Elastic-crystal gel

• US 6,117,176 A
• Filed: 05/27/1997
• Issued: 09/12/2000
• Est. Priority Date: 11/15/1993
• 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:
  US08/863,794
• Time in Patent Office: 1,204 Days
• Field of Search: 524/270, 524/474, 524/476, 524/490, 524/505, 428/319.3, 428/319.7, 428/319.9, 428/328, 428/441, 428/462, 428/521, 428/537.1, 428/688, 623/11, 623/36, 623/37, 623/8, 623/18, 623/20, 623/33
• US Class Current: 623/36
• 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
• CPC Class Codes: Y10T 428/249991 Synthetic resin or natural rubbers
• CPC Class Codes: Y10T 428/249992 Linear or thermoplastic
• CPC Class Codes: Y10T 428/249993 Hydrocarbon polymer
• CPC Class Codes: Y10T 428/2938 Coating on discrete and individual rods, strands or filaments
• CPC Class Codes: Y10T 428/31645 Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31696 Including polyene monomers [e.g., butadiene, etc.]
• CPC Class Codes: Y10T 428/31931 Polyene monomer-containing
• CPC Class Codes: Y10T 428/31989 Of wood

Abstract

Novel crystal gels and articles are formed from one or more block copolymers having at least one crystalline midblock and high levels of a plasticizer, said midblock segment having an amount of crystallinity sufficient to achieve improvements in one or more physical properties including improved crack propagation resistance, improved tear resistance, improved resistance to fatigue and resistance to catastrophic failure not obtainable in amorphous gels.

Claims

1. An improved gelatinous composition comprising:

a crystal gel formed from (I) 100 parts by weight of one or more linear, branched, star-shaped (radial), or multiarm block copolymers or mixtures of two or more such block copolymers, said block copolymers having one or more midblocks, said midblocks comprising one or more substantially crystalline polyethylene midblocks and with one or more or without amorphous midblocks;

optionally in combination with a selected amount of one or more of a (II) polymer or copolymer, and selected amounts of a plasticizing oil (III) sufficient to achieve gel rigidities of from less than about 2 gram Bloom to about 1,800 gram Bloom with the proviso that said block copolymers without amorphous midblocks are combined with at least one block copolymer having at least one amorphous midblock, wherein said block midblocks of copolymers forming said crystal gel having a selected amount of crystallinity sufficient to exhibit a melting endotherm of at least about 40°

C. as determined by DSC curve.

3. A gel according to claim 1 or 2, wherein said midblock copolymer segment having a crystallinity of at least about 20 mole % of (--CH₂ --)16 units forming said midblock of the block copolymer.

4. A gel according to claim 1 or 2, wherein said gel exhibits in differential scanning calorimeter (DCS) a melting endotherm of about 28°

C., 29°

C., 30°

C., 31°

C., 32°

C., 33°

C., 34°

C., 35°

C., 36°

C., 37°

C., 38°

C., 39°

C., 40°

C., 41°

C., 42°

C., 43°

C., 44°

C., 45°

C., 46°

C., 47°

C., 48°

C., 49°

C., 50°

C., 51°

C., 52°

C., 53°

C., 54°

C., 55°

C., 56°

C., 57°

C., 58°

C., 59°

C., 60°

C., 61°

C., 62°

C., 63°

C., 64°

C., 65°

C., 66°

C., 67°

C., 68°

C., 69°

C., 70°

C., 71°

C., 72°

C., 73°

C., 74°

C., 75°

C., 76°

C., 77°

C., 78°

C., 79°

C., 80°

C., 90°

C., 100°

C., 110°

C., or 120°

C.

5. A. A gel according to claim 1 or 2, wherein said (I) block copolymer is formed in combination with a selected amount of one or more selected polymer or copolymer selected from the group consisting of poly(styrene-butadiene-styrene), poly(styrene-butadiene), poly(styrene-isoprene-styrene), poly(styrene-isoprene), poly(styrene-ethylene-propylene), poly(styrene-ethylene-propylene-styrene), poly(styrene-ethylene-butylene-styrene), poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)n, poly(styrene-ethylene-butylene)n, maleated poly(styrene-ethylene-propylene-styrene), maleated poly(styrene-ethylene-butylene-styrene), maleated poly(styrene-ethylene-butylene), maleated poly(styrene-ethylene-propylene)n, maleated poly(styrene-ethylene-butylene)n, polystyrene, polybutylene, poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, polyethylene, polyethyleneoxide , poly(dimethylphenylene oxide), copolymers of trifluoromethyl-4,5-difuoro-1,3-dioxole and tetrafluoroethylene, tetrafluoroethylene, polycarbonate, ethylene vinyl alcohol copolymer, polyamide or polydimethylsiloxane;

wherein said selected copolymer is a linear, branched, radial, or multiarm copolymer.

6. A gel according to claim 1 or 2, wherein said gel is being denoted by G, is physically interlocked with a selected material M forming a composite of the combination G_n M_n, G_n M_n G_n, M_n G_n M_n, M_n G_n G_n M_n, G_n M_n M_n G_n, G_n M_n G_n M_n G_n, M_n M_n M_n G_n, M_n M_n M_n G_n M_n M_n M_n or a permutation of one or more of said G_n with M_n ;

wherein when n is a subscript of M, n is the same or different selected from the group consisting of paper, foam, plastic, fabric, metal, metal foil, concrete, wood, glass, glass fibers, ceramics, synthetic resin, synthetic fibers or refractory materials; and

wherein when n is a subscript of G, n denotes the same or a different gel rigidity.

7. A gel according to claim 1 or 2, wherein said gel being formed into a gel hand exercising grip, a gel shape floss suitable for use as a dental floss, a gel crutch cushion, a gel cervical pillow, a gel bed wedge pillow, a gel leg rest, a gel neck cushion, a gel mattress, a gel bed pad, a gel elbow pad, a gel dermal pad, a gel wheelchair cushion, a gel helmet liner, a gel cold and hot pack, a gel exercise weight belt, a gel traction pad or belt, a gel cushion for splints, a gel sling, a gel brace for the hand, wrist, finger, forearm, knee, leg, clavicle, shoulder, foot, ankle, neck, back, rib, a gel sole for orthopedic shoe, a gel shaped toy article, a gel optical cladding for cushioning optical fibers from bending stresses, a gel swab tip, a gel fishing bate, a gel seal against pressure, a gel thread, a gel strip, a gel yarn, a gel tape, a weaved gel cloth, a gel fabrics, a gel balloon for valvuloplasty of the mitral valve, a gel trointestinal balloon dilator, a gel esophageal balloon dilator, a gel dilating balloon catheter use in coronary angiogram, a gel condom, a gel toy balloon, a gel surgical and examination glove, a self sealing enclosures for splicing electrical and telephone cables and wires, a gel film, or a gel liner.

8. A gel according to claim 1 or 2, wherein said gel is being denoted by G, is physically interlocked with a selected material M forming a composite of the combination G_n G_n, G_n G_n G_n, M_n G_n G_n, M_n M_n M_n G_n M_n, G_n M_n G_n G_n, G_n GM_n M_n, G_n G_n M_n G_n M_n G_n G_n, G_n M_n G_n, M_n G_n M_n G_n M_n G_n, G_n G_n M_n M_n G_n, G_n G_n M_n G_n M_n G_n or a permutation of one or more of said G_n with M_n ;

wherein when n is a subscript of M, n is the same or different selected from the group consisting of paper, foam, plastic, fabric, metal, metal foil, concrete, wood, glass, glass fibers, ceramics, synthetic resin, synthetic fibers or refractory materials; and

wherein when n is a subscript of G, n denotes the same or a different gel rigidity.

9. A composite of claim 6 shaped in the form of a gel liner for lower limb or above the knee amputee prosthesis formed by injection molding, extruding, spinning, casting, or dipping of said gel in combination with M selected from foam, plastic, fabric, metal, ceramics, synthetic resin, synthetic fibers or refractory materials.

10. A composite of claim 8 shaped in the form of a gel liner for lower limb above the knee amputee prosthesis formed by injection molding, extruding, spinning, casting, or dipping of said gel in combination with or without M selected from foam, plastic, fabric, metal, ceramics, synthetic resin, synthetic fibers, or refractory materials and in combination with or without one or more gels having a different rigidity.

2. An improved gelatinous composition comprising:

a crystal gel formed from 100 parts by weight of one or more block copolymers or mixtures of two or more such block copolymers, said block copolymers having the formula poly(styrene-ethylene-ethylene-butylene-styrene), poly(styrene-ethyleneb₄₅ -ethylene-propylene-styrene), poly(styrene-ethylene-ethylene-butylene₂₅ -styrene), poly(styrene-ethylene-ethylene-propylene-ethylene-s), poly(styrene-ethylene-propylene-ethylene-styrene), poly(styrene-ethylene-propylene-ethylene-ethylene-propylene-styrene), poly(styrene-ethylene-ethylene-butylene)_n, poly(styrene-ethyleneb₄₅ -ethylene-propylene)_n, poly(styrene-ethylene ethylene-butylene₂₅)_n, poly(styrene-ethylene-ethylene-propylene-ethylene)_n, poly(styrene-ethylene-propylene-ethylene)_n, poly(styrene-ethylene-propylene-ethylene-ethylene)_n, midblocks comprising one or more substantially crystalline polyethylene midblock segment, wherein subscript n is two or more in combination with or without a selected amount of one or more of a (II) polymer or copolymer, and selected amounts of a plasticizing oil (III) sufficient to achieve gel rigidities of from less than about 2 gram Bloom to about 1,800 gram Bloom, said gel having greater tear resistance or greater fatigue resistance than amorphous poly(styrene-ethylene-butylene-styrene) or poly(styrene-ethylene-propylene-styrene) gels.