Polyketal polymers, and methods of making and using same

Abstract

Polyketal polymers, and methods of making and using such polyketal polymers are disclosed herein. The polyketal poylmers can be useful for applications including, for example, medical devices and pharmaceutical compositions. In a preferred embodiment, the polyketal polymers are biodegradable.

1 . A method of preparing a polymer, the method comprising:
 combining components comprising a polymerization agent, a polymerizable compound selected from the group consisting of monofunctional compounds, polyfunctional compounds, imagable compounds, compounds having latent reactive sites, and combinations thereof, and additionally at least one cyclic oxygen-containing compound under conditions effective to polymerize the at least one cyclic oxygen-containing compound, wherein the at least one cyclic oxygen-containing compound is selected from the group consisting of:   a compound of the formula (Formula I)   
       
         
           
           
               
               
           
         
         a compound of the formula (Formula II) 
       
       
         
           
           
               
               
           
         
       
       and
 combinations thereof; 
 
       wherein:
 each X independently represents NR 5 , CR 5 R 6 , SiR 5 R 6 , S, a sulfur-bonded group, a phosphorus-bonded group, or 
 
       
         
           
           
               
               
           
         
         each Y independently represents O, NR 5 , CR 5 R 6 , SiR 5 R 6 , S, a sulfur-bonded group, a phosphorus-bonded group, or 
       
       
         
           
           
               
               
           
         
         each n is independently from 0 to 5; 
         each R 1  independently represents an organic group; 
         each R 2 , R 3 , R 4 , R 5 , and R 6  independently represents H or an organic group; and 
         R 1 , R 2 , R 3 , R 4 , R 5 , and/or R 6  can optionally be joined to each other to form one or more rings. 
       
     
     
         2 . The method of  claim 1  wherein the polymerizable compound is a cyclic oxygen-containing compound different than the at least one cyclic oxygen-containing compound. 
     
     
         3 . The method of  claim 1  wherein the polymerizable compound is selected from the group consisting of lactides, glycolides, butyrolactones, valerolactones, caprolactones, cyclic carbonates, cyclic ethers, cyclic acetals, and combinations thereof. 
     
     
         4 . The method of  claim 1  wherein the polymerization agent comprises a Lewis acid or a Brønsted-Lowry acid. 
     
     
         5 . The method of  claim 4  wherein the Lewis acid comprises an element selected from the group consisting of Al, Fe, B, Zn, Sb, Ti, Cu, Sn, Si, and combinations thereof. 
     
     
         6 . The method of  claim 1  wherein the polymerization agent comprises an organometallic compound or a metal salt. 
     
     
         7 . The method of  claim 6  wherein the metal salt is selected from the group consisting of metal halides, metal pseudohalides, metal sulfonates, metal carboxylates, metal carbonates, and combinations thereof. 
     
     
         8 . The method of  claim 7  wherein the metal salt comprises a metal selected from the group consisting of Zn, Cs, and combinations thereof. 
     
     
         9 . The method of  claim 1  wherein the polymerization agent comprises a plurality of sites for initiating polymerization. 
     
     
         10 . The method of  claim 1  wherein conditions effective to polymerize comprise combining at least a portion of the components without adding a solvent. 
     
     
         11 . The method of  claim 1  wherein conditions effective to polymerize comprise combining at least a portion of the components in a dry organic solvent. 
     
     
         12 . The method of  claim 1  wherein conditions effective to polymerize comprise combining at least a portion of the components under an inert atmosphere. 
     
     
         13 . The method of  claim 1  wherein conditions effective to polymerize comprise combining at least 0.0000001 mole % polymerization agent, based on the total moles of monomers and polymerization agents. 
     
     
         14 . A method of preparing a biodegradable medical device, the method comprising:
 providing a medical device; and   applying one or more polymers to at least a portion of the device the one or more polymers prepared by a method comprising:   combining components comprising a polymerization agent and at least one cyclic oxygen-containing compound under conditions effective to polymerize the at least one cyclic oxygen-containing compound, wherein the at least one cyclic oxygen-containing compound is selected from the group consisting of:   a compound of the formula (Formula I)   
       
         
           
           
               
               
           
         
         a compound of the formula (Formula II) 
       
       
         
           
           
               
               
           
         
       
       and
 combinations thereof; 
 
       wherein:
 each X independently represents NR 5 , CR 5 R 6 , SiR 5 R 6 , S, a sulfur-bonded group, a phosphorus-bonded group, or 
 
       
         
           
           
               
               
           
         
         each Y independently represents O, NR 5 , CR 5 R 6 , SiR 5 R 6 , S, a sulfur-bonded group, a phosphorus-bonded group, or 
       
       
         
           
           
               
               
           
         
         each n is independently from 0 to 5; 
         each R 1  independently represents an organic group; 
         each R 2 , R 3 , R 4 , R 5 , and R 6  independently represents H or an organic group; and 
       
       R 1 , R 2 , R 3 , R 4 , R 5 , and/or R 6  can optionally be joined to each other to form one or more rings. 
     
     
         15 . A medical device comprising one or more polymers prepared by a method comprising combining components comprising a polymerization agent and at least one cyclic oxygen-containing compound under conditions effective to polymerize the at least one cyclic oxygen-containing compound, wherein the at least one cyclic oxygen-containing compound is selected from the group consisting of:
 a compound of the formula (Formula I)   
       
         
           
           
               
               
           
         
         a compound of the formula (Formula II) 
       
       
         
           
           
               
               
           
         
       
       and
 combinations thereof; 
 
       wherein:
 each X independently represents NR 5 , CR 5 R 6 , SiR 5 R 6 , S, a sulfur-bonded group, a phosphorus-bonded group, or 
 
       
         
           
           
               
               
           
         
         each Y independently represents O, NR 5 , CR 5 R 6 , SiR 5 R 6 , S, a sulfur-bonded group, a phosphorus-bonded group, or 
       
       
         
           
           
               
               
           
         
         each n is independently from 0 to 5; 
         each R 1  independently represents an organic group; 
         each R 2 , R 3 , R 4 , R 5 , and R 6  independently represents H or an organic group; and 
       
       R 1 , R 2 , R 3 , R 4 , R 5 , and/or R 6  can optionally be joined to each other to form one or more rings. 
     
     
         16 . The medical device of  claim 15  further comprising a biologically active agent. 
     
     
         17 . The medical device of  claim 16  wherein the biologically active agent is disposed in the polymer.