Fluoropolymer compositions and treated substrates

1. A composition comprising an aqueous solution or dispersion of at least one polyurethane having at least one urea 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 1 -L-X  (I)

wherein

R f 1 is a monovalent, partially or fully fluorinated, linear or branched, alkyl radical having 2 to 100 carbon atoms; optionally interrupted by 1 to 50 oxygen atoms; wherein the ratio of carbon atoms to oxygen atoms is at least 2:1 and no oxygen atoms are bonded to each other;

L is a bond or a linear or branched divalent linking group having 1 to about 20 carbon atoms, said linking group optionally interrupted by 1 to about 4 hetero-radicals selected from the group consisting of —O—, —NR 1 —, —S—, —SO—, —SO 2 —, and —N(R 1 )C(O)— wherein R 1 is H or C 1 to C 6 alkyl, and said linking group optionally substituted with CH 2 Cl;

X is OH, N(R 1 )H, or SH wherein R 1 is H or C 1 -C6 alkyl; and thereafter

(ii) reacting with (c) water and (d) 0.05 to about 2.0% by weight of an isocyanate-reactive fluorinated particulate component, based on a total dry weight of the composition;

wherein the isocyanate-reactive fluorinated particulate component comprises inorganic oxides of Si, Ti, Zn, Mn, Al, and Zr having at least one particle having a surface covalently bonded to at least one group represented by formula (IV)

(L 2 ) d (L 3 ) c Si—(CH 2 ) n —(Z 1 ) a —[C(X 1 )] x —(Z 2 ) l -Q 1 -R f   (IV)

wherein:

L 2 represents an oxygen covalently bonded to M; and

each L 3 is independently selected from the group consisting of H, a C 1 -C 2 alkyl, and OH;

d and c are each integers such that: d is greater than or equal to 1, c is greater than or equal to 0, and d+c is 3;

n is independently an integer from 1 to 12;

a, x, and l are each integers such that the moiety of Formula (IV) represented by —(Z 1 ) a —[C(X 1 )] x —(Z 2 ) l — is at least one of the following moieties:

i) a first moiety wherein a=1, x=1, and l=1;

ii) a second moiety wherein a=1, x=0; and l=0; and

iii) a third moiety wherein a=1, x=0, and l=1;

R f is a C 2 -C 12 perfluoroalkyl optionally interrupted by oxygen or methylene,

Q 1 is selected from the group consisting of a C 2 -C 12 hydrocarbylene optionally interrupted by at least one divalent organic group;

X 1 is O or S;

wherein in said first moiety Z 1 and Z 2 are chosen such that:

a) Z 1 is —NH— and Z 2 is selected from the group consisting of —NH—, —O—, —S—, —NH—S(O) 2 —, —N[C(O)H]—, —[HC(COOH)(R 14 )]CH—S—, and —(R 14 )CH[HC(COOH)]—S—;

wherein

each R 14 is independently hydrogen, phenyl, or a monovalent C 1 -C 8 alkyl optionally terminated by —C 6 H 5 , or

b) Z 2 is —NH— and Z 1 is selected from the group consisting of —O—, —S—, —N[-Q 2 -(R f )]—, or

wherein Q 2 is independently selected from the group consisting of a C 2 -C 12 hydrocarbylene optionally interrupted by at least one divalent organic group;

c) provided that when Z 1 or Z 2 is O, Q 1 is interrupted by at least one divalent moiety selected from the group consisting of —S—, —S(O)—, —S(O) 2 —, —NH—S(O) 2 —, —N(CH) 3 S(O) 2 —, and

and

wherein in said second moiety

a) Z 1 is —N(-Q 3 -R f )—; and

b) Q 1 and Q 3 are independently chosen from the group consisting of a C 2 -C 12 hydrocarbylene interrupted by at least one of —C(O)—O— or —O—CO(O)—, and optionally further interrupted by at least one divalent organic group; and

wherein in said third moiety

a) Z 1 and Z 2 are mutually exclusive and are selected from the group consisting of —N(Q 4 )- and —S(O) 2 —; and

b) Q 4 is a monovalent moiety selected from the group consisting of C 2 -C 12 alkyl, —C 6 H 6 , and —(CH 2 ) g —NH—S(O) 2 —(CH 2 ) g —R f where g is 1 or 2, and R f is as defined above.

2. The composition of claim 1 wherein R f 1 is F(CF 2 ) n , F(CF 2 ) n (CH 2 ) x [(CF 2 CF 2 ) p (CH 2 CH 2 ) q ] m ,

F(CF 2 ) n OF(CF 2 ) n , F(CF 2 ) n OCFHCF 2 , or F(CF 2 ) n [OCF 2 CF(CF 3 )] p [OCF 2 CF 2 ] q , wherein n is 1 to about 6; x is 1 to about 6; and p, q, and m are each independently 1 to about 3.

3. The composition of claim 1 wherein L is a bond, R 5 , R 5 -A, or ethylene oxide, wherein

A is a divalent C 1 -C 6 alkyl and R 5 is a divalent radical selected from the group consisting of —S(CH 2 ) u —,

u is an integer of from about 2 to about 4;

s is an integer of 1 to about 4; and

R 2 , R 3 , and R 4 are each independently hydrogen or an alkyl group containing 1 to about 6 carbon atoms.

4. The composition of claim 1 wherein formula (I) is selected from the group consisting of F(CF 2 ) n (CH 2 ) t (R 5 ) r OH,

F(CF 2 ) n (CH 2 ) x [CF 2 CF 2 ) p (CH 2 CH 2 ) q ] m (R 5 ) r OH,

F(CF 2 ) n O(CF 2 ) n CH 2 (C t H 2t )(R 5 ) r OH, and

F(CF 2 ) n OCFHCF 2 (OCH 2 CH 2 ) v OH,

wherein

n is an integer of 1 to about 6;

t is an integer of 1 to about 10;

p, q, and m are each independently an integer of 1 to about 3;

r is 0 or 1;

v is an integer of 1 to about 4;

R 5 is a divalent radical selected from the group consisting of —S(CH 2 ) u —,

u is an integer of 2 to about 4;

s is an integer of 1 to about 4; and

R 2 , R 3 , and R 4 are each independently hydrogen or an alkyl group containing 1 to about 6 carbon atoms.

5. The composition of claim 4 wherein n is 4 to 6; p, q, and m are each 1; and r is 0.

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

7. 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-isocyanatocylohexyl)methane and diisocyanate trimers of formulas (IIa), (IIb), (IIc) and (IId):

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

R 10 —(R 11 ) k —X

wherein

R 10 is a C 1 -C 18 alkyl, a C 1 -C 18 omega-alkenyl radical or a C 1 -C 18 omega-alkenoyl;

R 11 is selected from the group consisting of

wherein

R 2 , R 3 and R 4 are each independently, H or C 1 to C 6 alkyl, and

s is an integer of 1 to about 50;

k is 0 or 1,

X is an isocyanate-reactive group selected from the group consisting of —OH, —N(R)H, and —SH, and R is H or C 1 -C 6 alkyl.

9. The composition of claim 8 , wherein the compound of formula R 10 —(R 11 ) k —X comprises a hydrophilic water-solvatable material comprising at least one hydroxy-terminated polyether of formula (III):

wherein

R 12 is a monovalent C 1 -C 6 alkyl or cycloalkyl radical;

m1 is a positive integer, and m2 and m3 are each independently a positive integer or zero; said polyether having a weight average molecular weight up to about 2000.

10. The composition of claim 8 wherein said non-fluorinated compound reacts with about 0.1 mol % to about 60 mol % of said isocyanate groups.

11. The composition of claim 1 the inorganic oxides are at least partially surface-modified with hydrophobic groups, said hydrophobic groups derived from reaction of inorganic oxides with hydrophobic surface treatment reagents selected from the group consisting of alkyl halosilanes including C 1 -C 18 alkyl trichlorosilanes, C 1 -C 18 dialkyl dichlorosilanes, C 1 -C 18 trialkyl chlorosilanes; alkyl alkoxysilanes including C 1 -C 18 alkyl trimethoxysilanes, C 1 -C 18 dialkyl dimethoxysilanes, C 1 -C 18 trialkyl methoxysilanes, and C 1 -C 18 alkyl triethoxysilanes; perfluoroalkyl chlorosilanes including C 1 -C 18 perfluoroalkylethyl trichlorosilanes, perfluoroalkyl alkoxysilanes including C 1 -C 18 perfluoroalkylethyl trimethoxysilanes, and C 1 -C 18 perfluoroalkylethyl trimethoxysilanes; alkyl disilazanes including hexamethyl disilazane; polydialkyl siloxanes including polydimethyl siloxane; aminoalkyl alkoxysilanes including 3-aminopropyl trimethoxysilane and 3-aminopropyl triethoxysilane; and mixtures thereof.

12. The composition of claim 1 wherein M is Si.

13. The composition of claim 1 wherein formula (IV) comprises a urea or thiourea wherein:

a is 1, x is 1, and l is 1;

Z 1 and Z 2 are both —NH—; and

X 1 is O or S.

14. The composition of claim 1 wherein (ii) reacting with (c) water and (d) 0.05 to about 2.0% by weight of an isocyanate-reactive particulate component, further comprises (f) a linking agent that is a diamine or polyamine.

15. The composition 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 repellency, soil release, water repellency, oil repellency, stain resist, odor control, antimicrobial, and sun protection.

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

17. A method of providing water repellency, oil repellency and soil resistance to a substrate comprising contacting said substrate with a composition of an aqueous solution or dispersion of at least one polyurethane having at least one urea 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 1 -L-X  (I)

wherein

R f 1 is a monovalent, partially or fully fluorinated, linear or branched, alkyl radical having 2 to 100 carbon atoms; optionally interrupted by 1 to 50 oxygen atoms; wherein the ratio of carbon atoms to oxygen atoms is at least 2:1 and no oxygen atoms are bonded to each other;

L is a bond or a linear or branched divalent linking group having 1 to about 20 carbon atoms, said linking group optionally interrupted by 1 to about 4 hetero-radicals selected from the group consisting of —O—, —NR 1 —, —S—, —SO—, —SO 2 —, and —N(R 1 )C(O)— wherein R 1 is H or C 1 to C 6 alkyl, and said linking group optionally substituted with CH 2 Cl;

X is an isocyanate-reactive group selected from the group consisting of —OH, —N(R)H, and —SH; and thereafter

(iii) reacting with (c) water and (d) 0.05 to about 2.0% by weight of an isocyanate-reactive fluorinated particulate component, based on a total dry-weight of the composition;

wherein the isocyanate-reactive fluorinated particulate component comprises inorganic oxides of Si, Ti, Zn, Mn, Al, and Zr having at least one particle having a surface covalently bonded to at least one group represented by formula (IV)

(L 2 ) d (L 3 ) c Si—(CH 2 ) n —(Z 1 ) a —[C(X 1 )] x —(Z 2 ) l -Q 1 -R f   (IV)

wherein:

L 2 represents an oxygen covalently bonded to M; and

each L 3 is independently selected from the group consisting of H, a C 1 -C 2 alkyl, and OH;

d and c are each integers such that d is greater than or equal to 1, c is greater than or equal to 0, and d+c is 3;

n is independently an integer from 1 to 12;

a, x, and l are each integers such that the moiety of Formula (IV) represented by —(Z 1 ) a —[C(X 1 )] x —(Z 2 ) l — is at least one of the following moieties:

i) a first moiety wherein a=1, x=1, and l=1;

ii) a second moiety wherein a=1, x=0; and l=0; and

iii) a third moiety wherein a=1, x=0, and l=1;

R f is a C 2 -C 12 perfluoroalkyl optionally interrupted by oxygen or methylene,

Q 1 is selected from the group consisting of a C 2 -C 12 hydrocarbylene optionally interrupted by at least one divalent organic group;

X 1 is O or S;

wherein in said first moiety Z 1 and Z 2 are chosen such that:

a) Z 1 is —NH— and Z 2 is selected from the group consisting of —NH—, —O—, —S—, —NH—S(O) 2 —, —N[C(O)H]—, —[HC(COOH)(R 14 )]CH—S—, and —(R 14 )CH[HC(COOH)]—S—;

wherein

each R 14 is independently hydrogen, phenyl, or a monovalent C 1 -C 8 alkyl optionally terminated by —C 6 H 5 , or

b) Z 2 is —NH— and Z 1 is selected from the group consisting of —O—, —S—, —N[-Q 2 -(R f )]—, or

wherein Q 2 is independently selected from the group consisting of a C 2 -C 12 hydrocarbylene optionally interrupted by at least one divalent organic group;

c) provided that when Z 1 or Z 2 is O, Q 1 is interrupted by at least one divalent moiety selected from the group consisting of —S—, —S(O)—, —S(O) 2 —, —NH—S(O) 2 —, —N(CH) 3 S(O) 2 —, and

and

wherein in said second moiety

a) Z 1 is —N(-Q 3 -R f )—; and

b) Q 1 and Q 3 are independently chosen from the group consisting of a C 2 -C 12 hydrocarbylene interrupted by at least one of —C(O)—O— or —O—C(O)—, and optionally further interrupted by at least one divalent organic group; and

wherein in said third moiety

a) Z 1 and Z 2 are mutually exclusive and are selected from the group consisting of —N(Q 4 )- and —S(O) 2 —; and

b) Q 4 is a monovalent moiety selected from the group consisting of C 2 -C 12 alkyl, —C 6 H 5 , and —(CH 2 ) g —NH—S(O) 2 —(CH 2 ) g —R f where g is 1 or 2, and R f is as defined above.

18. The method of claim 17 wherein the contacting is by exhaustion, foam, flex-nip, nip, pad, kiss-roll, beck, skein, winch, liquid injection, overflow flood, roll, brush, roller, spray, dipping or immersion.

19. A substrate treated according to the method of claim 16 .

20. The substrate of claim 19 which is a fiber, yarn, fabric, fabric blend, textile, spunlaced nonwoven, carpet, paper or leather of cotton, cellulose, wool, silk, rayon, nylon, aramid, acetate, acrylic, jute, sisal, sea grass, coir, polyamide, polyester, polyolefin, polyacrylonitrile, polypropylene, polyaramid, or blends thereof.