Composite articles including a fluoropolymer blend

Abstract

A composite article is provided which includes a blend component comprising a vinylidene fluoride containing fluoropolymer and a substantially non-vinylidene fluoride containing fluoropolymer, and a component including a substantially non-fluorinated polymer having pendant amine groups intimately bonded to the blend component. Increased adhesion is observed by a greater peel strength value between the blend component and a substantially non-vinylidene fluoride containing fluoropolymer when compared to a peel strength value between a substantially non-vinylidene fluoride containing fluoropolymer and the substantially non-fluorinated polymer having pendant amine groups.

1. A composite article comprising:
 (a) a blend component having first and second surfaces, the blend component comprising: 
 (i) a vinylidene fluoride containing fluoropolymer; and  
 (ii) a substantially non-vinylidene fluoride containing fluoropolymer than is substantially free of interpolymerized units of vinylidene fluoride or microstructure sequences of a carbon bonded hydrogen atom between carbon bonded fluorine atoms; and  
 
 (b) a substantially non-fluorinated polymer component adhered to the first surface of the blend component, the non-fluorinated polymer component 
 (i) having one or more pendant primary or secondary amine groups; and  
 (ii) providing an exposed surface.  
 
 
     
     
       2. The composite article of  claim 1  wherein the vinylidene-fluoride containing fluoropolymer of component (a) comprises interpolymerized units of vinylidene fluoride or interpolymerized units of other monomers which, when polymerized, form a polymer microstructure sequence of a carbon bonded hydrogen atom between carbon bonded fluorine atoms. 
     
     
       3. The composite article of  claim 1  wherein the vinylidene-fluoride containing fluoropolymer of component (a) comprises a fluoropolymer of interpolymerized units derived from (i) at least one fluorine-containing monomer selected from the group of vinylidene fluoride, trifluoroethylene, 1-hydropentafluoropropylene, 2-hydropentafluoropropylene, and, optionally, (ii) at least one monomer copolymerizable therewith. 
     
     
       4. The composite article of  claim 3  wherein the monomer (ii) is selected from a fluorine-containing monomer, a fluorine-free, unsaturated olefin monomer, an iodine- or a bromine-containing unsaturated olefin monomer, or a combination thereof. 
     
     
       5. The composite article of  claim 4  wherein
 (a) the fluorine-containing monomer is selected from the group consisting of hexafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, a fluorinated vinyl ether, and a fluoride-containing di-olefin;  
 (b) the fluorine-free, unsaturated olefin monomer is selected from ethylene, propylene, or butadiene; and  
 (c) the iodide- or bromide-containing unsaturated olefin monomer is selected from the group consisting of bromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, and 4-bromo-3,3,4,4- tetrafluoro-1-butene.  
 
     
     
       6. The composite article of  claim 5  wherein the fluorine containing monomer is hexafluoropropylene. 
     
     
       7. The composite article of  claim 1  wherein the substantially non-vinylidene fluoride-containing fluoropolymer of component (a) is formed of interpolymerized units of (i) fluorine-containing monomers selected from the group consisting of hexafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, a fluorinated vinyl ether, and combinations thereof, and optionally, (ii) a fluorine-free unsaturated olefin comonomers, and optionally, (iii) an iodine- or bromine-containing unsaturated olefin monomer. 
     
     
       8. The composite article of  claim 7  wherein the fluorine-free unsaturated olefin monomer is selected from ethylene, propylene, or butadiene, and the iodine- or bromine-containing unsaturated olefin monomer is selected from bromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, or 4-bromo-3,3,4,4-tetrafluoro-1-butene. 
     
     
       9. The composite article of  claim 7  wherein the substantially non-vinylidene fluoride-containing fluoropolymer of component (a) is formed of interpolymerized units of tetrafluoroethylene and at least one other monomer selected from the group consisting of hexafluoropropylene, a fluorinated vinyl ether, ethylene, and propylene. 
     
     
       10. The composite article of  claim 1  wherein the component (b) is selected from a polyamide, a polyimide, a polyurethane, a polyolefin, a polystyrene, a polyester, a polycarbonate, a polyketone, a polyurea, a polyarcylate, or a polymethacrylate. 
     
     
       11. The composite article of  claim 1  wherein the component (b) is an elastomer. 
     
     
       12. The composite article of  claim 1  wherein the pendant amine group is a primary amine group. 
     
     
       13. The composite article of  claim 1  wherein the blend component comprises about 5% by weight to about 75% by weight of the vinylidene fluoride containing fluoropolymer, and about 25% by weight to about 95% by weight of the substantially non-vinylidene fluoride containing fluoropolymer. 
     
     
       14. The composite article of  claim 1  wherein the blend component comprises about 10% by weight to about 75% by weight of the vinylidene fluoride containing fluoropolymer, and about 25% by weight to about 90% by weight of the substantially non-vinylidene fluoride containing fluoropolymer. 
     
     
       15. The composite article of  claim 1  wherein the blend component comprises about 10% by weight to about 50% by weight of the vinylidene fluoride containing fluoropolymer, and about 50% by weight to about 90% by weight of the substantially non-vinylidene fluoride containing fluoropolymer. 
     
     
       16. The composite article of  claim 1  which is shaped. 
     
     
       17. The composite article of  claim 16  selected from the group of a wire coating, a tube, a container, a sheet, a cable jacket, and a film. 
     
     
       18. The composite article of  claim 1  further comprising
 (c) a second substantially non-fluorinated polymer component adhered to the exposed surface of the component (b).  
 
     
     
       19. The composite article of  claim 18  wherein the component (c) is selected from a polyamine, a polyimide, a polyurethane, a polyolefin, a polystyrene, a polyester, a polycarbonate, a polyketone, a polyurea, a polyacrylate, or a polymethacrylate. 
     
     
       20. The composite article of  claim 18  wherein the component (c) is an elastomer. 
     
     
       21. The composite article of  claim 18  wherein the component (c) is a polyamide. 
     
     
       22. The composite article of  claim 18  further comprising
 (d) a fourth component comprising a second substantially non-vinylidene fluoride containing fluoropolymer that is substantially free of interpolymerized units of vinylidene fluoride or microstructure sequences of a carbon bonded hydrogen atom between carbon bonded fluorine atoms adhered to the second surface of the blend component (a).  
 
       wherein a peel strength value between the blend component (a) and the component (b) is greater than a peel strength value between the component (d) and the component (b). 
     
     
       23. The composite article of  claim 22  wherein the second substantially non-vinylidene fluoride-containing fluoropolymer of component (d) is formed of interpolymerized units of (i) fluorine-containing monomers selected from the group consisting of hexafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, a fluorinated vinyl ether, and combinations thereof, and optionally, (ii) a fluorine-free unsaturated olefin comonomer, and optionally, (iii) an iodine- or bromide-containing unsaturated olefin monomer. 
     
     
       24. The composite article of  claim 23  wherein the fluorine-free unsaturated olefin monomer is selected from ethylene, propylene, or butadiene, and the iodide- or bromide-containing olefin monomer is selected from bromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethyene, 4-bromo-3,3,4,4-tetrafluoro-1-butene. 
     
     
       25. The composite article of  claim 23  wherein the second substantially non-vinylidene fluoride-containing fluoropolymer of component (d) is formed of interpolymerized units of tetrafluoroethylene and at least one other monomer selected from the group consisting of hexafluoropropylene, a fluorinated vinyl ether, ethylene, and propylene. 
     
     
       26. The composite article of  claim 22  further comprising:
 (c) a second substantially non-fluorinated polymer component adhered to the exposed surface of the component (b).  
 
     
     
       27. The composite article of  claim 26  further comprising additives in at least one of the components. 
     
     
       28. The composite article of  claim 22  further comprising additives in at least one of the components. 
     
     
       29. The composite article of  claim 18  further comprising additives in at least one of the components. 
     
     
       30. A composite article comprising:
 (a) a blend component having first and second surfaces, the blend component comprising: 
 (i) a vinylidene fluoride containing fluoropolymer; and  
 (ii) a substantially non-vinylidene fluoride containing fluoropolymer that is substantially free of interpolymerized units of vinylidene fluoride or microstructure sequences of a carbon bonded hydrogen atom between carbon bonded fluorine atoms; and  
 
 (b) a substantially non-fluorinated polymer component adhered to the first surface of the blend component, the non-fluorinated polymer component 
 (i) having one or more pendant primary or secondary amine groups; and  
 (ii) providing an exposed surface, and  
 
 (c) a catalyst.  
 
     
     
       31. The composite article of  claim 30  wherein the catalyst comprises a combination of an oregano-onium compound and an acid acceptor. 
     
     
       32. The composite article of  claim 30  wherein the catalyst comprises an amine compound selected from an aliphatic, aryl, or amidine amine compound. 
     
     
       33. The composite article of  claim 30  wherein the catalyst is selected from the group consisting of (i) an oregano-onium compound and an acid acceptor, and (ii) an amine compound. 
     
     
       34. The composite article of  claim 33  wherein the catalyst is the oregano-onium compound and the acid acceptor. 
     
     
       35. The composite article of  claim 33  wherein the catalyst is the amine compound. 
     
     
       36. The composite article of  claim 35  wherein the amine compound is selected from an aliphatic, aryl, or amidine amine. 
     
     
       37. The composite article of  claim 30  wherein the catalyst is present in component (a). 
     
     
       38. The composite article of  claim 30  wherein the catalyst is present in component (b). 
     
     
       39. A multi-layer polymer article comprising, in order:
 a first layer of a substantially non-vinylidene fluoride containing fluoropolymer that is substantially free of interpolymerized units of vinylidene fluoride or microstructure sequences of a carbon bonded hydrogen atom between carbon bonded fluorine atoms;  
 a second layer comprising blend of 
 (i) a vinylidene fluoride containing fluoropolymer; and  
 (ii) a substantially non-vinylidene fluoride containing fluoropolymer that is substantially free of interpolymerized units of vinylidene fluoride or microstructure sequences of a carbon bonded hydrogen atom between carbon bonded fluorine atoms;  
 
 a third layer comprising a substantially non-fluorinated polymer having one or more pendant primary or secondary amine groups; and  
 a fourth layer comprising a substantially non-fluorinated polymer; wherein a peel strength between the second layer and the third layer is greater than a peel strength between the first layer and the third layer.  
 
     
     
       40. The shaped composite article of  claim 39 . 
     
     
       41. The shaped article of  claim 40  selected from a sheet, a hose, a tube, a wire coating, a cable jacket, and a container. 
     
     
       42. A blend component having first and second surfaces, the blend component comprising:
 ( i )  a vinylidene fluoride containing fluoroplastic copolymer, wherein  22   %  by weight to  36   %  by weight of the interpolymerized units are derived from at least one fluorine - containing monomer selected from the group of vinylidene fluoride, trifluoroethylene,  1   - hydropentafluoropropylene, and  2   - hydropentafluoropropylene, and wherein at least one comonomer in the copolymer is HFP; and      ( ii )  a substantially non - vinylidene fluoride containing fluoroplastic consisting of the polymerization product of one or more fluorine containing monomers selected from HFP, TFE, a fluorinated vinyl ether, and cure site monomers.     
     
     
       43. The blend component of  claim 42  wherein the substantially non- vinylidene fluoride containing fluoroplastic consists essentially of interpolymerized units of TFE.   
     
     
       44. The blend component of  claim 42  wherein the substantially non- vinylidene fluoride containing fluoroplastic consists of interpolymerized units derived from two or more fluorine containing monomers selected from HFP, TFE, a fluorinated vinyl ether, and cure site monomers.   
     
     
       45. The blend component of  claim 42  further comprising an additive selected from the group of a polymer, a pigment, a tackifier, a filler, electrically conductive materials, electrically insulative materials, a stabilizer, an antioxidant, a lubricant, a processing aid, an impact modifier, a viscosity modifier, and mixtures thereof. 
     
     
       46. The blend component of  claim 42  wherein the vinylidene fluoride containing fluoroplastic comprises about  10 %  by weight to about  50   %  by weight of the blend; and the substantially non - vinylidene fluoride containing fluoroplastic comprises about  50   %  by weight to about  90   %  by weight of the blend.   
     
     
       47. The blend component of  claim 42  which is shaped, the shape optionally selected from a wire coating, a tube, a container, a sheet, a cable jacket, and a film. 
     
     
       48. The blend component of  claim 42 , wherein about  22 %  by weight to about  36   %  by weight of the interpolymerized units of the vinylidene fluoride containing fluoroplastic copolymer are derived vinylidene fluoride.   
     
     
       49. The blend component of  claim 42 , wherein the vinylidene fluoride containing fluoroplastic copolymer comprises interpolymerized units derived from VDF, HFP and TFE. 
     
     
       50. The blend component of  claim 42 , wherein the substantially non- vinylidene fluoride containing fluoropolymer consists of the polymerization product of HFP and TFE.   
     
     
       51. A blend component having first and second surfaces, the blend component comprising:
 ( i )  a vinylidene fluoride containing fluoroplastic copolymer, wherein  3   %  by weight to  36   %  by weight of the interpolymerized units are derived from fluorine - containing monomers selected from the group of vinylidene fluoride, trifluoroethylene,  1   - hydropentafluoropropylene, and  2   - hydropentafluoropropylene; and      ( ii )  a substantially non - vinylidene fluoride containing fluoroplastic consisting of interpolymerized units formed from polymerizing two or more monomers selected from HFP, TFE, CTFE, a fluorinated vinyl ether, and cure site monomers.     
     
     
       52. The blend component of  claim 51  wherein the vinylidene- fluoride containing fluoroplastic comprises a fluoropolymer of interpolymerized units derived from  ( A )  at least one fluorine - containing monomer selected from the group of vinylidene fluoride, trifluoroethylene,  1   - hydropentafluoropropylene, and  2   - hydropentafluoropropylene; and,  ( B )  at least one monomer copolymerizable therewith, wherein the monomer  ( B )  is selected from a fluorine - containing monomer, a fluorine - free, unsaturated olefin monomer, an iodine -  or a bromine - containing unsaturated olefin monomer, or a combination thereof.   
     
     
       53. The blend component of  claim 52  wherein ( a )  the fluorine - containing monomer is selected from hexafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, a fluorinated vinyl ether, and a fluorine - containing di - olefin;  ( b )  the fluorine - free, unsaturated olefin monomer is selected from ethylene, propylene, and butadiene; and  ( c )  the iodide -  or bromide - containing unsaturated olefin monomer is selected from bromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, and  4   - bromo -   3 , 3 , 4 , 4   - tetrafluoro -   1   - butene.   
     
     
       54. The blend component of  claim 51  wherein the fluoroplastic ( ii )  consists of interpolymerized units of  ( a )  two or more fluorine - containing monomers selected from HFP, TFE, CTFE, a fluorinated vinyl ether, and combinations thereof, and  ( b )  at least one cure site monomer selected from an iodine -  or bromine - containing unsaturated olefin monomer.   
     
     
       55. The blend component of  claim 54  wherein the iodine-  or bromine - containing unsaturated olefin monomer is selected from bromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, and  4   - bromo -   3 , 3 , 4 , 4   - tetrafluoro -   1   - butene.   
     
     
       56. The blend component of  claim 51  further comprising an additive selected from the group of a polymer, a pigment, a tackifier, a filler, electrically conductive materials, electrically insulative materials, a stabilizer, an antioxidant, a lubricant, a processing aid, an impact modifier, a viscosity modifier, and mixtures thereof. 
     
     
       57. The blend component of  claim 51  wherein the vinylidene fluoride containing fluoroplastic comprises about  10 %  by weight to about  50   %  by weight of the blend; and the substantially non - vinylidene fluoride containing fluoroplastic comprises about  50   %  by weight to about  90   %  by weight of the blend.   
     
     
       58. The blend component of  claim 51  which is shaped, the shape optionally selected from a wire coating, a tube, a container, a sheet, a cable jacket, and a film. 
     
     
       59. The blend component of  claim 51 , wherein at least one monomer in the substantially non- vinylidene fluoride containing fluoroplastic is a fluorinated vinyl ether.   
     
     
       60. The blend component of  claim 51 , wherein about  22 %  by weight to about  36   %  by weight of the interpolymerized units of the vinylidene fluoride containing fluoroplastic copolymer are derived from at least one fluorine - containing monomer selected from the group of vinylidene fluoride, trifluoroethylene,  1   - hydropentafluoropropylene, and  2   - hydropentafluoropropylene.   
     
     
       61. The blend component of  claim 51 , wherein about  22 %  weight to about  36   %  by weight of the interpolymerized units are derived from vinylidene fluoride.   
     
     
       62. A composite article comprising:
 ( a )  a blend component having first and second surfaces, the blend component consisting of:  
 ( i )  a vinylidene fluoride containing fluoroplastic copolymer, wherein  22   %  by weight to  36   %  by weight of the interpolymerized units are derived from fluorine - containing monomers selected from the group of vinylidene fluoride, trifluoroethylene,  1   - hydropentafluoropropylene, and  2   - hydropentafluoropropylene, and wherein at least one comonomer in the copolymer is HFP; and    
 ( ii )  a substantially non - vinylidene fluoride containing fluoroplastic that is substantially free of interpolymerized units of vinylidene fluoride or microstructure sequences of a carbon bonded hydrogen atom bonded between carbon bonded fluorine atoms; and    
   ( b )  a substantially non - vinylidene fluoride containing fluoroplastic component that is substantially free of interpolymerized units of vinylidene fluoride or microstructure sequences of a carbon bonded hydrogen atom bonded between carbon bonded fluorine atoms adhered to a surface of the blend component  ( a ).   
     
     
       63. The article of  claim 62  wherein the substantially non- vinylidene fluoride containing fluoroplastic in the blend component and the substantially non - vinylidene fluoride containing fluoroplastic component are the same polymer.   
     
     
       64. The article of  claim 62  wherein the substantially non- vinylidene fluoride containing fluoroplastic in the blend component and the substantially non - vinylidene fluoride containing fluoroplastic component are different fluoropolymers.   
     
     
       65. The article of  claim 62  wherein the substantially non- vinylidene fluoride containing fluoroplastic in component  ( a )  and/or  ( b )  is a perfluoropolymer.   
     
     
       66. The article of  claim 65  wherein the substantially non- vinylidene fluoride containing perfluoroplastic in component  ( a )  and/or  ( b )  comprises interpolymerized units of TFE.   
     
     
       67. The article of  claim 65  wherein the substantially non- vinylidene fluoride containing perfluoroplastic in component  ( a )  and/or  ( b )  consists essentially of interpolymerized units of TFE.   
     
     
       68. The article of  claim 62  wherein the vinylidene- fluoride containing fluoroplastic of component  ( a )  comprises a fluoropolymer of interpolymerized units derived from  ( i )  at least one fluorine - containing monomer selected from the group of vinylidene fluoride, trifluoroethylene,  1   - hydropentafluoropropylene,  2   - hydropentafluoropropylene,  ( ii )  HFP, and  ( iii )  at least one additional monomer copolymerizable therewith.   
     
     
       69. The article of  claim 68  wherein the monomer ( iii )  is selected from a fluoride - containing monomer, a fluorine - free, unsaturated olefin monomer, an iodine -  or a bromine - containing unsaturated olefin monomer, or a combination thereof.   
     
     
       70. The article of  claim 69  wherein ( a )  the fluorine - containing monomer is selected from tetrafluoroethylene, chlorotrifluoroethylene, a fluorinated vinyl ether, and a fluorine - containing di - olefin;  ( b )  the fluorine - free, unsaturated olefin monomer is selected from ethylene, propylene, and butadiene; and  ( c )  the iodide -  or bromide - containing unsaturated olefin monomer is selected from bromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, and  4   - bromo -   3 , 3 , 4 , 4   - tetrafluoro -   1   - butene.   
     
     
       71. The article of  claim 62  wherein the substantially non- vinylidene fluoride - containing fluoropolymer of component  ( a )  is formed of interpolymerized units of  ( i )  fluorine - containing monomers selected from hexafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, a fluorinated vinyl ether, and combinations thereof, and optionally,  ( ii )  a fluorine - free unsaturated olefin comonomer, and optionally,  ( iii )  an iodine -  or bromine - containing unsaturated olefin monomer.   
     
     
       72. The article of  claim 71  wherein the fluorine- free unsaturated olefin monomer is selected from ethylene, propylene, and butadiene, and the iodine -  or bromine - containing unsaturated olefin monomer is selected from bromodifluoroethylene, bromotrifluoroethylene, iodotrifluoroethylene, and  4   - bromo -   3 , 3 , 4 , 4   - tetrafluoro -   1   - butene.   
     
     
       73. The article of  claim 71  wherein the substantially non- vinylidene fluoride - containing fluoroplastic of component  ( a )  is formed of interpolymerized units of tetrafluoroethylene and at least one other monomer selected from hexafluoropropylene, a fluorinated vinyl ether, ethylene, and propylene.   
     
     
       74. The article of  claim 62  wherein component ( b )  further comprises an additive selected from a polymer, a pigment, a tackifier, a filler, electrically conductive materials, electrically insulative materials, a stabilizer, an antioxidant, a lubricant, a processing aid, an impact modifier, a viscosity modifier, and mixtures thereof.   
     
     
       75. The article of  claim 62  wherein the blend component comprises about  5 %  by weight to about  75   %  by weight of the vinylidene fluoride containing fluoroplastic; and about  25   %  by weight to about  95   %  by weight of the substantially non - vinylidene fluoride containing fluoroplastic.   
     
     
       76. The article of  claim 62  which is shaped, the shape optionally selected from a wire coating, a tube, a container, a sheet, a cable jacket, and a film. 
     
     
       77. The composite article of  claim 62 , wherein the substantially non- vinylidene fluoride containing fluoroplastic in the blend component consists essentially of the polymerization product of one or more fluorine containing monomers selected from HFP, TFE, a fluorinated vinyl ether, and cure site monomers.   
     
     
       78. A blend component having first and second surfaces, the blend component comprising:
 ( i )  a vinylidene fluoride containing fluoroplastic copolymer consisting of interpolymerized units formed from  
 ( a )  a fluorine - containing monomer selected from the group consisting of vinylidene fluoride, trifluoroethylene,  1   - hydropentafluoropropylene,  2   - hydrofluoropentafluoropropylene, and combinations thereof; and    
 ( b )  at least one monomer copolymerizable therewith selected from the group consisting of HFP, TFE, a cure site monomer, and combinations thereof:    
     wherein  3   %  by weight to  36   %  by weight of the interpolymerized units are derived from  ( a ) ; and      ( ii )  a substantially non - vinylidene fluoride containing fluoroplastic consisting of the polymerization product of one or more fluorine containing monomers selected from HFP, TFE, CTFE, and cure site monomers.     
     
     
       79. The blend component of  claim 78  further comprising an additive selected from the group of a polymer, a pigment, a tackifier, a filler, electrically conductive materials, electrically insulative materials, a stabilizer, an antioxidant, a lubricant, a processing aid, an impact modifier, a viscosity modifier, and mixtures thereof. 
     
     
       80. The blend component of  claim 78  wherein the vinylidene fluoride containing fluoroplastic comprises about  10 %  by weight to about  50   %  by weight of the blend; and the substantially non - vinylidene fluoride containing fluoroplastic comprises about  50   %  by weight to about  90   %  by weight of the blend.   
     
     
       81. The blend component of  claim 78  which is shaped, the shape optionally selected from a wire coating, a tube, a container, a sheet, a cable jacket, and a film.