Coating for a Surface

Abstract

Coatings for a surface, especially a priming coating, of the present invention have been found to be durable, resistant to oxidative degradation, erosion and depolymerisation, stable to sterilization and low particulating, and are easily applied to the required surface of a substrate in a surface-independent manner. Such coatings, when used as priming coatings to be coated with a subsequent coating, in at least some embodiments, form exterior coatings which are also highly durable and are stable to sterilisation and aging.

1 . A method of coating a surface, comprising the steps of:
 (a) contacting the surface with a mixture comprising components A and B, wherein
 component A is a molecule capable of self-polymerisation comprising catechol functionality and amine and/or amide and/or hydroxyl functionality; and 
 component B is 
 (i) a cross-linking molecule comprising two or more photosensitive or thermosensitive moieties capable of forming covalent bonds with component A; or 
 (ii) a polymer comprising photosensitive or thermosensitive moieties capable of forming covalent bonds with component A, 
 or a mixture thereof; 
 such that component A self-polymerises in the presence of component B and in the case of (ii) forms an interpenetrating network with component B; and 
   (b) activating the photosensitive or thermosensitive moieties of component B such that at least some of said moieties form covalent bonds with component A.   
     
     
         2 . A method of coating a surface, comprising the steps of:
 (a) contacting the surface with a mixture comprising components A and B, wherein
 component A is a molecule capable of self-polymerisation comprising catechol functionality and amine and/or amide and/or hydroxyl functionality; and 
 component B is a molecule comprising one or more groups capable of participating in the polymerisation of component A, wherein said molecule comprises one or more photosensitive or thermosensitive moieties capable of forming covalent bonds with component A such that a copolymer of components A and B is formed; and 
   (b) activating the photosensitive or thermosensitive moieties of component B in the copolymer such that at least some of said moieties form covalent bonds with component A.   
     
     
         3 . A method according to  claim 1 , wherein component A is a catecholamine capable of self-polymerisation. 
     
     
         4 . A method according to  claim 3 , wherein component A is dopamine. 
     
     
         5 . A method according to  claim 2 , wherein the one or more groups capable of participating in the polymerisation with component A are selected from amino, hydroxyl, catechol, thiol, hydrazine, hydrazone, oxime, keto, aldehyde, carboxyl, imino, amido, alkenyl and alkynyl group. 
     
     
         6 . A method according to  claim 5 , wherein at least one of the one or more groups capable of participating in polymerisation with component A is selected from the group consisting of amino, hydroxyl, catechol, amido and C 2 -C 8  alkenyl. 
     
     
         7 . A method according  claim 1 , wherein component B is a cross-linking molecule comprising two or more photosensitive or thermosensitive moieties, at least some of which moieties form covalent bonds with component A. 
     
     
         8 . A method according to  claim 1 , wherein component B is a polymer comprising photosensitive or thermosensitive moieties at least some of which moieties form covalent bonds with component A and which polymer forms an interpenetrating network with component A. 
     
     
         9 . A method according to  claim 1 , wherein component B is a mixture of a cross-linking molecule comprising two or more photosensitive or thermosensitive moieties, at least some of which moieties form covalent bonds with component A, and a polymer comprising photosensitive or thermosensitive moieties at least some of which moieties form covalent bonds with component A and which polymer forms an interpenetrating network with component A. 
     
     
         10 . A method according to  claim 2 , wherein component B is of formula (VI):
   ZY—X] q   (VI)
   wherein,   each Z is independently a photosensitive or thermosensitive group;   each X is a moiety comprising a functional group capable of participating in the polymerisation of component A;   each Y is independently selected from the group consisting of a covalent bond, C 1 -C 8  alkyl, C 2 -C 8  alkenyl, C 2 -C 8  alkynyl, —(CH 2 CH 2 O) 1-20 —, —C(O)—NH—(C 1 -C 8  alkyl)-, —NH—C(O)—(C 1 -C 8  alkyl)-, —C(O)—NH—(C 1 -C 8  alkyl)-NH—(C(O)—, —NH—C(O)—(C 1 -C 8  alkyl)-C(O)—NH—, —NH—C 1 -C 8  alkyl-NH(CO)—, —N(C 1 -C 8  alkyl-NH(CO)—) 2 , N(C 1 -C 8  alkyl-NH(CO)—) 3 , phenyl and —(C 1 -C 8  alkyl)-phenyl; wherein, each Y is optionally independently substituted with C 1 -C 8  alkyl, C 2 -C 8  alkenyl or —O(C 1 -C 8  alkyl); and   q is 1-4.   
     
     
         11 . A method according to  claim 10 , wherein component B is of formula (IV) wherein, Z is benzophenone or C 2 -C 8  alkenyl; each Y is independently selected from the group consisting of a covalent bond, C 1 -C 8  alkyl, C 2 -C 8  alkenyl, —(CH 2 CH 2 O) 1-20 —, —C(O)—NH—(C 1 -C 8  alkyl)-, —NH—C(O)—(C 1 -C 8  alkyl)-, —C(O)—NH—(C 1 -C 8  alkyl)-NH—(C(O)—, or —NH—C(O)—(C 1 -C 8  alkyl)-C(O)—NH—, phenyl or —(C 1 -C 8  alkyl)-phenyl, wherein each Y is optionally independently substituted with C 1 -C 8  alkyl, C 2 -C 8  alkenyl or —O(C 1 -C 8  alkyl); X is selected from the group consisting of amino, hydroxyl, catechol, thiol, hydrazine, hydrazone, oxime, keto, aldehyde, carboxyl, imino, amido, C 2 -C 8  alkenyl and C 2 -C 8  alkynyl; and q is 1-4. 
     
     
         12 . A method according to  claim 11 , wherein component B is of formula (VI) and is selected from the group consisting of dopamine benzoyl benzamide, 3-amido(4-benzoylbenzoyl)propyl methacrylamide, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-dihydroxybenzophenone, 3,4-diaminobenzopheneone and eugenol. 
     
     
         13 . A method according to  claim 12 , wherein component B is dopamine benzoyl benzamide. 
     
     
         14 . A method according to  claim 1 , wherein the coating is covalently bonded to the surface. 
     
     
         15 . A method according to  claim 1 , wherein the one or more photosensitive or thermosensitive moieties of component B are capable of hydrogen abstraction. 
     
     
         16 . A method according to  claim 15 , wherein the surface comprises abstractable hydrogen atoms and the coating is covalently bonded to the surface via abstraction of hydrogen atoms from the surface by at least some of the photosensitive or thermosensitive moieties of component B. 
     
     
         17 . A method according to  claim 1 , wherein component B comprises one or more photosensitive moieties. 
     
     
         18 . A method according to  claim 17 , wherein the one or more photosensitive moieties are selected from the group consisting of aryl ketone, diaryl ketone, aryl azide, alkenyl and alkynyl. 
     
     
         19 . A method according to  claim 17 , wherein the one or more photosensitive moiety is a Type I or a Type II photoinitiator. 
     
     
         20 . A method according to  claim 18 , wherein the one or more photosensitive moiety is a Type II photoinitiator. 
     
     
         21 . A method according to  claim 20 , wherein the one or more photosensitive moiety is a diaryl ketone. 
     
     
         22 . A method according to  claim 20 , wherein the one or more photosensitive moiety is benzophenone. 
     
     
         23 . A method according to  claim 1 , wherein the one or more photosensitive moiety is activated by exposure to UV light. 
     
     
         24 . A method according to  claim 1 , wherein component B comprises one or more thermosensitive moieties. 
     
     
         25 . A method according to  claim 1 , wherein component B comprises one or more photosensitive or thermosensitive moieties capable of forming a carbene or nitrene. 
     
     
         26 . A method according to  claim 1 , wherein component B is selected from benzoylbenzoic dopamide, amidobenzoylbenzoyl methacrylamide, tris-[amino(ethylbenzoylbenzamide)], 4-aminobenzophenone, eugenol, 4,4′-diaminobenzophenone, 4,4′-dihydroxybenzophenone, 3,4-diaminobenzopheneone and a polymeric photoinitiator such as a polyaryl ketone e.g. a polybenzophenone. 
     
     
         27 . A method according to  claim 1 , further comprising the step of (c) applying a subsequent coating to the surface. 
     
     
         28 . A method according to  claim 27 , wherein the subsequent a coating is selected from the group consisting of a synthetic or naturally occurring organic or inorganic polymer or material, such as polyolefins, polyesters, polyurethanes, polyamides, polyether block amides, polyimides, polycarbonates, polyphenylene sulfides, polyphenylene oxides, polyethers, silicones, polycarbonates, polyhydroxyethylmethacrylate, polyvinyl pyrrolidone, polyvinyl alcohol, rubber, silicone rubber, polyhydroxyacids, polyallylamine, polyallylalcohol, polyacrylamide, polyacrylic acid, styrenic polymers, polytetrafluoroethylene and copolymers thereof, bioresorbables, such as poly(D,L-lactide), polyglycolids and copolymers thereof, non-woven, bioabsorbable web materials comprising a tri-block copolymer such as poly(glycolide-co-trimethylene carbonate) tri-block copolymer (PGA:TMC), nylon 12, nylon 11, nylon 9, nylon 6/9 and nylon 6/6, polyetheresteramide, polyethylene terephthalate and polybutylene terephthalate, polyester ethers, polyester elastomer copolymers, block copolymer elastomers such as those copolymers having styrene end blocks, and midblocks formed from butadiene, isoprene, ethylene/butylene, ethylene/propene, styrenic block copolymers including acrylonitrile-styrene and acrylonitrile-butadiene-styrene block copolymers, polystyrenes, poly(methyl)methacrylates, polyacrylonitriles, poly(vinylacetates), poly(vinyl alcohols), chlorine-containing polymers such as poly(vinyl) chloride, polyoxymethylenes, polycarbonates, polyamides, polyimides, polyurethanes, phenolics, amino-epoxy resins, polyesters, silicones, cellulose-based plastics, rubber-like plastics, fluorinated polymers such as fluoropolymers, e.g expanded polytetrafluoroethylene (ePTFE), polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene (FEP), perfluorocarbon copolymers, e.g. tetrafluoroethylene perfluoroalkylvinyl ether (TFE/PAVE) copolymers, copolymers of tetrafluoroethylene (TFE) and perfluoromethyl vinyl ether (PMVE), copolymers of TFE with functional monomers that comprise acetate, alcohol, amine, amide, sulfonate, functional groups, expanded polyethylene, polyvinylchloride, polyurethane, silicone, polyethylene, polypropylene, polyurethane, polyglycolic acid, polyesters, polyamides, elastomers and their mixtures, blends and copolymers or derivatives. 
     
     
         29 . A method according to  claim 27 , wherein the coating is covalently bonded to the subsequent coating. 
     
     
         30 . A method according to  claim 27 , wherein the subsequent coating comprises a therapeutic agent. 
     
     
         31 . A method according to  claim 30 , wherein the therapeutic agent is selected from the group consisting of an anti-thrombogenic agent, a hemostatic agent, an anti-angiogenic agent, an angiogenic agents, an anti-microbial agent, an anti-proliferative agent, a proliferative agent or an anti-inflammatory agent, or a combination thereof. 
     
     
         32 . A method according to  claim 1 , wherein step (a) is carried out in the presence of an oxidant. 
     
     
         33 . A method according to  claim 32 , wherein the oxidant is ammonium persulfate or sodium persulfate. 
     
     
         34 . A method according to  claim 1 , wherein the surface is the surface of a substrate comprising a medical device. 
     
     
         35 . A method according to  claim 34 , wherein the medical device is selected from the group consisting of stents including bifurcated stents, balloon expandable stents and self-expanding stents, stent-grafts including bifurcated stent-grafts, grafts including vascular grafts and bifurcated grafts, dialators, vascular occluders, embolic filters, embolectomy devices, catheters including microcatheters, central venous catheters, peripheral intravenous catheters and hemodialysis catheters, artificial blood vessels, sheaths including retractable sheaths, blood indwelling monitoring devices, artificial heart valves, pacemaker electrodes, guidewires, cardiac leads, cardiopulmonary bypass circuits, cannulae, plugs, drug delivery devices, balloons, tissue patch devices and blood pumps.