Methods of preparing polymer-organoclay composites and articles derived therefrom

1. An article comprising a polymer-organoclay composite prepared by a method comprising:

combining a solvent and an unexfoliated organoclay to form a first mixture, wherein the organoclay comprises alternating inorganic silicate layers and organic layers, and has an initial spacing between the silicate layers, and further wherein the organoclay comprises a quaternary phosphonium or pyridinum cation of formula (2), formula (3), formula (4) or formula (5):

wherein Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently C 6 - 50 aromatic radicals; “a” is a number from 1 to about 200; “c” is a number from 0 to 3; R 1 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and R 2 is a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, a C 6 - 50 aromatic radical, or a polymer chain,

wherein Ar 12 , Ar 13 , Ar 14 and Ar 15 are independently C 6 -C 50 aromatic radicals; and Ar 16 is a C 6 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group,

wherein Ar 6 , Ar 7 , and Ar 8 are independently C 6 -C 50 aromatic radicals; “b” is a number from 0 to 2; R 3 is independently at each occurrence a halogen atom a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and Ar 11 is a C 6 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group,

wherein Ar 6 , Ar 7 , and Ar 8 are independently C 6 - 50 aromatic radicals; “b” is a number from 0 to 2; “d” is a number from 0 to 4; R 3 and R 4 are independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 6 -C 20 aromatic radical; Z is a bond, a divalent C 1 -C 20 aliphatic radical, a divalent C 5 -C 20 cycloaliphatic radical, a divalent C 6 -C 20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO 2 linking group, or a Se linking group; and Ar 9 is a C 10 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group;

exposing the first mixture to an energized condition of a sufficient intensity and duration to increase the initial spacing of the inorganic silicate layers, to form a second mixture;

contacting the first or second mixture with a polymer precursor;

polymerizing the polymer precursor to form a polymer; and

removing at least a portion of the solvent from the second mixture, wherein the inorganic silicate layers remain separated by the polymer after removal of the solvent.

2. The article of claim 1 , in the form of a film having a thickness from 0.1 to 1000 micrometers.

3. The article of claim 2 , wherein the film is a solvent cast film.

4. An article comprising a polymer-organoclay composite prepared by the method of

combining a solvent and an unexfoliated organoclay to provide a first mixture, wherein the unexfoliated organoclay comprises alternating inorganic silicate layers and organic layers, and has an initial spacing between the silicate layers;

exposing the first mixture to an energized condition of a sufficient intensity and duration to increase the initial spacing of the inorganic silicate layers, to provide a second mixture;

contacting the second mixture with a thermoplastic polymer composition so that the polymer composition fills at least one region located between at least one pair of silicate layers, wherein the polymer composition is at least partially soluble in the solvent; and

removing at least a portion of the solvent from the second mixture, wherein the inorganic silicate layers remain separated by the polymer after removal of the solvent,

wherein the organoclay comprises a quaternary phosphonium or pyridinium cation of formula (2), formula (3), formula (4) or formula (5):

wherein Ar 1 , Ar 2 , Al 3 and Ar 4 are independently C 6 - 50 aromatic radicals; “a” is a number from 1 to about 200; “c” is a number from 0 to 3; R 1 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and R 2 is a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, a C 6 - 50 aromatic radical, or a polymer chain,

wherein Ar 12 , Ar 13 , Ar 14 and Ar 15 are independently C 6 - 50 aromatic radicals; and Ar 16 is a C 6 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group,

wherein Ar 6 , Ar 7 , and Ar 8 are independently C 6 - 50 aromatic radicals; “b” is a number from 0 to 2; R 3 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and Ar 11 is a C 6 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group,

wherein Ar 6 , Ar 7 , and Ar 8 are independently C 6 - 50 aromatic radicals; “b” is a number from 0 to 2; “d” is a number from 0 to 4; R 3 and R 4 are independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 6 -C 20 aromatic radical; Z is a bond, a divalent C 1 C 20 aliphatic radical, a divalent C 5 -C 20 cycloaliphatic radical, a divalent C 6 -C 20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO 2 linking group, or a Se linking group; and Ar 9 is a C 10 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.

5. The article of claim 4 , in the form of a film having a thickness from 0.1 to 1000 micrometers.

6. The article of claim 5 , wherein the film is a solvent cast film.

7. The article of claim 1 , wherein the energized condition is produced by a sonic energy source.

8. The article of claim 1 , wherein the energized condition is produced by a high shear mixer.

9. The article of claim 1 , wherein the energy is of sufficient intensity and duration to effect a net increase in the initial d-spacing of the organoclay.

10. The article of claim 1 , wherein the first mixture is exposed to an energized condition of sufficient intensity and duration to increase the initial spacing of the inorganic silicate layers by an amount from 5 Angstroms to 90 Angstroms.

11. The article of claim 1 , wherein the increase in the initial spacing of the inorganic silicate layers results in random spacing of the inorganic silicate layers.

12. The article of claim 1 , wherein the net increase in the initial d-spacing of the organoclay is from about 10 to about 500 percent.

13. The article of claim 1 , wherein the polymerizing occurs at least partly during the exposing.

14. The article of claim 1 , wherein the polymerizing occurs at least partly after the exposing.

15. The article of claim 1 , wherein the polymerizing occurs at least partly during the removal of the solvent.

16. The article of claim 1 , wherein the polymer precursor is a polyamic acid.

17. The article of claim 1 , wherein the polymer precursor comprises a dianhydride component and a diamine component.

18. The article of claim 1 , wherein removing at least a portion of the solvent is carried out in a devolatilizing extruder.

19. The article of claim 1 , wherein the organoclay comprises a quaternary phosphonium cation of formula (2):

wherein Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently C 6 - 50 aromatic radicals; “a” is a number from 1 to about 200; “c” is a number from 0 to 3; R 1 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and R 2 is a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, a C 6 - 50 aromatic radical, or a polymer chain.

20. The article of claim 1 , wherein the organoclay comprises a quaternary phosphonium cation of formula (3):

wherein Ar 12 , Ar 13 , Ar 14 and Ar 15 are independently C 6 - 50 aromatic radicals; and Ar 16 is a C 6 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.

21. The article of claim 1 , wherein the organoclay comprises a pyridinium cation of formula (4):

wherein Ar 6 , Ar 7 , and Ar 8 are independently C 6 - 0 50 aromatic radicals; “b” is a number from 0 to 2; R 3 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and Ar 11 is a C 6 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.

22. The article of claim 21 , wherein the organoclay comprises a quaternary pyridinium cation of formula (5):

wherein Ar 6 , Ar 7 , and Ar 8 are independently C 6 - 50 aromatic radicals; “b” is a number from 0 to 2; “d” is a number from 0 to 4; R 3 and R 4 are independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 6 -C 20 aromatic radical; Z is a bond, a divalent C 1 -C 20 aliphatic radical, a divalent C 5 -C 20 cycloaliphatic radical, a divalent C 6 -C 20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO 2 linking group, or a Se linking group; and Ar 9 is a C 10 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.

23. The article of claim 1 , wherein the polymer-organoclay composite comprises a polymer selected from the group consisting of polyvinylchloride, a polyolefin, a polyester, a polyamide, a polysulfone, a polyimide, a polyetherimide, a polyether sulfone, a polyphenylene sulfide, a polyether ketone, a polyether ether ketone, an acrylonitrile-butadiene-styrene, a polystyrene, a polybutadiene, a polyacrylate, a polyalkylacrylate, a polyacrylonitrile, a polyacetal, a polycarbonate, a polyphenylene ether, an ethylene-vinyl acetate copolymer, a polyvinyl acetate, a liquid crystalline polymer, an aromatic polyester, an ethylene-tetrafluoroethylene copolymer, a polyvinyl fluoride, a polyvinylidene fluoride, a polyvinylidene chloride, a polytetrafluoroethylene, and a combination comprising at least one of the foregoing polymers.

24. The article of claim 1 , wherein the polymer-organoclay comprises a polyethersulfone.

25. The article of claim 1 , wherein the polymer-organoclay composite comprises a polyimide.

26. The article of claim 1 , wherein the polymer-organoclay composite comprises a polyetherimide.

27. The article of claim 1 , wherein the polymer-organoclay composite comprises a polyether ketone.

28. The article of claim 1 , wherein the polymer-organoclay composite comprises a polymer having a glass transition temperature from about 180° C. to about 450° C.

29. The article of claim 4 , wherein the energized condition is produced by a sonic energy source.

30. The article of claim 4 , wherein the energized condition is produced by a high shear mixer.

31. The article of claim 4 , wherein the energy is of sufficient intensity and duration to effect a net increase in the initial d-spacing of the organoclay.

32. The article of claim 4 , wherein the first mixture is exposed to an energized condition of sufficient intensity and duration to increase the initial spacing of the inorganic silicate layers by an amount from 5 Angstroms to 90 Angstroms.

33. The article of claim 4 , wherein the increase in the initial spacing of the inorganic silicate layers results in random spacing of the inorganic silicate layers.

34. The article of claim 4 , wherein the net increase in the initial d-spacing of the organoclay is from about 10 to about 500 percent.

35. The article of claim 4 , wherein the thermoplastic polymer is a polymer selected from the group consisting of polyvinylchloride, a polyolefin, a polyester, a polyamide, a polysulfone, a polyimide, a polyetherimide, a polyether sulfone, a polyphenylene sulfide, a polyether ketone, a polyether ether ketone, an acrylonitrile-butadiene-styrene, a polystyrene, a polybutadiene, a polyacrylate, a polyalkylacrylate, a polyacrylonitrile, a polyacetal, a polycarbonate, a polyphenylene ether, an ethylene-vinyl acetate copolymer, a polyvinyl acetate, a liquid crystalline polymer, an aromatic polyester, an ethylene-tetrafluoroethylene copolymer, a polyvinyl fluoride, a polyvinylidene fluoride, a polyvinylidene chloride, a polytetrafluoroethylene, and a combination comprising at least one of the foregoing polymers.

36. The article of claim 4 , wherein removing at least a portion of the solvent is carried out in a devolatilizing extruder.

37. The article of claim 4 , wherein the organoclay comprises a quaternary phosphonium cation of formula (2):

wherein Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently C 6 - 50 aromatic radicals; “a” is a number from 1 to about 200; “c” is a number from 0 to 3; R 1 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and R 2 is a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, a C 6 - 50 aromatic radical, or a polymer chain.

38. The article of claim 4 , wherein the organoclay comprises a quaternary phosphonium cation of formula (3):

wherein Ar 12 , Ar 13 , Ar 14 and Ar 15 are independently C 6 - 50 aromatic radicals; and Ar 16 is a C 6 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.

39. The article of claim 4 , wherein the organoclay comprises a pyridinium cation of formula (4):

wherein Ar 6 , Ar 7 , and Ar 8 are independently C 6 - 50 aromatic radicals; “b” is a number from 0 to 2; R 3 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and Ar 11 is a C 6 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.

40. The article of claim 39 , wherein the organoclay comprises a quaternary pyridinium cation of formula (5):

wherein Ar 6 , Ar 7 , and Ar 8 are independently C 6 - 0 50 aromatic radicals; “b” is a number from 0 to 2; “d” is a number from 0 to 4; R 3 and R 4 are independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 6 -C 20 aromatic radical; Z is a bond, a divalent C 1 -C 20 aliphatic radical, a divalent C 5 -C 20 cycloaliphatic radical, a divalent C 6 -C 20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO 2 linking group, or a Se linking group; and Ar 9 is a C 10 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.

41. The article of claim 4 , wherein the polymer-organoclay comprises a polyethersulfone.

42. The article of claim 4 , wherein the polymer-organoclay composite comprises a polyimide.

43. The article of claim 4 , wherein the polymer-organoclay composite comprises a polyetherimide.

44. The article of claim 4 , wherein the polymer-organoclay composite comprises a polyether ketone.

45. The article of claim 4 , wherein the polymer-organoclay composite comprises a polymer having a glass transition temperature from about 180° C. to about 450° C.