Tear resistant, multiblock copolymer gels and articles

• US 6,148,830 A
• Filed: 09/30/1996
• Issued: 11/21/2000
• Est. Priority Date: 04/19/1994
• 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:
  US08/719,817
• Time in Patent Office: 1,513 Days
• Field of Search: 428/409, 428/521, 428/515, 524/270, 524/474, 524/476, 524/490, 524/505, 2/411, 5/632, 5/636, 5/640, 132/321, 135/68, 135/71, 427/162, 521/148, 525/95, 174/77 R, 174/92, 174/93
• US Class Current: 132/321
• 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 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 428/2998 including synthetic resin or polymer
• CPC Class Codes: Y10T 428/31909 Next to second addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31931 Polyene monomer-containing

Abstract

Novel gels and articles are formed from an intimate melt blend admixture of one or more of a linear or star-shaped multiblock copolymers having two or more midblock polymer chains and high levels of a plasticizing oil.

The gels can be 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 gels of this invention are extremely soft, flexible, and have elastic memory, characterized by a gel rigidity of from about less than 2 gram to about 1,800 gram Bloom and higher. These and other properties are particularly essential for the gels to have utility as composites, toys, therapeutic hand excercising grips, electrical and electronic encapsulation, shock absorbers, acoustical isolators, components for cushions, medical, sports medical, and many other uses. The gels are characterized by a rigidity of about 350 grams to about 1,800 gram Bloom, a tear resistance of at least about 1 Kg/cm, and strands of the gel are capable of flossing at least ten cycles without completely breaking apart as tested under fully contacting surfaces under a uniform spring load of 0.9027 Kg.

Claims

1. A gel composite comprising:

(i) one or more of a poly(ethylene) crystallite forming linear or star-shaped multiblock copolymers with glassy polymer end blocks or a mixture of two or more of said copolymers;

said copolymers having two or more midblock polymer chains and

(ii) a selected amount of a plasticizing oil;

(iii) said gel, denoted by G, is physically interlocked with a selected material M forming said gel 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 M_n M_n G_n, M_n M_n M_n G_n M_n, M_n G_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 M_n, G_n G_n M_n G_n M_n, G_n M_n G_n M_n M_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 foam, plastic, fabric, metal, concrete, wood, glass, 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;

said gel characterized by a gel rigidity of from about 2 gram to about 1,800 gram Bloom;

wherein said gel is capable of exhibiting greater tear propagation resistance than a gel having a corresponding rigidity made from poly(styrene-ethylene-butylene-styrene) or poly(styrene-ethylene-propylene-styrene) block copolymers having substantially non-crystallite forming poly(ethylene) midblocks.

6. A gel composite according to claim 1, wherein said multiblock copolymer is poly(styrene-ethylene-ethylene-propylene-styrene) or poly(styrene-ethylene-ethylene-butylene-styrene), and said tear propagation resistance is measured using a 180°

U bend tear propagation test.

13. A gel composite according to claims 1, wherein said glassy polymer end blocks is polystyrene, said composite combination is G_n M_n, and said M is foam, fabric, or synthetic fibers.

14. A gel composite according to claims 1, wherein said glassy polymer end blocks is polystyrene, said composite combination is 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 M is foam, fabric, or synthetic fibers.

16. A composite according to claims 1, wherein said glassy polymer end blocks is polystyrene, said composite combination is G_n M_n, G_n M_n G_n, M_n G_n M_n or a permutation of one or more of said G_n with M_n, wherein M is foam, fabric, or synthetic fibers.

17. A composite according to claims 1, wherein said glassy polymer end blocks is polystyrene, said composite combination is G_n M_n, G_n M_n G_n, M_n G_n M_n, G_n G_n M_n or a permutation of one or more of said G_n with M_n, wherein M is foam, fabric, or synthetic fibers.

18. A composite according to claims 1, wherein said glassy polymer end blocks is polystyrene, said composite combination is G_n M_n, G_n M_n G_n, M_n G_n M_n, G_n G_n M_n, M_n M_n M_n G_n, M_n M_n M_n G_n M_n, M_n G_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 M_n, or a permutation of one or more of said G_n with M_n, wherein M is foam, fabric, or synthetic fibers.

2. A gel composite comprising:

(i) 100 parts by weight of one or more of a crystalline linear or star-shaped multiblock copolymers or a mixture of two or more of said copolymers;

said gel characterized by a gel rigidity of from about 2 gram to about 1,800 gram Bloom;

said linear multiblock copolymer have the general configuration A--Z--A and said star-shaped multiblock copolymer have the general configuration (A--Z)_n, the subscript n is an integer;

wherein each A is a selected glassy polymer end block segment of polystyrene and wherein Z is a midblock of one or more polymer chains of crystallite forming poly(ethylene) in combination with one or more polymer chains of poly(ethylene-butylene) or poly(ethylene-propylene); and

(ii) a selected amount of a plasticizing oil;

(iii) said gel, denoted by G, is physically interlocked with a selected material M forming said gel 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 M_n M_n G_n, M_n M_n M_n G_n M_n, M_n G_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 M_n, G_n G_n M_n G_n M_n, G_n M_n G_n M_n M_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 foam, plastic, fabric, metal, concrete, wood, glass, 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;

wherein said gel is capable of exhibiting greater tear propagation resistance than a gel having a corresponding rigidity made from poly(styrene-ethylene-butylene-styrene) or poly(styrene-ethylene-propylene-styrene) block copolymers having substantially non-crystallite forming poly(ethylene) midblocks.

5. A gel composite according to claim 2, wherein said gel is being denoted by G, is physically interlocked with a selected material M forming 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, 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 a fabric, a fiber, or a film;

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

7. A gel composite according to claim 2, wherein said multiblock copolymer is poly(styrene-ethylene-ethylene-propylene-styrene), poly(styrene-ethylene-ethylene-butylene-styrene), poly(styrene-ethylene-ethylene-propylene)_n, and poly(styrene-ethylene-ethylene-butylene)_n ;

and said tear propagation resistance is determined by repeatedly inserting a 3.0 mm diameter gel strand held in position under a tensile force of 1 Kg/cm² between two stainless steel rollers (3/8 inches diameter) facing lengthwise parallel and forced together so as to form a contact length of 1/2 inches under a spring load of two pounds.

8. A gel composite according to claim 2, wherein said gel is formed 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, polystyrene, polybutylene, poly(ethylene-propylene), poly(ethylene-butylene), polypropylene, or polyethylene, wherein said selected copolymer is a linear, branched or star-shaped, or multiarm copolymer.

9. A gel composite according to claim 2, wherein said copolymer is a linear multiblock copolymers of the formula poly(styrene-ethylene-ethylene-propylene-styrene), poly(styrene-ethylene-ethylene-butylene-styrene), poly(styrene-ethylene-ethylene-propylene-ethylene-butylene-styrene), poly(styrene-ethylene-ethylene-propylene-ethylene-styrene), and poly(styrene-ethylene-ethylene-propylene-ethylene-ethylene-propylene-ethylene-styrene).

10. A gel composite according to claim 2, wherein said star-shaped multiblock copolymers is of the formula poly(styrene-ethylene-ethylene-butylene)_n, poly(styrene-ethylene-ethylene-propylene)_n, poly(styrene-ethylene-ethylene-propylene-ethylene)_n, poly(styrene-ethylene-ethylene-propylene-ethylene-ethylene-propylene).sub.n, and poly(styrene-ethylene-ethylene-propylene-ethylene-ethylene-propylene-ethylene)_n.

11. A gel composite according to claim 2, wherein said gel, 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 M_n M_n G_n, M_n M_n M_n G_n M_n, M_n G_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 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 M, n is the same or different selected from the group consisting of foam, plastic, fabric, metal, synthetic resin, or synthetic fibers;

and wherein when n is a subscript of G, n denotes the same or a different gel rigidity of from about 2 gram to about 1,800 gram Bloom.

19. A gel composite according to claim 2 wherein said gel composite of said gel and said fibers being extruded into a thread or tape and weaved into a fine or coarse fabric article.

20. A gel composite according to claim 2, wherein said gel being formed into a shape floss suitable for use as a dental floss in combination with or without one or more selected polymers or copolymers of polybutylene, polypropylene, or polyethylene.

3. A gel composite comprising:

(i) 100 parts by weight of one or more of a crystalline linear multiblock copolymers or a mixture of two or more of said copolymers;

said gel characterized by a gel rigidity of from about 2 gram to about 1,800 gram Bloom;

said linear multiblock copolymer have the general configuration A--Z--A;

wherein each A is a selected glassy polymer end block segment of polystyrene and wherein Z is a midblock of one or more polymer chains of crystallite forming poly(ethylene) in combination with one or more polymer chains of poly(ethylene-butylene) or poly(ethylene-propylene); and

(ii) a selected amount of a plasticizing oil;

(iii) said gel, denoted by G, is physically interlocked with a selected material M forming said gel composite of the combination G_n M_n, G_n M_n G_n, M_n G_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 foam, fabric, or synthetic fibers; and

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

wherein said gel is capable of exhibiting greater tear propagation resistance than a gel having a corresponding rigidity made from poly(styrene-ethylene-butylene-styrene) or poly(styrene-ethylene-propylene-styrene) block copolymers having substantially non-crystallite forming poly(ethylene) midblocks.

4. A gel composite comprising:

(i) 100 parts by weight of one or more of a crystalline star-shaped multiblock copolymers or a mixture of two or more of said copolymers;

said gel characterized by a gel rigidity of from about 2 gram to about 1,800 gram Bloom;

said star-shaped multiblock copolymer have the general configuration (A--Z)_n, the subscript n is an integer;

wherein each A is a selected glassy polymer end block segment of polystyrene and wherein Z is a midblock of one or more polymer chains of crystallite forming poly(ethylene) in combination with one or more polymer chains of poly(ethylene-butylene) or poly(ethylene-propylene); and

(ii) a selected amount of a plasticizing oil;

(iii) said gel, denoted by G, is physically interlocked with a selected material M forming said gel 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 M_n M_n G_n, M_n M_n M_n G_n M_n, M_n G_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 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 foam, plastic, fabric, metal, or synthetic resin, synthetic fibers; and

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

wherein said gel is capable of exhibiting greater tear propagation resistance than a gel having a corresponding rigidity made from poly(styrene-ethylene-butylene-styrene) or poly(styrene-ethylene-propylene-styrene) block copolymers having substantially non-crystallite forming poly(ethylene) midblocks.

12. A gel composite comprising:

(i) 100 parts by weight of one or more of a crystalline linear or star-shaped multiblock copolymers or a mixture of two or more of said copolymers;

said gel characterized by a gel rigidity of from about 2 gram to about 1,800 gram Bloom;

said linear multiblock copolymer have the general configuration A--Z--A and said star-shaped multiblock copolymer have the general configuration (A--Z)_n, the subscript n is an integer;

wherein each A is a selected glassy polymer end block segment of polystyrene, poly(alpha-methylstyrene), poly(o-methylstyrene), poly(m-methylstryene), poly(p-methylstyrene) or poly(tertiary-butylstyrene) and wherein Z is a midblock of one or more polymer chains of crystallite forming poly(ethylene) in combination with one or more polymer chains of poly(ethylene-butylene) or poly(ethylene-propylene); and

(ii) a selected amount of a plasticizing oil;

wherein said gel is capable of exhibiting greater tear resistance than a gel having a corresponding rigidity made from poly(styrene-ethylene-butylene-styrene) or poly(styrene-ethylene-propylene-styrene) block copolymers having substantially non-crystallite forming poly(ethylene) midblocks; and

wherein said gel, 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 M_n M_n G_n, M_n M_n M_n G_n M_n, M_n G_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 M_n, G_n G_n M_n G_n M_n, G_n M_n G_n M_n M_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 foam, plastic, fabric, or synthetic fibers; and

wherein when n is a subscript of G, n denotes the same or a different gel rigidity of from about 2 gram to about 1,800 gram Bloom.

15. A gel composite comprising:

(i) 100 parts by weight of one or more of a crystalline linear or star-shaped multiblock copolymers or a mixture of two or more of said copolymers; and

(ii) a selected amount of a plasticizing oil;

(iii) said gel, denoted by G, is physically interlocked with a selected material M forming said gel 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 M_n M_n G_n, M_n M_n M_n G_n M_n, M_n G_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 M_n, G_n G_n M_n G_n M_n, G_n M_n G_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 foam, plastic, fabric, metal, concrete, wood, glass, 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;

said gel characterized by a gel rigidity of from about 2 gram to about 1,800 gram Bloom;

said linear multiblock copolymer have the general configuration A--Z--A and said star-shaped multiblock copolymer have the general configuration (A--Z)_n, the subscript n is an integer;

wherein each A is a selected glassy polymer end block segment of polystyrene, poly(alpha-methylstyrene), poly(o-methylstyrene), poly(m-methylstryene), poly(p-methylstyrene) or poly(tertiary-butylstyrene) and wherein Z is a midblock of one or more polymer chains of crystallite forming poly(ethylene) in combination with one or more polymer chains of poly(ethylene-butylene) or poly(ethylene-propylene);

wherein said linear multiblock copolymers having a solution viscosity at 5 weight percent solution in toluene at 30°

C. of at least 150 cps and said star-shaped multiblock copolymers having a solution viscosity at 5 weight percent solution in toluene at 30°

C. of a least 200 cps;

said gel upon heat treatment for a selected temperatures and time period exhibits delay deformation recovery and greater tear resistance than a gel having a corresponding rigidity made from poly(styrene-ethylene-butylene-styrene) or poly(styrene-ethylene-propylene-styrene) block copolymers having substantially non-crystallite forming poly(ethylene) midblocks.