Oxirane (ethylene oxide) polyurethane coatings

Abstract

The present invention relates to hydrophilic, i.e., water loving coatings (hereafter referred to as “WLC”). Polyurethane epoxy alkylene oxide coatings usable as coatings on for example, medical devices are a preferred WLC.

1 . A composition comprising epoxy urethane alkylene oxide reactive coating compositions of the structure of formula (1). 
       
         
           
           
               
               
           
         
       
     
     
         2 . The composition of  claim 1 , wherein the epoxy urethane alkylene oxide reactive coating compositions are
 (a) Polytrimethylene ether glycol, with n having a number average molecular weight in the range of about 1,000 to about 4,000,000 where n=11 to about 46.   (b) Optional Polyethylene oxide, with m having a number average molecular weight in the range of about 18,000 to about 2,000,000 where n=375 to about 41,667   (c) Optional Poly[di(ethylene glycol) adipate, with o having a number average molecular weight in the range of about 400 to about 10,000.00 where n=2 to about 50   (d) Glycidyl moieties are represented by the addition of glycidol   
     
     
         3 . A composition comprising epoxy urethane ester carboxylic acid alkylene oxide reactive coating compositions of the following structure (H): 
       
         
           
           
               
               
           
         
       
     
     
         4 . The composition of  claim 3 , wherein the epoxy urethane ester carboxylic acid alkylene oxide reactive coating compositions are
 (a) Poly[di(ethylene glycol) adipate having a number average molecular weight in the range of about 400 to about 10,000.00 where n=2 to about 50   (b) Optional Polytrimethylene ether glycol having a number average molecular weight in the range of about 1,000 to about 4,000,000 where n=11 to about 46.   (c) Optional Polyethylene oxide having a number average molecular weight in the range of about 18,000 to about 2,000,000 where n=375 to about 41,667   (d) Acid moieties are represented by the addition of dimethylol propionic acid   (e) Glycidyl moieties are represented by the addition of glycidol   (f) Excess isocyanate can react with dimethylol propionic acid to form an amide resulting in a urea   
     
     
         5 . A composition comprising epoxy urethane urea carboxylic acid alkylene oxide reactive coating compositions of the following structure (III): 
       
         
           
           
               
               
           
         
       
     
     
         6 . The composition of  claim 5 , wherein the epoxy urethane urea carboxylic acid alkylene oxide reactive coating compositions are:
 (a) Poly[di(ethylene glycol) adipate having a number average molecular weight in the range of about 400 to about 10,000.00 where n=2 to about 50   (b) Optional Polytrimethylene ether glycol having a number average molecular weight in the range of about 1,000 to about 4,000,000 where n=11 to about 46.   (c) Optional Polyethylene oxide having a number average molecular weight in the range of about 18,000 to about 2,000,000 where n=375 to about 41,667   (d) Acid moieties are represented by the addition of dimethylol propionic acid   (e) Glycidyl moieties are represented by the addition of glycidol   (f) Urea moieties are represented by the addition of adipic acid dihydrazide   (g) Excess isocyanate can react with dimethylol propionic acid to form an amide resulting in a urea   
     
     
         7 . A composition comprising epoxy urethane urea (based off water addition) carboxylic acid alkylene oxide reactive coating compositions of the following structure (IV): 
       
         
           
           
               
               
           
         
       
     
     
         8 . The composition of  claim 7 , wherein the epoxy urethane urea carboxylic acid alkylene oxide reactive coating compositions are:
 (a) Poly[di(ethylene glycol) adipate having a number average molecular weight in the range of about 400 to about 10,000.00 where n=2 to about 50   (b) Optional Polytrimethylene ether glycol having a number average molecular weight in the range of about 1,000 to about 4,000,000 where n=11 to about 46.   (c) Optional Polyethylene oxide having a number average molecular weight in the range of about 18,000 to about 2,000,000 where n=375 to about 41,667   (d) Acid moieties are represented by the addition of dimethylol propionic acid   (e) Glycidyl moieties are represented by the addition of glycidol   (f) Urea moieties are represented by the addition of reduced isocyanate system then adding water   
     
     
         9 . A composition comprising epoxy urethane urea (based off excess iscoyanate) carboxylic acid alkylene oxide reactive coating compositions of the following structure (V): 
       
         
           
           
               
               
           
         
       
     
     
         10 . The composition of  claim 9 , wherein the epoxy urethane urea carboxylic acid alkylene oxide reactive coating compositions are:
 (a) Poly[di(ethylene glycol) adipate having a number average molecular weight in the range of about 400 to about 10,000.00 where n=2 to about 50   (b) Optional Polytrimethylene ether glycol having a number average molecular weight in the range of about 1,000 to about 4,000,000 where n=11 to about 46.   (c) Optional Polyethylene oxide having a number average molecular weight in the range of about 18,000 to about 2,000,000 where n=375 to about 41,667   (d) Acid moieties are represented by the addition of dimethylol propionic acid   (e) Glycidyl moieties are represented by the addition of glycidol   (f) Urea moieties are represented by the addition of excess isocyanate, in the system, to adipic acid dihydrazide   
     
     
         11 . An aqueous soluble or solvent soluble or mixture comprising  claims 1 - 10 . 
     
     
         12 . A composition of  claim 11 , where an aqueous soluble solvent is water and solvent soluble solvents are aprotic. 
     
     
         13 . A composition of  claim 12 , where the aprotic solvents are NMP, DMSO or DMF. 
     
     
         14 . A composition of  claim 11 , where the solvent can be a polar non-reactive solvent 
     
     
         15 . A composition of  claim 14 , where the solvent can be PMA, Acetone or MEIN. 
     
     
         16 . A composition of  claims 1 - 10  where a chain extender is added. 
     
     
         17 . A composition of  claims 1 - 10  where the curing agent is a self-crosslinking reaction via homopolymerization or polyetherification. 
       
         
           
           
               
               
           
         
       
     
     
         18 . A composition of  claim 17 , where kinetics of the reaction are improved with temperature 
     
     
         19 . A composition comprising a mixture compounds with structures (I), (II), (III), (IV) and (V) 
     
     
         20 . A coating composition of  claims 1 - 10  further comprising a curing agent 
     
     
         21 . A coating composition of  claim 3 - 10 , wherein the curing agent is an aziridine curing agent 
     
     
         22 . A composition of  claim 21 , where basecoat carboxylic acid groups can react with polyaziridine (PZ-28 or PZ-33): 
       
         
           
           
               
               
           
         
         a) Polyaziridine PZ-28 reaction with basecoat ( claims 22 ): 
         b) Polyaziridine PZ-28 or PZ-33, added to basecoat ( claims 3 - 10 ), reacts with carboxylic acid in modified Hyaluronic Acid topcoat: 
       
       
         
           
           
               
               
           
         
         c) Polyaziridine PZ-28 or PZ-33 ( claim 22 ), connecting basecoat to modified Hyaluronic Acid topcoat: 
       
       
         
           
           
               
               
           
         
       
     
     
         23 . A composition of  claims 1 - 10 , where epoxy groups can react with an amine cross-linking agents (Figure below). 
       
         
           
           
               
               
           
         
       
     
     
         24 . The coating composition of  claim 23 , wherein the amine curing agent is Poly(ethylene oxide), 4-arm, amine terminated 
     
     
         25 . Basecoat epoxy groups can react with Poly(ethylene oxide), 4-arm, amine terminated found in topcoat.
 a. The '956 patent epoxy groups can react with Poly(ethylene oxide), 4-arm, amine terminated and Poly(ethylene oxide), 4-arm, amine terminated can react with basecoat to increase adhesive strength.   
       
         
           
           
               
               
           
         
       
     
     
         26 . A composition of  claims 1 - 10 , where open hydroxyl groups from epoxy group ring opening can react with isocyanate cross-linking agents (Figure below). 
     
     
         27 . The coating composition of  claim 26 , wherein the isocyanate curing agent is Easaqua XM-502
 a) Easaqua XM-502 added to the basecoat reacts with basecoat carboxylic acid:   
       
         
           
           
               
               
           
         
         b. Easaqua XM-502 added to the basecoat reacts with Polyethylene oxide), 4-arm, amine added as a crosslinker to the top-coat: 
       
       
         
           
           
               
               
           
         
         c. Easaqua XM-502 added to the basecoat reacts with open hydroxyls when the base-coat epoxy ring opens: 
       
       
         
           
           
               
               
           
         
         d. Easaqua XM-502 added to the basecoat reacts with open hydroxyls when the '956 patent ring opens: 
       
       
         
           
           
               
               
           
         
         e. Easaqua XM-502 reacts with hydroxyl groups found in Hyaluronic acid: 
       
       
         
           
           
               
               
           
         
         f. Easaqua XM-502 reacts with carboxylic groups found in Hyaluronic acid: 
       
       
         
           
           
               
               
           
         
       
     
     
         28 . A composition of  claims 1 - 10 , where epoxy groups can be end-capped with mono-functional amines: 
       
         
           
           
               
               
           
         
       
     
     
         29 . A composition of  claims 3 - 10  where adding dimethylpropionic acid (DMPA) can lead to cross-linking sites and also help with water dispersion by forming water reducible epoxy polyurethanes. 
     
     
         30 . A composition of  claim 29 , where acid groups of DMPA can be neutralized with an amine then dispersed in water. 
     
     
         31 . A composition of  claims 1 - 10 , where linear polyurethane epoxy polymers are elastomeric and can elongate. 
     
     
         32 . A composition of  claims 1 - 10 , where hydration forms a hydrogel via physical cross-links; or, slight cross-linking can cause a swelling (hydrogel formation) or plasticization effect resulting in a lubricious polyurethane end capped glycidyl based polymers. 
     
     
         33 . Epoxy termination of  claims 1 - 10  may crosslink by amines, amides, carboxylic acids and hydroxyl functionality. 
     
     
         34 . A coating composition of  claim 33 , where open hydroxyl functionality, from epoxy ring group opening, can undergo hydroxyl reactions. 
     
     
         35 . A composition of  claims 1 - 10 , are affected by diisocyanate type. 
     
     
         36 . The coating composition of  claims 1 - 10 , wherein the diisocyanate is selected from 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate, 4,4′methylene diphenyl diisocyanate, polymeric MDI, naphthalene diisocyanate, 4,4′-diisocynatodicyclohexylmethane, 1,4-benzene diisocyanate, trans-cyclohexane-1,4-diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexamethylene diisocyanate, 4,6-xylene diisocyanate, isophorone diisocyanate, with combinations and isomers thereof. 
     
     
         37 . A composition of  claims 1 - 10 , are reacted with polyol cross-linkers. 
     
     
         38 . A composition of  claims 1 - 10 , are reacted with amine cross-linkers. 
     
     
         39 . A composition of  claim 5 - 10 , where a diol or amine chain extender is added. 
     
     
         40 . The coating composition of  claim 20 , wherein the diol chain extender is selected from hydroquinone-bis-(hydroxymethyl)ether, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol,2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol,2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,5-pentanediol,2-methyl-2-ethyl-1,3-propanediol, 1,4-bis(hydroxyethoxy)benzene, bis(hydroxyethylene)terephthalate, hydroquinone bis(2-hydroxyethyl)ether, and combinations and isomers thereof. 
     
     
         41 . The coating composition of  claim 20 , wherein the amine chain extender is selected from 2,4 and 2,6 diethtltoluene diamine, methylene-bis-orthochloroaniline, unilink (UOP LLC), 4,4′-methylene-bis(3-chloro-2,6-diethylaniline), 1,2-ethylenediamine, 1,6-hexanediamine, 1,2-propanediamine, 4,4′-methylene-bis(3-chloroaniline), dimethylthiotoluenediamine, 4,4′diaminodiphenylmethane, 1,3-diaminobenzene, 1,4-diaminobenzene, 3,3′dimethoxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diamino biphenyl, and combinations and isomers thereof. 
     
     
         42 .  claim 36  isocyanate selection, and isomers, affect physical crosslinks of the final epoxy terminated polyurethane polymer. 
     
     
         43 . A coating composition of  claim 42 , where 4-4′MDI terminated epoxy polyurethanes provides excellent hard block domains due to linearity and aromatic groups. 
     
     
         44 . A coating composition of  claim 42 , where isocyanate isomers of 2-4-TDI and 2,6-TDI react differently and impart different resin properties of the terminated polyurethane epoxy. 
     
     
         45 . A coating composition of  claim 36 , where isocyanate crosslinkers can react with open hydroxyl functional groups (epoxy ring opening) to improve durability. 
     
     
         46 . A composition of  claims 1 - 10 , where pre-polymers can be made first then terminated with glycidol. 
     
     
         47 . A composition of  claims 1 - 10 , where a one shot synthesis can be used with all monomers, including glycidol, are added all at once. 
     
     
         48 . A composition of  claim 47 , where monomers can be added to the reaction non-sequentially at any time during the reaction.