Polymerizable compositions and compounds comprising perfluorinated group, hydrolysable silane group, and (meth)acryl group

1 . A compound comprising a perfluorooxyalkylene moiety bonded to a silane compound comprising hydrolysable groups with an amine moiety; wherein the amine moiety further comprises a pendent group having a terminal (meth)acryl group.

2 . The compound of claim 1 having the following formula:

wherein

R f 1 is a monovalent perfluorooxyalkyl;

L 23 and L 24 are organic linking groups;

R 25 is a divalent alkylene group said alkylene groups optionally containing one or more catenary oxygen atoms;

Y is a hydrolysable group;

R 26 is a non-hydrolysable group;

p is 1, 2, or 3;

X 22 is —O—, —S—, or —NR 23 —, wherein R 23 is H or an alkyl group of 1 to 4 carbon atoms;

R 21 is H or CH 3 ;

m2 is 1 or 2; and

n2 is 1, 2, or 3.

3 . The compound of claim 1 having the following formula:

wherein

R f 1 is a monovalent perfluorooxyalkyl;

L 23 is an organic linking groups, wherein L 23 is optionally organic linking group that includes —C(O)NHR 25 ;

X 22 is —O—, —S—, or —NR 23 —, wherein R 23 is H or an alkyl group of 1 to 4 carbon atoms;

R 22 is —S— or —N(R 24 )—, wherein R 24 is C 1 -C 4 alkyl or R 25 Si(Y p ) p (R 26 ) 3-p

R 25 is a divalent alkylene group said alkylene groups optionally containing one or more catenary oxygen atoms;

Y is a hydrolysable group;

R 26 is a non-hydrolysable group;

R 21 is H or CH 3 ;

p is 1, 2, or 3; and

n2 is 1, 2, or 3.

4 . A compound having the following formula:

wherein

R 21 is H or CH 3 ;

X 22 is —O—, —S—, or —NR 23 — wherein R 23 is H or an alkyl group of 1 to 4 carbon atoms,

L 21 and L 22 are organic linking groups;

R f 2 is a divalent perfluorooxyalkylene;

R 22 is —S— or —N(R 24 )— wherein R 24 is C 1 -C 4 alkyl or —R 25 Si(Y) 3 ;

R 25 is a divalent alkylene group optionally comprising one or more catenary oxygen atoms;

Y is a hydrolysable group;

R 26 is a non-hydrolysable group; and

p is 1, 2, or 3.

5 . A mixture of compounds comprising the reaction product of

i) a compound comprising a perfluorooxyalkylene moiety and two (meth)acryl groups; and

ii) a silane compound comprising hydrolysable groups and a group selected from amine or mercapto group;

wherein i) and ii) are reacted at a molar ratio of excess compound i) such that (meth)acryl groups remain unreacted.

6 . The mixture of compounds of claim 5 wherein the molar ratio ranges from 2:1 to 10:1.

7 . The mixture of compounds of claim 5 wherein the mixture comprises a compound

having the following formula:

wherein

R 21 is H or CH 3 ;

X 22 is —O—, —S—, or —NR 23 — wherein R 23 is H or an alkyl group of 1 to 4 carbon atoms,

L 21 and L 22 are organic linking groups;

R f 2 is a divalent perfluorooxyalkylene;

R 22 is —S— or —N(R 24 )— wherein R 24 is C 1 -C 4 alkyl or —R 25 Si(Y) 3 ;

R 25 is a divalent alkylene group optionally comprising one or more catenary oxygen atoms;

Y is a hydrolysable group;

R 26 is a non-hydrolysable group; and

p is 1, 2, or 3.

8 . The mixture of compounds of claim 5 wherein the mixture of compounds further comprises unreacted compound i).

9 . The mixture of compounds of claim 5 wherein the mixture of compounds further comprises a compound wherein both (meth)acryl groups are reacted with compound ii).

10 . A polymerizable composition comprising

a fluorinated monomer, oligomer, or mixture thereof, and

a coupling agent comprising a (meth)acryl terminal group, a terminal silane comprising hydrolysable groups and a perfluorooxyalkyl or perfluorooxyalkylene moiety; wherein the coupling agent has a formula according to:

i) H 2 C═C(R 21 )C(O)X 22 L 21 R f 2 L 22 X 22 C(O)CH 2 CH 2 R 22 R 25 Si(Y) p (R 26 ) 3-p

wherein

R 21 is H or CH 3 ;

X 22 is —O—, —S—, or —NR 23 — wherein R 23 is H or an alkyl group of 1 to 4 carbon atoms,

L 21 and L 22 are organic linking groups;

R f 2 is a divalent perfluorooxyalkylene;

R 22 is —S— or —N(R 24 )— wherein R 24 is C 1 -C 4 alkyl or —R 25 Si(Y) 3 ;

R 25 is a divalent alkylene group optionally comprising one or more catenary oxygen atoms;

Y is a hydrolysable group;

R 26 is a non-hydrolysable group; and

p is 1, 2, or 3; or

ii)

R f 1 is a monovalent perfluorooxyalkyl;

L 23 and L 24 are organic linking groups;

R 25 is a divalent alkylene group said alkylene groups optionally containing one or more catenary oxygen atoms;

Y is a hydrolysable group;

R 26 is a non-hydrolysable group;

p is 1, 2, or 3;

X 22 is —O—, —S—, or —NR 23 —, wherein R 23 is H or an alkyl group of 1 to 4 carbon atoms;

R 21 is H or CH 3 ;

m2 is 1 or 2; and

n2 is 1, 2, or 3; or

iii)

wherein

R f 1 is a monovalent perfluorooxyalkyl;

L 23 is an organic linking groups, wherein L 23 is optionally organic linking group that includes —C(O)NHR 25 ;

X 22 is —O—, —S—, or —NR 23 —, wherein R 23 is H or an alkyl group of 1 to 4 carbon atoms;

R 22 is —S— or —N(R 24 )—, wherein R 24 is C 1 -C 4 alkyl or R 25 Si(Y p ) p (R 26 ) 3-p

R 25 is a divalent alkylene group said alkylene groups optionally containing one or more catenary oxygen atoms;

Y is a hydrolysable group;

R 26 is a non-hydrolysable group;

R 21 is H or CH 3 ;

p is 1, 2, or 3; and

n2 is 1, 2, or 3.

11 . The polymerizable composition of claim 10 wherein the fluorinated monomer, oligomer, or mixture thereof has a fluorine content of at least 25, 30 or 35 wt. %.

12 . The polymerizable composition of claim 10 wherein the composition comprises a fluorinated oligomer comprising a perfluorooxyalkylene group.

13 . The polymerizable composition of claim 10 wherein the coupling agent is linear or branched.

14 . The polymerizable composition of claim 10 wherein the coupling agent has a number average molecular weight of no greater than 3000, 2500, 2000, 1500, 1000, or 500 g/mole.

15 . The polymerizable composition of claim 10 wherein the coupling agent has a number average wt. % fluorine of at least 30, 35, 40, 50, 55, 60 or 65 wt. %.

16 . The polymerizable composition of claim 10 wherein the coupling agent has formula ii) and L 24 comprises an amide, ester or thioester moiety and optionally a pendent alcohol protecting group.