Thermoplastic elastomer gelatinous compositions

• US 4,369,284 A
• Filed: 03/28/1980
• Issued: 01/18/1983
• Est. Priority Date: 03/17/1977
• Status: Expired due to Term

• Current Assignee: Applied Elastomerics Incorporated
• Original Assignee: Applied Elastomerics Incorporated
• Inventors: Chen, John Y.
• Primary Examiner(s): Marquis, Melvyn I.
• Assistant Examiner(s): Lilling, Herbert J.
• Application Number:
  US06/134,977
• Time in Patent Office: 1,026 Days
• Field of Search: 260/33.6 R, 260/33.6 VA, 260/33.6 AQ, 525/95, 524/476, 524/490, 524/495
• US Class Current: 524/476
• CPC Class Codes: A61C 15/041 Dental floss chemical aspects A61Q11/00
• CPC Class Codes: C08K 5/01 Hydrocarbons C08K5/0091 takes precedence
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C08L 51/00 Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds for ABS polymers C08L55/02; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 53/02 of vinyl-aromatic monomers and conjugated dienes
• CPC Class Codes: C08L 53/025 modified
• CPC Class Codes: C08L 91/00 Compositions of oils, fats or waxes; Compositions of derivatives thereof

Abstract

A novel gelatinous composition is disclosed which contains an intimate melt blend admixture of poly(styrene-ethylene-butylene-styrene) triblock copolymer having said styrene end block to ethylene and butylene center block ratio within the range of from between 31:69 to 40:60, and high levels of an plasticizing oil.

The gelatinous composition is transparent and have a novel combination of properties including unexpectedly high elongation and tensile strength and excellent shape retention after extreme deformation under high-velocity impact and stress conditions. The gelatinous products of this invention are soft, flexible, and have elastic memory, characterized by a gel rigidity of from about 20 gram to about 700 gram Bloom. These and other properties are particularly essential for the gelatinous composition to have utility as toys, therapeutic hand exercising grips, shock absorbers, acoustical isolators, and other uses.

Claims

1. A gelatinous elastomer composition consisting essentially of:

(a) 100 parts by weight of a triblock copolymer of the general configuration poly(styrene-ethylene-butylene-styrene) wherein said styrene end block to ethylene and butylene center block ratio is within the range of from between 31;

69 to 40;

60;

(b) from about 300 to about 1,600 parts by weight of an plasticizing oil selected from the group consisting of petroleum paraffinic oils, petroleum naphthenic oils, synthetic polybutene oils, synthetic polypropene oils, synthetic polyterpene oils and mixtures thereof;

said oils having an average molecular weight of between about 200 to about 700; and

(c) said gelatinous elastomer composition being characterized as having an elongation at break of at least about 1,600%, an ultimate tensile strength of at least about 8×

10⁵ dyne/cm², and a gel rigidity of substantially not greater than about 700 gram Bloom.

2. A gelatinous elastomer composition as claimed in claim 1 wherein the melt blended composition exhibit at least seven measurable properties:

(a) tensil strength of about 8×

10⁵ dyne/cm² to about 10⁷ dyne/cm² as measured with crosshead separation speed of 25 cm per minute at 23°

C.;

(b) elongation of about 1,600% to about 3,000% as measured with crosshead separation speed of 25 cm per minute at 23°

C.;

(c) elasticity modulus of about 10⁴ dyne/cm² to about 10⁶ dyne/cm² as measured with crosshead separation speed of 25 cm per minute at 23°

C.;

(d) shear modulus of about 10⁴ dyne/cm² to about 10⁶ dyne/cm² as measured with a 1, 2, and 3 kilogram load at 23°

C.;

(e) gel rigidity of about 20 gram Bloom to about 700 gram Bloom as measured by the gram weight required to depress a gel a distance of 4 mm with a piston having a cross-sectional area of 1 square cm at 23°

C.;

(f) tear propagation resistance of at least 5×

10⁵ dyne/cm² as measured at a crosshead separation speed of 25 cm/minute at 23°

C.;

(g) and substantially 100% snap back recovery when extended at a crosshead separation speed of 25 cm/minute to 1,200% at 23°

C.

3. A gelatinous elastomer composition as claimed in claim 2 wherein said styrene end block to ethylene and butylene center block ratio is about 32:

68 to about 38;

62.

4. A gelatinous elastomer composition as claimed in claim 2 wherein said styrene end block to ethylene and butylene center block ratio is about 32:

68 to about 36.64.

5. A gelatinous elastomer composition as claimed in claim 2 wherein said styrene end block to ethylene and butylene center block ratio is about 32:

68 to about 34;

66.

6. A gelatinous elastomer composition as claimed in claim 2 wherein said styrene end block to ethylene and butylene center block ratio is about 33:

67 to about 36;

64.

7. A moulded gelatinous elastomer article wherein the article is a composition according to claim 1, 2, 3, 4, 5, or 6.

8. A gelatinous elastomer composition as claimed in claim 2 wherein said styrene end block to ethylene and butylene center block ratio is about 33:

67.

9. A moulded gelatinous elastomer article wherein the article is a composition according to claim 8.

10. A gelatinous elastomer composition consisting essentially of:

(a) 100 parts by weight of a triblock copolymer of the general configuration poly(styrene-ethylene-butylene-styrene) wherein said styrene end block to ethylene and butylene center block ratio is about 32;

68 to about 38;

62;

(b) from about 300 to about 1,600 parts by weight of an plasticizing oil selected from the group consisting of petroleum paraffinic oils, petroleum naphthenic oils, synthetic polybutene oils, synthetic polypropene oils, synthetic polyterpene oils and mixtures thereof;

said oils having an average molecular weight of between about 200 to about 700; and

(c) said gelatinous elastomer composition being characterized as having an elongation at break of at least about 1,600%, an ultimate tensile strength of at least about 8×

10⁵ dyne/cm², and a gel rigidity of substantially not greater than about 700 gram Bloom.

11. A moulded gelatinous elastomer article wherein the article is a composition according to claim 10.

12. A gelatinous elastomer composition consisting essentially of:

(a) 100 parts by weight of a triblock copolymer of the general configuration poly(styrene-ethylene-butylene-styrene) wherein said styrene end block to ethylene and butylene center block ratio is about 32;

68 to about 36;

64;

(b) from about 300 to about 1,600 parts by weight of an plasticizing oil selected from the group consisting of petroleum paraffinic oils, petroleum naphthenic oils, synthetic polybutene oils, synthetic polypropene oils, synthetic polyterpene oils and mixtures thereof;

said oils having an average molecular weight of between about 200 to about 700; and

(c) said gelatinous elastomer composition being characterized as having an elongation at break of at least about 1,600%, an ultimate tensile strength of at least about 8×

10⁵ dyne/cm², and a gel rigidity of substantially not greater than about 700 gram Bloom.

13. A moulded gelatinous elastomer article wherein the article is a composition according to claim 12.

14. A gelatinous elastomer composition consisting essentially of:

(a) 100 parts by weight of a triblock copolymer of the general configuration poly(styrene-ethylene-butylene-styrene) wherein said styrene end block to ethylene and butylene center block ratio is about 32;

68 to about 34;

66;

(b) from about 300 to about 1,600 parts by weight of an plasticizing oil selected from the group consisting of petroleum paraffinic oils, petroleum naphthenic oils, synthetic polybutene oils, synthetic polypropene oils, synthetic polyterpene oils and mixtures thereof;

said oils having an average molecular weight of between about 200 to about 700; and

(c) said gelatinous elastomer composition being characterized as having an elongation at break of at least about 1,600%, an ultimate tensile strength of at least about 8×

10⁵ dyne/cm², and a gel rigidity of substantially not greater than about 700 gram Bloom.

15. A moulded gelatinous elastomer article wherein the article is a composition according to claim 14.

16. A gelatinous elastomer composition consisting essentially of:

(A) 100 parts by weight of a triblock copolymer of the general configuration poly(styrene-ethylene-butylene-styrene) wherein said styrene end block to ethylene and butylene center block ratio is about 33;

67 to about 36;

64;

(B) from about 300 to about 1,600 parts by weight of an plasticizing oil selected from the group consisting of petroleum paraffinic oils, petroleum naphthenic oil, synthetic polybutene oils, synthetic polypropene oils, synthetic polyterpene oils and mixtures thereof;

said oils having an average molecular weight of between about 200 to about 700.

17. A moulded gelatinous elastomer article wherein the article is a composition according to claim 16.

18. A gelatinous elastomer composition consisting essentially of:

(A) 100 parts by weight of a triblock copolymer of the general configuration poly(styrene-ethylene-butylene-styrene) wherein said styrene end block to ethylene and butylene center block ratio is about 33;

67;

(B) from about 300 to about 1,600 parts by weight of an plasticizing oil selected from the group consisting of petroleum paraffinic oils, petroleum naphthenic oils, synthetic polybutene oils, synthetic polypropene oils, synthetic polyterpene oils and mixtures thereof;

said oils having an average molecular weight of between about 200 to about 700.

19. A moulded gelatinous elastomer article wherein the article is a composition according to claim 18.