POLYMERIC COMPOSITE INCLUDING NANOPARTICLE FILLER

• US 20070106006A1
• Filed: 08/31/2006
• Published: 05/10/2007
• Est. Priority Date: 09/02/2005
• Status: Active Grant

• Current Assignee: Naturalnano Corp
• Original Assignee: NaturalNano, Inc. (Omni Shrimp, Inc.)
• Inventors: Wagner, Aaron, Fleischer, Cathy, Duffy, Michael, Cooper, Sarah
• Granted Patent: US 7,888,419 B2
• Time in Patent Office: Days
• US Class Current: 524/445
• CPC Class Codes: C08K 3/04 Carbon
• CPC Class Codes: C08K 3/34 Silicon-containing compounds
• CPC Class Codes: C08K 9/04 Ingredients treated with organic substances treated with macromolecular compounds C08K9/08

Abstract

Disclosed is a novel polymeric composite including a nanoparticle filler and method for the production thereof. More particularly, the present invention provides a novel halloysite nanoparticle filler which has the generally cylindrical or tubular (e.g. rolled scroll-like shape), in which the mean outer diameter of the filler particle is typically less than about 500 nm. The filler is effectively employed in a polymer composite in which the advantages of the tubular nanoparticle filler are provided (e.g., reinforcement, flame retardant, chemical agent elution, etc.) with improved or equivalent mechanical performance of the composite (e.g., strength and ductility).

Claims

1. A polymeric nanoparticle composite, comprising:

a polymer matrix; and

a filler consisting essentially of mineral nanotubes.

2. The composite of claim 1, wherein the mineral nanotubes are halloysite nanoparticles.

3. The composite of claim 1, wherein said halloysite nanoparticles have a generally tubular shape.

4. The composite of claim 3, wherein said halloysite nanoparticles have a mean average outer diameter of less than about 500 nm.

5. The composite of claim 3, wherein said halloysite nanoparticles have a mean average length of less than about 40,000 nm.

6. The composite of claim 1, wherein said polymer matrix includes a polyolefin.

7. The composite of claim 1, wherein said polymer matrix includes a thermosetting material.

8. The composite of claim 1, wherein said thermosetting material is selected from the group consisting of:

epoxies;

epoxy-polyester hybrids;

phenol ics;

melamines; and

urethanes.

9. The composite of claim 1, wherein said polymer matrix includes a thermoplastic material.

10. The composite of claim 9, wherein said polymer matrix includes at least one material selected from the group consisting of:

polyesters;

polyethylene;

polypropylene;

polyvinyl chloride;

silicones;

acrylic polymers;

fluoropolymers;

polyurethanes;

polystyrene; and

polyamide.

11. The composite of claim 1, wherein said polymer matrix includes an elastomeric material.

12. The composite of claim 1, wherein said mineral nanotubes include at least one compatibilization agent.

18. The composite of claim 12, wherein said compatibilizing agent includes silane.

19. The composite of claim 12, wherein said composite exhibits a modulus of elasticity and a yield strength greater than that of said polymer matrix without filler.

20. The composite of claim 12, wherein said polymer matrix consists essentially of Nylon and where said composite exhibits a modulus of elasticity of at least about 1.9 GPa and a yield strength at least about 83 MPa.

21. The composite of claim 1, wherein said halloysite nanoparticles have a generally cylindrical shape and exhibit differential surface charges to form a localized network of tubes arranged generally end to wall.

22. The composite of claim 10 wherein the composite is a coating applied on a surface.

23. The composite of claim 3, wherein said nanoparticles include a metal cladding thereon.

24. The composite of claim 1, wherein said mineral nanotubes include at least one agent for elution.

25. The composite of claim 1, wherein said agent for elution is selected from the group consisting of:

biocides;

minerals;

light emitting substances;

fluorescent substances;

phosphorescent substances;

colorants;

antioxidants;

emulsifiers;

antifungal agents;

pesticides;

fragrances;

dyes;

optical brighteners;

fire retardants;

self-healing polymers; and

combinations thereof.

26. The composite of claim 1, wherein the mineral nanotubes are selected from the group consisting of:

imogolite;

cylindrite; and

boulangerite.

13. The composite of 12, wherein said compatibilization agent is an organic compound.

14. The composite of 13, wherein said organic compound is a neutral organic compound.

15. The composite of 12, wherein said organic compound is an ionic organic compound.

16. The composite of 14, wherein said neutral organic compound is selected from the group consisting of:

monomers;

oligomers; and

polymers.

17. The composite of claim 16, where said polymer is a copolymer.

27. A method for making a polymer composite, including:

producing a milled halloysite having a nanotubular structure; and

combining a polymer material with said surface treated halloysite to form the polymer composite.

28. The method of claim 27, where the milled halloysite is produced using an air milling process.

29. The method of claim 27, further including drying said surface treated halloysite.

30. The method of claim 27, further including surface modifying the halloysite.

31. The method of claim 27, further including forming the polymer composite using a manufacturing process selected from the group consisting of:

coating;

molding;

rotomolding;

thermoform ing;

vacuum forming;

calendaring;

matched-die molding;

hand lay-up;

filament winding;

casting;

forging;

extrusion;

co-extrusion;

fiber extrusion;

compounding and

film extrusion.

32. The method of claim 27, further including molding the polymer composite using a molding process selected from the group consisting of:

compression;

transfer;

injection;

blow;

extrusion;

expandable-bead; and

foam.

33. The method of claim 30, wherein surface modifying said halloysite material includes exposing said halloysite material to benzalkonium chloride in the range of about 0.5 percent to about 1.0 percent.

34. The method of claim 30, wherein surface modifying said halloysite material includes exposing said halloysite material to benzalkonium chloride in the range of about 0.1 percent to about 2.0 percent.

35. The method of claim 27, wherein surface modifying said halloysite material includes exposing said halloysite material to a compatibilization agent.

36. The method of claim 35, wherein said compatibilization agent is an organic compound.

37. The method of claim 36, wherein said organic compound is a neutral organic compound.

38. The method of claim 36, wherein said organic compound is an ionic organic compound.

39. The method of claim 37, neutral organic compound is selected from the group consisting of:

monomers;

oligomers; and

polymers.

40. The method of claim 39, where said polymers are copolymers.

41. The method of claim 35, wherein said compatibilization agent is selected from the group consisting of:

organosilane;

organozirconate; and

organotitanate agents.

42. The method of claim 35, further including air milling the surface treated halloysite.

43. The method of claim 27, wherein said halloysite is combined with said polymer to produce a composite including a range of about 1 to about 20 weight-percent halloysite.

44. The method of claim 27, wherein said halloysite is combined with said polymer to produce a composite including a range of about 3 to about 10 weight-percent halloysite.

45. The method of claim 27, wherein said halloysite is combined with said polymer to produce a composite including about 5 weight-percent halloysite.

46. The method of claim 27, wherein combining includes blending by extruding said materials under flowing nitrogen.

47. The method of claim 27, further including adding at least one additive selected from the group consisting of:

colorants, antioxidants, emulsifiers, biocides, antifungal agents, pesticides, fragrances, dyes, optical brighteners, self-healing polymers and plasticizers, and fire retardants.

48. The method of claim 27, further including:

coating the halloysite with a metal;

drying the coated halloysite to provide hollow micro-capillary spaces; and

filling the micro-capillary spaces by exposing the dried halloysite to an active agent and the agent'"'"'s carrier or solvent.

49. The method of claim 48, wherein coating the halloysite is accomplished using an electroless deposition process.

50. The method of claim 48, further including applying the composite on a surface to provide a conductive coating thereon.

51. A polymer composition including about 1 to about 20 weight-percent of a nanotubular clay filler dispersed therein, based on the total weight of polymer, said nanoclay filler including nanotubes having an outer cylindrical diameter of less than about 500 nm and a length of less than about 40,000 nm.

52. The polymer composite of claim 51, including about 3 to about 10 weight-percent of the nanotubular clay filler.

53. The polymer composite of claim 52, including about 5 weight-percent of the nanotubular clay filler.

54. The polymer composition of claim 51, wherein said nanotubular clay consists essentially of halloysite.

55. The polymer composition of claim 51, wherein said nanotubular clay consists essentially of halloysite treated with an active agent.

56. The polymer composition of claim 55, wherein said active agent is adsorbed onto an inner surface of the nanotubes.

57. The polymer composition of claim 55, wherein said nanotubes further include an adherent barrier coating for controlling the release of said active agent from said nanotubes.

58. A method for producing a polymer composite part, including:

obtaining a tubular clay filler material;

surface modifying the tubular clay filler material;

air milling the surface treated material;

drying the material;

combining the dried material with a polymer to form a composite mixture; and

forming the composite mixture into the part.

59. The method of claim 58, wherein surface modifying includes exposing said tubular clay material to benzalkonium chloride in the range of about 0.5 percent to about 1.0 percent.

60. The method of claim 58, further including forming the composite using a manufacturing process selected from the group consisting of:

coating;

molding;

rotomolding;

thermoforming;

vacuum forming;

calendaring;

matched-die molding;

hand lay-up;

filament winding;

casting;

forging;

extrusion;

co-extrusion;

fiber extrusion;

compounding, and

film extrusion.

61. The method of claim 58, further including molding the polymer composite using a molding process selected from the group consisting of:

compression;

transfer;

injection;

blow;

extrusion;

expandable-bead; and

foam.

62. The method of claim 58, wherein surface modifying said tubular clay filler material includes exposing said material to a compatibilization agent.

63. The method of claim 62, wherein said compatibilization agent is an organic compound.

64. The method of claim 63, wherein said organic compound is a neutral organic compound.

65. The method of claim 63, wherein said organic compound is an ionic organic compound.

66. The method of claim 64, neutral organic compound is selected from the group consisting of:

monomers;

oligomers; and

polymers.

67. The method of claim 66, where said polymers are copolymers.

68. The method of claim 62, wherein said compatibilization agent is selected from the group consisting of:

organosilane;

organozirconate; and

organotitanate agents.

69. The method of claim 62, further including air milling the tubular clay filler.

70. The method of claim 58, wherein said tubular clay filler is combined with said polymer to produce a composite including a range of about 1 to about 20 weight-percent tubular clay filler.

71. The method of claim 58, wherein said tubular clay filler is combined with said polymer to produce a composite including a range of about 3 to about 10 weight-percent tubular clay filler.

72. The method of claim 58, wherein said tubular clay filler is combined with said polymer to produce a composite including about 5 weight-percent tubular clay filler.

73. The method of claim 58, wherein combining includes blending by extruding said materials under flowing nitrogen.

74. The method of claim 58, further including adding at least one additive selected from the group consisting of:

colorants, antioxidants, emulsifiers, biocides, antifungal agents, pesticides, fragrances, dyes, optical brighteners, self-healing polymers and plasticizers, and fire retardants.

75. The method of claim 58, further including:

coating the tubular clay filler with a metal;

drying the coated tubular clay filler to provide hollow micro-capillary spaces; and

filling the micro-capillary spaces by exposing the dried tubular clay filler to an active agent and the agent'"'"'s carrier or solvent.

76. The method of claim 75, wherein the tubular clay filler is coated by electroless deposition.

77. The method of claim 75, further including applying the composite on a surface to provide a conductive coating thereon.