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 . A process for preparing an article, the process comprising:
preparing a compound having formula I by a process comprising
contacting a compound of a formula R 1 Si(OR A ) 3 with a compound of a formula R 2 Si(OR A ) 3 , in the presence of a base, wherein —OR A is a C 1 -C 8 alkoxy, and —OR A on R 1 Si(OR A ) 3 and R 2 Si(OR A ) 3 can be the same or different, wherein formula I is;
wherein further,
R 1 is a long chain fluorinated alkyl;
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;
n is an integer from 1 to 7; and,
each R 1 and R 2 is independently covalently attached at a silicon atom, and
preparing a synthetic blend copolymer by polymerizing of the compound having the formula I with at least one monomer.
2 . The process 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 ,
wherein each R 3 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 4 , —NR 4 R 5 , —OC(O)R 4 , —C(O)OR 4 , —C(O)R 4 , —OC(O)OR 4 , —C(O)NR 4 R 5 , —OC(O)NR 4 R 5 , —NR 4 C(O)R 5 , —NR 4 C(O)OR 5 and —NR 4 C(O)NR 4 R 5 , and when R 3 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 3 is independently optionally substituted by an R 6 ;
each R 4 and R 5 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 4 and R 5 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 ; and
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.
3 . The process of claim 2 , wherein R 3 is —NCO, —OR 4 , —OC(O)R 4 , —C(O)R 4 or —OC(O)OR 4 .
4 . The process of claim 2 , wherein R 4 is C 1 -C 8 alkyl and wherein each hydrogen atom in R 4 is independently optionally substituted by an R 6 .
5 . The process of claim 2 , wherein R 4 is C 2 -C 8 alkenyl, wherein each hydrogen atom in R 4 is independently optionally substituted by an R 6 .
6 . The process of claim 2 , 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 .
7 . The process of claim 2 , 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 .
8 . The process of claim 2 , 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 .
9 . The process of claim 2 , wherein R 9 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.
10 . The process of claim 2 , wherein R 2 is n-propyl, wherein each hydrogen atom in R 2 is independently optionally substituted by an R 3 .
11 . The process of claim 2 , wherein R 3 is —OC(O)R 4 or —OC(O)OR 4 .
12 . The process of claim 11 , wherein R 4 is methyl.
13 . The process of claim 11 , wherein R 4 is —CH═CH 2 , wherein each hydrogen atom in R 4 is independently optionally substituted by methyl.
14 . The process of claim 11 , wherein R 3 is —OC(O)R 4 .
15 . The process of claim 2 , wherein the base is potassium hydroxide or tetraethylammonium hydroxide.
16 . The process of claim 15 , wherein the long chain fluorinated alkyl is 8/2, 6/2 or 4/2.
17 . The process of claim 1 , wherein the monomer is an acrylate.
18 . The process of claim 17 , wherein the acrylate is methacrylate or methylmethacrylate.
19 . 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;
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 ;
n is an integer from 1 to 7; and,
each R 1 and R 2 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.
20 . The article of claim 19 , wherein the monomer is an acrylate.