Polycarbonates with fluoroalkylene carbonate end groups

Abstract

Polycarbonate compositions having an aromatic polycarbonate resin with 90% or greater fluoroalkylene carbonate end-groups are formed from a partially fluorinated alcohol or a partially fluorinated polymeric alcohol, and a bisphenol and a carbonate source using melt or interfacial polymerization methods. Copolymers and blends with a variety of other bisphenols and other thermoplastics are also described. The polycarbonate compositions show high water contact angles, fluorine enrichment on the surface layer of molded articles, and good flame retardant properties and are useful in a variety of applications including medical, automotive, telecommunication and weatherable applications.

1 . A polycarbonate composition comprising: an aromatic polycarbonate resin having fluoroalkylene carbonate end-groups, wherein the fluoroalkylene carbonate end-groups comprise 90% or greater of the total end-groups of the aromatic polycarbonate resin.  
     
     
         2 . The composition of  claim 1 , wherein the fluoroalkylene carbonate end-groups have structures corresponding to end-groups formed by the reaction of a fluorinated alcohol selected from the group consisting of 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-isopropanol, 1,1,1,2,3,3,-hexafluorobutanol, heptadecafluorononanol, and F(CF 2 CF 2 ) 3-8 CH 2 CH 2 O—(CH 2 CH 2 O) x H, wherein X=1 to 20.  
     
     
         3 . The composition of  claim 1 , wherein the aromatic polycarbonate resin is a co-polycarbonate selected from the group consisting of a polyarylester-co-aromatic polycarbonate, a polyalkylester-co-aromataic polycarbonate, and a polydimethylsiloxane-co-aromatic polycarbonate block copolymer.  
     
     
         4 . The composition of  claim 3 , wherein the aromatic polycarbonate resin is a polydimethylsiloxane-co-polycarbonate block copolymer having residues formed from eugenol, 2-allylphenol or 4-allylphenol.  
     
     
         5 . The composition of  claim 1  further comprising a thermoplastic polymer selected from the group consisting of an aromatic polycarbonate, a polyarylester-co-aromatic polycarbonate, a polyalkylester-co-aromatic polycarbonate, a polydimethylsiloxane-co-aromatic polycarbonate block copolymer, a polyester, and a polyimide.  
     
     
         6 . A polycarbonate according to  claim 1  wherein the aromatic polycarbonate resin comprises at least some aromatic carbonate end-groups that are not fluorinated.  
     
     
         7 . The composition according to  claim 1  further comprising an FR additive.  
     
     
         8 . The composition according to  claim 7 , wherein the FR additive is an akali metal, alkali earth metal, tetraorganophosphonium or tetraoorganoammonium salt of a perfluorinated alkyl sulfonic acid.  
     
     
         9 . The composition of  claim 7 , wherein the FR additive is a perfluorinated alkyl sulfonic acid selected from the group consisting of trifluoromethane sulfonic acid, nonafluorobutane sulfonic acid, and heptadecafluorooctane sulfonic acid.  
     
     
         10 . The composition of  claim 7 , wherein the FR additive is potassium nonofluorobutane sulfonate.  
     
     
         11 . A method for making a polycarbonate resin having fluoroalkylene carbonate end-group, said method comprising combining an aromatic dihydroxy compound, a fluorinated alcohol, phosgene, an organic solvent, water, an organic base and an inorganic base.  
     
     
         12 . A method for making a polycarbonate resin with fluoroalkylene carbonate end-groups, said method comprising the steps of producing a fluoroalkylene chloroformate and then adding the fluoroalkylene chloroformate to a mixture comprising an aromatic dihydroxy compound, phosgene, an organic solvent, water, an organic base and an inorganic base.  
     
     
         13 . The method of  claim 12 , wherein the fluoroalkylene chloroformate is formed in a tubular reactor.  
     
     
         14 . A method for making a polycarbonate resin comprising melt condensing a mixture comprising a fluorinated alcohol, an aromatic dihydroxy aromatic compound and a diarylcarbonate in the presence of a transesterfication catalyst.  
     
     
         15 . The method of  claim 14 , wherein the fluorinated alcohol is selected from the group consisting of HO—CH 2 —(CF 2 ) n1 —CF 3 , wherein n1=5-20 and F(CF 2 CF 2 ) 3-8 CH 2 CH 2 O—(CH 2 CH 2 O) x H, wherein X=1 to 20.  
     
     
         16 . The method of  claim 15 , wherein the diaryl carbonate is an activated diarylcarbonate.  
     
     
         17 . The method of  claim 16 , wherein the activated diarylcarbonate is bis(methylsalicyl)carbonate.  
     
     
         18 . The method of  claim 14 , wherein the aromatic dihydroxy compound is bisphenol-A.  
     
     
         19 . A method for improving the flame retardancy of a polycarbonate resin formulation comprising combining a polycarbonate resin, said polycarbonate resin having fluoroalkylcarbonate end groups, and an FR additive.  
     
     
         20 . The method of  claim 19  wherein the FR additive is potassium nonafluorobutane sulfonate.  
     
     
         21 . A method for determining the authenticity of a polycarbonate article comprising the steps of: producing a polycarbonate resin having fluoroalkylene carbonate end-groups, forming an article from the polycarbonate resin, and authenticating the article by identifying the presence of fluoroalkylene carbonate end-groups using an authentication method.  
     
     
         22 . The method of  claim 21  wherein the authentication method comprises using Raman spectroscopy or  19 F NMR.  
     
     
         23 . An article comprising the composition of  claim 1 .  
     
     
         24 . An article wherein part of a surface of said article comprises a surface having the composition of  claim 1  and wherein said surface having the composition of  claim 1  has a water contact angle of greater than 85°.  
     
     
         25 . An article from the composition of  claim 8 , which is V1 or V0 as measured by the method of UL 94 @2.3 mm or greater thickness.  
     
     
         26 . The article from the composition of  claim 10  which has a haze of less than 5.  
     
     
         27 . An article from the composition of  claim 7 , which is V1 or V0 as measured by the method of UL 94 @ 1.8 mm or greater thickness.  
     
     
         28 . The use of the polycarbonate composition of  claim 7  in a medical device, wherein said medical device is in contact with blood.  
     
     
         29 . The use of the polycarbonate composition of  claim 1  in a medical device, wherein said medical device is sterilized with ionizing radiation  
     
     
         30 . A process comprising exposing a medical device to blood, wherein the medical device comprises a blood contact surface made from the composition of  claim 1 , and sterilizing the medical device with ionizing radiation.  
     
     
         31 . A polycarbonate composition comprising an aromatic polycarbonate resin having fluoroalkylene carbonate end-groups and aromatic carbonate end-groups that are not fluorinated.  
     
     
         32 . A polycarbonate composition comprising an aromatic polycarbonate resin having fluroroalkylene carbonate end-groups and a fire-retardant additive.