US 6,090,901 A · Polymeric surface coatings

Abstract

A non-crosslinked polymer having pendant zwitterionic groups and pendant functional groups can be coated from a coating composition onto a surface having pendant coreactive functional groups and, after coating, may be cured so that covalent bonds are formed between the coreactive functional groups on the polymer and the surface. Alternatively the polymer can be crosslinked after coating, by formation of covalent intermolecular cross-links between coreactive pendant functional groups on the polymer. The zwitterionic pendant groups preferably have, as the anion, a phosphate ester group, and as the cation, a quaternary ammonium group. The polymer coating is stable and provides improved biocompatibility, especially haemocompatibility.

A substantially non-cross-linked polymer formed by radical polymerisation of radical polymerisable monomers including i) a zwitterionic monomer having the formula:

Y--B--X (I)
wherein
B is a straight or branched alkylene, oxaalkylene or oligo-oxaalkylene chain optionally containing one or more fluorine atoms up to and including perfluorinated chains, or if X contains a carbon-carbon chain between B and the centre of permanent position charge or if Y contains a terminal carbon atom bonded to B, a valence bond;
X is a zwitterionic group selected from groups IVC, IVD and IVF in which
group IVC has the formula ##STR26## where the groups R.sup.7 are the same or different and each is hydrogen or C.sub.1-4 alkyl, and e is from 1 to 4;
group IVD has the formula ##STR27## wherein the groups R.sup.8 are the same or different and each is hydrogen or C.sub.1-4 alkyl, R.sup.8a is hydrogen or a group --C(O)B.sup.1 R.sup.8b wherein R.sup.8b is hydrogen or methyl, B.sup.1 is a valence bond or straight or branched alkylene, oxaalkylene or oligo-oxaalkyene group, and f is from 1 to 4;
and if B is other than a valence bond z is 1 and if B is a valence bond z is 0, if X is directly bonded to an oxygen or nitrogen atom and otherwise z is 1;
group IVE has the formula ##STR28## wherein the groups R.sup.9 are the same or different and each is hydrogen or C.sub.1 -C.sub.4 alkyl, R.sup.9a is hydrogen or a group --C(O)B.sup.2 R.sup.9b, wherein R.sup.9b is hydrogen or methyl, B.sup.2 is a valence bond or a straight or branched alkylene, oxaalkylene or oligo-oxaalkylene group, and g is from 1 to 4;
and
if B is other than a valence bond z is 1 and if B is a valence bond z is 0 if X is directly bonded to an oxygen or nitrogen atom and otherwise z is 1;
and
group IVF has the formula ##STR29## wherein the groups R.sup.10 are the same or different and each is hydrogen or C.sub.1-4 alkyl, R.sup.10a is hydrogen or a group --C(O)B.sup.3 R.sup.10b wherein R.sup.10b is hydrogen or methyl, B.sup.3 is a valence bond or a straight or branched alkylene, oxaalkylene or oligo-oxaalkylene group, and h is from 1 to 4;
and
if B is other than a valence bond z is 1 and if B is a valence bond z is 0 if X is directly bonded to the oxygen or nitrogen and otherwise z is 1 and
Y is an ethylenically unsaturated polymerisable group selected from ##STR30## wherein:
R is hydrogen or a C.sub.1 -C.sub.4 alkyl group;
A is --O-- or --NR.sup.1 -- where R.sup.1 is hydrogen or a C.sub.1 -C.sub.4 alkyl group or R.sup.1 is --B--X where B and X are as defined above;
and
K.sup.2 is a group --(CH.sub.2).sub.p OC(O)--, --(CH.sub.2).sub.p C(O)O--, --(CH.sub.2).sub.p OC(O)O--, --(CH.sub.2).sub.p NR.sup.2 --, --(CH.sub.2).sub.p NR.sup.2 C(O)--, --CH.sub.2).sub.p C(O)NR.sup.2 --, --(CH.sub.2).sub.p NR.sup.2 C(O)--, --(CH.sub.2).sub.p OC(O)NR.sup.2 --, --(CH.sub.2).sub.p NR.sup.2 C(O)NR.sup.2 --, (in which the groups R.sup.2 are the same or different) --(CH.sub.2).sub.p O--, --(CH.sub.2).sub.p SO.sub.3 --, or, optionally in combination with B, a valence bond and p is from 1 to 12 and R.sup.2 is hydrogen or a C.sub.1 -C.sub.4 alkyl group and
ii) a monomer having a reactive group of the formula general formula (XII)
Y.sup.2 --B.sup.7 --Q.sup.3 (XII)
where
Y.sup.2 is an ethylenically unsaturated polymerisable group selected from ##STR31## where R.sup.26 is hydrogen or C.sub.1 -C.sub.4 alkyl;
T is --O-- or NR.sup.27 --, wherein R.sup.27 is hydrogen or a C.sub.1 -C.sub.4 alkyl group or R.sup.27 is a group --B.sup.7 Q.sup.3 ;
B.sup.7 is a valence bond a straight or branched alkylene oxaalkylene or oligo-oxaalkylene group;
K.sup.2 is a group --(CH.sub.2).sub.q OC(O)--, --(CH).sub.q C(O)O--, --(CH.sub.2).sub.q OC(O)O--, --(CH.sub.2).sub.q NR.sup.20 --, --(CH.sub.2).sub.q NR.sup.20 C(O)--, --(CH.sub.2).sub.q C(O)NR.sup.20 --, --(CH.sub.2).sub.q NR.sup.20 C(O)O--, --(CH.sub.2).sub.q OC(O)NR.sup.20 --, --(CH.sub.2).sub.q NR.sup.20 C(O)NR.sup.20 -- (in which the groups R.sup.20 are the same or different), --(CH.sub.2).sub.q O--, or --(CH.sub.2).sub.q SO.sub.3 --, or a valence bond and q is from 1 to 12 and R.sup.20 is hydrogen or a C.sub.1 -C.sub.4 alkyl group;
and
Q.sup.3 is a reactive group selected from the group consisting of aldehyde groups;
silane and siloxane groups containing one or more substituents selected from halogen atoms and C.sub.1-4 -alkoxy groups;
hydroxyl;
amino;
carboxyl;
epoxy;
--CHOHCH.sub.2 Hal (in which Hal is selected from chlorine, bromine and iodine atoms);
succinimido;
tosylate;
triflate;
imidazole carbonyl amino;
optionally substituted triazine groups;
cinnamyl;
ethylenically and acetylenically unsaturated groups;
acetoacetoxy;
methylol;
and chloroalkylsulphone groups.

41 more elements

Polymeric surface coatings

Life of this patent

Polymeric surface coatings

Life of this patent

Abstract

Claims15