Low compression, resilient golf balls including aromatic catalyst and method for making same

• US 6,291,592 B1
• Filed: 12/10/1999
• Issued: 09/18/2001
• Est. Priority Date: 12/24/1998
• Status: Expired due to Term

• Current Assignee: Acushnet Company (FILA Holdings Corp.)
• Original Assignee: Acushnet Company (FILA Holdings Corp.)
• Inventors: Bulpett, David A., Dalton, Jeffrey L., Bissonnette, Laurent, Rajagopalan, Murali, Ladd, Derek, Wrigley, Mark N., Gosetti, Steven M.
• Primary Examiner(s): Buttner, David J.
• Application Number:
  US09/458,676
• Time in Patent Office: 648 Days
• Field of Search: 525/248, 525/260, 525/274, 473/354, 473/357, 473/371, 473/372, 473/373, 473/374, 473/377
• US Class Current: 525/248
• CPC Class Codes: A63B 37/0003 Golf balls
• CPC Class Codes: A63B 37/0021 Occupation ratio, i.e. percentage surface occupied by dimples
• CPC Class Codes: A63B 37/003 Coefficient of restitution
• CPC Class Codes: A63B 37/0031 Hardness
• CPC Class Codes: A63B 37/0034 Deflection or compression
• CPC Class Codes: A63B 37/0037 Flexural modulus; Bending stiffness
• CPC Class Codes: A63B 37/0039 characterised by the material
• CPC Class Codes: A63B 37/0074 Two piece balls, i.e. cover and core
• CPC Class Codes: A63B 37/0075 Three piece balls, i.e. cover, intermediate layer and core
• 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: A63B 37/0092 Hardness distribution amongst different ball layers
• CPC Class Codes: C08K 3/30 Sulfur-, selenium- or tellurium-containing compounds
• CPC Class Codes: C08L 9/00 Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Abstract

A low compression, resilient golf ball having a center and a cover, made from a polybutadiene reaction product having polybutadiene, a cis-to-trans catalyst including an aromatic component, and a free radical source. The reaction product typically has a first dynamic stiffness measured at −50° C. that is less than about 130 percent of a second dynamic stiffness measured at 0° C. A multi-layer golf ball having a center, at least one intermediate layer disposed concentrically about the center, and a cover. At least a portion of at least one of the center, intermediate layer, or both, are made from a reaction product including polybutadiene having a cis-to-trans catalyst that includes at least one aromatic component and a free radical source. In particular, the use of various combinations of polybutadiene, cis-to-trans catalyst including at least one aromatic component, free radical source, filler, and crosslinker, produces golf balls and golf ball components that are resilient (fast) and have low compression (soft).

Claims

1. A golf ball comprising a material formed from the conversion reaction of an amount of polybutadiene, a free radical source, and a cis-to-trans catalyst comprising at least one aromatic component which reaction occurs at a sufficient temperature to form a polybutadiene reaction product which comprises:

an amount of trans-polybutadiene greater than the amount of trans-polybutadiene present before the conversion reaction; and

a cis-to-trans catalyst comprising the at least one aromatic component, wherein the aromatic component comprises the formula (R₁)_x—

R₃—

M—

R₄—

(R₂)_y, wherein R₁ and R₂ are each hydrogen or a substituted or unsubstituted C_1-20 linear, branched, or cyclic alkyl, or alkoxy group, or a single, multiple, or fused ring C₆ to C₂₄ aromatic group;

x and y are each an integer from 0 to 5;

R₃ and R₄ are each selected from a single, multiple, or fused ring C₆ to C₂₄ aromatic group; and

M comprises at least one of an azo group or a metal component.

2. The golf ball of claim 1, wherein the golf ball comprises a cover having at least one of a dimple coverage of greater than about 60 percent, a hardness from about 35 to 80 Shore D, or a flexural modulus of greater than about 500 psi, and wherein the golf ball has at least one of a compression from about 50 to 120 or a coefficient of restitution of greater than about 0.7.

3. The golf ball of claim 1, wherein the reaction product has a first dynamic stiffness measured at −

50°

C. that is less than about 130 percent of a second dynamic stiffness measured at 0°

C.

4. The golf ball of claim 1, wherein the reaction product comprises a portion of a golf ball core which has a midpoint having a first amount of trans-polybutadiene and a surface having a second amount of trans-polybutadiene, wherein the first amount is at least about 6 percent less than the second amount.

5. The golf ball of claim 1, wherein M comprises at least one of tellurium or selenium.

6. The golf ball of claim 1, wherein R₃ and R₄ are each selected from a C₆ to C₁₀ aromatic group and R₁ and R₂ are each selected from a substituted or unsubstituted C_1-10 linear, branched, or cyclic alkyl, or alkoxy group or a C₆ to C₁₀ aromatic group.

7. The golf ball of claim 6, wherein the cis-to-trans catalyst is present in an amount from about 0.1 to 25 parts per hundred of polybutadiene.

8. The golf ball of claim 7, wherein the cis-to-trans catalyst is present in an amount from about 0.1 to 12 parts per hundred of polybutadiene.

9. The golf ball of claim 1, wherein the cis-to-trans catalyst further comprises at least one of an inorganic sulfur compound, an organosulfur compound, an aromatic organometallic compound, a metal-organosulfur compound, a Group VIA component, or an aromatic organic compound.

10. The golf ball of claim 1, wherein the polybutadiene reaction product comprises less than about 7 percent vinyl isomer content based on the total polybutadiene.

11. The golf ball of claim 10, wherein the polybutadiene reaction product comprises less than about 4 percent vinyl isomer.

12. The golf ball of claim 11, wherein the polybutadiene reaction product comprises less than about 2 percent vinyl isomer.

13. The golf ball of claim 9, further comprising a vulcanization accelerator.

14. The golf ball of claim 13, wherein the vulcanization accelerator comprises at least one of sulfenamide, thiazole, dithiocarbamate, thiuram, xanthate, thiadiazine, thiourea, guanadine, or aldehyde-amine.

15. The golf ball of claim 13, wherein the accelerator is present in an amount from about 0.05 phr to 2 phr.

16. The golf ball of claim 15, wherein the accelerator is present in an amount from about 0.1 phr to 1 phr.

17. The golf ball of claim 1, wherein the golf ball comprises a one-piece golf ball.

18. The golf ball of claim 1, wherein the golf ball comprises a core and a over disposed concentrically about the core and the reaction product is disposed in at least a portion of the core.

19. The golf ball of claim 1, wherein the golf ball comprises:

a core comprising a center and at least one intermediate layer; and

a cover disposed concentrically about the core, wherein the reaction product is disposed in a portion of the core.

20. The golf ball of claim 19, wherein the portion of the core having the reaction product is the center.

21. The golf ball of claim 19, wherein a portion of the center comprises a fluid.

22. The golf ball of claim 19 wherein the at least one intermediate layer comprises a wound layer of tensioned elastomeric material.

23. The golf ball of claim 22, wherein the tensioned elastomeric material comprises the reaction product.

24. The golf ball of claim 1, further comprising a density-modifying filler.

25. A method for forming a golf ball which comprises:

combining (a) a cis-to-trans catalyst comprising at least one aromatic component having the formula (R₁)_x—

R₃—

M—

R₄—

(R₂)_y;

(b) a free radical source; and

(c) a first resilient polymer component comprising a cis-polybutadiene component present in an amount greater than about 70 percent of the total polymer component;

converting a portion of the first resilient polymer component to a second resilient polymer component in about 5 to 18 minutes at a sufficient temperature to convert at least a portion of the cis-polybutadiene component to a trans-polybutadiene component and wherein the polybutadiene in the second resilient polymer component is at least about 10 percent trans-polybutadiene and less than about 7 percent vinyl-polybutadiene; and

forming the second resilient polymer component into at least a portion of the golf ball, wherein R₁ and R₂ are each hydrogen or a substituted or unsubstituted C_1-20 linear, branched, or cyclic alkyl, or alkoxy group, or a single, multiple, or fused ring C₆ to C₂₄ aromatic group;

x and y are each an integer from 0 to 5;

R₃ and R₄ are each selected from a single, multiple, or fused ring C₆ to C₂₄ aromatic group; and

M includes an azo group or a metal component.

26. The method of claim 25, wherein the portion of the second resilient polymer component is formed into a solid sphere.

27. The method of claim 26, which further comprises forming at least one layer over the solid sphere.

28. The method of claim 25, which further comprises forming the portion of the second resilient polymer component into at least one layer disposed concentrically about a sphere.

29. The method of claim 25, which further comprises forming the portion of the second resilient polymer component into a cover disposed concentrically about a sphere.

30. The method of claim 25, wherein the polybutadiene component comprises a cis-polybutadiene present in an amount of at least about 80 percent of the total first resilient polymer component.

31. The method of claim 25, wherein the combining further comprises a density-modifying filler.

32. The method of claim 25, wherein the forming comprises forming a sphere having a midpoint having a first amount of trans-polybutadiene and a surface having a second amount of trans-polybutadiene, wherein the first amount is at least about 6 percent less than the second amount.

33. The method of claim 25, wherein the second amount of trans-polybutadiene component is selected to comprise a vinyl polybutadiene component present in an amount of less than about 4 percent of the total resilient polymer component.

34. The method of claim 25, wherein R₃ and R₄ are each selected from a C₆ to C₁₀ aromatic group and R₁ and R₂ are each selected from a substituted or unsubstituted C_1-10 linear, branched, or cyclic alkyl, or alkoxy group or a C₆ to C₁₀ aromatic group.

35. The method of claim 25, wherein M comprises at least one of tellurium or selenium.

36. The method of claim 25, wherein the cis-to-trans catalyst is present in an amount from about 0.1 to 25 parts per hundred of the total resilient polymer component.

37. The method of claim 36, wherein the cis-to-trans catalyst is present in an amount from about 0.1 to 12 parts per hundred of the total resilient polymer component.

38. The method of claim 37, wherein the cis-to-trans catalyst is present in an amount from about 0.1 to 8 parts per hundred of the total resilient polymer component.

39. The method of claim 25, wherein the cis-to-trans catalyst is selected to further comprise at least one of an inorganic sulfide, organosulfur compound, an aromatic organometallic compound, a metal-organosulfur compound, a Group VIA component, or an aromatic organic compound.

40. The method of claim 39, which further comprises providing an accelerator in an amount sufficient to facilitate cis-to-trans conversion.

41. The method of claim 40, wherein the accelerator is selected to comprise at least one of sulfenamide, thiazole, dithiocarbamate, thiuram, xanthate, thiadiazine, thiourea, guanadine, or aldehyde-amine.

42. The method of claim 40, wherein the accelerator is provided in an amount from about 0.05 to 2 phr of the total resilient polymer component.

43. The method of claim 42, wherein the accelerator is provided in an amount from about 0.1 to 1 phr of the total resilient polymer component.

44. The method of claim 28 wherein a portion of the sphere comprises a fluid.

45. The method of claim 28 wherein a tensioned elastomeric material is wound about the sphere.

46. The method of claim 45, wherein the tensioned elastomeric material comprises the reaction product.

47. The method of claim 25, wherein the forming comprises:

a single-step compression molding of the first resilient polymer component to convert the first resilient polymer component to the second resilient polymer in about 8 to 15 minutes; and

forming the second resilient polymer component into a solid sphere.

48. The method of claim 47, wherein the converting and forming are substantially simultaneous.

49. A golf ball prepared by a process which comprises:

combining (a) at least one of a cis-to-trans catalyst comprising at least one aromatic component having the formula (R₁)_x—

R₃—

M—

R₄—

(R₂)_y;

(b) a free radical source; and

(c) a first resilient polymer component comprising a cis-polybutadiene component present in an amount greater than about 70 percent of the resilient polymer component;

converting a portion of the first resilient polymer component to a second resilient polymer component in about 5 to 18 minutes, wherein at least a portion of the cis-isomer content is converted to a trans-isomer content and wherein the polybutadiene in the second resilient polymer component is at least about 10 percent trans-polybutadiene and less than about 7 percent vinyl-polybutadiene; and

forming the second resilient polymer component into at least a portion of the golf ball, wherein R₁ and R₂ are each hydrogen or a substituted or unsubstituted C_1-20 linear, branched, or cyclic alkyl, or alkoxy group, or a single, multiple, or fused ring C₆ to C₂₄ aromatic group;

x and y are each an integer from 0 to 5;

R₃ and R₄ are each selected from a single, multiple, or fused ring C₆ to C₂₄ aromatic group; and

M includes an azo group or a metal component.

50. A golf ball comprising a material formed from the conversion reaction of a sufficient amount of polybutadiene, a free radical source, and a cis-to-trans catalyst comprising at least one aromatic component having the formula (R₁)_x—

R₃—

M—

R₄—

(R₂)_y, which reaction occurs at a sufficient temperature to form a polybutadiene reaction product which comprises;

an amount of trans-polybutadiene greater than the amount of trans-polybutadiene present before the conversion reaction; and

a cis-to-trans catalyst comprising the at least one aromatic component, wherein the reaction product comprises a sphere which has a midpoint having a first hardness and a surface having a second hardness such that the second hardness differs from the first hardness by greater than 10 percent of the first hardness and wherein R₁ and R₂ are hydrogen or a substituted or unsubstituted C_1-20 linear, branched, or cyclic alkyl, or alkoxy, group, or a single, multiple, or fused ring C₆ to C₂₄ aromatic group;

x and y are each an integer from 0 to 5;

R₃ and R₄ are each selected from a single, multiple, or fused ring C₆ to C₂₄ aromatic group; and

M includes an azo group or a metal component.

51. A method for forming a golf ball which comprises:

combining (a) a cis-to-trans catalyst comprising at least one aromatic component having the formula (R₁)_x—

R₃—

M—

R₄—

(R₂)_y;

(b) a free radical source; and

(c) a first resilient polymer component comprising a cis-polybutadiene component present in an amount greater than about 70 percent of the total polymer component;

converting a portion of the first resilient polymer component to a second resilient polymer component in about 5 to 18 minutes at a sufficient temperature to convert at least a portion of the cis-polybutadiene component to a trans-polybutadiene component and wherein the polybutadiene in the second resilient polymer component is at least about 10 percent trans-polybutadiene and less than about 7 percent vinyl-polybutadiene; and

forming the second resilient polymer component into at least a portion of the golf ball, wherein the second resilient component comprises a sphere which has a midpoint having a first hardness and a surface having a second hardness such that the second hardness differs from the first hardness by greater than 10 percent of the first hardness and wherein R₁ and R₂ arc each hydrogen or a substituted or unsubstituted C_1-20 linear, branched, or cyclic alkyl, or alkoxy group, or a single, multiple, or fused ring C₆ to C₂₄ aromatic group;

x and y are each an integer from 0 to 5;

R₃ and R₄ are each selected from a single, multiple, or fused ring C₆ to C₂₄, aromatic group; and

M includes an azo group or a metal component.

52. A method for forming a golf ball which comprises:

combining (a) a cis-to-trans catalyst comprising at least one aromatic component having the formula (R₁)_x—

R₃—

M—

R₄—

(R₂)_y;

(b) a free radical source; and

(c) a first resilient polymer component comprising a cis-polybutadiene component present in an amount greater than about 70 percent of the total polymer component;

converting a portion of the first resilient polymer component to a second resilient polymer component in about 5 to 18 minutes at a sufficient temperature to convert at least a portion of the cis-polybutadiene component to a trans-polybutadiene component and wherein the polybutadiene in the second resilient polymer component is at least about 10 percent trans-polybutadiene and less than about 7 percent vinyl-polybutadiene; and

forming the second resilient polymer component into at least a portion of the golf ball, wherein the second resilient component has a first dynamic stiffness measured at −

50°

C. that is less than about 130 percent of a second dynamic stiffness measured at 0°

C., wherein R₁ and R₂ are each hydrogen or a substituted or unsubstituted C_1-20 linear, branched, or cyclic alkyl, or alkoxy group, or a single, multiple, or fused ring C₆ to C₂₄ aromatic group;

x and y are each an integer from 0 to 5;

R₃ and R₄ are each selected from a single, multiple, or fused ring C₆ to C₂₄ aromatic group; and

M includes an azo group or a metal component.