Gelatinous elastomer and methods of making and using the same and articles made therefrom

• US 5,994,450 A
• Filed: 01/10/1997
• Issued: 11/30/1999
• Est. Priority Date: 07/01/1996
• Status: Expired due to Fees

• Current Assignee: Edizone LC (Edizone)
• Original Assignee: Lc Teksource
• Inventors: Pearce, Tony M.
• Primary Examiner(s): Warzel, Mark L.
• Application Number:
  US08/783,413
• Time in Patent Office: 1,054 Days
• Field of Search: 525/89, 525/95, 525/98, 525/92, 524/505
• US Class Current: 524/505
• CPC Class Codes: A43B 13/04 Plastics, rubber or vulcanised fibre
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 51/006 grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08L 53/025 modified

Abstract

The present invention relates to gelatinous elastomers, methods for making gelatinous elastomers, methods for using gelatinous elastomers, products made from gelatinous elastomers, and products which include gelatinous elastomers as a component or ingredient. More particular, the invention includes a gelatinous elastomer formed from a combination of a block copolymer of the general configuration A-B-A and a plasticizer. The preferred A-B-A copolymer of the invention is polystyrene-hydrogenated poly(isoprene+butadiene)-polystyrene and the preferred plasticizer is either mineral oil or a combination of mineral oil and resin. Various other components may be included in the preferred recipes according to the invention.

Claims

1. An elastomeric material having

a plasticizer and a triblock copolymer of the general configuration A-B-A;

wherein A is selected from the group consisting of monoalkenylarene polymers;

wherein B is a hydrogenated polymer including a plurality of isoprene monomers and a plurality of butadiene monomers;

wherein said isoprene monomers comprise at least about 30 weight percent of said hydrogenated polymer B;

wherein said butadiene monomer comprise at least about 30 weight percent of said hydrogenated polymer B;

wherein a mixture including about 20 weight percent of said triblock copolymer and about 80 weight percent toluene, the weight percentages based on the total weight of the mixture, at from about 25 degrees Celsius to about 30 degrees Celsius, does not form a solution;

wherein said plasticizer associates with said hydrogenated polymer B;

wherein said triblock copolymer has a measurable percent elongation at break;

wherein said plasticizer tends to increase the percent elongation at break of said triblock copolymer;

wherein said triblock copolymer has a rigidity measurable on the Gram Bloom scale; and

wherein said plasticizer tends to decrease the Gram Bloom rigidity of said triblock copolymer.

2. An elastomeric material as recited in claim 1, and further comprising a plurality of gas pockets.

3. An elastomeric material as recited in claim 2, wherein said gas pockets comprise at least about 40% of the material, by volume.

4. An elastomeric material as recited in claim 2, wherein said gas pockets comprise at least about 70% of the material, by volume.

5. An elastomeric material as recited in claim 1, and further comprising a plurality of hollow spherical objects embedded within the material and having a diameter of less than about 2000 microns.

6. An elastomeric material as recited in claim 5, wherein said spherical objects comprise at least about 30% of the material, by volume.

7. An elastomeric material as recited in claim 5, wherein said spherical objects comprise at least about 50% of the material, by volume.

8. An elastomeric material as recited in claim 1, and further comprising:

a plurality of gas pockets and

a plurality of microspheres;

wherein said gas pockets comprise at least about 20% of the material, by volume; and

wherein said microspheres comprise at least about 20% of the material, by volume.

9. An elastomeric material as recited in claim 1, wherein said plasticizer comprises a plurality of components;

wherein at least one of said components is a hydrocarbon resin; and

wherein at least one of said components is selected from the group consisting of naturally derived oils, synthetic oils, and liquid oligomers.

10. An elastomeric material as recited in claim 1, wherein said plasticizer increases said percent elongation at break of said triblock copolymer by at least about a factor of two.

11. An elastomeric material as recited in claim 1, wherein said plasticizer decreases said Gram Bloom rigidity of said triblock copolymer by at least about a factor of two.

12. An elastomeric material having

a plasticizer and

a triblock copolymer of the general configuration A-B-A;

wherein A is a hygrogenated polymer including ethylene/propylene and ethylene/butylene;

wherein the combined weights of said ethylene/propylene and said ethylene/butylene comprise more than about 50 weight percent of said hydrogenated polymer B;

wherein a mixture including about 20 weight percent of said triblock copolymer and about 80 weight percent toluene, the weight percentages base don the total weight of the mixture, at from about 25 degrees Celsius to about 30 degrees Celsius does not form a solution;

wherein said plasticizer associates with said hydrogenated polymer B;

wherein said triblock copolymer has a measurable percent elongation at break;

wherein said plasticizer tends to increase the percent elongation at break of said triblock copolymer;

wherein said triblock copolymer has a rigidity measurable on the Gram Bloom scale; and

wherein said plasticizer tends to decrease the Gram Bloom rigidity of said triblock copolymer.

13. An elastomeric material as recited in claim 12, and further comprising a plurality of gas pockets.

14. An elastomeric material as recited in claim 13, wherein said gas pockets comprise at least about 40% of the material, by volume.

15. An elastomeric material as recited in claim 13, wherein said gas pockets comprise at least about 70% of the material, by volume.

16. An elastomeric material as recited in claim 12, wherein said triblock copolymer has a molecular weight of at least about 300,000, as determined by gel permeation chromatography.

17. An elastomeric material as recited in claim 12, and further comprising a plurality of hollow spherical objects embedded within the material and having a diameter of less than about 2000 microns.

18. An elastomeric material as recited in claim 17, wherein said spherical objects comprise at least about 30% of the material, by volume.

19. An elastomeric material as recited in claim 17, wherein said spherical objects comprise at least about 50% of the material, by volume.

20. An elastomeric material as recited in claim 12, and further comprising:

a plurality of gas pockets and

a plurality of microspheres;

wherein said gas pockets comprise at least about 20% of the material, by volume; and

wherein said microsphers comprise at least about 20% of the material, by volume.

21. An elastomeric material as recited in claim 12, wherein said plasticizer comprises a plurality of components;

wherein at least one of said components is a hydrocarbon resin; and

wherein at least one of said components is selected from the group consisting of naturally derived oils, synthetic oils, and liquid oligomers.

22. An elastomeric material as recited in claim 12, wherein said plasticizer increases said percent elongation at break of said triblock copolymer by at least about a factor of two.

23. An elastomeric material as recited in claim 12, wherein said plasticizer decreases said Gram Bloom rigidity of said triblock copolymer by at least about a factor of two.

24. An elastomeric material having

a plasticizer and a triblock copolymer of the general configuration A-B-A;

wherein said triblock copolymer has a weight average molecular weight of at least about 300,000 or more;

wherein A is selected from the group consisting of monoalkenylarene polymers;

wherein B is a hydrogenated polymer including a plurality of ethylene/propylene monomers and a plurality of ethylene/butylene monomers;

wherein the combined weights of said ethylene/propylene monomers and said ethylene/butylene monomers comprise at least about 50 weight percent of said hydrogenated polymer B;

wherein said plasticizer associates with said hydrogenated polymer B;

wherein said triblock copolymer has a measurable percent elongation at break;

wherein said plasticizer tends to increase the percent elongation at break of said triblock copolymer;

wherein said triblock copolymer has a rigidity measurable on the Gram Bloom scale; and

wherein said plasticizer tends to decrease the Gram Bloom rigidity of said triblock copolymer.

25. An elastomeric material as recited in claim 24, and further comprising a plurality of gas pockets.

26. An elastomeric material as recited in claim 25, wherein said gas pockets comprise at least about 40% of the material, by volume.

27. An elastomeric material as recited in claim 25, wherein said gas pockets comprise at least about 70% of the material, by volume.

28. An elastomeric material as recited in claim 24, and further comprising a plurality of hollow spherical objects embedded within the material and having a diameter of less than about 2000 microns.

29. An elastomeric material as recited in claim 28, wherein said spherical objects comprise at least about 30% of the material, by volume.

30. An elastomeric material as recited in claim 28, wherein said spherical objects comprise at least about 50% of the material, by volume.

31. An elastomeric material as recited in claim 24, and further comprising:

a plurality of gas pockets and

a plurality of microspheres;

wherein said gas pockets comprise at least about 20% of the material, by volume; and

wherein said microsphers comprise at least about 20% of the material, by volume.

32. An elastomeric material as recited in claim 24, wherein said plasticizer comprises a plurality of components;

wherein at least one of said components is a hydrocarbon resin; and

wherein at least one of said components is selected from the group consisting of naturally derived oils, synthetic oils, and liquid oligomers.

33. An elastomeric material as recited in claim 24, wherein said plasticizer increases said percent elongation at break of said triblock copolymer by at least about a factor of two.

34. An elastomeric material as recited in claim 24, wherein said plasticizer decreases said Gram Bloom rigidity of said triblock copolymer by at least about a factor of two.

35. An elastomeric material as recited in claim 24, wherein a mixture including about 20 weight percent of said triblock copolymer and about 80 weight percent toluene, the weight percentages based on the total weight of the mixture, at from about 25°

C. to about 30°

C., has a solution viscosity of at least about 100,000 cps.

36. An elastomeric material as recited in claim 24, wherein a mixture including about 20 weight percent of said triblock copolymer and about 80 weight percent toluene, the weight percentages based on the total weight of the mixture, at from about 25°

C. to about 30°

C., does not form a solution.

37. A gelatinous elastomeric material comprising:

a plasticizer including a plurality of plasticizing polymer molecules,

an elastomer comprising a plurality of elastomeric triblock copolymers of the general configuration A-B-A, each of said triblock copolymers having;

two end blocks A and

one mid block B, and

a plurality of hollow spherical objects;

wherein each of said mid block B is covalently linked to one of said end blocks A;

wherein said end blocks A are non-elastomeric polymers;

wherein said mid block B is an elastomeric polymer,

wherein said mid block B of at least some of said triblock copolymers includes a plurality of backbone carbon molecules and a plurality of side chains;

wherein said elastomer has a weight average molecular weight of at least about 300,000 when determined by gel permeation chromatography;

wherein said plasticizing polymer molecules, upon placement of the material under a load, tend to facilitate disentanglement and elongation of said mid blocks B during elongation of the material;

wherein said plasticizing polymer molecules, upon release of the load from the material, tend to facilitate recontraction of the material;

wherein said plasticizing polymer molecules comprise at least about 60 weight percent of the material, based on the combined weights of said triblock copolymers and said plasticizing polymers;

wherein said elastomer has a measurable percent elongation at break;

wherein said plasticizer tends to increase the percent elongation at break of said elastomer;

wherein said elastomer has a rigidity measurable on the Gram Bloom scale, and

wherein said plasticizer tends to decrease the Gram Bloom rigidity of said elastomer.

38. A gelatinous elastomeric material as recited in claim 37

wherein said hollow spherical objects are elastic;

wherein said hollow spherical objects deform under a compression force; and

wherein said hollow spherical objects instantaneously rebound to substantially their original shape and size following cessation of a force which compresses said spherical objects to a thickness of from about 50% to less than about 100% of the original diameter of said spherical objects.

39. A gelatinous elastomeric material as recited in claim 37, wherein said plasticizer increases the percent elongation at break of said elastomer by at least about a factor of two.

40. A gelatinous elastomeric material as recited in claim 37, wherein said plasticizer decreases the Gram Bloom rigidity of said elastomer by at least about a factor of two.

41. A gelatinous elastomeric material comprising:

a triblock copolymer of the general configuration A-B-A;

a plasticizing agent; and

an additive;

wherein said triblock copolymer, said plasticizing agent, and said additive are mixed together to form the gelatinous elastomeric material;

wherein A is a polymer selected from the group consisting of monoalkenylarene polymers;

wherein B is a hydrogenated polymer comprising a plurality of covalently linked conjugated diene monomers;

wherein at least one of said conjugated diene monomers is isoprene;

wherein said triblock copolymer has a weight average molecular weight of about 300,000 or more;

wherein said plasticizer comprises at least about 60 weight percent of the material, based on the combined weights of said plasticizer and said triblock copolymer;

wherein said additive is selected from the group consitisting of detackifying layers, foaming facilitators, tack modifiers, plasticizer bleed modifiers, flame retardants, melt viscosity modifiers, melt temperature modifiers, tensile strength modifiers and shrinkage inhibitors;

wherein the gelatinous material has a rigidity measurable on the Gram Bloom scale;

wherein said plasticizer tends to reduce the Shore A rigidity of the gelatinous elastomeric material; and

wherein the gelatinous elastomeric material has a durometer of about 15 Shore A or lower.

42. A gelatinous elastomeric material as recited in claim 41, wherein the additive is a melt temperture modifier selected from the group consisting of diblock copolymers of the general configuration A-B, triblock copolymers of the general configuration A-B-A, cross-linking agents, and hydrocarbon resins;

wherein A is a polymer comprising functionalized styrene monomers.

43. A gelatinous elastomeric material as recited in claim 41, wherein the additive is a tack modifier selected from the group consisting of surfactants, dispersants, and emulsifiers.

44. A gelatinous elastomeric material as recited in claim 41, wherein the additive is a tack modifier selected from the group consisting of hydrocarbon resins, polyisobutylene, and butyl rubber.

45. A gelatinous elastomeric material as recited in claim 41, wherein the additive is a foam facilitator selected from the group consisting of polyisobutylene, butyl rubber, surfactants, emulsifiers and dispersants.

46. A gelatinous elastomeric material as recited in claim 41, wherein the additive is a plasticizer bleed modifier selected from the group consisting of hydrocarbon resins, elastomeric diblock copolymers, polyisobutylene, butyl rubber, and transpolyoctenylene rubber.

47. A gelatinous elastomeric material as recited in claim 41, wherein the additive is a plasticizer bleed modifier selected from the group consisting of hydrocarbon resins, elastomeric diblock copolymers, polyisobutylene, butyl rubber, and transpolyoctenylene rubber.

48. A gelatinous elastomeric material as recited in claim 41, wherein the additive is a flame retardant selected from the group consisting of halogenated flame retardants, non-halogenated flame retardants, and volatile, non-oxygen gas forming chemicals.

49. A gelatinous elastomeric material as recited in claim 41,

wherein said additive is a melt viscosity modifier selected from the group consisting of hydrocarbon resins, transpolyoctenylene rubber, castor oil, linseed oil, non-ultra high molecular weight thermoplastic rubbers, surfactants, dispersants, and emulsifiers;

and

wherein said additive reduces the melt viscosity of the gelatinous elastomeric material.

50. A gelatinous elastomeric material as recited in claim 41,

wherein said additive is a melt viscosity modifier selected from the group consisting of hydrocarbon resins, butyl rubber, polyisobutylene, additional triblock copolymers having the general configuration A-B-A, particulate fillers, microspheres, butadiene rubber, ethylene/propylene rubber, and ethylene/butylene rubber;

wherein the weight average molecular weight of said additional triblock copolymers is greater than the weight average molecular weight of said triblock copolymer; and

wherein said additive increases the melt viscosity of the gelatinous elastomeric material.

51. A gelatinous elastomeric material as recited in claim 41,

wherein said additive is a tensile strength modifier selected from the group consisting of mid block B associating hydrocarbon resins, non-end block A solvating hydrocarbon resins, and particulate reinforcers;

wherein said additive increases the tensile strength of the gelatinous elastomeric material.

52. A gelatinous elastomeric material as recited in claim 41, wherein said additive is a shrinkage reducer selected from the group consisting of hydrocarbon resins, particulate fillers, microspheres, and transpolyoctenylene rubber.

53. A gelatinous elastomeric material comprising:

a triblock copolymer of the general configuration A-B-A;

a plasticizing agent; and

an additive;

wherein said triblock copolymer, said plasticizing agent, and said additive are mixed together to form the gelatinous elastomeric material;

wherein A is a polymer selected from the group consisting of monoalkenylarene polymers;

wherein B is a hydrogenated polymer comprising a plurality of covalently linked conjugated diene monomers;

wherein said triblock copolymer is of the general configuration A-B-A and has a weight average molecular weight of at least about 300,000 or more;

wherein said triblock copolymer has a measurable solution viscosity at 5 weight percent solids in 95% toluene at 25 degrees Celsius and said triblock copolymer remains a solid at 20 weight percent solids in 80% toluene at 25 degrees Celsius;

wherein said plasticizer comprises at least about 60 weight percent of the material, based on the combined weights of said plasticizer and said triblock copolymer;

wherein said additive is selected from the group consisting of detackfying layers, foaming facilitators, tack modifiers, plasticizer bleed modifiers, flame retardants, melt viscosity modifiers, melt temperature modifiers, tensile strength modifiers, and shrinkage inhibitors;

wherein said gelatinous material has a rigidity measurable on the Gram Bloom scale;

wherein said plasticizer tends to reduce Shore A rigidity of the gelatinous elastomeric material; and

wherein the gelatinous elastomeric material has a durometer of about 15 Shore A or lower.

54. A gelatinous elastomeric material as recited in claim 53, wherein the additive is a melt temperture modifier selected from the group consisting of diblock copolymers of the general configuration A-B, triblock copolymers of the general configuration A-B-A, cross-linking agents, and hydrocarbon resins;

wherein A is a polymer comprising functionalized styrene monomers.

55. A gelatinous elastomeric material as recited in claim 53, wherein the additive is a tack modifier selected from the group consisting of surfactants, dispersants, and emulsifiers.

56. A gelatinous elastomeric material as recited in claim 53, wherein the additive is a tack modifier selected from the group consisting of hydrocarbon resins, polyisobutylene, and butyl rubber.

57. A gelatinous elastomeric material as recited in claim 53, wherein the additive is a foam facilitator selected from the group consisting of polyisobutylene, butyl rubber, surfactants, emulsifiers and dispersants.

58. A gelatinous elastomeric material as recited in claim 53, wherein the additive is a plasticizer bleed modifier selected from the group consisting of hydrocarbon resins, elastomeric diblock copolymers, polyisobutylene, butyl rubber, and transpolyoctenylene rubber.

59. A gelatinous elastomeric material as recited in claim 53, wherein the additive is a plasticizer bleed modifier selected from the group consisting of hydrocarbon resins, elastomeric diblock copolymers, polyisobutylene, butyl rubber, and transpolyoctenylene rubber.

60. A gelatinous elastomeric material as recited in claim 53, wherein the additive is a flame retardant selected from the group consisting of halogenated flame retardants, non-halogenated flame retardants, and volatile, non-oxygen gas forming chemicals.

61. A gelatinous elastomeric material as recited in claim 53,

wherein said additive is a melt viscosity modifier selected from the group consisting of hydrocarbon resins, transpolyoctenylene rubber, castor oil, linseed oil, non-ultra high molecular weight thermoplastic rubbers, surfactants, dispersants, and emulsifiers;

and

wherein said additive reduces the melt viscosity of the gelatinous elastomeric material.

62. A gelatinous elastomeric material as recited in claim 53,

wherein said additive is a melt viscosity modifier selected from the group consisting of hydrocarbon resins, butyl rubber, polyisobutylene, additional tri block copolymers having the general configuration A-B-A, particulate fillers, microspheres, butadiene rubber, ethylene/propylene rubber, and ethylene/butylene rubber;

wherein the weight average molecular weight of said additional triblock copolymers is greater than the weight average molecular weight of said triblock copolymer; and

wherein said additive increases the melt viscosity of the gelatinous elastomeric material.

63. A gelatinous elastomeric material as recited in claim 53,

wherein said additive is a tensile strength modifier selected from the group consisting of mid block B associating hydrocarbon resins, non-end block A solvating hydrocarbon resins, and particulate reinforcers;

wherein said additive increases the tensile strength of the gelatinous elastomeric material.

64. A gelatinous elastomeric material as recited in claim 53, wherein said additive is a shrinkage reducer selected from the group consisting of hydrocarbon resins, particulate fillers, microspheres, and transpolyoctenylene rubber.

65. An elastomeric material comprising:

a triblock copolymer elastomer of the configuration A-B-A and having a weight average molecular weight of about 300,000 or above, block A being a non-elastomeric polymer and block B being an elastomeric polymer, said A-B-A triblock copolymer having no solution viscosity at 20% solids in 80% toluene at 25 degrees Celcius as it remains a solid under those conditions, and

a plasticizer combined with said triblock copolymer elastomer to form a visco-elastic material, said plasticizer being compatible with said B block.

66. A material as recited in claim 65 wherein said A-B-A triblock copolymer has a solution viscosity of about 30040 to 5800 cps at 10% solids in 90% toluene at 25 degrees Celcius.

67. A material as recited in claim 65 wherein said "B" blocks of said A-B-A triblock copolymer have a plurality of side chains having a length of at least one carbon atom.

68. A material as recited in claim 67 wherein said side chains are found to typically occur on about one of every four backbone carbon atoms.

69. A material as recited in claim 67 wherein said elastomer and said plasticizer are found in a ratio of about 4:

1 to 20;

1.

70. A material as recited in claim 65 wherein said A-B-A triblock copolymer has a solution viscosity in the range of about 3040 to 5800 cps at 10% solids in 90% toluene at 25 degrees Celcius.

71. A material as recited in claim 65 wherein said A-B-A triblock copolymer has a solution viscosity of about 90 cps at 5% solids in 95% toluene at 25 degrees Celcius.