# US 5,705,583 A · Polymeric surface coatings

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- Number: US 5,705,583 A
- Document ID: US5705583A
- Status: Granted
- Kind: A
- Application number: 08/475,620
- Filed: 1995-06-07
- Granted: 1998-01-06
- Earliest claimed: 1991-07-05
- Assignees: Biocompatibles Limited
- Inventors: Roderick W. J. Bowers; Stephen A. Jones; Peter W. Stratford; Stephen A. Charles
- Web page: https://patentgrep.com/patent/US5705583A

## CPC

- C08F 246/00: Copolymers in which the nature of only the monomers in minority is defined
- C07F 9/091: {with hydroxyalkyl compounds with further substituents on alkyl}
- C07F 9/65742: {non-condensed with carbocyclic rings or heterocyclic rings or ring systems}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

Polymers of one or more radical polymerisable monomers which polymer has pendant groups bearing a center of permanent positive charge and other pendant groups capable of stably binding the polymer to a surface are useful in the treatment of surfaces to render them biocompatible. The polymers may contain pendant groups which bind the polymer to a surface by physisorption, covalent bonding or ionic interactions. Additionally reactive groups in the polymer may serve as points for attachment of ligands to the polymer when coated on a surface.

## Claims

### Claim 1

A process in which a substrate having a surface is coated with a coating composition containing a polymer formed from radical polymerisable monomers including a radical polymerisable zwitterionic monomer containing a zwitterionic group and a radical polymerisable monomer containing reactive groups to form a polymer having zwitterionic groups and pendant reactive groups and the pendant reactive groups are reacted to form a stable coating of polymer on the surface by reaction of the pendant reactive groups with one another to crosslink the polymer, and wherein the zwitterionic monomer has 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 group IVB, IVC, IVD and IVF in which group IVB has the formula ##STR21## wherein the groups R.sup.6 are the same or different and each is hydrogen or C.sub.1-4 alkyl and d is from 2 to 4;
group IVC has the formula ##STR22## 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 ##STR23## 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.l 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 ##STR24## 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 ##STR25## 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 ##STR26## 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 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)O--, --(CH.sub.2).sub.p OC(O)NR.sup.2 --, --(CH.sub.2).sub.p NR.sup.2 CO)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 wherein the radical polymerisable monomer containing reactive groups has the general formula (XII)
Y.sup.2' --B.sup.9' --O.sup.5' (XII)
where Y.sup.2' is an ethylenically unsaturated polymerisable group selected from ##STR27## where R.sup.26' is hydrogen or C.sub.1 -C.sub.4 alkyl; A"' is --O-- or NR.sup.27' --, wherein R.sup.27' is hydrogen or a C.sub.1 -C.sub.4 alkyl group or R.sub.27' is a group --B.sup.9' Q.sup.5' ;
B.sup.9' is a valence bond, a straight or branched alkylene oxaalkylene or oligo-oxaalkylene group;
K.sup.3' is a group --(CH.sub.2).sub.x OC(O)--, --(CH).sub.x C(O))--, --(CH.sub.2).sub.x OC(O)O--, --(CH.sub.2).sub.x NR.sup.28' --, --(CH.sub.2).sub.x NR.sup.28' C(O)--, --(CH.sub.2).sub.x C(O)NR.sup.28' --, --(CH.sub.2).sub.x NR.sup.28' C(O)O--, --(CH.sub.2).sub.x OC(O)NR.sup.28' --, --(CH.sub.2).sub.x NR.sup.28' C(O)NR.sup.28' --(in which the groups R.sup.28' are the same or different), --CH.sub.2).sub.x O--, --(CH.sub.2).sub.x SO.sub.3 --, a valence bond, x' is from 1 to 12 and R.sup.28' is hydrogen or a C.sub.1 -C.sub.4 alkyl group; and
O.sup.5' is a reactive group selected from the group consisting of cinnamyl, epoxy, --CHOHCH.sub.2 Hal (in which Hal is selected from chlorine, bromine, and iodine atoms), methylol, silyl, ethylenically and acetylenically unsaturated groups, acetoacetoxy and chloroalkylsulphone groups.

### Claim 2 (depends on 1)

A process according to claim 1 in which the pendant reactive groups on the polymer are reacted with one another to cross-link the polymer to form the said stable coating.

### Claim 3 (depends on 1)

A process according to claim 1 in which the monomer of the general formula XII' is 3-trimethoxysilylpropyl methacrylate and in which crosslinking is achieved by incorporation of a tin-containing catalyst into the coating solution.

### Claim 4 (depends on 1)

A process according to claim 1 in which the polymer is formed from monomers including a comonomer of formula (VI):
Y'--Q (VI)
where Y' is an ethylenically unsaturated polymerisable group selected from:
(a) ##STR28## wherein R.sup.14 is selected from the group consisting of hydrogen and a C.sub.1 -C.sub.4 alkyl group,
A' is --O-- or --NR.sup.15 -- wherein R.sup.15 is selected from the group consisting of hydrogen; a C.sub.1 -C.sub.4 alkyl group; a Q group which is selected from the group consisting of a straight and branched alkyl group, an alkoxyalkyl group and an (oligo-alkoxy)alkyl group containing 6 to 24 carbon atoms, any of which Q group is unsubstituted or substituted by one or more fluorine atoms and optionally contains one or more carbon-carbon double or triple bonds; and a siloxane group --(CR.sup.16a.sub.2).sub.qq (SiR.sup.16b.sub.2) (OSiR.sup.16b.sub.2).sub.pp R.sup.16b in which each R.sup.16a group is the same or different and is selected from the group consisting of hydrogen, an alkyl group of 1 to 4 carbon atoms and an aralkyl group, each R.sup.16b group is alkyl of 1 to 4 carbon atoms, qq is from 1 to 6 and pp is from 0 to 49; and
(b) ##STR29## wherein K.sup.1 is selected from the group consisting of --(CH.sub.2).sub.l OC(O)--, --(CH.sub.2).sub.l C(O)O--, --(CH.sub.2).sub.l OC(O)O--, --(CH.sub.2).sub.l NR.sup.16 --, --(CH.sub.2).sub.l NR.sup.16 C(O)--, --(CH.sub.2).sub.l C(O)NR.sup.16 --, --(CH.sub.2).sub.l NR.sup.16 C(O)O--, --(CH.sub.2).sub.l OC(O)NR.sup.16 --, --(CH.sub.2).sub.l NR.sup.16 C(O)NR.sup.16 -- in which the groups R.sup.16 are the same or different, --(CH.sub.2).sub.l --, --(CH.sub.2).sub.l SO.sub.3 --, and a bond, in which l is from 1 to 12 and R.sup.16 is selected from the group consisting of hydrogen and C.sub.1 -C.sub.4 alkyl groups; and
O is selected from the group consisting of a straight and branched alkyl group, an alkoxyalkyl group and an (oligo-alkoxy) alkyl group containing 6 to 24 carbon atoms, any of which O group is unsubstituted or substituted by one or more fluorine atoms and optionally contains one or more carbon-carbon double or triple bonds; and a siloxane group --(CR.sup.16a.sub.2).sub.qq (SiR.sup.16b.sub.2) (OSiR.sup.16b.sub.2).sub.pp R.sup.16b in which each R.sup.16a group is the same or different and is selected from the group consisting of hydrogen, an alkyl group of 1 to 4 carbon atoms and an aralkyl group, each R.sup.16b group is alkyl of 1 to 4 carbon atoms, qq is from 1 to 6 and pp is from 0 to 49.

### Claim 5 (depends on 4)

A process according to claim 4 in which Y' is ##STR30## in which R.sup.14 is methyl and A' is --O-- and Q is an alkyl group of formula --(CR.sup.17.sub.2).sub.m CR.sup.17.sub.3, wherein the --(CR.sup.17.sub.2)-- groups are the same or different and in each --(CR.sup.17.sub.2)-- group, the R.sup.17 groups are the same or different and each R.sup.17 group is selected from the group consisting of hydrogen, a C.sub.1-4 alkyl group, a C.sub.1-4 fluoroalkyl group, and fluorine and n is in the range 5 to 23.

### Claim 6 (depends on 4)

A process according to claim 4 in which the comonomer is selected from the group consisting of n-dodecyl methacrylate, octadecyl methacrylate, hexadecyl methacrylate, 1H,1H,2H,2H-heptadecafluorodecyl methacrylate, p-octyl styrene, p-dodecyl styrene and monomethacryloxypropyl terminated siloxanes.

### Claim 7 (depends on 6)

A process according to claim 6 in which the comonomer is dodecyl methacrylate.

### Claim 8 (depends on 1)

A process according to claim 1 in which the polymer is formed from monomers including a diluent monomer selected from the group consisting of, C.sub.1-4 -alkyl(alk)acrylates, N,N-dialkylamino alkyl(alk)acrylates containing 1 to 4 carbon atoms in each N-alkyl group and 1 to 4 carbon atoms in the alkylene group, C.sub.1-4 -alkyl(alk)acrylamide, hydroxy C.sub.1-4 -alkyl(alk)acrylate, N-vinyl lactam having 5-7 atoms in the lactam ring, styrene, derivatives of styrene having ring substituents selected from C.sub.1-4 -alkyl groups and halogen atoms, polyhydroxyl (alk)acrylates, alkenes, butadiene, maleic anhydride and acrylonitrile.

### Claim 9 (depends on 8)

A process according to claim 8 in which the diluent monomer is selected from hydroxy C.sub.1-4 -alkyl(alk)acrylates and polyhydroxyl(alk)acrylates.

### Claim 10 (depends on 1)

A process according to claim 1 in which the substrate is selected from polyethylene, poly (vinylchloride), poly (imide), steel, aluminum, cellulose, and poly(vinylidene fluoride).

### Claim 11 (depends on 1)

A process according to claim 1 in which the substrate is steel.

### Claim 12 (depends on 1)

A process according to claim 1 in which the polymer is formed from monomers including at least 5% by weight zwitterionic monomer and at least 0.1% by weight monomer containing a reactive group.

### Claim 13 (depends on 1)

A process according to claim 1 in which the polymer is formed from monomers including at least 5% by weight zwitterionic monomer and 0.1% to 20% by weight monomer of the formula XII.

### Claim 14 (depends on 8)

A process according to claim 8 in which the polymer is formed from monomers including at least 5% by weight zwitterionic monomer, at least 0.1% by weight monomer containing a reactive group and 5 to 20% by weight diluent monomer.

### Claim 15 (depends on 4)

A process according to claim 4 in which the polymer is formed from monomers including at least 5% by weight zwitterionic monomer, at least 0.1% by weight monomer including a reactive group and 5 to 90% by weight of said comonomer.