Fluoropolymer emulsions

1. A fluoropolymer composition comprising monomers copolymerized in the following percentages by weight:

(a) from about 20% to about 95% of a fluoroalkyl monomer, or mixture of monomers, of formula (I)

R f 1 -L-X—C(O)—C(R)═CH 2   (I)

wherein

R f 1 is a monovalent, partially or fully fluorinated, linear or branched, alkyl radical having from about 2 to about 100 carbon atoms; optionally interrupted by 1 to about 50 oxygen atoms; wherein the ratio of carbon atoms to oxygen atoms is at least about 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 —O—, —N R 1 —, or —S—;

R is hydrogen, or CH 3 ;

(b) from about 5% to about 80% of at least one of:

(i) an alkyl (meth)acrylate monomer having a linear, branched or cyclic alkyl group of from about 6 to about 18 carbons; or

(ii) one or more ionizable water solvatable monomers; and

(c) from about 0.05% to about 2% non-fluorinated polymerizable nanoparticles, wherein the polymerizable nanoparticles have ethylenically unsaturated moieties linked to the particle.

2. The composition of claim 1 wherein R f 1 is F(CF 2 ) n , F(CF 2 ) n (CH 2 CF 2 ) p , 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; p, q, and m are each independently 1 to about 3, and

r is 0 or 1.

3. The composition of claim 1 wherein L is a bond, —(C t H 2t )— wherein t is an integer of 1 to 10; phenylene; C 1 -C 4 alkyl substituted phenylene; ethylene oxide; R 5 ; or (A) p -R 5 ; wherein A is a divalent alkyl of 1 to 6 carbons, p is as defined above, and 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 50; 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 X—C(O)—C(R)═CH 2 , F(CF 2 ) n (CH 2 CF 2 ) p (CH 2 CH 2 ) q (R 5 ) r X—C(O)—C(R)═CH 2 , F(CF 2 ) n (CH 2 ) x [CF 2 CF 2 ) p (CH 2 CH 2 ) q ] m (R 5 ) r X—C(O)—C(R)═CH 2 , F(CF 2 ) n O(CF 2 ) n CH 2 (C t H 2t )(R 5 ) r X—C(O)—C(R)═CH 2 , and F(CF 2 ) n OCFHCF 2 (OCH 2 CH 2 ) v X—C(O)—C(R)═CH 2 ,

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 50; 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 composition of claim 1 wherein the one or more ionizable water solvatable monomers is selected from the group consisting of M 1 OC(O)—C(R)═CH 2 , (R 1 ) 2 N-L 11 -O—C(O)—C(R)═CH 2 , M 1 OC(O)-L 11 -O—C(O)—C(R)═CH 2 , (M 1 O) 3-k P(O)[-L 11 -O—C(O)—C(R)═CH 2 ] k , M 1 OS(O) 2 -L 11 -X—C(O)—C(R)═CH 2 , M 1 OS(O) 2 -L 11 -C(R)═CH 2 , and M 1 OS(O) 2 —C(R)═CH 2 , M 1 OS(O)-L 11 -C(R)═CH 2

wherein

R is hydrogen, Cl, F or CH 3 ;

R 1 is H or C 1 -C 6 alkyl;

M 1 is a hydrogen or cation;

k is 1 or 2;

L 11 is a bond or an organic linking group having from about 2 to about 20 carbon atoms optionally interrupted by one or two hetero-radicals selected from the group consisting of —O—, —NR 1 —, —S—, —SO—, —SO 2 —, —N(R 1 )C(O)—, and —OC(O)—, and optionally substituted with CH 2 Cl.

7. The composition of claim 1 further comprising at least one additional monomer copolymerized in the following percentage by weight:

(d) from about 1% to about 35% vinylidene chloride, vinyl chloride, or vinyl acetate, or a mixture thereof; or

(e) from about 0.5% to about 25% of at least one monomer selected from the group consisting of styrene, methyl-substituted styrene, chloromethyl-substituted styrene, 2-hydroxyethyl (meth)acrylate, ethylenediol di(meth)acrylate, N-methyloyl (meth)acrylamide, C 1 -C 5 alkyl (meth)acrylate, and a compound of formula (XX):

R 8 (OCH 2 CH 2 ) m O—C(O)—C(R)═CH 2   (XX)

wherein

m is 2 to about 10;

R 8 is hydrogen, a C 1 to C 4 alkyl, or CH 2 ═C(R)C(O)—O—; and

each R is hydrogen, Cl, F or CH 3 ; or

(f) from about 0.5% to about 10% of at least one monomer of formula (XXIa), (XXIb) or (XXIc):

wherein

each R is independently hydrogen, Cl, F or CH 3 ;

R 9 is a linear or branched C 1 to C 4 alkyl;

B 1 is a divalent linear or branched C 2 to C 4 alkylene;

B 2 is a covalent bond or a divalent linear or branched C 1 to C 4 alkylene; and

X is —O—, —NR 1 —, or —S—; wherein R 1 is H or C 1 -C 6 alkyl; or

(f) 1% to about 35% of any combination of (d), (e), or (f).

8. The composition of claim 1 wherein the polymerizable nanoparticles are surface modified inorganic oxide particles comprising an oxide of M atoms independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof; 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—(O) e —(R 7 ) f -(Z 1 ) a -[C(X 1 )] x -(Z 2 ) l -Q  (IV)

wherein:

L 2 is an oxygen covalently bonded to M; and each L 3 is independently selected from the group consisting of H, a C 1 to C 2 alkyl, and OH; d and c are each independently integers such that: d is greater than or equal to 1, c is greater than or equal to 0, and d+c is 3;

e, f, a, x, and l are each independently 0 or 1;

R 7 is C 1 to C 12 alkyl, linear or branched

Z 1 is —NH—;

X 1 is O or S;

Z 2 is NH, N—C(O)—OH, N—C(O)— or OCH 2 CH 2 N—C(O)— provided that when

Z 2 is N—C(O)— or OCH 2 CH 2 N—C(O)— that Q forms a 5 member heterocyclic ring represented by N—C(O)—CH═CH—C(O)—; and

Q is selected from the group consisting of a C 2 -C 12 hydrocarbylene optionally interrupted by —O—C(O)—, —C(O)—O— or one divalent organic group.

9. The composition of claim 1 wherein the ethylenically unsaturated moieties are selected from the group consisting of (meth)acrylates, maleates, maleimides, fumerates, and unsaturated hydrocarbons including styrenes and substituted styrenes, vinyl, allyl and dienes.

10. The composition of claim 1 wherein the polymerizable nanoparticles comprise inorganic oxides of Si, Ti, Zn, Mn, Al, or Zr.

11. The copolymer composition of claim 1 wherein the polymerizable nanoparticles are inorganic oxides of Si.

12. The composition of claim 11 wherein the polymerizable nanoparticles are inorganic oxides of Si containing acrylate groups.

13. The copolymer composition of claim 1 wherein the polymerizable nanoparticles have an average particle size of from about 10 to about 500 nm.

14. A method of treating a fibrous substrate comprising applying to the surface of the substrate a fluoropolymer composition comprising monomers copolymerized in the following percentages by weight:

(a) from about 20% to about 95% of a fluoroalkyl monomer, or mixture of monomers, of formula (I)

R f 1 -L-X—C(O)—C(R)═CH 2   (I)

wherein

R f 1 is a monovalent, partially or fully fluorinated, linear or branched, alkyl radical having from about 2 to about 100 carbon atoms; optionally interrupted by 1 to about 50 oxygen atoms; wherein the ratio of carbon atoms to oxygen atoms is at least about 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 —O—, —NR 1 —, or —S— wherein R 1 is H or C 1 to C 6 alkyl;

R is hydrogen, or CH 3 ;

(b) from about 5% to about 80% of at least one of:

(i) an alkyl (meth)acrylate monomer having a linear, branched or cyclic alkyl group of from about 6 to about 18 carbons; or

(ii) one or more ionizable water solvatable monomers; and

(c) from about 0.05% to about 2% polymerizable non-fluorinated nanoparticles, wherein the polymerizable nanoparticles have ethylenically unsaturated moieties linked to the particle,

said composition providing oil repellency and water repellency to substrates contacted therewith.

15. The method of claim 14 wherein the fluoropolymer composition has a concentration of from about 5 g/L to about 100 g/L in water.

16. A fibrous substrate treated according to the method of claim 14 .

17. The substrate of claim 16 which is woven and nonwoven fibers, yarns, fabrics, fabric blends, textiles, nonwovens, paper, leather, rugs and carpets.