Fluffy, strong, solid elastic gels, articles and method of making same

• US 6,333,374 B1
• Filed: 10/20/1997
• Issued: 12/25/2001
• Est. Priority Date: 05/21/1990
• Status: Expired due to Term

• Current Assignee: Applied Elastomerics Incorporated
• Original Assignee: Applied Elastomerics Incorporated
• Inventors: Chen, John Y.
• Primary Examiner(s): Lilling, Herbert J.
• Application Number:
  US08/954,424
• Time in Patent Office: 1,527 Days
• Field of Search: 524/270, 524/474, 524/476, 524/490, 524/505, 525/95, 525/98
• US Class Current: 524/270
• CPC Class Codes: A61C 15/00 Devices for cleaning between the teeth
• CPC Class Codes: A61C 15/041 Dental floss chemical aspects A61Q11/00
• CPC Class Codes: A63H 1/32 Whirling or spinning discs driven by twisted cords
• CPC Class Codes: A63H 33/185 Aerial toy rotating automatically when descending under gravity
• 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

Abstract

Novel fluffy, solid, strong elastic gels exhibiting resistance to elastic deformation, capable of shape-memory recovery, being dimensionally stable and having a density of at least less than about 0.60 g/cm³, a gel rigidity of from about 20 to about 3,000 gram Bloom, and an elongation of at least 200% can be formed with or physically interlocked with selected material substrates to form composites including any sequential additions or permutations of said combinations of gels and substrates.

Claims

1. A gel comprising a fluffy, solid, strong elastic gelatinous elastomer composition, G_n, exhibiting resistance to elastic deformation, capable of shape-memory recovery, being dimensionally stable formed from (I) 100 parts by weight of at least one or more a linear, multi-arm, branched, or star shaped high viscosity block copolymer, (II) about 300 to about 1,600 parts by weight of a plasticizing oil, (III) a selected amount of one or more heat expandable plastic or synthetic particulates of material dispersed in one or more predetermined ordered or separate phases, said dispersed particulate material being capable of producing a predetermined selected volume of closed cell particulate dispersion forming said gel, wherein said gel having a density of at least about 0.70 g/cm³, a gel rigidity of from about 20 to about 3,000 gram Bloom, and an elongation of at least 200%, said gel capable of being formed with or physically interlocked with a selected substrate material, M_n, to form one or more combinations of a gel-substrate composites including a sequential addition or permutation of said combinations of one or more gels of the same or different gel rigidity and one or more substrates of the same or different material;

said gel formed with or without (IV) one or more of a selected polar polymer and in combination with or without (V) one or more of a selected crystalline or non-crystalline polymer or copolymer.

2. A gel according to claim 2 having a density of about 0.70 g/cm³, 0.65 g/cm³, 0.60 g/cm³, 0.55 g/cm³, 0.50 g/cm³, 0.45 g/cm³, 0.40 g/cm³, 0.35 g/cm³, 0.30 g/cm³, or 0.28 g/cm³.

3. A gel according to claim 2, wherein said G_n as denoted by the subscript n is the same or different gel or gel rigidity and M_n, as denoted by the subscript n is the same or different substrate selected from the group consisting of foam, plastic, fabric, metal, concrete, wood, glass, ceramics, synthetic resin, synthetic fibers or refractory materials.

4. A gel according to claim 3, wherein said G_n is formed with or physically interlocked with said material M_n to form a composite of the combination M_nG_n, G_nM_nG_n, M_nG_nM_n, M_nG_nG_n, M_nM_nG_n, M_nG_nG_nG_n, M_nM_nM_nG_n or one or more of the same or different sequential additions or one or more of the same or different permutations of said combination.

5. A gel according to claim 2, wherein said (I) block copolymer is poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-propylene-styrene), poly(styrene-ethylene-styrene), poly(styrene-butylene-styrene), poly(styrene-ethylene-ethylene/butylene-styrene), poly(styrene-ethylene-ethylene/propylene-styrene), poly(styrene-butylene-ethylene/propylene-styrene), poly(styrene-butylene-ethylene/butylene-styrene), poly(styrene-ethylene-ethylene/propylene-ethylene-styrene), poly(styrene-ethylene-ethylene/butylene-butylene-styrene), poly(styrene-butylene-ethylene/propylene-butylene-styrene), poly(styrene-butylene-ethylene/butylene-butylene-styrene), poly(styrene-ethylene-butylene-ethylene/butylene-styrene), poly(styrene-ethylene-butylene-ethylene/propylene-styrene), poly(styrene-ethylene-butylene-ethylene/propylene-styrene), poly(styrene-ethylene-ethylene/butylene-ethylene/propylene-styrene), poly(styrene-ethylene-ethylene/propylene-ethylene/butylene-styrene), poly(styrene-butylene-ethylene/butylene-ethylene/propylene-styrene), poly(styrene-butylene-ethylene/propylene-ethylene/butylene-styrene), poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-styrene), poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene-styrene), poly(styrene-ethylene/propylene-butylene-ethylene/propylene-styrene), poly(styrene-butylene-ethylene/butylene-butylene-ethylene/butylene-styrene), poly(styrene-butylene-ethylene/butylene-butylene-ethylene/propylene-styrene), poly(styrene-ethylene-ethylene/butylene-butylene-ethylene/propylene-styrene), poly(styrene-ethylene-ethylene/propylene-butylene-ethylene/butylene-styrene), poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene-styrene), poly(styrene-butylene-ethylene/propylene-butylene-ethylene/propylene-butylene-styrene), poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene-styrene), poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene/butylene-styrene), poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene-styrene), poly(styrene-ethylene-ethylene/propylene-ethylene/butylene-ethylene/propylene-ethylene/butylene-butylene-styrene), poly(styrene-ethylene-butylene)_n, poly(styrene-ethylene-propylene)_n, poly(styrene-ethylene)_n, poly(styrene-butylene)_n, poly(styrene-ethylene-ethylene/butylene)_n, poly(styrene-ethylene-ethylene/propylene)_n, poly(styrene-butylene-ethylene/propylene)_n, poly(styrene-butylene-ethylene/butylene)_n, poly(styrene-ethylene-ethylene/propylene-ethylene)_n, poly(styrene-ethylene-ethylene/butylene-butylene)_n, poly(styrene-butylene-ethylene/propylene-butylene)_n, poly(styrene-butylene-ethylene/butylene-butylene)_n, poly(styrene-ethylene-butylene-ethylene/butylene)_n, poly(styrene-ethylene-butylene-ethylene/propylene)_n, poly(styrene-ethylene/butylene-ethylene/propylene)_n, poly(styrene-ethylene-ethylene/butylene-ethylene/propylene)_n, poly(styrene-ethylene-ethylene/propylene-ethylene/butylene)_n, poly(styrene-butylene-ethylene/butylene-ethylene/propylene)_n, poly(styrene-butylene-ethylene/propylene-ethylene/butylene)_n, poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene)_n, poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene)_n, poly(styrene-ethylene/propylene-butylene-ethylene/propylene)_n, poly(styrene-butylene-ethylene/butylene-butylene-ethylene/butylene)_n, poly(styrene-butylene-ethylene/butylene-butylene-ethylene/propylene)_n, poly(styrene-ethylene-ethylene/butylene-butylene-ethylene/propylene)_n, poly(styrene-ethylene-ethylene/propylene-butylene-ethylene/butylene)_n, poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene)_n, poly(styrene-butylene-ethylene/propylene-butylene-ethylene/propylene-butylene)_n, poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene)_n, poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene/butylene)_n, poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene)_n, poly(styrene-ethylene-ethylene/propylene-ethylene/butylene-ethylene/propylene-ethylene/butylene-butylene)_n or a mixture thereof.

6. A gel according to claim 2, wherein said (IV) polar polymer is ethylene-butyl acrylate, ethylene-ethyl acrylate, ethylene-methyl acrylate, ethylene-vinyl acetate, ethylene-vinyl acrylate, ethylene-vinyl alcohol, acrylonitrile-styrene-acrylate, styrene-acrylonitrile, styrene-maleic anhydride, meleated poly(styrene-ethylene-propylene-styrene), meleated poly(styrene-ethylene-butylene-styrene) or a mixture thereof.

7. A gel according to claim 2, wherein said selected (V) crystalline or non-crystalline polymer or copolymer is poly(styrene-butadiene-styrene), poly(styrene-butadiene), poly(styrene-isoprene-styrene), poly(styrene-isoprene), poly(styrene-ethylene-propylene), low viscosity poly(styrene-ethylene-propylene-styrene), low viscosity poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-butylene), meleated poly(styrene-ethylene-butylene-styrene), high vinyl content poly(styrene-ethylene-butylene-styrene) poly(styrene-ethylene-propylene-styrene-ethylene-propylene), poly(ethylene-propylene), poly(styrene-butadiene)_n, poly(styrene-butadiene)n, poly(styrene-isoprene)_n, poly(styrene-isoprene)_n, poly(styrene-ethylene-propylene)_n, low viscosity poly(styrene-ethylene-propylene)_n, low viscosity poly(styrene-ethylene-butylene)_n, poly(styrene-ethylene-butylene)_n, meleated poly(styrene-ethylene-butylene)_n, high vinyl content poly(styrene-ethylene-butylene)_n, poly(styrene-ethylene-propylene-styrene-ethylene-propylene)_n, poly(ethylene-propylene)_n, polystyrene, polybutylene, poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, polyethylene, polypthalamide or polyurethane elastomer formed from one or more saturated hydrocarbon diols, wherein said selected block copolymer is a linear, branched, multiarm, or star shaped copolymer.

8. A gel according to claim 2, wherein said gel is a crystal gel formed from one or more (I) block copolymers having a selected amount of crystallinity sufficient to exhibit a melting endotherm of at least about 40°

C. as determined by DSC curve.

9. A gel according to claim 2, wherein said gel exhibits in differential scanning calorimeter (DSC) a melting endotherm of about 40°

C., 41°

C., 42°

C., 43°

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C., 79°

C., or 80°

C.

10. A gel according to claim 2, wherein said (I) copolymer of said gel is a thermoplastic polyurethane elastomer made with diisocyanates and chain extenders 2,2,4-trimethyl1,3-pentancdiol or 2-Butyl-2-ethyl-1,3-pentanediol and a saturated hydrocarbon diol, said polyurethane having one or more crystalline groups of about 22% to about 45% wy weight of said elastomer and capable of exhibiting a glass transition of at least about −

40°

C.

11. A gel according to claim 10, wherein said hydrocarbon diols is a hydroxyl terminated oligomer of poly(ethylene-butylene) or poly(ethylene-propylene).

12. A gel according to claim 2, wherein said gel is capable of exhibiting a full recovery delay time of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 40, 50, 60, 70, 80, 90, 100, 120 seconds after extension or deformation.

13. A gel according to claim 2, wherein said selected amount of particulates of material is a thermoplastic polymer of methacrylonitrile containing a hydrocarbon liquid, said particulates capable of being soften by heat thereby transforming said hydrocarbon liquid into a vapor state and expanding said particulates into a predetermined closed cell volume of expanded microspheres, said closed cell expanded microspheres being substantially dispersed to form said fluffy gelatinous elastomer composition.