Reduced Density Glass Bubble Polymer Composite

• US 20100279100A1
• Filed: 04/28/2010
• Published: 11/04/2010
• Est. Priority Date: 04/29/2009
• Status: Active Grant

• Current Assignee: Tundra Composites, LLC.
• Original Assignee: Tundra Composites, LLC.
• Inventors: Heikkila, Kurt E., Kroll, John S., Williams, Rodney K.
• Granted Patent: US 9,249,283 B2
• Time in Patent Office: Days
• US Class Current: 428/313.9
• CPC Class Codes: B60C 1/00 Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
• CPC Class Codes: C08J 2327/16 Homopolymers or copolymers of vinylidene fluoride
• CPC Class Codes: C08J 2327/18 Homopolymers or copolymers of tetrafluoroethylene
• CPC Class Codes: C08J 2327/20 Homopolymers or copolymers of hexafluoropropene
• CPC Class Codes: C08J 5/04 Reinforcing macromolecular compounds with loose or coherent fibrous material
• CPC Class Codes: C08K 2003/2227 of aluminium
• CPC Class Codes: C08K 2201/005 Additives being defined by their particle size in general
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08K 7/28 Glass
• CPC Class Codes: C08K 9/00 Use of pretreated ingredients
• CPC Class Codes: C08K 9/04 Ingredients treated with organic substances treated with macromolecular compounds C08K9/08
• CPC Class Codes: C08L 21/00 Compositions of unspecified rubbers
• CPC Class Codes: Y10T 428/249974 Metal- or silicon-containing element

Abstract

The invention relates to a hollow glass microsphere and polymer composite having enhanced viscoelastic and rheological properties.

Claims

1. A hollow glass microsphere and polymer composite comprising:

(a) about 30 to 87 vol-% of a hollow glass microsphere having a particle size greater than about 5 microns having a coating of about 0.005 to 8 wt-% of an interfacial modifier, the percentage based on the composite; and

(b) a polymer phase.

2. The composite of claim 1 wherein the composite density is about 0.2 to 5 gm-cm⁻

3

3. The composite of claim 1 wherein the composite density is about 0.2 to 2 gm-cm⁻

3

4. The composite of claim 1 wherein the composite density is about 0.2 to 0.8 gm-cm⁻

3

5. The composite of claim 1 wherein the polymer has a density greater than 1.7 gm-cm⁻

3.

6. The composite of claim 1 wherein the composite has a tensile strength of about 0.1 to 10 times that of the base polymer.

7. The composite of claim 1 wherein the composite has a tensile strength of about 0.1 to 5 times that of the base polymer.

8. The composite of claim 1 wherein the composite has a tensile elongation of about 5% to 100% of the base polymer.

9. The composite of claim 1 wherein the composite has a tensile elongation of about 20% to 100% of the base polymer.

10. The composite of claim 1 wherein the composite has a tensile strength of about 0.1 to 10 times that of the base polymer and a tensile elongation of about 15% to 90% of base polymer.

11. The composite of claim 1 wherein the composite has a thermoplastic shear at least about 5 sec⁻

1.

12. The composite of claim 1 wherein the composite has a tensile strength of at least 0.2 MPa and a thermoplastic shear of at least 5 sec⁻

1.

13. The composite of claim 1 wherein the composite comprises greater than 30 vol-% of the hollow glass microsphere and the composite has a density of about 0.4 to 0.8 gm-cm⁻

3.

14. The composite of claim 1 wherein the composite comprises greater than 50 vol-% of the hollow glass microsphere.

15. The composite of claim 1 wherein the composite comprises a hollow glass microsphere, the majority of the microspheres having a particle size P_S of about 10 to 1000 microns.

16. The composite of claim 1 wherein the hollow glass microsphere has a particle size P_s of about 5 to 300 microns.

17. The composite of claim 1 wherein the hollow glass microsphere has a particle size P_S of about 10 to 300 microns.

18. The composite of claim 1 wherein the hollow glass microsphere has a particle size P_s of about 15 to 250 microns.

19. The composite of claim 1 wherein the particulate additionally comprises a solid glass sphere having a particle size (P_s) of about 5 to 1000 microns.

20. The composite of claim 1 wherein the hollow glass microspheres have a particle size P_S of about 10 to 200 microns and the composite additionally comprises a particulate with a particle size P_S¹ that differs from the hollow glass microsphere by at least 5 microns.

21. The composite of claim 20 wherein the particle has particle size P_S¹ distibution ranging from about 10 to about 1000 microns.

22. The composite of claim 20 wherein the particle has particle size P_S¹ distibution ranging from about 10 to 500 microns.

23. The composite of claim 22 wherein the particulate has a particle size according to the formula P_S≧

2 P_S¹ or P_S<

0.5 P_S¹ wherein P_S is the particle size of the hollow glass microsphere and P_S¹ is the particle size of the particulate.

24. The composite of claim 20 wherein the particulate comprises a metal particulate, a solid glass sphere, or a second hollow glass microsphere.

25. The composite of claim 20 wherein the circularity of the particle is 12.5 to 25.

26. The composite of claim 1 wherein the polymer comprises a polyamide.

27. The composite of claim 1 wherein the polymer comprises a nylon.

28. The composite of claim 1 wherein the polymer comprises a poly(ethylene-co-vinyl acetate).

29. The composite of claim 1 wherein the polymer comprises a synthetic rubber.

30. The composite of claim 1 wherein the polymer comprises a polyvinyl chloride.

31. The composite of claim 1 wherein the polymer comprises a fluoropolymer or fluoroelastomer.

32. The composite of claim 1 wherein the polymer comprises a polyolefin.

33. The composite of claim 1 wherein the polymer comprises a thermoset polymer.

34. The composite of claim 1 wherein the polymer comprises a high-density polyolefin.

35. The composite of claim 23 wherein the particle composite comprises greater than 5 vol-% of a particle having a particle size P_s distribution ranging from about 10 to about 200 microns.

36. The composite of claim 23 wherein the composite contains greater than 10 vol-% of a particulate in the range of about 2.5 to 1000 microns.

37. The composite of claim 20 wherein the particulate comprises a mixture of particles of differing nonmetallic composition.

38. The composite of claim 20 wherein the particulate comprises a mixture of particles of differing nonmetallic composition.

39. The composite of claim 1 wherein the composite comprises about 0.01 to 4 wt % of an interfacial modifier.

40. The composite of claim 1 wherein the composite additionally comprises an organic or inorganic pigment.

41. The composite of claim 1 wherein the composite additionally comprises an organic dye.

48. An insulating layer comprising the composite of claim 1 wherein the thermal transfer rate of the composite layer is less than 85% of the thermal transfer rate of a conventional polymer composite layer.

49. The layer of claim 48 wherein the layer comprises a sealant.

50. The layer of claim 48 wherein the layer comprises an adhesive.

51. The acoustically insulating layer comprising the composite of claim 1.

42. A hollow glass microsphere and polymer composite comprising:

(a) about 90 to 30 volume-% of a hollow glass microsphere having a density greater than 0.10 gm-cm<sup>−

3</sup> and less than 5 gm-cm<sup>−

3</sup> and a particle size greater than 8 microns; and

(b) about 10 to 70 volume-% of a polymer phase;

wherein the microsphere has a coating comprising about 0.005 to 3 wt.-% of an interfacial modifier; and

wherein the composite density is about 0.20 to 15 gm-cm<sup>−

3</sup>.

43. The composite of claim 42 wherein the composite density is about 0.2 to 5 gm-cm⁻

3

44. The composite of claim 42 wherein the composite density is about 0.2 to 2 gm-cm⁻

3

45. The composite of claim 42 wherein the composite density is about 0.2 to 0.8 gm-cm⁻

3

46. A shaped article comprising the composite of claim 42 wherein the composite comprises about 87 to 50 vol-% of a hollow glass microsphere, and having a particle size distribution having at least 10 wt.-% of a particulate within about 10 to 100 microns and at least 10 wt.-% of the polymer particulate within about 100 to 1000 microns.

47. The article of claim 46 wherein the density is about 0.2 to 0.8 gm-cm⁻

3

53. A protective layer having improved impact resistance comprising the composite of claim 42 wherein the composite further comprises layers of tunable tensile strengths that respond to impact forces.

54. An article having improved impact resistance comprising the composite of claim 42 wherein the composite further comprises layers of tunable tensile strengths that respond to impact forces.

52. The acoustic insulator layer having a reduced sound transfer rate.

55. A structural member used in a structure assembled using a fastener, wherein the structural member has an improved fastener retention.

56. A barrier layer, acting as a barrier to gas mass transfer, the barrier layer comprising a composition of claim 55.

57. The gas mass transfer barrier of claim 56 wherein the permeability of the layer to argon, nitrogen, or a mixed gas having a major proportion of nitrogen is reduced by at least 50%.

58. The barrier layer of claim 56 wherein the permeability of the layer to water or solvent(s) is reduced by at least 50%.

59. A tire rubber formulation comprising:

(a) a vulcanizable rubber;

(b) a hollow glass microsphere having a coating of about 0.0005 to 8 wt. % an interfacial modifier.

60. A tire rubber formulation of claim 59 comprising:

(a) a vulcanizable rubber;

(b) about 1 to 10 phr of a hollow glass microsphere having a coating of about 0.001 to 5 wt. an interfacial modifier;

(c) about 1 to 50 phr of carbon black;

(d) about 1 to 50 phr of a process oil;

(e) about 0.1 to 10 phr of a vulcanizing agent; and

(f) about 0.1 to 10 phr of a vulcanization accelerator.

61. A process of compounding a tire rubber formulation, the method comprising adding about a hollow glass microsphere, having a coating of about 0.0005 to 8 wt. % of an interfacial modifier, to a tire formulation in a compounding mixer comprising a un-vulcanized rubber