Grafted cyclodextrin

• US 8,334,343 B2
• Filed: 06/11/2007
• Issued: 12/18/2012
• Est. Priority Date: 12/10/2002
• Status: Active Grant

• Current Assignee: Verdant Technologies, Inc.
• Original Assignee: Cellresin Technologies, LLC
• Inventors: Wood, Willard E., Beaverson, Neil J., Seethamraju, Kasyap V.
• Primary Examiner(s): Wu, David W
• Assistant Examiner(s): JONES JR., ROBERT STOCKTON
• Application Number:
  US11/761,017
• Publication Number:
  US 20080032110A1
• Time in Patent Office: 2,017 Days
• Field of Search: 525/54.2, 525/54.24, 525/54.26, 525/185, 525/186, 525/190, 525/451
• US Class Current: 525/54.26
• CPC Class Codes: B32B 27/02 in the form of fibres or filaments not used
• CPC Class Codes: B32B 27/28 comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• CPC Class Codes: B32B 27/32 comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: C08B 37/0012 Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
• CPC Class Codes: C08L 23/04 Homopolymers or copolymers of ethene
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C08L 5/16 Cyclodextrin; Derivatives thereof
• CPC Class Codes: C08L 51/06 grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• CPC Class Codes: Y10T 428/13 Hollow or container type article [e.g., tube, vase, etc.]
• CPC Class Codes: Y10T 428/1352 Polymer or resin containing [i.e., natural or synthetic]
• CPC Class Codes: Y10T 428/1393 Multilayer [continuous layer]
• CPC Class Codes: Y10T 428/1397 Single layer [continuous layer]
• CPC Class Codes: Y10T 428/249926 Including paper layer
• CPC Class Codes: Y10T 428/24998 Composite has more than two layers
• CPC Class Codes: Y10T 428/269 including synthetic resin or polymer layer or component
• CPC Class Codes: Y10T 428/2878 including addition polymer from unsaturated monomer
• CPC Class Codes: Y10T 428/2929 Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
• CPC Class Codes: Y10T 428/298 Physical dimension
• CPC Class Codes: Y10T 428/31895 Paper or wood
• CPC Class Codes: Y10T 428/31902 Monoethylenically unsaturated

Abstract

Thermoplastic polymer compositions, films, continues, closures, laminates can comprise a modified vinyl polymer said modified polymer having a moiety comprising a cyclodextrin compound. The cyclodextrin compound, locked into the polymer structure, can absorb impurities, permeants, or other undesirable volatile materials. The cooperation between the cyclodextrin grafted onto the thermoplastic polymer and the polymer structure can provide barrier properties to a film, web or other polymer structure. A permeant or a contaminant can be complexed or trapped within the polymer and held within the film or Web preventing the permeant or contaminant from passing into the interior of a container or enclosure.

Claims

1. A film comprising a blend of a thermoplastic polyolefin polymer and a modified polyolefin, the blend comprising a polyolefin resin and an acid anhydride or carboxylic acid modified polyolefin resin, the acid anhydride or carboxylic acid modified polyolefin resin comprising at least one pendant substituent derived from a cyclodextrin, wherein the cyclodextrin is bonded to the polyolefin resin by the reaction product of cyclodextrin with the acid anhydride or carboxylic acid, wherein the cyclodextrin is substantially free of a compound in its central pore.

2. The film of claim 1 wherein the film is a flexible film having a thickness of about 4 μ

m to 200 μ

m.

3. The film of claim 2 wherein the modified polyolefin resin comprises a tie layer.

4. The film of claim 2 wherein the modified polyolefin comprises a heat sealable layer.

5. The film of claim 2 wherein the film is uniaxially or biaxially oriented.

6. The film of claim 2 wherein the film is a multilayer film comprising at least one layer comprising a polyolefin and a modified polyolefin resin.

7. The film of claim 6 wherein the film is a single resin multilayer film.

8. The film of claim 6 wherein the layers are symmetrically disposed on top of one another to form a balanced multilayer film.

9. The film of claim 6 wherein the layers are asymmetrically disposed on top of one another to form an unbalanced multilayer film.

10. The film of claim 6 further comprising a support layer comprising paper or paperboard, wherein the support layer has a first major side and second major side, wherein the multilayer film is disposed on said first major side.

11. The film of claim 10 wherein a heat sealable layer is disposed on the second major side of the support layer.

12. The film of claim 10 further comprising a layer of aluminum foil disposed between the first major side of the support layer and the multilayer film.

13. The film of claim 11 further comprising a layer of aluminum foil disposed between the first major side of the support layer and the multilayer film.

14. The film of claim 10 wherein the multilayer film comprises one or more polymeric barrier layers and a heat sealing layer, wherein the heat sealing layer comprises a modified polyolefin resin layer.

15. The film of claim 11 wherein the multilayer film comprises one or more polymeric barrier layers and a heat sealing layer, wherein the heat sealing layer comprises a modified polyolefin resin layer.

16. The film of claim 14 further comprising one or more polymeric tie layers disposed between the support layer and the one or more barrier layers, between the support layer and the heat seal layer, or between the one or more barrier layers and the heat seal layer.

17. The film of claim 15 further comprising one or more polymeric tie layers disposed between the support layer and the one or more barrier layers, between the support layer and the heat seal layer, or between the one or more barrier layers and the heat seal layer.

18. The film of claim 14 further comprising one or more polymeric bulk layers disposed between the support layer and the heat sealing layer of the multilayer film.

19. The film of claim 15 further comprising one or more polymeric bulk layers disposed between the support layer and the heat sealing layer of the multilayer film.

20. The film of claim 16 further comprising one or more polymeric bulk layers disposed between the support layer and the heat sealing layer of the multilayer film.

21. The film of claim 17 further comprising one or more polymeric bulk layers disposed between the support layer and the heat sealing layer of the multilayer film.

22. The film of claim 18 wherein at least one of the one or more polymeric bulk layers comprises a modified polyolefin resin.

23. The film of claim 19 wherein at least one of the one or more polymeric bulk layers comprises a modified polyolefin resin.

24. The film of claim 20 wherein at least one of the one or more polymeric bulk layers comprises a modified polyolefin resin.

25. The film of claim 21 wherein at least one of the one or more polymeric bulk layers comprises a modified polyolefin resin.

26. The film of claim 18 wherein at least one of the one or more polymeric bulk layers comprise a blend of a polyolefin and a modified polyolefin resin.

27. The film of claim 20 wherein at least one of the one or more polymeric bulk layers comprise a blend of a polyolefin and a modified polyolefin resin.

28. The film of claim 21 wherein at least one of the one or more polymeric bulk layers comprise a blend of a polyolefin and a modified polyolefin resin.

29. The film of claim 10 wherein the multilayer film comprises a layer of nylon disposed on top of the paperboard, a layer of ethylene-vinyl alcohol copolymer disposed on top of the nylon layer, a second layer of nylon disposed on top of the ethylene-vinyl alcohol copolymer layer, a polymeric tie layer disposed on top of the second layer of nylon, and a modified polyolefin resin disposed on top of the polymeric tie layer, wherein the modified polyolefin resin layer comprises a heat sealing layer.

30. The film of claim 29 further comprising a layer of polyolefin resin disposed between the polymeric tie layer and the modified polyolefin resin.

31. The film of claim 10 wherein the multilayer film comprises a first layer of nylon disposed on top of the paperboard, a layer of ethylene-vinyl alcohol copolymer disposed on top of the first nylon layer, a second nylon layer disposed on top of the ethylene-vinyl alcohol copolymer layer, a polymeric tie layer disposed on top of the second nylon layer, a polyolefin resin layer disposed on top of the polymeric tie layer, and a layer of modified polyolefin resin disposed on top of the polyolefin resin layer, wherein the modified polyolefin resin layer comprises a heat sealable layer.

32. The film of claim 6 wherein the multilayer film is a barrier film, a storage bag, or a sheet.

33. The film of claim 6 wherein the multilayer film is a food packaging film capable of reducing the concentration of vapor phase compounds that cause undesirable flavors in food that accumulate in the headspace of the food package.

34. The film of claim 1 wherein the film is disposed on top of a monolithic member.

35. The film of claim 1 wherein the film is disposed inside a monolithic member.

36. The film of claim 1 wherein the film is a semi-rigid film having a thickness of about 200 μ

m to about 1 mm.

37. The film of claim 36 wherein the film comprises a multilayer film having at least one layer comprising a modified polyolefin resin.

38. The film of claim 37 wherein the film is a single resin multilayer film.

39. The film of claim 37 wherein the layers are symmetrically disposed on top of one another to form a balanced multilayer film.

40. The film of claim 37 wherein the layers are asymmetrically disposed on top of one another to form an unbalanced multilayer film.

41. The film of claim 36 wherein the film comprises a packaging component comprising a tub, a pot, a blister, a tray, a punnet, or a lid.

42. The film of claim 1 wherein the film is a rigid film having a thickness of greater than about 1 mm.

43. The film of claim 42 wherein the film has a thickness of about 1 mm to 20 mm.

44. The film of claim 42 wherein the rigid film comprises a tray, a tub, a bottle, a jar, a parison, a closure, an I-beam, a plank, a pole, a diaper pail, a food storage container, a garbage container, a solvent container, or a laundry container.

45. The film of claim 42 wherein the rigid film comprises a multilayer film having at least one layer comprising a modified polyolefin resin.

46. The film of claim 45 wherein the film comprises a multilayer film having at least one layer comprising a modified polyolefin resin.

47. The film of claim 46 wherein the film is a single resin multilayer film.

48. The film of claim 46 wherein the layers are symmetrically disposed on top of one another to form a balanced multilayer film.

49. The film of claim 46 wherein the layers are asymmetrically disposed on top of one another to form an unbalanced multilayer film.

50. The film of claim 45 wherein the rigid film comprises a fuel tank.

51. The film of claim 50 wherein the layers comprise a first layer of high density polyethylene as the inner layer for contact with fuel, a first tie layer disposed on top of the high density polyethylene layer, a barrier layer disposed on top of the tie layer, a second tie layer disposed on top of the barrier layer, and a second layer of high density polyethylene disposed on top of the second tie layer.

52. The film of claim 51 wherein the barrier layer comprises nylon or ethylene-vinyl alcohol copolymer.

53. The film of claim 51 wherein at least the first layer of high density polyethylene comprises a modified polyolefin resin.

54. The film of claim 50 wherein the layers comprise a first layer of high density polyethylene as the inner layer for contact with fuel, a barrier layer disposed on top of the first high density polyethylene layer, an adhesive resin layer disposed on top of the barrier layer, and a second layer of high density polyethylene disposed on top of the adhesive resin layer.

55. The film of claim 54 wherein at least the first layer of high density polyethylene comprises a modified polyolefin resin.

56. The film of claim 1 wherein the film encloses a food material.

57. The film of claim 56 wherein the food is a solid food.

58. The film of claim 56 wherein the food comprises ripening material.

59. The film of claim 58 wherein the ripening materials is a fruit, vegetable, herb, or flower.

60. The film of claim 56 wherein the film comprises a multilayer structure.

61. The film of claim 60 wherein the structure contacting the food comprises the modified polyolefin resin.