Fluoropolymer compositions and treated substrates

• US 8,128,711 B2
• Filed: 05/16/2011
• Issued: 03/06/2012
• 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: Qiu, Weiming, Yang, Yun, Ober, Michael Henry, Raghavanpillai, Anilkumar
• Primary Examiner(s): Cano, Milton I
• Assistant Examiner(s): Leonard, Michael L
• Application Number:
  US13/108,507
• Publication Number:
  US 20110217506A1
• Time in Patent Office: 295 Days
• Field of Search: 811/56, 811/564, 811/567, 811/551, 427/372.2, 428/423.1, 428/423.7, 428/423.5, 428/423.9, 428/424.2, 528/45, 528/49, 528/69, 528/70, 528/76
• US Class Current: 8/115.6
• 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 method of providing water repellency, oil repellency, soil resistance, hydrophilic stain release, and wicking to substrates comprising contacting said substrate with 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)_r—

XH 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;

R^l is a divalent radical selected from the group consisting of S(CH₂)_n—

,

2. The method of claim 1 wherein the polymer is contacted with the substrate as an aqueous dispersion or solution.

3. The method of claim 1 wherein the polymer is contacted with the substrate by means of exhaustion, spray, foam, flex-nip, nip, pad, kiss-roll, beck, skein, winch, liquid injection, overflow flood, brush, roll, spray, dip, roll coating, foaming, or immersion.

4. The method of claim 1 wherein the polymer is contacted with the substrate in the presence of an agent 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.

5. A substrate to which has been applied 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)_r—

XH 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—

,

6. The substrate of claim 5 wherein, within said fluorinated compound of formula (I), x is 2, y and z are each 1, m is 1 or 2, r is 0, X is —

O—

, and R_f has 6 carbon atoms.

7. The substrate of claim 5, wherein the diisocyanate or polyisocyanate is selected from the group consisting of hexamethylene diisocyanate homopolymer;

3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate;

bis-(4-isocyanatocylohexyl)methane; and

diisocyanate trimers of formulas (IIa), (IIb), (IIc) and (IId);

8. The substrate of claim 5 wherein, within said fluorinated compound of formula (I), when R_f has 1 to 4 carbon atoms, said at least one organic diisocyanate, polyisocyanate, or mixture thereof, comprises about 25 wt % to about 100 wt % of one or more cyclic diisocyanates selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane 4,4′

-diisocyanate, diphenylmethane 2,4′

-diisocyanate, 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate, bis-(4-isocyanatocylohexyl)methane and diisocyanate trimers of formula (IIa), (IIb), (IIc), and (IId);

9. The substrate of claim 5 comprising a fibrous substrate selected from the group consisting of a fiber, yarn, fabric, fabric blend, textile, rug, carpet, paper and leather.

10. The substrate of claim 5 which is selected from the group consisting of polyamide, wool, polyester, polyolefin, polyaramid, acrylic, wool, cotton, jute, sisal, sea grass, coir, and blends thereof.