Articles produced from VDF-co-(TFE or TrFE) polymers
VDF-co-(TFE or TrFE) polymers having a molecular weight of at least about 1,000,000 g/mol and a melt temperature less than about 240° C. The VDF copolymer contains at least about 50 mol % VDF monomer and may include an amount of at least one other monomer. The VDF copolymer may be used to form a membrane that has a node and fibril structure. The membrane has a percent porosity of at least 25%. A VDF-co-(TFE or TrFE) polymer membrane may be formed by lubricating the VDF copolymer, subjecting the lubricated polymer to pressure at a temperature below the melting point of the VDF copolymer to form a preform material, and expanding the preform material at a temperature below the melting temperature of the VDF copolymer. Dense VDF copolymer articles, filled VDF copolymer membranes, and VDF copolymer fibers are also provided.
1. A process for making a vinylidene fluoride (VDF) copolymer article comprising:
lubricating a VDF copolymer having a weight average molecular weight of at least about 1,000,000 g/mol and about 50 mol % to about 85 mol % VDF monomer to form a lubricated VDF copolymer;
subjecting said lubricated VDF copolymer to pressure at a temperature below the melt temperature of said VDF copolymer to form a preform; and
expanding said preform at a temperature below the melt temperature of said VDF copolymer to form a porous article having a structure of nodes interconnected by fibrils.
2. The process of claim 1 , wherein said subjecting step comprises calendering said lubricated VDF copolymer at a temperature that is below said melt temperature of said VDF copolymer to form said preform.
3. The process of claim 2 , wherein said calendering occurs at a temperature that is about 80° C. or less below said melt temperature.
4. The process of claim 1 , wherein said subjecting step comprises ram extruding said lubricated VDF copolymer at a temperature that is below said melt temperature of said VDF copolymer to form said preform.
5. The process of claim 4 , wherein said ram extruding occurs at a temperature that is about 80° C. or less below said melt temperature.
6. The process of claim 1 , further comprising removing said lubricant from said preform prior to expanding.
7. The process of claim 1 , wherein said VDF copolymer has a weight average molecular weight from about 1,000,000 g/mol to about 100,000,000 g/mol.
8. The process of claim 1 , wherein said melting temperature of said VDF copolymer is less than about 240° C.
9. The process of claim 1 , wherein said article has a porosity of at least about 25%.
10. The process of claim 1 , wherein said VDF copolymer further comprises at least one additional comonomer in an amount from about 0.001 mol % to about 10 mol %.
11. The process of claim 1 , further comprising compressing said porous article to form a dense article.
12. The process of claim 1 , further comprising adding a filler material to said VDF copolymer.
13. A process for manufacturing thin, strong porous VDF copolymer articles comprising subjecting a lubricated vinylidene fluoride (VDF) copolymer including from about 50 mol % to about 85 mol % VDF monomer to pressure and heat below a melt temperature of said VDF copolymer to form a preform article followed by expansion of said preform article below the melt temperature of said VDF copolymer to form a porous VDF copolymer article.
14. The process of claim 13 , wherein said subjecting said lubricated VDF copolymer comprises calendering said lubricated VDF copolymer at a temperature below said melt temperature to form said preform article.
15. The process of claim 14 , wherein said calendering occurs at a temperature about 80° C. or less below said melt temperature.
16. The process of claim 13 , wherein said subjecting said lubricated VDF copolymer comprises ram extruding said lubricated VDF copolymer at a temperature below said melt temperature to form said preform article.
17. The process of claim 16 , wherein said ram extruding occurs at a temperature about 80° C. or less below said melt temperature.
18. The process of claim 13 , further comprising removing said lubricant prior to said expansion below the melt temperature of said VDF copolymer.
19. The process of claim 13 , wherein said VDF copolymer has a weight average molecular weight from about 1,000,000 g/mol to about 100,000,000 g/mol.
20. The process of claim 13 , wherein said melt temperature of said VDF copolymer is less than about 240° C.
21. The process of claim 13 , wherein said porous VDF copolymer article has a porosity of at least about 25%.
22. The process of claim 13 , wherein said porous VDF copolymer article has a matrix tensile strength of least about 55 MPa in at least one direction.
23. The process of claim 13 , further comprising compressing said porous VDF copolymer article to form a dense article.
24. The process of claim 13 , further comprising adding at least one filler material to said VDF copolymer.
25. A porous VDF copolymer article comprising:
an expanded vinylidene fluoride (VDF) copolymer membrane comprising a single VDF copolymer, said VDF copolymer having a weight average molecular weight from about 1,000,000 g/mol to about 100,000,000 g/mol, and
at least 50 mol % VDF monomers,
wherein said expanded VDF copolymer membrane has a microstructure of nodes interconnected by fibrils.
26. The porous article of claim 25 , wherein said VDF copolymer has a melt temperature less than about 240° C.
27. The porous article of claim 25 , wherein said expanded VDF copolymer membrane has a porosity of at least about 25%.
28. The porous article of claim 25 , wherein said VDF copolymer further comprises at least one comonomer in an amount from about 0.001 mol % to about 10 mol %.
29. The porous article of claim 25 , wherein said expanded VDF copolymer membrane has a melt temperature that is less than about 240° C.
30. The porous article of claim 25 , wherein said expanded VDF copolymer membrane comprises at least one filler material.