Tear resistant elastic crystal gels gel composites and their uses

• US 6,420,475 B1
• Filed: 03/28/1999
• Issued: 07/16/2002
• Est. Priority Date: 04/19/1994
• Status: Expired due to Fees

• Current Assignee: Applied Elastomerics Incorporated
• Original Assignee: Applied Elastomerics Incorporated
• Inventors: Chen, John Y.
• Primary Examiner(s): SANDERS, KRIELLION ANTIONETTE
• Application Number:
  US09/274,498
• Time in Patent Office: 1,206 Days
• Field of Search: 523/113, 523/105, 524/487, 524/505, 524/507, 524/508, 524/578
• US Class Current: 524/505
• 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: 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 crystal gels and articles are formed from one or more copolymers having at least one crystalline poly(ethylene) components 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 triblock copolymers, multi-arm block copolymers, branched block copolymers, radial block copolymers, multiblock copolymers, poly(ethylene-styrene) random copolymers produced by metallocene catalysts, using single site, constrained geometry addition polymerization catalysts resulting in poly(ethylene-styrene) substantially random copolymers, or thermoplastic crystalline polyurethane copolymers with hydrocarbon midblocks or a mixture of two or more said copolymers having one or more crystalline poly(ethylene) components (ii) from about 250 to about 1,600 parts of a plasticizer sufficient to achieve a gel rigidity of from less than about 2 gram Bloom to about 1,800 gram Bloom;

wherein said crystalline poly(ethylene) components of said (i) copolymer having a selected amount of crystallinity sufficient to achieve improvements in one or more crystal gel properties including improved tear resistance and improved resistance to fatigue;

wherein said improvements in properties of said crystal gel being greater than an amorphous gel made from poly(styrene-ethylene-butylene-styrene) or poly(styrene-ethylene-propylene-styrene) having substantially non-crystalline components at corresponding said gel rigidity;

in combination with or without a selected amount of (iii) one or more of a selected polymer copolymer.

2. A crystal gel according to claim 1, wherein said gel having a selected crystallinity as exhibited in differential scanning calorimeter (DSC) a melting endotherm values of about 20°

C., 21°

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C. or higher.

3. A crystal gel according to claim 1, wherein said copolymer having a selected crystallinity as exhibited in differential scanning calorimetry (DSC) a melting endotherm values of about 40°

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C. or higher.

4. A crystal gel according to claim 1, wherein said crystal gel is formed from said (i) copolymer in combination with or without a selected amount of (iii) one or more polymer or copolymer 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, polyethylene copolymers, polyethyleneoxide, poly(dimethylphenylene oxide), copolymers of trifluoromethyl-4,5difuoro-1,3-dioxole and tetrafluoroethylene, tetrafluoroethylene, polycarbonate, ethylene vinyl alcohol copolymer, polyamide, polyethyleneoxide, poly(dimethylphenylene oxide), polystyrene, polybutylene, polyethylene, polypropylene, high ethylene content EPDM, amorphous copolymers based on 2,2-bistrifluoromethyl-4,5-difuoro-1,3-dioxole/tetrafluoroethylene or polydimethylsiloxane;

wherein said (i)copolymer and said (iii) copolymer is a linear, branched, radial, or a multiarm copolymer.

5. A composite comprising a crystal gel of claim 1, where said gel is denoted by G being physically interlocked with a selected material M forming the combination G_nM_n, G_nM_nG_n, M_nG_nM_n, M_nG_nG_nM_n, G_nM_nM_nG_n, G_nM_nG_nM_nG_n, M_nM_nM_nG_n, M_nM_nM_nG_nM_nM_nM_n, G_nG_n, G_nG_nG_n, M_nG_nG_n, M_nM_nM_nG_nM_n, M_nG_nG_nM_n, G_nM_nG_nG_n, G_nM_nM_nG_n, G_nM_nM_nG_n, G_nG_nM_nM_n, G_nG_nM_nG_nM_n, G_nM_nG_nG_n, G_nM_nG_nM_nM_n, M_nG_nM_nG_nG_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, natural fibers, 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.

6. A prosthetic device comprising a lower extremity socket insert for below the knee or above the knee with or without a cuff suspension formed from a crystal gel of claim 1.

7. A prosthetic device comprising a lower extremity socket insert for below the knee or above the knee with or without a cuff suspension formed from a crystal gel composite claim 5, wherein M is a fabric.

8. A crystal gel of claim 1, wherein said crystal gel is formed from said copolymer and one or more polyphenolic low coefficient of friction agents in combination with one or more of an internal nucleating agent or one or more of an external nucleating agent sufficient to achieve a coefficient of friction of less than 1.0 to about less than 0.40.

9. A dental floss comprising a crystal gel of claim 1, wherein said floss is formed into a strand, thread, tape, or yarn suitable for use as a dental floss.

10. A low tack gelatinous composition comprising:

a crystal gel formed from

(i) 100 parts by weight of one or more copolymers having a selected amount of one or more elastomeric segments and a selected amount of one or more glassy segments, said elastomeric segments having a selected amount of one or more crystalline poly(ethylene) components and said glassy segments being a poly(styrene), poly(alpha-methylstyrene), poly(o-methylstyrene), poly(m-methylstyrene), or poly(p-methylstyrene);

(ii) from about 250 to about 1,600 parts of a plasticizer sufficient to achieve a gel rigidity of from less than about 2 gram Bloom to about 1,800 gram Bloom;

(iii) said low tack being achieved by a combination of said selected amount of crystalline poly(ethylene) components of said selected amount of said glassy segments forming said crystal gel, wherein said elastomeric segments and said glassy segments being a ratio of about 37;

63 and said tack of said crystal gel being less than amorphous gels of poly(styrene-ethylene-butylene-styrene) or poly(styrene-ethylene-propylene-styrene) of substantially same rigidities.

11. An improved gelatinous composition comprising:

a crystal gel formed from (i) 100 parts by weight of one or more of a substantially random poly(ethylene-styrene) copolymers produced by metallocene catalysts or in combination as a mixture with or without one or more of (a) a linear triblock copolymers, (b) multi-arm block copolymers, (c) branched block copolymers, or (d) radial block copolymers, said substantially random poly(ethylene-styrene), linear triblock, multi-arm block, branched block, and radial block copolymers having one or more crystalline poly(ethylene) components (ii) from about 250 to about 1,600 parts of a plasticizer sufficient to achieve a gel rigidity of from less than about 2 gram Bloom to about 1,800 gram Bloom;

wherein said crystalline poly(ethylene) components of said substantially random copolymer and said (a), (b), (c), (d) copolymers having a selected amount of crystallinity sufficient to achieve improvements in one or more crystal gel properties including improved tear resistance and improved resistance to fatigue;

wherein said improvements in properties of said crystal gel being greater than an amorphous gel made from poly(styrene-ethylene-butylenestyrene) or poly(styrene-ethylene-propylene-styrene) having substantially non-crystalline components at corresponding said gel rigidity;

in combination with or without a selected amount of (iii) one or more of a selected polymer or copolymer.

12. A composite comprising a crystal gel of claim 11, where said gel is denoted by G being physically interlocked with a selected material M forming the combination G_nM_n, G_nM_nG_n, M_nG_nM_n, M_nG_nG_nM_n, G_nM_nM_nG_n, G_nM_nG_nM_nG_n, M_nM_nM_nG_n, M_nM_nM_nG_nM_nM_nM_n, G_nG_n, G_nG_nG_n, M_nG_nG_n, M_nM_nM_nG_nM_n, M_nG_nG_nM_n, G_nM_nG_nG_n, G_nM_nM_nG_n, G_nM_nM_nG_n, G_nG_nM_nM_n, G_nG_nM_nG_nM_n, G_nM_nG_nG_n, G_nM_nG_nM_nM_n, M_nG_nM_nG_nG_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, natural fibers, 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.

13. A crystal gel according to claim 11, wherein said copolymer having a selected amount of about 20%, 22%, 25%, 30%, 40%, 50%, 60%, 65%, or about 70% of (—

CH2-)¹⁶ units of the total mole % forming the midblocks of the substantially random copolymer so as to exhibit in differential scanning calorimetry (DSC) a crystallinity melting endotherm values of about 20°

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C. or higher.

14. A crystal gel according to claim 11, wherein said copolymer having a selected amount of about 20%, 22%, 25%, 30%, 40%, 50%, 60%, 65%, or about 70% of (—

CH2-)¹⁶ units of the total mole % forming the midblocks of the substantially copolymer so as to exhibit in differential scanning calorimetry (DSC) a crystallinity melting endotherm values of about 40°

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C., or higher.