Fluorine containing polymers
The present invention relates to novel fluorine containing polymers, compositions comprising the polymers, the use of the polymers in coatings, especially in water and dirt repellent coatings, and products coated with polymer containing coatings.
1. A polymer comprising monomer units derived from at least one monomer of formulae (I) or (II)
(Rf 1 —CHF—CF 2 —O—CHR 1 ) m1 -L 1 -(X 1 ) n1 (I)
(Rf 2 —CHF—CF 2 —S—CHR 2 ) m2 -L 2 -(X 2 ) n2 (II)
wherein
Rf 1 and Rf 2 are each, independently of one another, a perfluorinated alkyl group which optionally contains heteroatoms,
R 1 and R 2 are each, independently of one another, H or an alkyl group,
L 1 and L 2 are each, independently of one another, a single bond or a bivalent organic group,
X 1 and X 2 are each, independently of one another, an acrylate or methacrylate group,
m 1 and m 2 are each, independently of one another, another ≥1, and
n 1 and n 2 are each, independently of one another, ≥1.
2. The polymer according to claim 1 , wherein Rf 1 and Rf 2 are each, independently of one another, selected from the groups
CF 3 —(CF 2 ) 0-3 —, CF 3 —(CF 2 ) 0-3 —O—,
CF 3 —(CF 2 ) 0-3 —O—(CF 2 ) 1-3 —,
CF 3 —(CF 2 ) 0-3 —O—(CF 2 ) 1-3 —O—,
CF 3 —(CF 2 ) 0-3 —O—(CF 2 ) 1-3 —O—CF 2 —,
CF 3 —(CF 2 ) 0-3 —O—(CF 2 —O) 1-8 —, and
CF 3 —(CF 2 ) 0-3 —O—(CF 2 —O) 1-8 —CF 2 —.
3. The polymer according to claim 1 , wherein Rf 1 and Rf 2 are each, independently of one another, selected from the groups
CF 3 —(CF 2 ) 1-2 —, CF 3 —(CF 2 ) 1-2 —O—,
CF 3 —O—(CF 2 ) 1-3 —,
CF 3 —O—(CF 2 ) 1-2 —O—,
CF 3 —(CF 2 ) 1-2 —O—CF 2 —,
CF 3 —O—(CF 2 ) 1-2 —O—CF 2 —,
CF 3 —O—(CF 2- O) 1-8 —, and
CF 3 —O—(CF 2 —O) 1-8 —CF 2 —.
4. The polymer according to claim 1 , wherein R 1 and R 2 are each, independently of one another, selected from H or C1-C3 alkyl.
5. The polymer according to claim 1 , wherein L 1 and L 2 are each, independently of one another, selected from a single bond and a saturated, branched or not branched alkylene group that optionally contains heteroatoms and/or functional groups.
6. The polymer according to claim 1 , wherein m 1 and m 2 are each, independently of one another, equal to 1-3.
7. The polymer according to claim 1 , wherein n 1 and n 2 are each, independently of one another, equal to 1-3.
8. The polymer according to claim 1 , wherein Rf 1 and Rf 2 are each, independently of one another, selected from
CF 3 —(CF 2 ) 1-2 —, CF 3 —(CF 2 ) 1-2 —O—, CF 3 —O—(CF 2 ) 1-3 —, CF 3 —O—(CF 2 ) 1-3 —O—,
CF 3 —(CF 2 ) 1-2 —O—CF 2 —, CF 3 —O—(CF 2 ) 1-2 —O—CF 2 —, CF 3 —O—(CF 2 —O) 1-8 — and
CF 3 —O—(CF 2 —O) 1-8 —CF 2 —,
R 1 and R 2 are each, independently of one another, H or CH 3 ,
L 1 and L 2 are each, independently of one another, a single bond or a C1-C4 alkylene group, optionally branched, and optionally containing hetero atoms and/or a functional group,
m 1 and m 2 are each, independently of one another, equal to 1 or 2, and
n 1 and n 2 are each, independently of one another, equal to 1.
9. The polymer according to claim 1 , wherein the monomer is selected from formulae (Ia), (Ib), (Ic), (Ha), (IIb), and (IIc):
wherein
Rf is a perfluorinated alkyl group optionally containing heteroatoms, and
R′ and R″ are each, independently of one another, H or an alkyl group.
10. The polymer according to claim 9 , wherein Rf is CF 3 —CF 2 —CF 2 —O—, CF 3 —CF 2 —O— or CF 3 —O— and R′ and R″ are each, independently of one another, H or methyl.
11. The polymer according to claim 1 , wherein the polymer comprises at least one functional and/or non-functional co-monomer.
12. The polymer according to claim 1 , wherein the polymer comprises at least one functional co-monomer selected from co-monomers comprising OH, epoxy, —Si(OMe) 3 , —Si(OEt) 3 , CO 2 H or tertiary amino groups, wherein Me is methyl and Et is ethyl.
13. The polymer according to claim 1 , wherein the polymer comprises at least one non-functional monomer selected from co-monomers comprising linear or branched alkyl groups or polyether groups or from styrene like monomers.
14. A method for the production of functional coatings and/or surface modifications, applying a coating or surface modification containing at least one polymer according to claim 1 .
15. A method for treating a substrate comprising:
contacting a substrate with a composition comprising at least one polymer according to claim 1 , optionally a film forming binder, optionally a solvent, and optionally an additive, and
drying said composition on said substrate.
16. A coated substrate formed according to the method of claim 15 .
17. A paint, coating, printing ink, protective coating, special coating for in electronic or optical applications, photoresist, top antireflective coating, bottom antireflective coating, cosmetic product, agrochemical, floor polish, photographic coating, or coating for optical elements, comprising: a polymer according to claim 1 .
18. A composition comprising at least one polymer according to claim 1 , optionally a film forming binder, optionally a solvent, and optionally an additive.
19. A composition according to claim 18 , wherein said composition is a paint composition, a coating composition, a fire-extinguishing composition, a lubricant, a de-icer composition, a photoresist composition, a photolithographic composition, a cosmetic product, an agrochemical, a floor polish or a hydrophobicizing composition for textile finishing or glass treatment.
20. A film produced by curing a composition according to claim 18 .
21. A product having a coating comprising at least one polymer according to claim 1 .
22. A process for the preparation of a polymer comprising:
(a) polymerizing at least one monomer of formulae (I) or (II) to obtain a polymer according to claim 1
(Rf 1 —CHF—CF 2 —O—CHR 1 ) m1 -L 1 -(X 1 ) n1 (I)
(Rf 2 —CHF—CF 2 —S—CHR 2 ) m2 -L 2 -(X 2 ) n2 (II)
wherein
Rf 1 and Rf 2 are each, independently of one another, a perfluorinated alkyl group optionally containing heteroatoms,
R 1 and R 2 are each, independently of one another, H or an alkyl group,
L 1 and L 2 are each, independently of one another, a single bond or a bivalent organic group,
X 1 and X 2 are each, independently of one another, an acrylate or a methacrylate group,
m 1 and m 2 are each, independently of one another, another ≥1
and n 1 and n 2 each, independently of one another, another ≥1,
in a composition comprising at least one initiator, optionally at least one solvent, and optionally at least co-monomer, and
(b) optionally isolating the polymer.