Flame Retardant Polycarbonate Compositions

Abstract

The present invention relates to novel flame retardant polycarbonate resin compositions comprising at least one aromatic polycarbonate resin, at least one anti-drip agent, and at least one salt as defined herein. The present invention also provides methods for preparing articles comprising said flame retardant composition, and articles made therefrom.

1 . A flame retardant polycarbonate resin composition comprising:
 (A) at least one aromatic polycarbonate resin;   (B) at least one anti-drip agent; and   (C) at least one salt having the Formula M + Q- wherein M +  is a cation selected from the group consisting of the following eleven cations:   
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are independently selected from the group consisting of:
 (a) H; 
 (b) halogen; 
 (c) —CH 3 , —C 2 H 5 , or C 3  to C 25  straight-chain, branched or cyclic alkane or alkene, optionally substituted with at least one member selected from the group consisting of Cl, Br, F, I, OH, NH 2  and SH; 
 (d) —CH 3 , —C 2 H 5 , or C 3  to C 25  straight-chain, branched or cyclic alkane or alkene comprising one to three heteroatoms selected from the group consisting of O, N, Si, and S, and optionally substituted with at least one member selected from the group consisting of Cl, Br, F, I, OH, NH 2  and SH; 
 (e) C 6  to C 25  unsubstituted aryl or C 6  to C 25  unsubstituted heteroaryl having one to three heteroatoms independently selected from the group consisting of O, N, Si, and S; and 
 (f) C 6  to C 25  substituted aryl or C 6  to C 25  substituted heteroaryl having one to three heteroatoms independently selected from the group consisting of O, N, Si, and S; and wherein said substituted aryl or substituted heteroaryl has one to three substituents independently selected from the group consisting of:
 (1) —CH 3 , —C 2 H 5 , or C 3  to C 25  straight-chain, branched or cyclic alkane or alkene, optionally substituted with at least one member selected from the group consisting of Cl, Br, F, I, OH, NH 2  and SH, 
 (2) OH, 
 (3) NH 2 , and 
 (4) SH; 
 
 
       R 7 , R 8 , R 9 , and R 10  are independently selected from the group consisting of:
 (g) —CH 3 , —C 2 H 5 , or C 3  to C 25  preferably straight-chain, branched or cyclic alkane or alkene, optionally substituted with at least one member selected from the group consisting of Cl, Br, F, I, OH, NH 2  and SH; 
 (h) —CH 3 , —C 2 H 5 , or C 3  to C 25  straight-chain, branched or cyclic alkane or alkene comprising one to three heteroatoms selected from the group consisting of O, N, Si, and S, and optionally substituted with at least one member selected from the group consisting of Cl, Br, F, I, OH, NH 2  and SH; 
 (i) C 6  to C 25  unsubstituted aryl or C 6  to C 25  unsubstituted heteroaryl having one to three heteroatoms independently selected from the group consisting of O, N, Si, and S; and 
 (j) C 6  to C 25  substituted aryl or C 6  to C 25  substituted heteroaryl having one to three heteroatoms independently selected from the group consisting of O, N, Si, and S; and wherein said substituted aryl or substituted heteroaryl has one to three substituents independently selected from the group consisting of
 (1) —CH 3 , —C 2 H 5 , or C 3  to C 25  straight-chain, branched or cyclic alkane or alkene, optionally substituted with at least one member selected from the group consisting of Cl, Br, F, I, OH, NH 2  and SH, 
 (2) OH, 
 (3) NH 2 , and 
 (4) SH; and wherein 
 
 
       optionally at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10  can together form a cyclic or bicyclic alkanyl or alkenyl group; 
       and wherein Q −  is an anion selected from the group consisting of Formula I and Formula II: 
       
         
           
           
               
               
           
         
       
       wherein: 
       R 11  is selected from the group consisting of:
 (1) halogen; 
 (2) —CH 3 , —C 2 H 5  or C 3  to C 15  straight-chain or branched alkane or alkene, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2  and SH; 
 (3) —OCH 3 , —OC 2 H 5  or C 3  to C 15  straight-chain or branched alkoxy, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2  and SH; 
 (4) C 1  to C 15  straight-chain or branched fluoroalkyl, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2  and SH; 
 (5) C 1  to C 15  straight-chain or branched fluoroalkoxy, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2  and SH; 
 (6) C 1  to C 15  preferably straight-chain or branched perfluoroalkyl; and 
 (7) C 1  to C 15  straight-chain or branched perfluoroalkoxy; and 
 
       
         
           
           
               
               
           
         
       
       wherein: 
       R 12  is selected from the group consisting of:
 (1) halogen; 
 (2) —CH 3 , —C 2 H 5  or C 3  to C 15  straight-chain or branched alkane or alkene, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2  and SH; 
 (3) —OCH 3 , —OC 2 H 5  or C 3  to C 15  straight-chain or branched alkoxy, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2  and SH; 
 (4) C 1  to C 15  straight-chain or branched fluoroalkyl, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2  and SH; 
 (5) C 1  to C 15  straight-chain or branched fluoroalkoxy, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2  and SH; 
 (6) C 1  to C 15  straight-chain or branched perfluoroalkyl; and 
 (7) C 1  to C 15  straight-chain or branched perfluoroalkoxy. 
 
     
     
         2 . The composition of  claim 1  having about 100 parts of component (A), about 0.01 to about 5.0 parts of component (B), and about 0.001 to about 2.0 parts of component (C). 
     
     
         3 . The composition of  claim 2  having about 100 parts of component (A), and about 0.1 to about 3.0 parts of component (B). 
     
     
         4 . The composition of  claim 2  having about 100 parts of component (A), and about 0.01 to about 1.0 parts of component (C). 
     
     
         5 . The composition of  claim 1 , wherein the at least one aromatic polycarbonate resin is prepared from the reaction of diphenylcarbonate and 2,2-bis(4-hydroxyphenyl)propane. 
     
     
         6 . The composition of  claim 1 , wherein an anti-drip agent is poly-tetrafluoroethylene. 
     
     
         7 . The composition of  claim 1 , wherein Q −  is selected from the group consisting of 1,1,2,2-tetrafluoroethanesulfonate; 2-chloro-1,1,2-trifluoroethanesulfonate; 1,1,2,3,3,3-hexafluoropropanesulfonate; 1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate; 1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate; 2-(1,2,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate; 2-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate; 2-(1,1,2,2-tetrafluoro-2-iodoethoxy)-1,1,2,2-tetrafluoroethanesulfonate; 1,1,2,2-tetrafluoro-2-(pentafluoroethoxy)ethanesulfonate; N,N-bis(1,1,2,2-tetrafluoroethanesulfonyl)imide; and N,N-bis(1,1,2,3,3,3-hexafluoropropanesulfonyl)imide. 
     
     
         8 . The composition of  claim 1 , wherein component (C) is selected from the group consisting of 1-butyl-2,3-dimethylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-butyl-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-ethyl-3-methylimidazolium 1,1,2,3,3,3-hexafluoropropanesulfonate, 1-hexyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-dodecyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-hexadecyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-octadecyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, N-(1,1,2,2-tetrafluoroethyl)propylimidazole 1,1,2,2-tetrafluoroethanesulfonate, N-(1,1,2,2-tetrafluoroethyl)ethylperfluorohexylimidazole 1,1,2,2-tetrafluoroethanesulfonate, 1-butyl-3-methylimidazolium 1,1,2,3,3,3-hexafluoropropanesulfonate, 1-butyl-3-methylimidazolium 1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate, 1-butyl-3-methylimidazolium 1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate, tetradecyl(tri-n-hexyl)phosphonium 1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate, tetradecyl(tri-n-butyl)phosphonium 1,1,2,3,3,3-hexafluoropropanesulfonate, tetradecyl(tri-n-hexyl)phosphonium 1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate, 1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoro-2-(pentafluoroethoxy)sulfonate, (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-trioctylphosphonium 1,1,2,2-tetrafluoroethanesulfonate, 1-methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)imidazolium 1,1,2,2-tetrafluoroethanesulfonate, and tetra-n-butylphosphonium 1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate. 
     
     
         9 . A composition comprising at least one anti-drip agent and at least one salt according to  claim 1 . 
     
     
         10 . The composition of  claim 1  or  claim 9  comprising poly-tetrafluoroethylene micropowder as said at least one anti-drip agent. 
     
     
         11 . The composition of  claim 1  or  claim 9  comprising poly-tetrafluoroethylene dispersion as said at least one anti-drip agent. 
     
     
         12 . The composition of  claim 1 , further comprising at least one component selected from the group consisting of (1) at least one additive selected from the group consisting of antioxidants, ultraviolet absorbents, light stabilizers, internal lubricants, and flame retardants or flame retarding aids, mold release agents, antistatic agents, coloring agents, and combinations thereof; (2) at least one filler; and (3) combinations thereof. 
     
     
         13 . The composition of  claim 12 , wherein an antioxidant comprises a hindered phenol, ester of phosphorous acid, ester of phosphoric acid or amine; an ultraviolet absorbent comprises a benzotriazole or benzophenone; a light stabilizer comprises a hindered amine; an internal lubricant comprises an aliphatic carboxylic acid ester, paraffin, silicone oil or polyethylene wax; a mold release agent comprises pentaerythritol or glycerol; and a filler is selected from the group consisting of potassium titanate whisker, mineral fiber, glass fiber, carbon fiber, metallic fiber, aluminum borate whisker, silicon nitride whisker, boron fiber, zinc oxide whisker of tetrapod-shap, talc, clay, mica, pearl mica, aluminum foil, alumina, glass flake, glass beads, glass balloon, carbon black, graphite, calcium carbonate, calcium sulfate, calcium silicate, titanium dioxide, zinc sulfide, zinc oxide, silica, asbestos, and quartz powder. 
     
     
         14 . The composition of  claim 12 , wherein a filler is present at about 1 part to about 70 parts by weight. 
     
     
         15 . A method for preparing a flame retardant polycarbonate article comprising:
 (a) mixing the components of the polycarbonate resin composition as defined in  claim 1  to form a mixed composition;   (b) forming the mixed composition into particles;   (c) melt forming the particles of step (b) into a flame retardant polycarbonate article.   
     
     
         16 . The method of  claim 15 , wherein the mixing is carried out using a Banbury mixer, a single-screw extruder, a twin-screw extruder, or a multi-screw extruder. 
     
     
         17 . The method of  claim 15 , wherein the melt forming is carried out using injection molding, blow molding, extrusion molding, compression molding, calender molding, or rotation molding. 
     
     
         18 . A flame retardant polycarbonate article comprising a flame retardant polycarbonate resin composition according to  claim 1 , selected from the group consisting of glazing or sheet; an automotive component; a home appliance; packaging; an electrical, electronic, or technical component; a medical or health care related article; and a leisure or safety article. 
     
     
         19 . A flame retardant polycarbonate article according to  claim 18  selected from the group consisting of a component of a window for an airplane, a train, a school, a high speed aircraft canopy, automotive headlamp assembly, automotive interior instrument panel, automotive bumper, automotive window glazing, a houseware item, a houseware power tool, a refillable water bottle, a refillable milk bottle, an electrical connector, telephone network device, outlet box, computer housing, business machine housing, instrument panel, membrane switch, insulator, protective goggles, safety glasses, safety sideshields, eyeglasses, mask, sports helmet, motorcycle helmet, and a safety helmet for firefighters or construction workers.