein the diisocyanate or polyisocyanate is selected from the group consisting of hexamethylene diisocyanate homopolymer, 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate, bis-(4-isocyantatocyclohexyl)methane and diisocyanate trimers of formulas (IIa), (IIb), (IIc) and (IId):

7. The polymer of claim 1 wherein step (i) reacting, further comprises (d) a non-fluorinated organic compound selected from the group consisting of formula

R¹⁰—

(R¹¹)_k—

YH

wherein

R¹⁰ is a C₁-C₁₈ alkyl, a C₁-C₁₈ omega-alkenyl radical or a C₁-C₁₈ omega-alkenyl;

R¹¹ is selected from the group consisting of

8. The polymer of claim 7, wherein the compound of formula

R¹⁰—

(R¹¹)_k—

YH comprises a hydrophilic water-solvatable material comprising at least one hydroxy-terminated polyether of formula (III);

9. The polymer of claim 7 wherein said non-fluorinated compound reacts with about 0.1 mol % to about 60 mol % of said isocyanate groups.

10. The polymer of claim 1 wherein the linking agent is a diamine or polyamine.

11. The polymer of claim 1 in the form of an aqueous dispersion or solution.

12. The polymer of claim 1 further comprising one or more agents providing at least one surface effect selected from the group consisting of no iron, easy to iron, shrinkage control, wrinkle free, permanent press, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stain repellency, stain release, soil resistance, soil release, water repellency, oil repellency, stain resist, odor control, antimicrobial, and sun protection.

13. The polymer of claim 1 further comprising a surfactant, pH adjuster, cross linker, wetting agent, blocked isocyanate, wax extender, or hydrocarbon extender.