Reduced density glass bubble polymer composite

• US 9,249,283 B2
• Filed: 04/28/2010
• Issued: 02/02/2016
• Est. Priority Date: 04/29/2009
• Status: Active Grant

• Current Assignee: Tundra Composites, LLC.
• Original Assignee: Tundra Composites, LLC.
• Inventors: Heikkila, Kurt E., Williams, Rodney K., Kroll, John S.
• Primary Examiner(s): Choi, Ling
• Assistant Examiner(s): REUTHER, ARRIE L
• Application Number:
  US12/769,553
• Publication Number:
  US 20100279100A1
• Time in Patent Office: 2,106 Days
• Field of Search: 524/494
• US Class Current: 1/1
• 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 shaped structural article formed by melt processing of a thermoplastic composite comprising a dispersion of a hollow glass sphere particulate in a continuous thermoplastic polymer phase, wherein the thermoplastic composite comprises:

(a) greater than 70-90 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 interfacial modifier free of a coupling agent, wherein the interfacial modifier coating allows for greater freedom of movement of the particles within the polymer phase of the composite, the percentages based on the composite; and

(b) the polymer phase of the composiute free of tetrafluoroethylene, hexafluoropropylene, perfluoroalkylvinyl ether, polycarbonate, polyetherimid, and polysulfone.

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

3.

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

3.

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

3.

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

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

7. The shaped structural article of claim 1 wherein the composite has a tensile elongation of about 5% to 100% of the base polymer.

8. The shaped structural article of claim 1 wherein the composite has a tensile elongation of about 20% to 100% of the base polymer.

9. The shaped structural article 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.

10. The shaped structural article of claim 1 wherein the composite has a thermoplastic shear at least about 5 sec⁻

1.

11. The shaped structural article 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.

12. The shaped structural article of claim 1 wherein the composite comprises a density of about 0.4 to 0.8 gm-cm⁻

3.

13. The shaped structural article 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.

14. The shaped structural article of claim 1 wherein the hollow glass microsphere has a particle size P_S of about 5 to 300 microns.

15. The shaped structural article of claim 1 wherein the hollow glass microsphere has a particle size P_S of about 10 to 300 microns.

16. The shaped structural article of claim 1 wherein the hollow glass microsphere has a particle size P_S of about 15 to 250 microns.

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

18. The shaped structural article 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.

19. The shaped structural article of claim 18 wherein the particulate has particle size P_S¹ distribution ranging from about 10 to about 1000 microns.

20. The shaped structural article of claim 18 wherein the particulate has particle size P_S¹ distribution ranging from about 10 to 500 microns.

21. The shaped structural article of claim 20 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.

22. The shaped structural article of claim 21 wherein the particulate comprises greater than 5 vol-% of the particulate having a particle size P_S distribution ranging from about 10 to about 200 microns.

23. The shaped structural article of claim 21 wherein the particulate comprises greater than 10 vol-% of the particulate in the range of about 2.5 to 1000 microns.

24. The shaped structural article of claim 18 wherein the particulate comprises a metal particulate, a solid glass sphere, or a second hollow glass microsphere.

25. The shaped structural article of claim 18 wherein the circularity of the particulate is 12.5 to 25.

26. The shaped structural article of claim 18 wherein the particulate comprises a mixture of particles of differing nonmetallic composition.

27. The shaped structural article of claim 1 wherein the polymer comprises a polyamide.

28. The shaped structural article of claim 1 wherein the polymer comprises a nylon.

29. The shaped structural article of claim 1 wherein the polymer comprises a poly(ethylene-co-vinyl acetate).

30. The shaped structural article of claim 1 wherein the polymer comprises a synthetic rubber.

31. The shaped structural article of claim 1 wherein the polymer comprises a polyvinyl chloride.

32. The shaped structural article of claim 1 wherein the polymer comprises a polyolefin.

33. The shaped structural article of claim 1 wherein the polymer comprises a high-density polyolefin.

34. The shaped structural article of claim 1 wherein the composite comprises about 0.01 to 4 wt % of an interfacial modifier.

35. The shaped structural article of claim 1 wherein the composite additionally comprises an organic or inorganic pigment.

36. The shaped structural article of claim 1 wherein the composite additionally comprises an organic dye.

37. A thermoplastic composite comprising a dispersion of a hollow glass sphere particulate in a continuous thermoplastic polymer phase, wherein the thermoplastic composite comprises:

(a) greater than 70-90 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 5 microns; and

(b) the polymer phase free of tetrafluoroethylene, hexafluoropropylene, perfluoroalkylvinyl ether, polycarbonate, polyetherimide, and polysulfone;

wherein the microsphere has a coating comprising about 0.005 to 3 wt. % of an interfacial modifier, the interfacial modifier free of a coupling agent wherein the interfacial modifier coating allows for greater freedom of movement of the particles within the polymer phase of the composite; and

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

3</sup>, the percentage based on the composite.

38. The shaped structural article of claim 37 wherein the composite density is about 0.2 to 5 gm-cm⁻

3.

39. The shaped structural article of claim 37 wherein the composite density is about 0.2 to 2 gm-cm⁻

3.

40. The shaped structural article of claim 37 wherein the composite density is about 0.2 to 0.8 gm-cm⁻

3.