Biocompatible polycarbonate and radiopaque polymer compositions and methods of manufacturing medical devices with same

Abstract

The invention relates to biocompatible polycarbonate/polyamide polymer compositions for use in medical and surgical devices. Additional additives, crosslinking agents, phosphites, and optionally a radiopaque filler or fillers can be used to produce the high performance compositions desired. The polymer compositions have improved melt processability along with balanced or enhanced physical and mechanical properties, especially when combined or over-extruded onto or covering other polymer layers, such as soft and/or flexible layers commonly used in medical device applications and catheter tips, for example. The ability to incorporate radiopaque compounds into these polymer compositions during melt processing offers improved methods for monitoring and visualizing medical devices when used inside the body and as well as improving the operating characteristics of the medical device components

1 . A biocompatible polymer composition comprising
 poly(bisphenol A carbonate), homopolymer   a polyamide or a polyamide-based thermoplastic elastomer, and   optionally an inorganic radiopaque filler.   
   
   
       2 . The polymer composition of  claim 1 , wherein the polyamide is an aromatic polyamide. 
   
   
       3 . The polymer composition of  claim 1 , wherein the polyamide is an aliphatic polyamide. 
   
   
       4 . The polymer composition of  claim 3 , wherein the aliphatic polyamide is selected from: nylon-6,6; nylon-6; nylon-11; nylon-12; and nylon 6T. 
   
   
       5 . The polymer composition of  claim 1 , wherein the polyamide-based thermoplastic elastomer is a poly(ether-block-amide) copolymer. 
   
   
       6 . The polymer composition of  claim 1 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       7 . The polymer composition of  claim 4 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       8 . The polymer composition of  claim 5 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       9 . The polymer composition of  claim 1 , further comprising one or more organic phosphites having the general structure:
 wherein R, R1, and R2 are selected from: phenyl; substituted phenyl groups; phenyl groups substituted by an alkyl group of 1 to 20 carbon atoms in length.   
   
   
       10 . The polymer composition of  claim 9 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       11 . The polymer composition of  claim 1 , further comprising one or more functionalized polyolefins, thermoplastic olefins, and thermoplastic olefins having an anhydride reactive group. 
   
   
       12 . The polymer composition of  claim 11 , wherein the polyolefin or olefin is selected from one or more of: maleic anhydride-grafted polyethylene and polypropylene; maleated SBS (styrene-butadien-styrene copolymer); maleated SIBS (styrene-isobutylene-styrene); and maleated SIS (styrene-isoprene-styrene copolymer). 
   
   
       13 . The polymer composition of  claim 12 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       14 . The polymer composition of  claim 1 , further comprising a functionalized polymer containing an epoxide group. 
   
   
       15 . The polymer composition of  claim 14 , wherein the functionalized polymer containing an epoxide group is one or more of: ethylene-butyl acrylate-acrylic acid terpolymer with epoxide group; and glycidal methacrylate (GMA). 
   
   
       16 . The polymer composition of  claim 15 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       17 . The polymer of  claim 1 , further comprising or more oxazoline or bis-oxazoline compounds having the following formula: 
     
       
         
         
             
             
         
       
     
     wherein R5 is an alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 12 carbon atoms, or an alkylene-arylene group having from 7 to 20 carbon atoms;
 R3 is selected from hydrogen, or alkyl group having 1 to 20 carbons, or aryl group having 6 to 12 carbon atoms, or alkyl-aryl group having 7 to 20 carbon atoms; and 
 R4 is selected from hydrogen, alkyl group having 1 to 20 carbons, or aryl group having 6 to 12 carbon atoms, or alkyl-aryl group having 7 to 20 carbon atoms. 
 
   
   
       18 . The polymer composition of  claim 17 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       19 . The polymer compound of  claim 1 , wherein the polyamide component is nylon-11. 
   
   
       20 . The polymer composition of  claim 19 , wherein the poly(bisphenol A carbonate) component is present from about 30 to about 90 wt % and the nylon-11 is present from about 2 to about 5 wt. %. 
   
   
       21 . The polymer composition of  claim 20 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       22 . The polymer compound of  claim 1 , wherein the polyamide component is nylon-12. 
   
   
       23 . The polymer composition of  claim 22 , wherein the poly(bisphenol A carbonate) component is present from about 30 to about 90 wt % and the nylon-12 is present at about to 2 to about 5 wt. %. 
   
   
       24 . The polymer composition of  claim 23 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       25 . The polymer composition of  claim 1 , wherein the inorganic radiopaque filler component is present and is barium sulfate. 
   
   
       26 . The polymer composition of  claim 25 , wherein the barium sulfate is loaded at about 5 to 60 wt. %. 
   
   
       27 . The polymer composition of  claim 25 , wherein the barium sulfate is loaded at about 10 to 40 wt. %. 
   
   
       28 . The polymer composition of  claim 1 , further comprising 1,3-phenylenebisoxazoline. 
   
   
       29 . The polymer composition of  claim 28 , wherein the 1,3-phenylenebisoxazoline is present at a concentration of about 0.2 to about 5 phr (parts per hundred resin). 
   
   
       30 . The polymer composition of  claim 28 , wherein the 1,3-phenylenebisoxazoline is present at a concentration of about 0.5 to about 1.0 phr. parts per hundred resin). 
   
   
       31 . The polymer composition of  claim 28 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       32 . The polymer composition of  claim 1 , further comprising a maleated polyolefin. 
   
   
       33 . The polymer composition of  claim 32 , wherein the concentration of maleated polyolefin is about 2 to about 20 wt. %. 
   
   
       34 . The polymer composition of  claim 33 , wherein the concentration of maleated polyolefin is about 5 to about 10 wt. %. 
   
   
       35 . The polymer composition of  claim 32 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       36 . The polymer composition of  claim 1 , further comprising a glycidal methacrylate copolymer. 
   
   
       37 . The polymer composition of  claim 36 , wherein the glycidal methacrylate copolymer is present at a concentration of about 2 to 20 wt %. 
   
   
       38 . The polymer composition of  claim 36 , wherein the glycidal methacrylate copolymer is present at a concentration of about 5 to 10 wt %. 
   
   
       39 . The polymer composition of  claim 36 , wherein an inorganic radiopaque filler is present and is selected from one or more of: barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, tantalum, and tungsten. 
   
   
       40 . A method of producing a biocompatible, radiopaque polymer composition comprising poly(bisphenol A carbonate), a polyamide, and an inorganic radiopaque filler, the method comprising: dry mixing the poly(bisphenol A carbonate) and polyamide; melting the mixture and adding the inorganic radiopaque filler at temperatures from about 220 to about 300° C. 
   
   
       41 . The method of  claim 40 , wherein the temperatures is from about 220 to about 260° C. 
   
   
       42 . The method of  claim 40 , further comprising adding a phosphite to the polymer mixture, wherein the mixing is through an extruder. 
   
   
       43 . The method of  claim 40 , further comprising coating a medical or surgical device or part thereof with the biocompatible, radiopaque polymer composition. 
   
   
       44 . A method of producing a biocompatible polymer composition comprising a polycarbonate, a polyamide, and an inorganic radiopaque filler, the method comprising: melting the polycarbonate and the polyamide components together to form a mixture, and optionally adding an inorganic radiopaque filler to the mixture.