Polyester compositions, methods of manufacturing said compositions, and articles made therefrom

Abstract

Crosslinked polymer compositions have backbones with first and second divalent saturated aliphatic moieties, a divalent saturated aliphatic secondary alcohol moiety, and a trivalent saturated aliphatic moiety. Hydrolytically labile ester bonds joined together these moieties. These polyesters may be polycondensation reaction products of a diol, a triol and a diacid. A molar ratio of the first divalent saturated aliphatic moiety, the divalent saturated aliphatic secondary alcohol moiety, and the trivalent saturated aliphatic moiety to the second divalent saturated aliphatic moiety is in the range of about 0.85 to about 1.5. Preferably, these polyesters are non-cytotoxic, biocompatible, bioabsorbable, or exhibit shape memory behavior with at least one transition temperature of greater than about 30° C. and less than about 100° C. and most preferably exhibit each of these qualities. The compositions may be adapted for a wide variety of uses, including medical applications.

1 . An article comprising a composite of at least one fluoropolymer material and shape memory polymer having at least one transition temperature of greater than about 30° C. and less than about 100° C., the transition temperature being selected from the group consisting of a crystalline melting temperature and a glass transition temperature. 
     
     
         2 . The article of  claim 1  in which said fluoropolymer material is selected from the group consisting of: poly(fluorinated ethylene-co-propylene), poly(tetrafluoroethylene-co-ethylene), poly(tetrafluoroethylene-co-hexafluoropropylene), poly(tetrafluoroethylene-co-perfluorobutyl vinyl ether), poly(tetrafluoroethylene-co-perfluoroethyl vinyl ether), poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether), poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether), and polytetrafluoroethylene. 
     
     
         3 . The article of  claim 2  in which said fluoropolymer material is a polytetrafluoroethylene material that has been expanded. 
     
     
         4 . The article of  claim 3  in which said shape memory polymer is securely adhered to a microstructure of the expanded polytetrafluoroethylene material. 
     
     
         5 . The article of  claim 4  in which said shape memory polymer substantially fills the pores of the expanded polytetrafluoroethylene material. 
     
     
         6 . The article of  claim 1  in which said fluoropolymer material is in a form selected from the group consisting of: films, fibrous materials and porous membranes. 
     
     
         7 . The article of  claim 6  in which said fluoropolymer material comprises a fibrous material. 
     
     
         8 . The article of  claim 7  in which the fibrous material is a nonwoven expanded porous polytetrafluoroethylene material. 
     
     
         9 . The article of  claim 7  in which the fibrous material is discontinuously distributed within said shape memory polymer. 
     
     
         10 . The article of  claim 1  in which said shape memory polymer bonds together a plurality of fluoropolymer films to form a multilayer laminate article. 
     
     
         11 . The article of  claim 10  in which said shape memory polymer comprises at least two crosslinked polyester compositions, and said multi-layer laminate article exhibits at least two stages of controlled shape memory behavior at two predetermined transition temperatures. 
     
     
         12 . The article of  claim 1  in which said shape memory polymer comprises a porous foam material. 
     
     
         13 . The article of  claim 1  in which the at least one transition temperature is a crystalline melting temperature of said shape memory polymer. 
     
     
         14 . The article of  claim 13  in which the crystalline melting temperature of said shape memory polymer is greater than about 30° C. and less than about 50° C. 
     
     
         15 . The article of  claim 14  in which the crystalline melting temperature of said shape memory polymer is greater than about 30° C. and less than about 45° C. 
     
     
         16 . The article of  claim 1  in which said fluoropolymer and said shape memory polymer are biocompatible. 
     
     
         17 . The article of  claim 16  in which the shape memory polymer is bioabsorbable. 
     
     
         18 . A biocompatible implant comprising the article of  claim 16 . 
     
     
         19 . A composite comprising a porous polymeric membrane in which the porosity of the membrane is at least partially filled with a crosslinked aliphatic polyester shape memory polymer and in which the polyester shape memory polymer has at least one transition temperature of greater than about 30° C. and less than about 100° C. 
     
     
         20 . The composite of  claim 19  in which said porous polymeric membrane comprises a fluoropolymer. 
     
     
         21 . The composite of  claim 20  in which said fluoropolymer comprises expanded polytetrafluoroethylene. 
     
     
         22 . The composite of  claim 19  in which said porous polymeric membrane is bioabsorbable. 
     
     
         23 . The composite of  claim 22  in which said porous polymeric membrane comprises a poly(glycolide-co-trimethylenecarbonate) non-woven material. 
     
     
         24 . The composite of  claim 19  in which the at least one transition temperature of said shape memory polymer is greater than about 30° C. and less than about 50° C. 
     
     
         25 . The composite of  claim 24  in which the at least one transition temperature of said shape memory polymer is greater than about 30° C. and less than about 45° C. 
     
     
         26 . A biocompatible implant comprising the composite of  claim 19 . 
     
     
         27 . A biocompatible implant comprising a composite of at least two polymer materials and in which at least one of the polymer materials is bioabsorbable and the implant exhibits shape memory behavior upon heating to at least one transition temperature of greater than about 30° C. and less than about 100° C. 
     
     
         28 . The biocompatible implant of  claim 27  in which the one of the polymer materials that is bioabsorbable has a residual acidity in concentrations of greater than about 0.0001 meq. acid/gram and less than about 1.0 meq. acid/gram. 
     
     
         29 . The biocompatible implant of  claim 28  in which the residual acidity is less than about 0.5 meq. acid/gram. 
     
     
         30 . The biocompatible implant of  claim 29  in which the residual acidity is less than about 0.3 meq. acid/gram measured by titration. 
     
     
         31 . The biocompatible implant of  claim 27  in which both of the two polymer materials are bioabsorbable. 
     
     
         32 . The biocompatible implant of  claim 27  in which one of the two polymer materials is a shape memory foam. 
     
     
         33 . The biocompatible implant of  claim 27  in which the at least one transition temperature corresponds to a crystalline melting temperature of one of the two polymer materials. 
     
     
         34 . The biocompatible implant of  claim 33  in which the crystalline melting temperature is greater than about 30° C. and less than about 50° C. 
     
     
         35 . The biocompatible implant of  claim 34  in which one of the two polymer materials is a fibrous aliphatic polyester. 
     
     
         36 . The biocompatible implant of  claim 35  in which the fibrous aliphatic polyester is selected from the group consisting of: poly(glycolide-co-trimethylene carbonate), poly(L-lactide), poly(D-lactide), poly(D,L-lactide), poly(glycolide-co-lactide) and poly(ε-caprolactone). 
     
     
         37 . The biocompatible implant of  claim 35  in which the fibrous aliphatic polyester defines a structure having pores and the other one of the two polymer materials is a bioabsorbable shape memory polymer is at least partially disposed within some of the pores. 
     
     
         38 . The biocompatible implant of  claim 37  in which the bioabsorbable shape memory polymer is a crosslinked aliphatic polyester.