Polymerizable compositions, methods of making the same, and composite articles therefrom
Polymerizable fluorinated polyethers are formed by Michael-type addition of a reactive fluorinated polyether to a poly(meth)acryl compound. The polymerizable fluorinated polyethers may be used to form composite articles.
1. A method of making a polymerizable composition comprising combining:
a reactive fluorinated polyether; and
a poly(meth)acryl compound
under conditions sufficient to form a Michael-type adduct thereof, wherein the Michael-type adduct has at least one (meth)acryl group, wherein the reactive fluorinated polyether is described by the formula
F(R f O) x QZ 1 R 1 NR 2 H
or
X(R f O) x QZ 1 R 1 NR 2 H
wherein
each R f independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms;
each x independently represents an integer greater than or equal to 2;
each Q independently represents —CF 2 —, —CF(CF 3 )—, —CF 2 CF 2 —, —CF 2 CF 2 CF 2 —, —CF 2 CF(CF 3 )—, —CF(CF 3 )CF 2 —, —CF 2 CF 2 CH 2 —, —CF 2 CH 2 —, —CF 2 CF 2 C(═O)—, —CF 2 C(═O)—, —CF(CF 3 )C(═O)—, —CF(CF 3 )CH 2 —, an alkylene group having from 1 to 6 carbon atoms, or a heteroalkylene group having from 1 to 6 carbon atoms;
Z 1 represents —S—, —O—, —NH—, or —NR 2 —;
R 1 represents an alkylene, aralkylene, or heteroalkylene group;
R 2 independently represents H or alkyl having from 1 to 6 carbon atoms; and
X represents a polyvalent organic group.
2. A method according to claim 1 , wherein R 1 has from 1 to 6 carbon atoms.
3. A method according to claim 1 , wherein x is greater than or equal to 3.
4. A method according to claim 1 , wherein Z 1 represents —NR 2 —.
5. A method according to claim 1 , wherein Z 1 represents —NH—.
6. A method according to claim 1 , further comprising combining the Michael-type adduct and at least one additional polymerizable monomer.
7. A method according to claim 6 , further comprising at least partially polymerizing the combination of the Michael-type adduct and at least one additional polymerizable monomer.
8. A method according to claim 6 , further comprising applying the combination of Michael-type adduct and at least one additional polymerizable monomer to a substrate.
9. A method according to claim 8 , further comprising at least partially polymerizing the combination of the Michael-type adduct and at least one additional polymerizable monomer to provide a polymerized mixture.
10. A method according to claim 1 , further comprising combining the Michael-type adduct, at least one additional polymerizable monomer, and at least one free-radical photoiniator.
11. A method according to claim 10 , further comprising at least partially polymerizing the combination of the Michael-type adduct and at least one additional polymerizable monomer.
12. A method according to claim 10 , further comprising applying the at least partially polymerized combination of the Michael-type adduct and at least one polymerizable additional monomer to a substrate.
13. A method according to claim 12 , further comprising at least partially polymerizing the polymerizable additional monomer.