Functionalized F-POSS monomer compositions and uses thereof
Functionalized F-POSS compounds comprising synthetic blends of at least two feedstocks that produce a distribution of fluorinated polyhedral oligomeric silsesquioxane molecule structures and/or functional groups.
1. An article comprising a synthetic blend copolymer prepared by polymerization of a compound having a formula I
wherein,
R 1 is a long chain fluorinated alkyl that is a straight chain or a branched chain alkyl group having 5 to 12 carbon atoms in a longest continuous chain of carbon atoms as counted from a point of attachment of the longest continuous chain of carbon atoms to a silicon atom at any apex of a silicon-oxide core, where at least one hydrogen atom in the straight chain or the branched chain alkyl group is replaced by a fluorine atom;
R 2 is selected from the group consisting of C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 10 aryl, C 3 -C 8 cycloalkyl, 5-7 membered heterocyclic and 5-7 membered heteroaryl, wherein each hydrogen atom in R 2 is independently optionally substituted by an R 3 ;
R 3 is —OC(O)R 4 or —OC(O)OR 4 ;
R 4 is methyl, wherein each hydrogen atom in R 4 is independently optionally substituted by an R 6 ;
each R 6 is independently selected from the group consisting of halo, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 10 aryl, C 3 -C 8 cycloalkyl, 5-7 membered heterocyclic, 5-7 membered heteroaryl, —NCO, —OR 7 , —NR 7 R 8 , —OC(O)R 7 , —C(O)OR 7 , —C(O)R 7 , —OC(O)OR 7 , —C(O)NR 7 R 8 , —OC(O)NR 7 R 8 , —NR 7 C(O)R 8 , —NR 7 C(O)OR 8 and —NR 7 C(O)NR 7 R 8 , and when R 6 is C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 10 aryl, C 3 -C 8 cycloalkyl, 5-7 membered heterocyclic or 5-7 membered heteroaryl, each hydrogen atom in R 6 is independently optionally substituted by an R 9 ;
each R 7 and R 8 is independently selected from the group consisting of hydrogen, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 10 aryl, C 3 -C 8 cycloalkyl, 5-7 membered heterocyclic and 5-7 membered heteroaryl, wherein each hydrogen atom in R 7 and R 8 is independently optionally substituted by one or more R 9 ;
each R 9 is independently selected from the group consisting of hydrogen, halo, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 10 aryl, C 3 -C 8 cycloalkyl, 5-7 membered heterocyclic, 5-7 membered heteroaryl, —NCO, —OR 10 , —NR 10 R 11 , —OC(O)R 10 , —C(O)OR 10 , —C(O)R 10 , OC(O)OR 10 , —C(O)NR 10 R 11 , —OC(O)NR 10 R 11 , —NR 10 C(O)R 11 , —NR 10 C(O)OR 11 and NR 10 C(O)NR 10 R 11 , and when R 9 is C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 10 aryl, C 3 -C 8 cycloalkyl, 5-7 membered heterocyclic, C 3 -C 8 cycloalkyl or 5-7 membered heteroaryl, each hydrogen in R 9 is independently optionally substituted by a moiety selected from the group consisting of halo, —NCO, —OR 10 , —NR 10 R 11 , —OC(O)R 10 , —C(O)OR 10 , —C(O)R 10 , OC(O)OR 10 , C(O)NR 10 R 11 , —OC(O)NR 10 R 11 , —NR 10 C(O)R 11 , —NR 10 C(O)OR 11 and NR 10 C(O)NR 10 R 11 ;
each R 10 and R 11 is independently selected from the group consisting of H, C 1 -C 8 alkyl, C 2 -C 8 alkenyl and C 2 -C 8 alkynyl, and when R 10 or R 11 are C 1 -C 8 alkyl, C 2 -C 8 alkenyl or C 2 -C 8 alkynyl, each hydrogen atom in R 10 and R 11 is independently optionally substituted by a fluorine atom;
n is an integer from 1 to 7; and,
each R 10 and R 11 is independently covalently attached at a silicon atom,
with at least one monomer; wherein the compound of the formula I is prepared by a process comprising:
(a) contacting a compound of the formula R 1 Si(OR A ) 3 with a compound of the formula R 2 Si(OR A ) 3 , in the presence of a base, wherein —OR A is a C 1 -C 8 alkoxy, and the —OR A on R 1 Si(OR A ) 3 and R 2 Si(OR A ) 3 can be the same or different.
2. The article of claim 1 , wherein R 2 is C 1 -C 8 alkyl, wherein each hydrogen atom in R 2 is independently optionally substituted by an R 3 .
3. The article of claim 1 , wherein R 3 is —OC(O)R 4 .
4. The article of claim 1 , wherein each hydrogen atom in R 4 is independently optionally substituted by C 2 -C 8 alkenyl.
5. The article of claim 1 , wherein R 6 is C 1 -C 8 alkyl, —NCO, —OR 7 , —NR 7 R 8 , —OC(O)R 7 , C(O)OR 7 , —C(O)R 7 or —OC(O)OR 7 .
6. The article of claim 1 , wherein R 7 is C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 6 -C 10 aryl or 5-7 membered heteroaryl, wherein each hydrogen atom in R 7 is independently optionally substituted by one or more R 9 .
7. The article of claim 1 , wherein R 9 is hydrogen or C 1 -C 8 alkyl, and when R 9 is C 1 -C 8 alkyl, R 9 is optionally substituted by a —OC(O)R 10 .
8. The article of claim 1 , wherein R 10 is H or C 1 -C 8 alkyl, and when R 10 is C 1 -C 8 alkyl, each hydrogen atom in R 10 is independently optionally substituted by a fluorine atom.
9. The article of claim 1 , wherein R 2 is n-propyl, wherein each hydrogen atom in R 2 is independently optionally substituted by an R 3 .
10. The article of claim 9 , wherein each hydrogen atom in R 4 is independently optionally substituted by —CH═CH 2 .
11. The article of claim 1 , wherein R 3 is —OC(O)R 4 —.
12. The article of claim 1 , wherein the base is potassium hydroxide or tetraethylammonium hydroxide.
13. The article of claim 12 , wherein the long chain fluorinated alkyl is 8/2, 6/2 or 4/2.
14. The article of claim 1 , wherein the monomer is an acrylate.
15. The article of claim 14 , wherein the acrylate is methacrylate or methylmethacrylate.