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

A compound having the following formula:

• wherein
• R21 is H or CH3;
• X22 is —O—, —S—, or —NR23— wherein R23 is H or an alkyl group of 1 to 4 carbon atoms,
• L21 and L22 are organic linking groups;
• Rf2 is a divalent perfluorooxyalkylene;
• R22 is —S— or —N(R24)— wherein R24 is C1-C4 alkyl or —R25Si(Y)3;
• R25 is a divalent alkylene group optionally comprising one or more catenary oxygen atoms;
• Y is a hydrolysable group;
• R26 is a non-hydrolysable group;
• and
• p is 1, 2, or 3.

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.

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) H2C═C(R21)C(O)X22L21Rf2L22X22C(O)CH2CH2R22R25Si(Y)p(R26)3-p
• wherein
• R21 is H or CH3;
• X22 is —O—, —S—, or —NR23— wherein R23 is H or an alkyl group of 1 to 4 carbon atoms,
• L21 and L22 are organic linking groups;
• Rf2 is a divalent perfluorooxyalkylene;
• R22 is —S— or —N(R24)— wherein R24 is C1-C4 alkyl or —R25Si(Y)3;
• R25 is a divalent alkylene group optionally comprising one or more catenary oxygen atoms;
• Y is a hydrolysable group;
• R26 is a non-hydrolysable group;
• and
• p is 1, 2, or 3;
• or
• ii)
• Rf1 is a monovalent perfluorooxyalkyl;
• L23 and L24 are organic linking groups;
• R25 is a divalent alkylene group said alkylene groups optionally containing one or more catenary oxygen atoms;
• Y is a hydrolysable group;
• R26 is a non-hydrolysable group;
• p is 1, 2, or 3;
• X22 is —O—, —S—, or —NR23—, wherein R23 is H or an alkyl group of 1 to 4 carbon atoms;
• R21 is H or CH3;
• m2 is 1 or 2;
• and
• n2 is 1, 2, or 3;
• or
• iii)
• wherein
• Rf1 is a monovalent perfluorooxyalkyl;
• L23 is an organic linking groups, wherein L23 is optionally organic linking group that includes —C(O)NHR25;
• X22 is —O—, —S—, or —NR23—, wherein R23 is H or an alkyl group of 1 to 4 carbon atoms;
• R22 is —S— or —N(R24)—, wherein R24 is C1-C4 alkyl or R25Si(Yp)p(R26)3-p
• R25 is a divalent alkylene group said alkylene groups optionally containing one or more catenary oxygen atoms;
• Y is a hydrolysable group;
• R26 is a non-hydrolysable group;
• R21 is H or CH3;
• p is 1, 2, or 3;
• and
• n2 is 1, 2, or 3.