Processes for preparing functionalized F-POSS monomers
View Patent ↗The present disclosure relates to compositions of matter comprising synthetic blends of at least two feedstocks that produce a distribution of fluorinated polyhedral oligomeric silsesquioxane compounds. The present disclosure also relates to methods of making such fluorinated polyhedral oligomeric silsesquioxane compounds from such synthetic blends. The present disclosure also relates to uses of such fluorinated polyhedral oligomeric silsesquioxane compounds.
1. A process for preparing a derivatized F-POSS of the formula
comprising the step of contacting at least one F-POSS molecule of the formula
with a compound of the formula R 1 R 2 Si(OR 3 ) 2 ,
wherein
R is a long chain fluorinated alkyl;
R 1 and R 2 are each independently 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 1 and R 2 is independently optionally substituted by an R 4 ;
R 3 is a C 1 -C 8 alkoxy;
each R 4 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 5 , —NR 5 R 6 , —OC(O)R 5 , —C(O)OR 5 , —C(O)R 5 , —OC(O)OR 5 , —C(O)NR 5 R 6 , —OC(O)NR 5 R 6 , —NR 5 C(O)R 6 , —NR 5 C(O)OR 6 and —NR 5 C(O)NR 5 R 6 , and when R 4 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 4 is independently optionally substituted by an R 7 ;
each R 5 and R 6 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 5 and R 6 is independently optionally substituted by an R 7 ;
each R 7 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 8 , —NR 8 R 9 , —OC(O)R 8 , —C(O)OR 8 , —C(O)R 8 , —OC(O)OR 8 , —C(O)NR 8 R 9 , —OC(O)NR 8 R 9 , —NR 8 C(O)R 9 , —NR 8 C(O)OR 9 and —NR 8 C(O)NR 8 R 9 , and when R 7 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 7 is independently optionally substituted by an R 10 ;
each R 8 and R 9 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 8 and R 9 is independently optionally substituted by one or more R 10 ;
each R 10 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 11 , —NR 11 R 12 , —OC(O)R 11 , —C(O)OR 11 , —C(O)R 11 , —OC(O)OR 11 , —C(O)NR 11 R 12 , —OC(O)NR 11 R 12 , —NR 11 C(O)R 12 , —NR 11 C(O)OR 12 and —NR 11 C(O)NR 11 R 12 , and when R 10 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 10 is independently optionally substituted by a moiety selected from the group consisting of halo, —NCO, —OR 11 , —NR 11 R 12 , —OC(O)R 11 , —C(O)OR 11 , —C(O)R 11 , —OC(O)OR 11 , —C(O)NR 11 R 12 , —OC(O)NR 11 R 12 , —NR 11 C(O)R 12 , —NR 11 C(O)OR 12 and —NR 11 C(O)NR 11 R 12 ; and
each R 11 and R 12 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 11 or R 12 are C 1 -C 8 alkyl, C 2 -C 8 alkenyl or C 2 -C 8 alkynyl, each hydrogen atom in R 11 and R 12 is independently optionally substituted by a fluorine atom,
in the presence of an aqueous base catalyst.
2. The process of claim 1 , wherein R 2 is C 1 -C 8 alkyl.
3. The process of claim 2 , wherein R 2 is methyl.
4. The process of claim 2 , wherein R 1 is C 1 -C 8 alkyl, wherein each hydrogen atom in R 1 is independently optionally substituted by an R 4 .
5. The process of claim 4 , wherein R 4 is —NCO, —OR 5 , —OC(O)R 5 , —C(O)OR 5 , —C(O)R 5 or —OC(O)OR 5 .
6. The process of claim 5 , wherein R 5 is C 1 -C 8 alkyl, wherein each hydrogen atom in R 5 is independently optionally substituted by an R 7 .
7. The process of claim 5 , wherein R 5 is C 2 -C 8 alkenyl, wherein each hydrogen atom in R 5 is independently optionally substituted by an R 7 .
8. The process of claim 7 , wherein R7 is C1-C8 alkyl, —NCO, —OR8, —NR8R9, —OC(O)R8, —C(O)OR8, —C(O)R8 or —OC(O)OR8.
9. The process of claim 8 , wherein R 8 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 8 is independently optionally substituted by one or more R 10 .
10. The process of claim 9 , wherein R 10 is hydrogen or C 1 -C 8 alkyl, and when R 10 is C 1 -C 8 alkyl, R 10 is optionally substituted by a —OC(O)R 11 .
11. The process of claim 10 , wherein R 11 is H or C 1 -C 8 alkyl, and when R 11 is C 1 -C 8 alkyl, each hydrogen atom in R 11 is independently optionally substituted by a fluorine atom.
12. The process of claim 1 , wherein R 1 is n-propyl, optionally substituted by an R 4 .
13. The process of claim 10 , wherein R 4 is —OC(O)R 5 or —OC(O)OR 5 .
14. The process of claim 13 , wherein R 5 is —CH═CH 2 , optionally substituted by an R 7 .
15. The process of claim 14 , wherein R 7 is methyl.
16. The process of claim 1 , wherein the aqueous base catalyst is an aqueous ammonium salt.
17. The process of claim 16 , wherein the aqueous base catalyst is a tetraethylammonium salt.
18. The process of claim 17 , wherein the aqueous base catalyst is tetraethylammonium hydroxide.
19. The process of claim 1 , wherein the long chain fluorinated alkyl is 8/2, 6/2 or 4/2.
20. The process of claim 1 , wherein the at least one F-POSS molecule is selected from the group consisting of 8/2 F-POSS, 6/2 F-POSS and 4/2 F-POSS.