Surface modified inorganic particles

1. Surface modified inorganic oxide particles comprising an oxide of M wherein M is independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof; at least one of said particles having a surface covalently bonded to at least one fluorosilane group represented by Formula (1)

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

wherein

L 1 represents an oxygen covalently bonded to an M; and each L 2 independently selected from the group consisting of H, a C 1 -C 2 alkyl, and OH; d and c are integers such that: d≧1, c≧0, d+c=3;

each n is independently an integer from 1 to 12;

a, x, and 1 are integers chosen such that the moiety of Formula 1 represented by —(Z 1 ) a —[C(X 1 )] x —(Z 2 ) l —

R f is chosen from a C 2 -C 12 perfluoroalkyl provided that: i) one fluorine atom of the perfluoroalkyl can be optionally replaced by hydrogen, and/or ii) the perfluoroalkyl can be optionally interrupted by at least one oxygen, methylene, or ethylene;

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

X 1 is chosen from O or S;

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

each R 1 is independently chosen from hydrogen, phenyl, or a monovalent C 1 -C 8 alkyl optionally terminated by —C 5 H 5 , preferably H or CH 3 ;

provided that when Z 1 is —NH— and Z 2 is —NH—, then Q 1 is chosen from the group consisting of a C 2 -C 12 hydrocarbylene interrupted by at least one divalent organic group.

2. The particles of claim 1 wherein the fluorosilane group represented by Formula (1) is a urea or thiourea fluorosilane group such that in Formula (1):

a=1, x=1, and l=1;

Z 1 is —NH— and Z 2 is —NH—;

said urea or thiourea fluorosilane group further represented by the formula:

(L 1 ) d (L 2 ) c Si—≦(CH 2 ) n —NH—C(X 1 )—NH-Q 1 -R f

wherein:

X 1 is O to form a urea fluorosilane group, or X 1 is S to form a thiourea fluorosilane group; and

Q 1 is independently chosen from the group consisting of a C 2 -C 12 hydrocarbylene interrupted by at least one divalent moiety chosen from the group consisting of —S—, —S(O)—, —S(O) 2 —, and —O—C(O)—NH—.

3. The particles of claim 2 wherein R f is chosen from a C 2 -C 12 perfluoroalkyl and Q 1 is independently chosen from the group consisting of a C 2 -C 12 hydrocarbylene interrupted by least one divalent moiety chosen from the group consisting of —S—, —S(O)—, —S(O) 2 —, and —O—C(O)—NH—.

4. The particles of claim 2 wherein R f is chosen from a C 2 -C 12 perfluoroalkyl provided that: i) one fluorine atom of the perfluoroalkyl is replaced by hydrogen, and/or ii) the perfluoroalkyl is interrupted by at least one oxygen, methylene, or ethylene.

5. The particles of claim 1 wherein the fluorosilane group represented by Formula (1) is a carbamate fluorosilane group such that in Formula (1):

Z 1 is —NH— and Z 2 is; and

X 1 is O;

said carbamate fluorosilane group further represented by the formulae:

(L 1 ) d (L 2 ) c Si—CH 2 ) 2 —NH—C(O)—O-Q 1 -

wherein:

Q 1 is a C 2 -C 12 hydrocarbylene optionally interrupted by at least one divalent moiety chosen from the group consisting of —NH—C(O)—NH—, —NH—C(S)—NH—, —S—, —S(O)—, S(O) 2 —, —(R 1 )N—S(O) 2 —,

6. The particles claim 5 wherein R f is chosen from a C 2 -C 12 perfluoroalkyl and Q 1 is independently chosen from the group consisting of a C 2 -C 12 hydrocarbylene interrupted by at least one divalent moiety chosen from the group consisting of —S—, —S(O)—, —S(O) 2 —, and —O—C(O)—NH—.

7. The particles of claim 5 wherein R f is chosen from a C 2 -C 12 perfluoroalkyl provided that: i) one fluorine atom of the perfluoroalkyl is replaced by hydrogen, and/or ii) the perfluoroalkyl is interrupted by at least one oxygen, methylene, or ethylene.

8. The particles of claim 1 wherein the fluorosilane group represented by Formula (1) is a thiolcarbamate fluorosilane group such that in Formula (1):

Z 1 is —NH— and Z 2 is —S—; and

X 1 is O;

said thiolcarbamate fluorosilane group further represented by the formulae:

(L 1 ) d (L 2 ) c Si—CH 2 ) n —NH—C(O)—S—-Q 1 -R f

wherein:

Q 1 is independently chosen from the group consisting of a C 2 -C 12 hydrocarbylene optionally interrupted by at least one divalent moiety chosen from the group consisting of —S—, —S(O)—, —S(O) 2 —, —N(R 1 )—C(O), —C(O)—N(R 1 )—, —(R 1 )N—S(O) 2 —, and

9. The particles of claim 8 wherein R f is chosen from a C 2 -C 12 perfluoroalkyl and Q 1 is independently chosen from the group consisting of a C 2 -C 12 hydrocarbylene interrupted by at least one divalent moiety chosen from the group consisting of —S—, —S(O)—, —S(O) 2 —, and —O—C(O)—NH—.

10. The particles of claim 8 wherein R f is chosen from a C 2 -C 12 perfluoroalkyl provided that: i) one fluorine atom of the perfluoroalkyl is replaced by hydrogen, and/or ii) the perfluoroalkyl is interrupted by at least one oxygen, methylene, or ethylene.

11. The particles of claim 1 further comprising at least one particle having a surface covalently bonded to a N-sulfone urea fluorosilane group such that in Formula (1):

Z 1 is —NH—, and Z 2 is —NH—S(O) 2 —; and

X 1 is O;

said N-sulfone urea fluorosilane group further represented by the formula:

(L 1 ) d (L 2 ) c Si—(CH 2 ) n —NH—C(O)—NH—S(O) 2 Q 1 -R f

wherein:

Q 1 is independently chosen from the group consisting of an uninterrupted C 2 -C 12 hydrocarbylene.

12. The particles of claim 1 further comprising at least one particle having a surface covalently bonded to a N-formyl urea fluorosilane group such that in Formula (1):

a=1, x=1, and l=1; and

Z 1 is —NH—, and Z 2 is —N[C(O)H]—;

said N-formyl urea group further represented by the formula:

(L 1 ) d (L 2 ) n Si—(CH 2 ) n —NH—C(X 1 )—N[C(O)H]-Q 1 -R f

wherein:

Q 1 is independently chosen from the group consisting of a C 2 -C 12 hydrocarbylene interrupted by at least one divalent moiety chosen from the group consisting of —S— and —NH—.

13. The particles of claim 1 further comprising at least one particle having a surface covalently bonded to a thioether succinamic acid fluorosilane group such that in Formula (1):

a=1, x=1, and l=1;

Z 1 is —NH— and Z 2 is —[HC(COOH)(R 1 )]CH—S— or —(R 1 )CH—[HC(COOH)]—S—;

X 1 is O; and Q 1 is —(CH 2 ) 2 —;

said thioether succinamic acid group further represented by the formulae:

(L) 3 Si—(CH 2 ) n —NH—C(O)—[HC(COOH)(R 1 )]CR 1 —(CH 2 ) m —S—(CH 2 ) 2 —R f , or

(L) 3 Si—(CH 2 ) n —NH—C(O)—(R 1 )CH—[CR 1 (COOH)]—(CH 2 ) m —S—(CH 2 ) 2 —R f

wherein m is 1 or 0; wherein each R 1 is independently chosen from methyl or hydrogen preferably H.