Golf ball containing graphite nanosheets in a polymeric network

• US 6,802,784 B2
• Filed: 05/29/2002
• Issued: 10/12/2004
• Est. Priority Date: 05/29/2002
• Status: Expired due to Fees

• Current Assignee: Acushnet Company (FILA Holdings Corp.)
• Original Assignee: Acushnet Company (FILA Holdings Corp.)
• Inventors: Sullivan, Michael J., Ladd, Derek A.
• Primary Examiner(s): Gorden, Raeann
• Application Number:
  US10/157,521
• Publication Number:
  US 20030224877A1
• Time in Patent Office: 867 Days
• Field of Search: 473/351, 473/367-378
• US Class Current: 473/352
• CPC Class Codes: A63B 37/0003 Golf balls
• CPC Class Codes: A63B 37/0051 Materials other than polybutadienes; Constructional details
• CPC Class Codes: A63B 37/0054 Substantially rigid, e.g. metal
• CPC Class Codes: A63B 37/0076 Multi-piece balls, i.e. having two or more intermediate layers
• CPC Class Codes: A63B 37/0082 Density; Specific gravity
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites

Abstract

A golf ball containing a layer, which comprises nanosheets of exfoliated graphite dispersed in a polymeric matrix, is provided. Exfoliated graphite is graphite that has been intercalated preferably by an oxidation process, where the atoms or molecules have been inserted into the inter-planar spacing between the layered planes of carbons, and expanded. The intercalated graphite is expanded or exfoliated preferably by brief exposure to high heat to expand the thickness of the graphite. The expanded or exfoliated graphite is then mixed with monomers and polymerized in situ to form a polymer with a network of nanosheets of the exfoliated graphite dispersed therein. The exfoliated graphite advantageously retains its nanostructure during the polymerization process. The resulting golf ball layer comprising such polymer with nanosheets of exfoliated graphite exhibits superior tensile strength, low permeability to gas and increased impact strength.

A golf ball comprising a water vapor barrier layer, wherein the water vapor barrier layer comprises a foil of compressed exfoliated graphite layer, is also provided. The expanded or exfoliated graphite is compressed together into flexible thin sheets or foils. Such sheets may also be made with a polymeric binder.

Claims

1. A golf ball comprising a plurality of layers, wherein at least one layer comprises nanosheets of exfoliated graphite dispersed in a polymeric matrix and wherein the nanosheets comprises a plurality of substantially parallel layered planes.

2. The golf ball of claim 1, wherein the exfoliated graphite comprises intercalated graphite expanded by a brief exposure to temperature higher than 500°

C.

3. The golf ball of claim 2, wherein the intercalated graphite is exposed to a temperature higher than 700°

C.

4. The golf ball of claim 3, wherein the temperature is higher than 1000°

C.

5. The golf ball of claim 4, wherein the temperature is of about 1050°

C.

6. The golf ball of claim 2, wherein the intercalated graphite is exposed to high heat for about 15 seconds.

7. The golf ball of claim 2, wherein the intercalated graphite comprises graphite intercalated by immersion in a solution containing an oxidizing agent.

8. The golf ball of claim 7, wherein the oxidizing agent is selected from a group consisting of nitric acid, potassium chlorate, chromic acid, potassium permanganate, potassium chromate, potassium dichromate, perchloric acid and the like, or mixtures, such as concentrated nitric acid and chlorate, chromic acid and phosphoric acid, sulfuric acid and nitric acid.

9. The golf ball of claim 7, wherein said solution comprises sulfuric acid and the oxidizing agent comprises nitric acid.

10. The golf ball of claim 9, wherein the sulfuric acid comprises about 80% by volume of the solution and nitric acid comprises about 20% of the volume.

11. The golf ball of claim 7, wherein said solution further comprises sulfuric acid, and the oxidizing agent is selected from a group consisting of nitric acid, perchloric acid, chromic acid, potassium permanganate, sodium nitrate, hydrogen peroxide, iodic or periodic acids.

12. The golf ball of claim 7, wherein said solution further comprises sulfuric acid and phosphoric acid, and the oxidizing agent is selected from a group consisting of nitric acid, perchloric acid, chromic acid, potassium permanganate, sodium nitrate, hydrogen peroxide, iodic or periodic acids.

13. The golf ball of claim 7, wherein the amount of intercalating solution is about 10 parts to about 150 parts to about 100 parts of graphite.

14. The golf ball of claim 13, wherein the amount of intercalating solution is about 50 parts to about 120 parts to about 100 parts of graphite.

15. The golf ball of claim 13, wherein the amount of intercalating solution is about 10 parts to about 50 parts to about 100 parts of graphite.

16. The golf ball of claim 2, wherein the intercalated graphite comprises graphite intercalated by exposure to a halogen.

17. The golf ball of claim 16, wherein the halogen is in solution with sulfuric acid.

18. The golf ball of claim 16, wherein the halogen is bromine.

19. The golf ball of claim 2, wherein the intercalated graphite comprises graphite intercalated by exposure to a metal halide.

20. The golf ball of claim 19, wherein the metal halide is in solution with sulfuric acid.

21. The golf ball of claim 19, wherein the metal halide is ferric chloride or aluminum chloride.

22. The golf ball of claim 2, wherein the intercalated graphite comprises graphite intercalated by a material selected from a group consisting of chromyl chloride, sulfur trioxide, antimony trichloride, chromium(III)chloride, iodine chloride, chromium(IV)oxide, gold(III)chloride, indium chloride, platinum(IV)chloride, chromyl fluoride, tantalum(V)chloride, samarium chloride, zirconium(IV)chloride, uranium chloride, and yttrium chloride.

23. The golf ball of claim 2, wherein the exfoliated graphite has a thickness of about 100 times to about 300 times the thickness of the intercalated graphite.

24. The golf ball of claim 23, wherein the exfoliated graphite has a thickness of about 300 times the thickness of the intercalated graphite.

25. The golf ball of claim 1, wherein the nanosheets of exfoliated graphite is dispersed in the polymeric matrix by mixing the exfoliated graphite with monomers and polymerizing the monomers and exfoliated graphite in situ.

26. The golf ball of claim 1, wherein the nanosheets of exfoliated graphite is dispersed in the polymeric matrix by mixing the exfoliated graphite with monomers and polymerizing the monomer and exfoliated graphite in situ and by blending with an encasing polymer.

27. The golf ball of claim 1, wherein the polymeric matrix is selected from the group consisting of natural rubber, stryene-butadiene rubber, stryene-propylene or ethylene-diene block copolymer rubber, polyisoprene, polybutadiene, copolymers comprising ethylene or propylene, as ethylene-propylene rubber (EPR), ethylene-propylene diene monomer (EPDM) elastomer, copolymers of acrylonitrile and a diene comprising elastomer, polychloroprene and copolymers including chloroprene, butyl rubber, halogenated butyl rubber, polysulfide rubber, or silicone comprising polymers.

28. The golf ball of claim 1, wherein the polymeric matrix is selected from a group consisting of polyethylene, polypropylene, acrylic and methacrylic polymers, polymethyl methacrylate, polystyrene, polyepoxides, any polymer comprising an epoxy moiety, phenol-formaldehydes, polyamides, polyesters, polyvinyl chlorides, polycarbonates, polyacetals, polytetrafluoroethylene, polyvinylidene fluoride, polyurethanes, copolymers of acrylic, copolymers of methacrylic, blends of acrylic polymer, blend of methacrylic polymer, one or more of partially or fully neutralized ionomers including those neutralized by a metal ion source wherein the metal ion is the salt of an organic acid, polybutylene, copolymers comprising one or more olefins such as ethylene, propylene or butylene, polyethylene acrylic acid copolymers, polyethylene methacrylic acid copolymers, terpolymers of ethylene, a softening acrylate class ester, and a carboxylic acid, polyethylene-methacrylic acid-n or iso-butyl acrylate and polyethylene-acrylic acid-methyl acrylate, polyethylene ethyl or methyl acrylate, polyethylene vinyl acetate, polyethylene glycidyl alkyl acrylates, metallocene catalyzed polyolefins, polyesters, polyamides, non-ionomeric thermoplastic elastomers, copolyether-esters, copolyether-amides, thermoplastic or thermosetting polyurethanes, polyureas, polyurethane ionomers, epoxies, polycarbonates, polybutadiene, polyisoprene, and blends thereof.

29. The golf ball of claim 26, wherein the encasing polymer is selected from a group consisting of polyethylene, polypropylene, acrylic and methacrylic polymers, polymethyl methacrylate, polystyrene, polyepoxides, any polymer comprising an epoxy moiety, phenol-formaldehydes, polyamides, polyesters, polyvinyl chlorides, polycarbonates, polyacetals, polytetrafluoroethylene, polyvinylidene fluoride, polyurethanes, copolymers of acrylic, copolymers of methacrylic, blends of acrylic polymer, blend of methacrylic polymer, one or more of partially or fully neutralized ionomers including those neutralized by a metal ion source wherein the metal ion is the salt of an organic acid, polybutylene, copolymers comprising one or more olefins such as ethylene, propylene or butylene, polyethylene acrylic acid copolymers, polyethylene methacrylic acid copolymers, terpolymers of ethylene, a softening acrylate class ester, and a carboxylic acid, polyethylene-methacrylic acid-n or iso-butyl acrylate and polyethylene-acrylic acid-methyl acrylate, polyethylene ethyl or methyl acrylate, polyethylene vinyl acetate, polyethylene glycidyl alkyl acrylates, metallocene catalyzed polyolefins, polyesters, polyamides, non-ionomeric thermoplastic elastomers, copolyether-esters, copolyether-amides, thermoplastic or thermosetting polyurethanes, polyureas, polyurethane ionomers, epoxies, polycarbonates, natural rubber, stryene-butadiene rubber, stryene-propylene or ethylene-diene block copolymer rubber, polyisoprene, polybutadiene, copolymers comprising ethylene or propylene, as ethylene-propylene rubber (EPR), ethylene-propylene diene monomer (EPDM) elastomer, copolymers of acrylonitrile and a diene comprising elastomer, polychloroprene and copolymers including chloroprene, butyl rubber, halogenated butyl rubber, polysulfide rubber, or silicone comprising polymers and blends thereof.

30. The golf ball of claim 1, wherein the exfoliated graphite comprises an exfoliated graphite-hydrogensulfate compound.

31. The golf ball of claim 1, wherein the exfoliated graphite is bonded to an auxiliary material.

32. The golf ball of claim 31, wherein the auxiliary material is selected from a group consisting of organic synthetic film, glass fibers, natural fibers, synthetic fibers, aramid fibers and carbon fibers.

33. The golf ball of claim 1, wherein said at least one layer is a water vapor barrier layer.

34. A golf ball comprising a plurality of layers including a water vapor barrier layer, wherein said water vapor barrier layer comprises a sheet of compressed exfoliated graphite.

35. The golf ball of claim 34, wherein the thickness of the sheet of compressed exfoliated graphite is between about 0.1 mil to about 600 mils.

36. The golf ball of claim 34, wherein the thickness of the sheet of compressed exfoliated graphite is between about 3 mils to about 600 mils.

37. The golf ball of claim 34, wherein the compressed exfoliated graphite includes a polymeric binder.

38. The golf ball of claim 37, wherein the polymeric binder is a thermosetting material.

39. The golf ball of claim 37, wherein the polymeric binder is a thermoplastic material.

40. The golf ball of claim 37, wherein the polymeric binder is selected from a group consisting of polyethylene, phenol-formaldehyde resin, epoxy resins, polyurethane, phenolic resin, natural rubber, stryene-butadiene rubber, stryene-propylene or ethylene-diene block copolymer rubber, polyisoprene, polybutadiene, copolymers comprising ethylene or propylene, as ethylene-propylene rubber (EPR), ethylene-propylene diene monomer (EPDM) elastomer, copolymers of acrylonitrile and a diene comprising elastomer, polychloroprene and copolymers including chloroprene, butyl rubber, halogenated butyl rubber, polysulfide rubber, or silicone comprising polymers.

41. The golf ball of claim 37, wherein the amount of polymeric binder is less than about 60% by weight of the compressed exfoliated graphite.

42. The golf ball of claim 41, wherein the amount of polymeric binder is less than about 35% by weight of the compressed exfoliated graphite.

43. The golf ball of claim 34, wherein the compressed exfoliated graphite includes high specific gravity fillers dispersed therein.

44. The golf ball of claim 43, wherein the specific gravity is greater than about 2.0.

45. The golf ball of claim 44, wherein the specific gravity is greater than about 5.0.

46. The golf ball of claim 45, wherein the specific gravity is greater than about 10.0.

47. The golf ball of claim 43, wherein the fillers comprise metal.

48. The golf ball of claim 47, wherein the fillers comprise tungsten.

49. The golf ball of claim 34, wherein the compressed exfoliated graphite includes an additive selected from a group consisting of metals, clays and polymers.

50. The golf ball of claim 34, wherein the sheet of compressed exfoliated graphite is coated with adhesive.

51. The golf ball of claim 34, wherein the compressed exfoliated graphite includes a binder.

52. The golf ball of claim 51, wherein the binder is selected from a group consisting of organic char materials, coal tar pitches, asphalts, phenol-formaldehyde, urea-formaldehyde, polyvinylidene chloride, polyacrylonitrile, sugars, saccharides, inorganic glass bonding agents, boric oxide, silica, phosphorous, pentoxide, germanium oxide, vanadium pentoxide, inorganic salts, beryllium fluoride, sulfates, chlorides and carbonates.