USOO5884639A United States Patent (19) 11 Patent Number: 5,884,639 Chen (45) Date of Patent: Mar 23, 1999

54 CRYSTAL GELS WITH IMPROVED 4,880,878 11/1989 Himes et al...... 525/98 PROPERTIES 5,262,468 11/1993 Chen ...... 524/476 5,334,646 8/1994 Chen ...... 524/474 75 Inventor: John Y. Chen, Pacifica, Calif. 5,336,708 8/1994 Chen ...... 524/474 73 Assignee: Applied Elastomerics, Inc., South San 5,508,334 4/1996 Chen ...... 524/474 Francisco, Calif. 5,633,286 5/1997 Chen ...... 5224/474 5,755,243 5/1998 Roberts et al...... 132/321 21 Appl. No.: 819,675 22 Filed: Mar 17, 1997 Primary Examiner Herbert J. Lilling Related U.S. Application Data 57 ABSTRACT 63 Continuation-in-part of Ser. No. 719,817, Sep. 30, 1996, and a continuation-in-part of Ser. No. 665,343, Jun. 17, 1996, Novel crystal gels and articles are formed from one or more and a continuation-in-part of Ser. No. 612,586, Mar. 8, 1996. of a linear SEBS or radial (SEB), triblock copolymers 51 Int. Cl...... B61C 15700; CO8J 5/02; having a Selected crystalline midblock Segment and high C08J 51/00; CO8K 5/01 levels of a plasticizer, Said midblock Segment having an 52 U.S. Cl...... 132/321; 428/521; 524/270; amount of crystallinity in the EB copolymer sufficient to 524/474; 524/476; 524/490; 524/505; 525/95; 525/98 achieve improvements in one or more physical properties 58 Field of Search ...... 529/474, 476, including improved crack propagation resistance, improved 529/505; 525/95, 98; 132/321 tear resistance, improved resistance to fatigue and resistance to catastrophic failure not obtainable in amorphous SEBS 56) References Cited gels. U.S. PATENT DOCUMENTS 3,772,234 11/1973 Porter ...... 524/534 9 Claims, No Drawings 5,884,639 1 2 CRYSTAL GELS WITH IMPROVED gel rigidity of from less than about 2 gram Bloom to about PROPERTIES 1,800 gram Bloom; wherein said ethylene-butylene being a midblock copolymer Segment of Said triblock copolymers RELATED APPLICATIONS having a Selected amount of crystallinity Sufficient to achieve improvements in one or more properties including This application is a continuation-in-part of the following improved tear resistance and improved resistance to fatigue; applications: U.S. Ser. No: 08/719,817 filed Sep. 30, 1996, wherein Said improvements in properties of Said crystal gel U.S. Ser. No: 08/665,343 filed Jun. 17, 1996 and U.S. Ser. being greater than an amorphous gel at corresponding Said No. 612,586 filed Mar. 8, 1996 which applications are gel rigidity formed from Said triblock copolymers having a Specifically incorporated herein by reference. substantially non-crystalline ethylene-butylene midblock Segment; Said Selected amount of crystallinity is capable of FIELD OF THE INVENTION exhibiting a broad melting endotherm in differential Scan ning calorimeter (DCS) curves as seen on heating and a The present invention is directed to novel Styrene Sharp crystallization exotherm as seen on cooling; (iii) ethylene-butylene-styrene (SEBS) triblock copolymer gels. optionally in combination with a Selected amount of one or 15 more of a Selected polymer or copolymer Selected from the BACKGROUND OF THE INVENTION group consisting of poly(styrene-butadiene-styrene), poly (styrene-butadiene), poly(styrene-isoprene-styrene), poly The random mixtures of ethylene and butylene midblock (styrene-isoprene), poly(styrene-ethylene- propylene), poly copolymer segment of conventional SEBS triblock copoly (styrene-ethylene-propylene-styrene), poly(styrene merS is almost totally amorphous, Substantially free of any ethylene-butylene-styrene), poly(styrene-ethylene crystantility or non-crystalline. Such SEBS triblock copoly butylene), poly(styrene-ethylene-propylene)n, poly(styrene mers with Substantially non-crystalline ethylene-butylene ethylene-butylene)n, maleated poly(styrene-ethylene elastomer midblock Segment are used for making elasto propylene-styrene), maleated poly(styrene-ethylene meric gels of varying rigidities which can vary from Soft to butylene-styrene), maleated poly(styrene-ethylene firm. Such gels are hereafter referred to as “non-crystalline butylene), maleated poly(styrene-ethylene-propylene)n, midblock gels” or “amorphous midblock gels” or more 25 maleated poly(styrene-ethylene-butylene)n, polystyrene, Simply “amorphous gels”. Generally, the properties of amor polybutylene, poly(ethylene-propylene), poly(ethylene phous gels increase with increasing gel rigidity. The amor butylene), polypropylene, polyethylene, polyethyleneoxide, phous gels at any rigidity, however, can fail catastrophically poly(dimethylphenylene oxide), copolymers of when cut or notched while under applied forces of high trifluoromethyl-4,5-difluoro-1,3-dioxole and dynamic and Static deformations, Such as extreme tetrafluoroethylene, tetrafluoroethylene, polycarbonate, eth compression, torsion, high tension, high elongation, and the ylene Vinyl alcohol copolymer, polyamide or polydimethyl like. Additionally, the development of cracks or crazes Siloxane, wherein Said Selected copolymer is a linear, resulting from a large number of deformation cycles can branched, radial, or multiarm copolymer. induce catastrophic fatigue failure of amorphous gel 35 The crystal gels of the invention are also Suitable in composites, Such as tears and rips between the Surfaces of physically interlocking with other Selected materials to form the amorphous gel and Substrates or at the interfaces of composites combinations. The materials are Selected from interlocking material(s) and amorphous gel. Consequently, the group consisting of paper, foam, plastic, fabric, metal, Such amorphous gels are inadequate for the most demanding applications involving endurance at high StreSS and Strain metal foil, concrete, wood, glass, glass fibers, ceramics, 40 Synthetic resin, Synthetic fibers or refractory materials. levels over an extended period of time. The ethylene-butylene (EB) and styrene (S) portions of the linear and radial triblock copolymers are incompatible SUMMARY OF THE INVENTION and form a two or more phase System consisting of Sub I have now discovered novel gels with improved proper micron glassy domains of Styrene S interconnected by ties made from SEBS triblock and (SEB), radial copolymers 45 flexible EB chains. These domains serve to crosslink and with crystalline ethylene-butylene elastomer midblock Seg reinforce the Structure. This physical elastomeric network ment (hereafter referred to as “crystalline midblock gels” or Structure is reversible, and heating the polymer above the “crystalline gels” or simpler "crystal gels'). The advances in Softening point of the glassy domains temporarily disrupt the improved properties of the crystal gels over amorphous gels Structure, which can be restored by lowering the tempera are many, these include: improved damage tolerance, 50 ture. improved crack propagation resistance, improved tear Advantageously, the elastomer midblock Segment should resistance, improved resistance to fatigue, etc. Such crystal have a crystallinity of at least about 10% by weight of said gels are advantageous for end-use involving repeated appli ethylene-butylene elastomer midblock Segment, more cations of StreSS and Strain resulting from large number of advantageously at least about 15%, Still more advanta cycles of deformations, including compression, 55 geously at least about 20%, especially advantageously at compression-extension (elongation), torsion, torsion least about 25% and especially more advantageously at least compression, torsion-elongation, tension, tension about 30% and higher. Broadly, the crystallinity by weight compression, tension-torsion, etc. The improvements of the of the midblock Segment should range from at least about crystal gel physical properties are an advance in the gel art 10% to about 80%. Because of the crystallinity of the not obtainable by amorphous gels at corresponding gel 60 elastomer midblock Segment, the crystal gels exhibit differ rigidities. ent characteristics than amorphous gels. The differences are The crystal gels of the invention comprises: (I) 100 parts most evident in differential scanning calorimeter (DCS) by weight of one or more high Viscosity triblock copolymers curves of crystal gels, the melting endotherm is Seen on of the general configurations poly(styrene-ethylene heating and a sharp crystallization eXotherm is seen on butylene-styrene), poly(styrene-ethylene-butylene), or a 65 cooling. Such midblock crystallization endothermic and mixture thereof, wherein the Subscript in denotes an integer, exothermic characteristics are missing from DCS curves of (II) a Selected amount of a plasticizer Sufficient to achieve a Substantially amorphous gels. 5,884,639 3 4 AS used herein, the term “gel rigidity in gram Bloom is of Ethylene-Butylene - 1 Block Copolymers', determined by the gram weight required to depress a gel a Macromolecules, Vol. 4, No. 2, pp. 152-154, March-April distance of 4 mm with a piston having a croSS-Sectional area 1971. Morton, Maurice, and et al., “Elastomeric Polydiene of 1 Square centimeter at 23° C. ABA Triblock Copolymers within Crystalline End Blocks”, Regarding resistance to fatigue, fatigue (as used herein) is University of Arkon, work supported by Grant No. DMR78 the decay of mechanical properties after repeated application 09024 from the National Science Foundation and Shell of StreSS and Strain. Fatigue tests give information about the Development Co. Yee, A. F., and et al., “Modification of PS ability of a material to resist the development of cracks or by SEBS Block Copolymers: Effect of Block Length”, crazes resulting from a large number of deformation cycles. General Electric Corporate Research & Development, Fatigue test can be conducted by Subjecting Samples of Schenectady, N.Y. 12301. Siegfried, D. L., and et al., “Ther amorphous and crystal gels to deformation cycles to failure moplastic Interpenetrating Polymer Networks of a Triblock Copolymer elastomer and an Ionomeric Plastic Mechanical (appearance of cracks, crazes, rips or tears in the gels). Behavior”, Polymer Engineering and Science, Jan. 1981, Tensile Strength can be determined by extending a Vol. 21, No.1, pp. 39–46. Clair, D. J., “SEBS Copolymers selected gel sample to break as measured at 180 U bend 15 Exhibit Improved Wax Compatibility”, Adhesives Age, around a 5.0 mm mandrel attached to a Spring Scale. November, 1988. Shell Chemical Technical Bulletin Likewise, tear Strength of a notched Sample can be deter SC: 1102–89, “Kratone(R). Thermoplastic Rubbers in oil mined by propagating a tear as measured at 180 U bend gels”, April 1989. The above applications, patents and around a 5.0 mm diameter mandrel attached to a Spring publications are specifically incorporated herein by refer Scale. CCC. The various aspects and advantages will become apparent Legge's paper teaches the development of (conventional to those skilled in the art upon consideration of the accom substantially amorphous elastomer midsegment) SEBS tri panying disclosure. block copolymers. In the polymerization of butadiene by DESCRIPTION OF THE INVENTION alkylithium initiators, 1,4-addition or 1,2-addition polymers, 25 mixtures, can be obtained. In forming Styrene butadiene Thermoplastic elastomer SEBS gels are described in my triblock copolymers involving the addition of Solvating earlier applications and patents: U.S. Ser. Nos: 581,188 filed agents Such as ethers just before the final Styrene charge is Dec. 29, 1995; 581,191 filed Dec. 29, 1995; 581,125 filed added, any excess of ethers can alter the polybutadiene Dec. 29, 1995; PCT/US94/04278 filed Apr. 19, 1994; PCT/ Structure from a 14-cis or trans Structure to a 1,2- or US94/07314 filed Jun. 27, 1994; 288,690 filed Aug. 11, 3,4-addition polymer. Using difunctional coupling agent 1994; 152,734, filed Nov. 15, 1993; 152,735, Nov. 15, 1993; would give linear block copolymers and multifuntional 114.688, filed Aug. 30, 1993; 935,540 filed Aug. 24, 1992; agents would give Star-shaped or radial block copolymers. 876,118 filed Apr. 29, 1992; 705,096 filed May 23, 1991; Hydrogenation of the 1,4-polybutadiene structure yields 527,058 filed May 21, 1990; 921,752 filed Oct. 21, 1986; polyethylene, while that of the 1,2-polybutadiene yields 458,703, filed Jan. 17, 1983; 916,731, filed Jun. 19, 1978; 35 polybutylene. The resulting polyethylene will be essentially 815,315, filed Jul 13, 1977; 778,343, filed Mar. 17, 1977; identical with linear, high-density polyethylene with a melt U.S. Pat. Nos. 5,262.468; 5,153,254; 4,618,213; and 4,369, ing point, Tm, of about 136 C. Hydrogenation of 1,2- 284. Various patents on thermoplastic elastomers are polybutadiene would yield at actic poly(1-bute ne) described in U.S. Pat. Nos. 3,595,942, Reissue 27,145-28, (polybutylene). The Tg of polybutylene is around -18°C. 236; 3,772,234; 4,116,917; and 4,687,815. Other non-patent 40 Random mixtures of ethylene and butylene units in the chain publications related to SEBS polymers include: W. P. would SuppreSS crystallinity arising from polyethylene Gergen, “Uniqueness of Hydrogenated Block Copolymers Sequences. The objective for a good elastomer should be to for Elastomeric Applications, presented at the German obtain a Saturated olefinelastomeric Segment with the lowest Rubber Meeting, Wiesbaden, 1983; Kautsch, Gummi, possible Tg and the best elastomeric properties. Such an Kunstst. 37,284 (1984). W. P. Gergen, et al., “Hydrogenated 45 elastomer favored using Styrene as the hard-block monomer Block Copolymers,” Paper No. 57, presented at a meeting of and Selecting the best monomer for hydrogenation of the the Rubber Division ACS, Los Angeles, Apr. 25, 1985. elastomer midsegment. Using a mixture of 1,4- and 1,2- Encyclopedia of Polymer Science and Engineering, Vol. 2, polybutadiene as the base polymer for the midsegment pp 324-434, “Block Copolymers”. L. Zotteri and et al., would result in an ethylene/butylene midsegment in the final “Effect of hydrogenation on the elastic properties of poly 50 product. The elements of Selection of the midsegment com (styrene-b-diene-b-styrene) copolymers”, Polymer, 1978, position is elastomer crystallinity and the elastomer Tg of an Vol. 19, April. J. Kenneth Craver, et al., Applied Polymer ethylene/butylene copolymer. Very low levels of crystallin Science, Ch. 29, “Chemistry and Technology of Block ity can be achieved around 40-50% butylene concentration. Polymers", pp. 394-429, 1975. Y. Mahajer and et al., “The The minimum in dynamic hysteresis around 35% butylene influence of Molecular Geometry on the Mechanical Prop 55 concentration in the elastomeric copolymer. A value of 40% erties of homopolymers and Block Polymers of Hydroge butylene concentration in the ethylene/butylene midsegment nated Butadiene and Isoprene' reported under U.S. ARO was chosen for the SEBS block copolymers. Grant No. DAAG29-78-G-0201. J. E. McGrath, et al., Clair's paper teaches that the EB midblock of conven “Linear and Star Branched Butadiene-Isoprene Block tional SEBS polymers is a random copolymer of ethylene Copolymers and Their Hydrogenated Derivatives”, Chem. 60 and 1-butene exhibiting nearly no crystallinity in the mid Dept, Virginia Polytechnic Institute and State University block. In the preparation of ethylene-butylene (EB) BlackSturg, VA, reported work Supported by Army Research copolymers, the relative proportions of ethylene and buty Office. Legge, Norman R., “Thermoplastic Elastomers', lene in the EB copolymer chain can be controlled over a Charles Goodyear Medal address given at the 131st Meeting broad range from almost all ethylene to almost all butylene. of the Rubber Division, American Chemical Society, 65 When the EB copolymer is nearly all ethylene, the methyl Montreal, Quebec, Canada, Vol. 60, G79-G115, May 26-29, ene Sequences will crystallize exhibiting properties similar 1987. Falk, John Carl, and et al., “Synthesis and Properties to low density polyethylene. In differential Scanning calo 5,884,639 S 6 rimeter (DCS) curves, the melting endotherm is seen on use, the amorphous gels can rip on the bottom of the liner in heating and a sharp crystallization eXotherm is seen on normal racewalk training of 40-60 miles over a Six weeks cooling. AS the amount of butylene in the EB copolymer is period. In Such demanding applications, the crystal gels are increased, the methylene Sequences are interrupted by the especially advantageous and is found to have greater tear ethyl side chains which shorten the methylene Sequences resistance and resistance to fatigue resulting from a large length So as to reduce the amount of crystallinity in the EB number of deformation cycles than amorphous gels. copolymer. In conventional SEBS polymers, the amount of 1-butene is controlled at a high enough level to make the EB The (I) linear triblock and radial copolymers utilized in copolymer midblock almost totally amorphous So as to make forming the crystal gels of the invention are characterized as the copolymer rubbery and soluble in hydrocarbon solvents. having an ethylene to butylene midblock ratio (E:B) of about 85:15 to about 65:35. Advantageously, the butylene concen An SEBS polymer retaining at least Some crystallinity in tration of the midblock is about 35% or less, more the EB copolymer midblock may be desirable. Therefore, a advantageously, about 30% or less, still more new family of SEBS polymers are developed (U.S. Pat. No. advantageously, about 25% or less, especially 3,772,234) in which the midblock contains a higher percent advantageously, about 20% or less. Advantageously, the age of ethylene. The molecular weights of the new crystal 15 ethylene to butylene midblock ratioS can range from about line midblock segment SEBS polymers can vary from low 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, molecular weight, intermediate molecular, to high molecular 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, weight; these are designated GR-3, GR-1, and GR-2 respec 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34 to tively. about 65:35. The broad melting endotherm in DSC curves of the new The SEBS and (SEB), copolymers forming the crystal SEBS polymers are much higher than conventional SEBS gels can have a broad range of Styrene to ethylene-butylene polymers. The maximum in the broad endortherm curves of ratios (S:EB) of about 20:80 or less to about 40:60 or higher. the new SEBS polymers occurs at about 40 C., but can The S:EB weight ratios can range from lower than about range from greater than about 25 C. to about 60° C. and 20:80 to above about 40:60 and higher. More specifically, higher. Advantageously, the new crystalline EB copolymer 25 midblock segment SEBS polymers can exhibit melting the values can be 15:85, 19:81, 20:80, 21:79. 22:78. 23:77, endotherms (as shown by DSC) of about 20° C. to about 75° 24:76, 25:75, 26:74, 27:73, 28:72, 29:71, 30:70, 31:69, C. and higher. More specific melting endotherm values of 32:68, 33:67, 34:66, 35:65, 36:64, 37:63, 38:62, 39:61, the new crystalline midblock segment SEBS triblock 40:60, 41:59, 42:58, 43:57, 44:65, 45:55, 46:54, 47:53, 48:52, 49:51, 50:50, 51:4952:48 and etc. Other ratio values copolymers include: about 20°C., 21°C., 22°C., 23°C., 24 of less than 19:81 or higher than 51:49 are also possible. C., 25°C., 26°C., 27°C., 28°C., 29° C., 30° C., 31° C., 34° Broadly, the styrene block to elastomeric block ratio of the C., 35° C., 36° C., 37° C., 38°C., 39° C., 40°C., 41° C., 42° high viscosity liner and star copolymers is about 20:80 to C., 43° C., 44° C., 45° C., 47°C., 48° C., 49°C.,50° C.,51° about 40:60 or higher, less broadly about 31:69 to about C., 52° C., 53° C.,54°C.,55°C.,56°C.,57°C., 58° C.,59° 40:60, preferably about 32:68 to about 38:62, more prefer C., 60° C., 61° C., 62° C., 63° C., 64° C., 65° C., 66° C., 67° 35 C., 68°C, 69° C., 70° C., 71°C., 72° C., 73°C., 74° C., 75° ably about 32:68 to about 36:64, particularly more prefer C., 76° C., 77° C., 78° C., 79° C., 80° C., and higher, ably about 32:68 to about 34:66, especially more preferably whereas, the melting endotherm (DSC) for conventional about 33:67 to about 36:64, and still more preferably about amorphous midblock segment SEBS triblock copolymers 30:70. are about 10 C. or lower. 40 In general, for block copolymers, various measured vis Since hydrogenation of 1,4-polybutadiene Structure yields cosities of 5, 10, 15, and 20, weight percent Solution values Substantially linear, high-density polyethylene with a melt in toluene at 30° C. can be extrapolated to a selected ing point, T., of about 136 C., by Selecting linear or radial concentration. For example, a Solution Viscosity of a 5 block copolymers and the proper 1,4-polybutadiene and weight percent copolymer Solution in toluene can be deter 1,2-polybutadiene ratios, linear low density, medium 45 mined by extrapolation of 10, 15, and 20 weight percent density and high-density polyethylene crystalline midblock measurements to 5 weight percent concentration. segment SEBS and (SEB), polymers can be prepared. Of most advantage, high Viscosity crystalline midblock Unexpectly, the highest molecular weight polymer, GR-2 segment SEBS triblock copolymers can have Brookfield exhibits an anomalously low Softening point. Moreover, the viscosities at 5 weight percent solution in toluene at 30° C. tensile Strength of the crystal gels also increases with 50 of from about 40 to about 50, 60, 70, 80, 90, 100 . . . 120, increases in molecular weight (i.e. increases in Viscosity). 150, 200, 380, 500, 1,000 cps and higher, while viscosities The selected amount of crystallinity in the EB copolymer of star-shaped tiblock copolymers are 25, 50, 100, 150, 200, should be Sufficient to achieve improvements in one or more cpS and higher. Due to Structural variations between the physical properties including improved damage tolerance, linear tiblock and Star-shaped copolymers, the high Viscosity improved crack propagation resistance, improved tear 55 Star-shaped or radial copolymers, typically, may exhibit a resistance, improved resistance to fatigue of the bulk gel and lower Brookfield Viscosity value than its counterpart linear resistance to catastrophic fatigue failure of crystal gel tiblock copolymers. However, when the tiblock copolymers composites, Such as between the Surfaces of the crystal gel are considered as Star-shaped or branched, then at equal and Substrate or at the interfaces of the interlocking material branch lengths, the Solution Viscosities of the tiblock copoly (S) and crystal gel, which improvements are not found in 60 merS and branched copolymers are about the same or amorphous gels at corresponding gel rigidities. AS an equivalent. example, when fabric interlocked or Saturated with amor The crystal gels can optionally comprise Selected major or phous SEBS gels (gel composites) are used as gel liners for minor amounts of one or more polymers or copolymers (III) lower limb or above the knee prosthesis to reduce pain over provided the amounts and combinations are Selected without preSSure areas and give relief to the amputee, the commonly 65 Substantially decreasing the desired properties. The poly used amorphous gels forming the liners can tear or rip apart mers and copolymers can be linear, Star-shaped (radial), during marathon racewalk after 50-70 miles. In extended branched, or multiarm; these including: (SBS) styrene 5,884,639 7 8 butadiene-styrene block copolymers, (SIS) styrene typically range about 20-35, about 25-150, about 60-150, isoprene-styrene block copolymers, low and medium vis about 200-400 respectively. Typical Brookfield Viscosities cosity (SEBS) styrene-ethylene-butylene-styrene block of a 10 weight percent solids solution in toluene at 30° C. of copolymers, (SEP) Styrene-ethylene-propylene block 1001, 1050, 2007, 2063, 2043, 4033, 2005, 2006, are about copolymers, (SEPS) styrene-ethylene/propylene-styrene 70, 70, 17, 29, 32, 50, 1200, and 1220 respectively. Typical block copolymers, (SE-EPS) styrene-ethylene-ethylene/ Brookfield Viscosity of a 25 weight percent solids solution propylene-styrene block copolymers, (SB), Styrene in toluene at 25 C. of Kraton D1101, D1116, D1184, butadiene and (SEB), (SEBS), (SE-EP), (SEP), (SI), D1300X, G1701X, G1702X are about 4000, 9000, 20000, Styrene-isoprene multi-arm, branched or Star-shaped 6000, 50000 and 50000 cps respectively. Typical Brookfield copolymers, polyethylene oxide (EO), poly Viscosity of a 10 weight percent Solids Solution in toluene at (dimethylphenylene oxide), teflon (TFE, PTFE, PEA, FEP, 25° C. of G1654X is about 370 cps. The Brookfield Vis etc), optical clear amorphous copolymers based on 2,2- cosities of a 20 and 30 weight percent solids solution in bistrifluoromethyl-4,5-difuoro-1,3-dioxole (PDD) and tet toluene at 30° C. of H-VS-3 are about 133 cps and 350 cps rafluoroethylene (TFE), maleated SEBS triblock copolymer, respectively. polycarbonate, ethylene Vinyl alcohol copolymer, and the 15 Suitable triblock copolymers (III) and their typical vis like. Still, other (III) polymers include homopolymers which cosities are further described. Shell Technical Bulletin can be utilized in minor amounts, these include: polystyrene, SC:1393-92 gives solution viscosity as measured with a polybutylene, polyethylene, polypropylene, Brookfield model RVT viscometer at 25 C. for Kraton G polydimethylsiloxane, etc. The conventional term “major 1654X at 10% weight in toluene of approximately 400 cps means about 51 weight percent and higher (e.g. 55%, 60%, and at 15% weight in toluene of approximately 5,600 cps. 65%, 70%, 75%, 80% and the like) and the term “minor" Shell publication SC:68-79 gives solution viscosity at 25 means 49 weight percent and lower (e.g. 2%, 5%, 10%, C. for Kraton G 1651 at 20 weight percent in toluene of 15%, 20%, 25% and the like). approximately 2,000 cps. When measured at 5 weight per Example of (III) polymers, copolymers, and blends cent solution in toluene at 30° C., the solution viscosity of include: (a) Kraton G 1651, G 1654X; (b) Kraton G 4600; 25 Kraton G 1651 is about 40. Examples of high viscosity (c) Kraton G4609; other suitable high viscosity polymer and SEBS triblock copolymers includes Kuraray’s SEBS 8006 oils include: (d) Tuftec H 1051; (e) Tuftec H 1041, (f) Tuftec which exhibits a solution viscosity at 5 weight percent at 30 H 1052; (g) Kuraray SEPS 4033; (h) Kuraray SEBS 8006; C. of about 51 cps. Kuraray's 2006 SEPS polymer exhibits (i) Kuraray SEPS 2005; (ii) Kuraray SEPS 2006, and (k) a viscosity at 20 weight percent solution in toluene at 30° C. blends (polyblends) of (a)-(h) with other polymers and of about 78,000 cps, at 5 weight percent of about 27 cps, at copolymers include: (1) SEBS-SBS; (2) SEBS-SIS; (3) 10 weight percent of about 1220 cps, and at 20 weight SEBS-(SEP); (4) SEBS-(SEB); (5) SEBS-(SEB); (6) percent 78,000 cps. Kuraray SEPS 2005 polymer exhibits a SEBS-(SEP); (7) SEBS-(SI); (8) SEBS-(SI) multiarm; (9) viscosity at 5 weight percent solution in toluene at 30° C. of SEBS-(SEB); (10) (SEB), star-shaped copolymer; (11) s about 28 cps, at 10 weight percent of about 1200 cps, and at made from blends of (a)-(k) with other homopolymers 35 20 weight percent 76,000 cps. Other grades of SEBS, SEPS, include: (12) SEBS/polystyrene; (13) SEBS/polybutylene; (SEB), (SEP), polymers can also be utilized in the present (14) SEBS/poly-ethylene; (14) SEBS/polypropylene; (16) invention provided Such polymers exhibits the required high SEP/SEBS, (17) SEP/SEPS, (18) SEP/SEPS/SEB, (19), viscosity. Such SEBS polymers include (high viscosity) SEPS/SEBS/SEP, (20), SEB/SEBS (21), EB-EP/SEBS (22), Kraton G 1855X which has a Specific Gravity of 0.92, SEBS/EB (23), SEBS/EP (24), (25) (SEB), s, (26) (SEP), 40 Brookfield Viscosity of a 25 weight percent solids solution (27) Kuraray 2007 (SEPS), (28) Kuraray 2002, (SEPS), (29) in toluene at 25° C. of about 40,000 cps or about 8,000 to Kuraray 4055(S-E-EP-S) (30) Kuraray 4077(S-E-EP-S) (31) about 20,000 cps at a 20 weight percent solids solution in Kuraray 4045(S-E-EP-S) (32) (S-E-EP), (33) (SEB), (34) toluene at 25 C. EPDM, (35) EPR, (36) EVA, (37) coPP, (38) EMA, (39) The styrene to ethylene and butylene (SEB) weight ratios EEA, (40) DuPont Teflon AF amorphous fluoropolymers, 45 for the Shell designated polymers can have a low range of (41) Dow polydimethylsiloxane, (42) maleated SEBS 20:80 or less. Although the typical ratio values for Kraton G (maleation level 2-30%), (43) (EP), and the like. 1651, 4600, and 4609 are approximately about 33:67 and for Representative examples of commercial elastomers that Kraton G 1855X approximately about 27:73, Kraton G can be combined with the tiblock and Star-shaped copoly 1654X (a lower molecular weight version of Kraton G 1651 mers (I) described above include: Shell Kratons D1101, 50 with Somewhat lower physical properties Such as lower D1102, D1107, D1111, D1112, D1113X, D1114X, D1116, Solution and melt Viscosity) is approximately about 31:69, D1117, D1118X, D1122X, D1125X, D1133X, D1135X, these ratioS can vary broadly from the typical product D1184, D1188X, D1300X, D 1320X, D4122, D4141, specification values. In the case of Kuraray's SEBS polymer D4158, D4240, G1650, G1652, G1657, G1701X, G1702X, 8006 the S:EB weight ratio is about 35:65. In the case of G1726X, G1750X, G1765X, FG1901X, FG1921X, D2103, 55 Kuraray’s 2005 (SEPS), and 2006 (SEPS), the S.EP weight D2109, D2122X, D3202, D3204, D3226, D5298, D5999X, ratios are 20:80 and 35:65 respectively. The styrene to D7340, G1650, G1651, G1652, G4609, G4600, G1654X, ethylene-ethylene/propylene (S:E-EP) ratios of Kuraray’s G2701, G2703, G2705, G1706, G2721X, G7155, G7430, SEPTON 4045,4055, and 4077 are typically about 37.6, 30, G7450, G7523X, G7528X, G7680, G7705, G7702X, 30 respectively. More typically the (S:E-EP) and (S:EP) G7720, G7722x, G7820, G7821X, G7827, G7890X, G7940, 60 ratios can vary broadly much like S:EB ratios of SEBS and FG1901X and FG1921X. Kuraray’s SEP, SEPS, SEBS, (SEB), from less than 19:81 to higher than 51:49 (as recited S-E-EP-S Nos. 1001, 1050, 2027, 2003, 2006, 2007, 2008, above) are possible. It should be noted that multiblock 2023, 2043, 2063, 2050, 2103, 2104, 2105, 4033, 4045, copolymers including SEPTON 4045, 4055, 4077 and the 4055, 4077, 8004, 8006, 8007, H-VS-3 (S-V-EP-S) and the like are described in my cited copending parent applications like. 65 and are the Subject matter of related inventions. The Brookfield Viscosity of a 5 weight percent solids The triblock copolymers (III) such as Kraton G 1654X Solution in toluene at 30° C. of 2006, 4045, 4055, 4077 having ratios of 31:69 or higher can be used and do exhibit 5,884,639 9 10 about the same physical properties in many respects to copolymers as well as in combination with polymers (III) Kraton G 1651 while Kraton G 1654X with ratios below such as SEPS, S-E-EP-S, (S-E-EP), (SEB), (SEP), poly 31:69 may also be use, but they are leSS advantageous due CS. to their decrease in the desirable properties of the final gel. The crystal gels can also contain useful amounts of Plasticizers (II) particularly advantageous for use in prac conventionally employed additives Such as Stabilizers, ticing the present invention are will known in the art, they antioxidants, antiblocking agents, colorants, fragrances, include rubber processing oils. Such as paraffinic and naph flame retardants, flavors, other polymers in minor amounts thenic petroleum oils, highly refined aromatic-free paraffinic and the like to an extend not affecting or Substantially and naphthenic food and technical grade white petroleum decreasing the desired properties. Additives useful in the mineral oils, and Synthetic liquid oligomers of polybutene, crystal gel of the present invention include: tetrakis polypropene, polyterpene, etc. The Synthetic Series proceSS methylene 3,-(3'5'-di-tert butyl-4"-hydroxyphenyl) oils are high Viscosity oligomers which are permanently propionate methane, octadecyl 3-(3".5"-di-tert-butyl-4"- fluid liquid nonolefins, isoparaffins or paraffins of moderate hydroxyphenyl) propionate, diste aryl-pentaerythritol to high molecular weight. diproprionate, thiodiethylene bis-(3,5-ter-butyl-4-hydroxy) Examples of representative commercially available plas 15 hydrocinnamate, (1,3,5-trimethyl-2,4,6-tris(3,5-di-tert ticizing oils include Amoco(E) polybutenes, hydrogenated butyl-4-hydroxybenzylbenzene), 4.4"-methylenebis(2,6-di polybutenes, polybutenes with epoxide functionality at one tert-butylphenol), Steraric acid, oleic acid, Stearamide, end of the polybutene polymer, liquid poly(ethylene/ be he namide, ole amide, eruca mide, N,N'- butylene), liquid hetero-telechelic polymers of poly ethylenebisstearamide, N.N"-ethylenebisoleamide, sterryl (ethylene/butylene/styrene) with epoxidized polyisoprene erucamide, erucyl erucamide, oleyl palmitamide, Stearyl and poly(ethylene/butylene) with epoxidized polyisoprene: Stearamide, erucyl Stearamide, calcium Sterate, other metal Example of such polybutenes include: L-14 (320 Mn), L-50 Sterates, Waxes (e.g., polyethylene, polypropylene, (420 Mn), L-100 (460 Mn), H-15 (560 Mn), H-25 (610 Mn), microcrystalline, carnauba, paraffin, montan, candelilla, H-35 (660 Mn), H-50 (750 Mn), H-100 (920 Mn), H-300 beeswax, Ozokerite, ceresine, and the like), teflon (TFE, (1290 Mn), L-14E (27–37 cst (a 100°F. Viscosity), H-300E 25 PTFE, PEA, FEP, etc), polysiloxane, etc. The crystal gel can (635-690 c.st (a 210° F. Viscosity), Actipol E6 (365 Mn), also contain metallic pigments (aluminum and brass flakes), E16 (973 Mn), E23 (1433 Mn), Kraton L-1203, EKP-206, TiO2, mica, fluorescent dyes and pigments, phosphorescent EKP-207, HPVM-2203 and the like. Example of various pigments, aluminatrihydrate, antimony oxide, iron oxides commercially oils include: ARCO Prime (55, 70, 90, 200, (Fe3O4, -Fe2O3, etc.), iron cobalt oxides, chromium 350, 400 and the like), Duraprime and Tufflo oils (6006, dioxide, iron, barium ferrite, Strontium ferrite and other 6016, 6016M, 6026, 6036,6056, 6206, etc), other white magnetic particle materials, molybdenum, Silicones, Silicone mineral oils include: Bayol, Bernol, American, Blandol, fluids, lake pigments, aluminates, ceramic pigments, Drake ol, Ervol, Gloria, Kaydol, Litetek, Lyondell ironblues, ultramarines, phthalocynines, azo pigments, car (Duraprime 55, 70,90, 200, 350, 400, etc), Marcol, Parol, bon blacks, Silicon dioxide, Silica, clay, feldspar, glass Peneteck, Primol, Protol, Sontex, Witco brand white oils 35 microSpheres, barium ferrite, Wollastonite and the like. The including RR-654-P and the like. Generally, plasticizing oils report of the committee on Magnetic Materials, Publication with average molecular weights less than about 200 and NMAB-426, National Academy Press (1985) is incorporated greater than about 700 may also be used (e.g., H-300 (1290 herein by reference. Mn)). The crystal gels can also be made into composites. The Comparisons of oil extended SEBS triblock copolymers 40 crystal gels can be casted unto various Substrates, Such as have been described in Shell Chemical Company Technical open cell materials, metals, ceramics, glasses, and plastics, Bullet in S C : 11 O2-89 (April 1989) elastomers, fluropolymers, expanded fluropolymers, Teflon “KRATONORTHERMOPLASTIC RUBBERS IN OIL (TFE, PTFE, PEA, FEP, etc), expanded Teflon, spongy GELS” which is incorporated herein by reference. expanded nylon, etc.; the molten crystal gel is deformed as The crystal gels can be made non-adhearing, non-Sticking, 45 it is being cooled. Useful open-cell plastics include: (non-tacky), by incorporating an advantage amount of polyamides, polyimides, polyesters, polyisocyanurates, Stearic acid (octadecanoic acid), metal Stearates (e.g., cal polyisocyanates, polyurethanes, poly(Vinyl alcohol), etc. cium Stearate, magnesium Stearate, Zinc Stearate, etc.), poly Suitable open-celled Plastic (sponges) are described in ethylene glycol distearate, polypropylene glycol ester or “Expanded Plastics and Related Products”, Chemical Tech fatty acid, and polytetramethylene oxide glycol disterate, 50 nology Review No. 221, Noyes Data Corp., 1983, and waxes, Stearic acid and waxes, metal Stearate and waxes, “ Applied Polymer Science”, Organic Coatings and Plastic metal Stearate and Stearic acid. The use of Stearic acid alone Chemistry, 1975. These publications are incorporated herein do not reduce tack. The amount of Stearic acid is also by reference. important. AS an example, ratio of 200 grams Stearic acid to The crystal gels denoted as “G” can be physically inter 2,000 gram of SEBS (a ratio of 0.1) will result in spotted 55 locked with a selected material denoted as “M” to form tack reduction on the surface of the gel. A ratio of 250 to composites as denoted for Simplicity by their combinations 2,000 will result in spotted crystallized stearic acid regions GG, G,G,G, G.M., G.M.G., M.G.M.,i. M.G.G., on the Surface of the gel or spotted tack reduction. A ratio of GGM, MMM i. i. i. M.G.M.,i. 2 M.G.G i. s 300 to 2,000 will result in complete tack reduction with large GMG, G, G.M i. i. i. i. M M, G, G, GM i. s Stearic acid crystallized regions on the Surface of the gel. 60 G.G.M.G.M., GMG,G,G,G 2 M. , G.M.G.M.M.,i. When microcrystalline waxes are incorporated together with MnGnMnGnMnGn, G.G.M.M.G., G.G.M.G.M.G., and Stearic acid, the crystallization of Stearic acid completely the like or any of their permutations of one or more G, with disappears from the Surface of the gel. For example excellent M, and the like, wherein when n is a subscript of M, n is the result is achieved with 200 grams of Stearic acid, 150 grams Same or different Selected from the group consisting of of microcrystalline wax and 2,000 grams of SEBS. The same 65 paper, foam, plastic, fabric, metal, concrete, Wood, glass, excellent result is achieved when SEBS is adjusted to 3,000 ceramics, Synthetic resin, Synthetic fibers or refractory mate grams, 4,000 grams, etc. The same result is achieved with (I) rials and the like, wherein when n is a Subscript of G, n 5,884,639 11 12 denotes the Same or a different gel rigidity of from about 2 substantially about 100% snap back when extended to gram to about 1,800 gram Bloom). The crystal gels of the 1,200% elongation, and a gel rigidity of Substantially from composites are formed from copolymers (I), polymers (III), about 2 gram to about 1,800 gram Bloom and higher, the and plasticizers (III) described above. crystal gels of the present invention exhibit improved tear Sandwiches of crystal gel-material (i.e., crystal gel resistance and resistance to fatigue not obtainable from material-crystal gel or material-crystal gel-material, etc.) are amorphous SEBS gels at corresponding gel rigidities. useful as dental floSS, Shock absorbers, acoustical isolators, The crystal gels of the present invention exhibit one or Vibration dampers, vibration isolators, and wrappers. For more of the following properties. These are: (1) tensile example the vibration isolators can be use under research strength of about 8x10 dyne/cm to about 107 dyne/cm microscopes, office equipment, tables, and the like to and greater; (2) elongation of less than about 1,600% to remove background vibrations. The tear resistance nature of about 3,000% and higher; (3) elasticity modules of about 10" the instant crystal gels are Superior in performance to dyne/cm to about 10° dyne/cm and greater; (4) shear amorphous triblock copolymer gels which are much leSS modules of about 10" dyne/cm to about 10° dyne/cm' and resistance to crack propagation caused by long term con greater as measured with a 1, 2, and 3 kilogram load at 23 15 C.; (5) gel rigidity of about less than about 2 gram Bloom to tinue dynamic loadings. about 1,800 gram Bloom and higher as measured by the The crystal gels are prepared by blending together the gram weight required to depress a gel a distance of 4 mm components including other additatives as desired at about with a piston having a croSS-Sectional area of 1 Square cm at 23 C. to about 100° C. forming a paste like mixture and 23 C.; (6) tear propagation resistance greater than the tear further heating said mixture uniformly to about 150° C. to resistance of amorphous SEBS gels at corresponding gel about 200 C. until a homogeneous molten blend is rigidities; (7) resistance to fatigue greater than the fatigue obtained. Lower and higher temperatures can also be utilized resistance of amorphous SEBS gels at corresponding gel depending on the Viscosity of the oils and amounts of rigidities; (8) and substantially 100% snap back recovery multiblock copolymers (I) and polymer (III) used. These when extended at a crosshead Separation Speed of 25 components blend easily in the melt and a heated vessel 25 cm/minute to 1,200% at 23° C. Properties (1), (2), (3), and equipped with a stirrer is all that is required. Small batches (6) above are measured at a crosshead separation speed of 25 can be easily blended in a test tube using a glass Stirring rod cm/minute at 23° C. for mixing. While conventional large vessels with pressure The crystal gel articles molded from the instant crystal and/or vacuum means can be utilized in forming large gels have additional important advantages in that they batches of the instant crystal gels in amounts of about 40 lbs end-use performance properties are greater than amorphous or less to 10,000 lbs or more. For example, in a large vessel, SEBS gels in that they are more resistant to cracking, inert gases can be employed for removing the composition tearing, crazing or rupture in flexural, tension, compression, from a closed vessel at the end of mixing and a partial vacuum can be applied to remove any entrapped bubbles. or other deforming conditions of use. Like amorphous gels, Stirring rates utilized for large batches can range from about the molded articles made from the instant composition 35 possess the intrinsic properties of elastic memory enabling less than 10 rpm to about 40 rpm or higher. the articles to recover and retain its original molded shape The crystal gel articles can be formed by blending, after many extreme deformation cycles. injection molding, extruding, Spinning, casting, dipping and Because of their improved tear resistance and improved other conventional methods. For example, Shapes having resistance to fatigue, the crystal gels of the present invention various cross-section can be extruded. The crystal gels can 40 achieve greater performance than amorphous gels in low also be formed directly into articles or remelted in any frequency vibration applications, Such as Viscoelastic layers Suitable hot melt applicator and extruded into shaped articles in constrained-layer damping of mechanical Structures and and films or spun into threads, Strips, bands, yarns, or other goods, as Viscoelastic layers used in laminates for isolation shapes. With respect to various shapes and yarn, its size are of acoustical and mechanical noise, as anti-Vibration elastic conventionally measured in denier (grams/9000 meter), tex 45 Support for transporting Shock Sensitive loads, as Vibration (grams/1000 meter), and gage (1/2.54 cm). Gage, tex, denier isolators for an optical table, as Viscoelastic layers used in can be converted as follows: tex=denier/9-specific gravity wrappings, enclosures and linings to control Sound, as (2135/gage), for rectangular cross Section, tex=Specific compositions for use in Shock and dielectric encapsulation gravity (5806x103) (th) (w)/9, where this the thickness and of optical, electrical, and electronic components. w the width of the strip, both in centimeters. General 50 Because of their improved tear resistance and improved descriptions of (1) block copolymers, (2) elastomeric fibers resistance to fatigue, the crystal gels are more useful as and conventional (3) gels are found in volume 2, Starting at molded shape articles for use in medical and Sport health pp. 324–415, volume 6, pp 733–755, and volume 7, pp. 515 care, Such use include therapeutic hand exercising grips, of ENCYCLOPEDIA OF POLYMER SCIENCE AND dental floSS, crutch cushions, cervical pillows, bed wedge ENGINEERING, 1987 which volumes are incorporated 55 pillows, leg rest, neck cushion, mattress, bed pads, elbow herein by reference. padding, dermal pads, wheelchair cushions, helmet liner, The crystal gels are excellent for cast molding and the cold and hot packs, exercise weight belts, traction pads and molded products have various excellent characteristics belts, cushions for splints, slings, and braces (for the hand, which cannot be anticipated form the properties of the raw wrist, finger, forearm, knee, leg, clavicle, shoulder, foot, components. Other conventional methods of forming the 60 ankle, neck, back, rib, etc.), and also Soles for orthopedic composition can be utilized. shoes. Other uses include various shaped articles as toys, Not only do the crystal gels have all the desirable com optical uses (e.g., cladding for cushioning optical fibers from bination of physical and mechanical properties Substantially bending stresses) and various optical devices, as lint Similar to high Viscosity amorphous SEBS gels Such as high removers, dental floSS, as tips for Swabs, as fishing bate, as elongation at break of at least 1,600%, ultimate tensile 65 a high vacuum Seal (against atmosphere pressure) which strength of about 8x10 dyne/cm and higher, low elonga contains a useful amount of a mineral oil-based magnetic tion Set at break of Substantially not greater than about 2%, fluid particles, etc. Moreover, the casted, extruded, or spun 5,884,639 13 14 threads, Strips, yarns, tapes can be weaved into cloths, fine gam alloy metal contact points showing no gap between the or coarse fabrics. teeth, it is critical that the crystal gel resist tearing, Shearing, The crystal gels can be formed in any shape; the original and crazing while being Stretched to a high degree in Such Situations. For example, dental crystal gel floSS can take the shape can be deformed into another shape (to contact a form of a disk where the Segments of the circumference of regular or irregular Surface) by pressure and upon removal the disk is stretched for flossing between the teeth. Other of the applied pressure, the composition in the deformed shaped articles Suitable for flossing include threads, Strips, shape will recover back to its original shape. yarns, tapes, etc., mentioned above. AS an example of the versatility of use of the instant In order for crystal gels to be useful as a dental floSS, it crystal gels, a hand exerciser can be made in any shape So must overcome the difficult barriers of high shearing and long as it is Suitable for use as a hand exerciser: a sphere high tearing under extreme elongation and tension loads. shape, a cube shape, a rectangular shape, etc. Likewise, a The difficulties that the crystal gels must overcome during wheelchair cushion can be made from the composition in flossing can be viewed as follows: during the action of any shape, So long as it meets the needs of the user of the flossing, the crystal gel is stretched from no less than about cushion. For example, a cushion can be made by forming the 15 200% to about 1,100% or higher, the crystal gel floss is composition into a Selected shape matching the contours of deformed as it is pulled down with tearing action between the Specific body part or body region. The composition can the contacting Surfaces of the teeth, then, the wedge of be formed into any desired shaped, size and thickneSS crystal gel floSS is sheared between the inner contacting Suitable as a cushion; the shaped composition can be addi Surfaces of the teeth, and finally, the elongated wedged of tionally Surrounded with film, fabric, foam, or any other crystal gel floSS is pulled upwards and out between the desired material or combinations thereof. Moreover, the Surfaces of the teeth. The forces encountered in the act of composition can be casted onto Such materials, provided flossing are: tension, shearing, tearing under eXtreme ten Such materials Substantially maintain their integrity (shape, appearance, texture, etc.) during the casting process. The SO. Same applies for brace cushions, liners, linings and protec The use of crystal gels advances the flossing art by 25 providing Strong, Soft, and more tear resistant gels than tive coverings for the hand, wrist, finger, forearm, knee, leg, amorphous gels. FloSS made from the crystal gels has many etc. advantages over conventional dental floSS Such as regular Because of their improved tear resistance and resistance and extra fine waxed and unwaxed nylon floSS, Spongy nylon to fatigue, the crystal gels exhibit versatility as balloons for fiber floSS, and waxed and unwaxed expanded and unex medical uses, Such as balloon for valvuloplasty of the mitral pended teflon floSS. Such conventional floSS are not recom Valve, gastrointestinal balloon dilator, esophageal balloon mended for use by children, Since a Slip or Sudden Snap in dilator, dilating balloon catheter use in coronary angiogram forcing the floSS between the teeth may cause injury to the and the like. Since the crystal gels are more tear resistant, gums which often times results in bleeding. For sensitive they are especially useful for making condoms, toy balloons, gums and inflamed gums which has become red and puffy, and Surgical and examination gloves. AS toy balloons, the 35 it is difficult to floss at, near, and below the gumline. The soft crystal gels are Safer because it will not rupture or explode crystal gel floSS with Softness Substantially matching the when punctured as would latex balloons which often times Softness of the gums are of great advantage for use by cause injures or death to children by choking from pieces of children and for flossing teeth Surrounded by Sensitive and latex rubber. The crystal gels are advantageously useful for tender gums. making gloves, thin gloves for Surgery and examination and 40 In all cases, the tear Strength of crystal gels are higher than thicker gloves for vibration damping which prevents damage that of amorphous gels. The rigidities of the crystal gels for to blood capillaries in the fingers and hand caused by use as dental floSS advantageously should be selected to handling Strong Shock and vibrating equipment. exhibit a propagating tear force (when propagating a tear as Other uses include Self Sealing enclosures for Splicing measured at 180 Ubend around a 5.0 mm diameter mandrel electrical and telephone cables and wires. For example, the 45 attached to a Spring Scale) of at least about 1. Kg/cm, more crystal gels can be pre-formed into a Small diameter tubing advantageously at least 2. Kg/cm, and Still more advanta within an outer elastic tubing, both the internal crystal gel geously of about 3 Kg/cm and higher. For any gel to be tubing and external elastic tubing can be axially expanded considered useful for flossing, the gels should exhibit tear and fixed in place by a removable continuous retainer. Upon Strengths of at least 2. Kg/cm and higher, advantageously of insertion of a spliced pair or bundle of cables or wires, the 50 at least 4Kg/cm and higher, more advantageously of at least retainer can be removed, as the retainer is removed, the 6 Kg/cm and higher, exceptionally more advantageously of crystal gel and elastic tubing impinges onto the inserted at least 8 Kg/cm and higher. Typically, the tear propagation cables or wires Splices, thereby Sealing the electrical Splices Strength should range from about 5 Kg/cm to about 20 against weather, water, dirt, corrosives and Shielding the Kg/cm and higher, more typically from about less than 5 Splice from external abuse. The enclosure is completed 55 Kg/cm to about 25 Kg/cm and higher, especially more without the use of heat or flame as is conventionally per typically form about less than 6 Kg/cm to about 30 Kg/cm formed. and higher, and exceptionally more typically from about leSS Because of their improved resistance to tearing, the crys than 8 Kg/cm to about 35 Kg/cm and higher. tal gels do not tear as readily as amorphous gels when used For any gel to be considered useful for floSSing, the gels, as dental floSS. The dental floSS can be almost any shape So 60 critically, should advantageously exhibit a propagating ten long as it is Suitable for dental flossing. A thick shaped piece Sion tear force (when a cylindrical sample is notched and a of the composition can be stretched into a thin shape and tear is initiated at the notched area and propagated past its used for flossing. A thinner shaped piece would require leSS maximum cylindrical diameter by length-wise Stretching of Stretching, etc. For purposes of dental flossing, while floSS the cylindrical Sample) of at least about 1. Kg/cm, more ing between two closely adjacent teeth, especially between 65 advantageously at least 2. Kg/cm, and Still more advanta two adjacent teeth with Substantial contact points and more geously of about 4 Kg/cm and higher. Although the crystal especially between two adjacent teeth with Substantial amal gels of the present invention have improved tear resistance 5,884,639 15 16 and resistance to fatigue greater than the amorphous gels at Strength, notched tear Strength, and resistance to fatigue are corresponding gel rigidities, the high and ultra-high tear found to decrease with increase amounts of plasticizers. resistant gels of my other related parent and c-i-p applica tions typically will exhibit even higher tear resistance Val EXAMPLE V CS. Example III is repeated using high Viscosity crystalline While advantageous components and formulation ranges midblock segment linear SEBS and radial (SEB), triblock based on the desired properties of the crystal gels have been copolymers with ethylene to butylene midblock ratios (E:B) disclosed herein. Persons of skill in the art can extend these of 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, ranges using appropriate material according to the principles 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, discussed herein. All Such variations and deviations which 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34 and rely on the teachings through which the present invention 65:35, the bulk gel rigidities are found to be within the range has advanced the art are considered to be within the Spirit of 2 gram to 1,800 gram Bloom and the notched tear strength and Scope of the present invention. and resistance to fatigue of the gel at corresponding rigidi The invention is further illustrated by means of the ties are found to be greater than that of amorphous gels of following illustrative embodiments, which are given for 15 Example III. purpose of illustration only and are not meant to limit the invention to the particular components and amounts dis EXAMPLE VI closed. Example IV is repeated using high Viscosity crystalline midblock segment linear SEBS and radial (SEB), triblock EXAMPLE I copolymers with ethylene to butylene midblock ratios (E:B) Gels of 100 parts of high viscosity linear Kraton G.1651 of 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, (amorphous SEBS), Septon 8006 (amorphous SEBS), and a 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, high Viscosity radial amorphous midblock segment (SEB), 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34 and triblock copolymers and 1,600, 1,200, 1,000, 800, 600, 500, 25 65:35, the bulk gel rigidities are found to be within the range 450, 300, 250 parts by weight of Duraprime 200 white oil of 2 gram to 1,800 gram Bloom and the notched tear strength (plasticizer) are melt blended and Samples molded, the bulk and resistance to fatigue of the gel at corresponding rigidi gel rigidities are found to be within the range of 2 to 1,800 ties are found to be greater than that of amorphous gels of gram Bloom and the tensile Strength, notched tear Strength, Example IV. and resistance to fatigue are found to decrease with increase amounts of plasticizers. EXAMPLE VII Example II is repeated and minor amounts of 2, 5, 10 and EXAMPLE II 15 parts of the following polymers are formulated with each Example I is repeated using high Viscosity crystalline of the triblock copolymers: Styrene-butadiene-Styrene block midblock segment linear SEBS and radial (SEB), triblock 35 copolymers, Styrene-isoprene-styrene block copolymers, copolymers with ethylene to butylene midblock ratios (E:B) low Viscosity Styrene-ethylene-butylene-styrene block of 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, copolymers, Styrene-ethylene-propylene block copolymers, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, Styrene-ethylene-propylene-Styrene block copolymers, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34 and Styrene-butadiene, Styrene-isoprene, polyethyleneoxide, 65:35, the bulk gel rigidities are found to be within the range 40 poly(dimethylphenylene oxide), polystyrene, polybutylene, of 2 gram to 1,800 gram Bloom and the notched tear strength polyethylene, polypropylene, high ethylene content EPDM, and resistance to fatigue of the gel at corresponding rigidi amorphous copolymers based on 2,2-bistrifluoromethyl-4, ties are found to be greater than that of amorphous gels of 5-difluoro-1,3-dioxole/tetrafluoroethylene. The bulk gel Example I. rigidities of each of the formulations are found to be within 45 the range of 2 gram to 2,000 gram Bloom and the notched EXAMPLE III tear Strength and resistance to fatigue of the gels at corre Gels of 100 parts of Kraton G1651 (amorphous SEBS), sponding rigidities are found to be greater than that of Septon 8006 (amorphous SEBS), and a high viscosity amor amorphous gels of Example I formulated with correspond ing amounts of the same polymers. phous midblock segment (SEB), linear and radial triblock 50 copolymers, 1,600, 1,200, 1,000, 800, 600, 500, 450, 300, 250 parts by weight of Duraprime 200 white oil (plasticizer), EXAMPLE VIII and 10 parts of Dow polydimethylsiloxane are melt blended Molten gels of Examples I-VII are formed into compos and Samples molded, the bulk gel rigidities are found to be ites with paper, foam, plastic, elastomers, fabric, metal, within the range of 2 to 1,800 gram Bloom and the tensile 55 concrete, wood, glass, ceramics, Synthetic resin, Synthetic Strength, notched tear Strength, and resistance to fatigue are fibers, and refractory materials and the resistance to fatigue found to decrease with increase amounts of plasticizers. of the composite-crystal gels at corresponding rigidities are found to be greater than that of the composite-amorphous EXAMPLE IV gels. Gels of 100 parts of Kraton G1651 (amorphous SEBS), 60 Septon 8006 (amorphous SEBS), and a high viscosity amor EXAMPLE IX phous midblock segment (SEB), linear and radial triblock Three cm thick sheets of each of the crystal gels of copolymers, 1,600, 1,200, 1,000, 800, 600, 500, 450, 300, Example II and the amorphous gels of Example I are tested 250 parts by weight of Duraprime 200 white oil (plasticizer), by repeatedly displacing the sheets to a depth of 1 cm using and 2 parts of Dupont Teflon AF 1600 are melt blended and 65 a 10 cm diameter Smooth (water Soaked) wood plunger for Samples molded, the bulk gel rigidities are found to be 1,000, 5,000, 10,000, 25,000, 50,000, and 100,000 cycles. within the range of 2 to 1,800 gram Bloom and the tensile The sheets of crystal gels are found capable of exhibiting 5,884,639 17 18 greater fatigue resistance than the sheets of amorphous gels ethylene-butylene being a midblock copolymer Segment of at corresponding rigidities. said (ii) triblock copolymers having a selected amount of While preferred components and formulation ranges have crystallinity Sufficient to achieve improvements in tear resis been disclosed herein perSons of Skill in the art can extend tance as measured using a 180 U-bend tear propagation test, these ranges using appropriate material according to the Said improvement in tear resistance of Said crystal gel being principles discussed herein. Furthermore, Crystalline mid greater than an amorphous gel at corresponding Said gel block segment SEBS block polymers can be use in blending rigidity formed from said (i) triblock or diblock copolymers with other engineering plastics and elastomeric polymers to having a non-crystalline ethylene-propylene midblock Seg make alloyed compositions having improved impact and ments; (iv) optionally in combination with a Selected amount tear resistance properties. All Such variations and deviations of one or more of a Selected polymer or copolymer. which rely on the teachings through which the present 5. An improved gelatinous composition comprising: a invention has advanced the art are considered to be within crystal gel formed from (i) 100 parts by weight of one or the Spirit and Scope of the present invention. more high Viscosity triblock copolymers of the general What I claim is: configurations poly(styrene-ethylene-butylene-styrene), 1. An improved gelatinous composition comprising: a 15 poly(styrene-ethylene-propylene-styrene), diblock copoly crystal gel formed from (i) 100 parts by weight of one or mers of the general configurations poly(styrene-ethylene more Substantially amorphous high Viscosity triblock butylene), poly(styrene-ethylene-propylene) or a mixture copolymers of the general configurations poly(styrene thereof, said triblock and diblock copolymerS having a ethylene-butylene-styrene), poly(styrene-ethylene non-crystalline ethylene-butylene and ethylene-propylene propylene-styrene), diblock copolymers of the general con midblock segment respectively in combination with (ii) a figurations poly(styrene-ethylene-butylene), poly(styrene minor amount of less than about 20 parts by weight of a ethylene-propylene) or a mixture thereof, said triblock and highly crystalline ethylene-butylene midblock Segment tri diblock copolymers having a non-crystalline ethylene block copolymer of the configuration poly(styrene-ethylene butylene and ethylene-propylene midblock Segment respec butylene-styrene); (iii) a selected amount of from about 250 tively in combination with (ii) a minor amount of less than 25 to about 1,600 parts of a plasticizer Sufficient to achieve a gel about 20 parts by weight of a highly crystalline ethylene rigidity of from less than about 2 gram Bloom to about 1,800 butylene midblock Segment triblock copolymer of the con gram Bloom; wherein Said crystalline ethylene-butylene figuration poly(styrene-ethylene-butylene-styrene); (iii) being a midblock copolymer segment of Said (ii) triblock from about 250 to about 1,600 parts of a plasticizer Sufficient copolymers having a Selected amount of crystallinity Suffi to achieve a gel rigidity of from less than about 2 gram cient to achieve improvements in one or more properties Bloom to about 1,800 gram Bloom; wherein said crystalline including improved tear resistance and improved resistance ethylene-butylene midblock copolymer segment of Said (ii) to fatigue; wherein Said improvements in properties of Said triblock copolymer having a Selected amount of crystallinity crystal gel being greater than an amorphous gel at corre Sufficient to achieve improvements in one or more properties sponding said gel rigidity formed from Said (i) triblock or including improved tear resistance and improved resistance 35 diblock copolymers having a Substantially non-crystalline to fatigue; wherein Said improvements in properties of Said ethylene-butylene and ethylene-propylene midblock Seg crystal gel being greater than an amorphous gel at corre ments, wherein Said Selected amount of crystallinity is sponding said gel rigidity formed from Said (i) triblock or capable of exhibiting a broad melting endotherm in differ diblock copolymers having a Substantially non-crystalline ential scanning calorimeter (DCS) curves as seen on heating ethylene-butylene and ethylene-propylene midblock Seg 40 and a sharp crystallization exotherm as seen on cooling; (iv) ments; (iv) optionally in combination with a Selected amount optionally in combination with a Selected amount of one or of one or more of a Selected polymer or copolymer Said more of a Selected polymer or copolymer. gelatinous composition exhibiting a tear Strength of at least 6. A gel according to claim 5, wherein Said gel exhibits in 1 kg/cm. differential Scanning calorimeter (DCS) a melting endot 2. A gel according to claim 1, wherein Said midblock 45 herm of about 20° C., 21 C., 22°C., 23°C., 24°C., 25°C., copolymer Segment having a crystallinity of at least about 26° C., 27° C., 28° C., 29° C., 30° C., 31° C., 32° C., 33° 10% by weight of said ethylene-butylene midblock copoly C., 34° C., 35° C., 36° C., 37° C., 38° C., 39° C., 40°C., 41° mer Segment. C., 42°C., 43° C., 44° C., 45° C., 46° C., 47°C., 48°C., 49° 3. A gel according to claim 1, wherein Said midblock C.,50° C., 51° C., 52° C., 53°C.,54°C.,55° C., 56°C.,57° copolymer Segment having a crystallinity of at least about 50 C., 58° C., 59° C., 60° C., 61° C., 62° C., 63° C., 64° C., 65° 15% by weight of said ethylene-butylene midblock copoly C., 66° C., 67° C., 68°C, 69° C., 70° C., 71° C., 72°C., 73° mer Segment. C., 74° C., 75° C., 76° C., 77° C., 78° C., 79° C., or 80° C. 4. An improved gelatinous composition comprising: a 7. An improved gelatinous composition comprising: a crystal gel formed from (i) 100 parts by weight of one or crystal gel formed from (i) 100 parts by weight of one or more high Viscosity triblock copolymers of the general 55 more high Viscosity triblock copolymers of the general configurations poly(styrene-ethylene-propylene-styrene), configurations poly(styrene-ethylene-butylene-styrene), diblock copolymers of the general configurations poly poly(styrene-ethylene-propylene-styrene), diblock copoly (styrene-ethylene-propylene) or a mixture thereof, said tri mers of the general configurations poly(styrene-ethylene block and diblock copolymers having a non-crystalline butylene), poly(styrene-ethylene-propylene) or a mixture ethylene-propylene midblock Segment in combination with 60 thereof, said triblock and diblock copolymerS having a (ii) a minor amount of less than about 98 parts by weight of non-crystalline ethylene-butylene and ethylene-propylene a highly crystalline ethylene-butylene midblock Segment midblock segment respectively in combination with (ii) a triblock copolymer of the configuration poly(styrene minor amount of less than about 20 parts by weight of a ethylene-butylene-styrene); (iii) a selected amount of from highly crystalline ethylene-butylene midblock Segment tri about 250 to about 1,600 parts of a plasticizer sufficient to 65 block copolymer of the configuration poly(styrene-ethylene achieve a gel rigidity of from less than about 2 gram Bloom butylene-styrene); (iii) a selected amount of from about 250 to about 1,800 gram Bloom; wherein said crystalline to about 1,600 parts of a plasticizer Sufficient to achieve a gel 5,884,639 19 20 rigidity of from less than about 2 gram Bloom to about 1,800 maleated poly(styrene-ethylene-butylene)n, polystyrene, gram Bloom; wherein Said crystalline ethylene-butylene polybutylene, poly(ethylene-propylene), poly(ethylene being a midblock copolymer segment of said (i) triblock butylene), polypropylene, polyethylene, polyethyleneoxide, copolymers having a Selected amount of crystallinity Suffi poly(dimethylphenylene oxide), copolymers of cient to achieve improvements in one or more properties trifluoromethyl-4,5-difluoro-1,3-dioxole and including improved tear resistance and improved resistance tetrafluoroethylene, tetrafluoroethylene, polycarbonate, eth to fatigue; wherein Said improvements in properties of Said ylene Vinyl alcohol copolymer, polyamide or polydimethyl crystal gel being greater than an amorphous gel at corre sponding said gel rigidity formed from said (i) triblock Siloxane, wherein Said copolymer is a linear, branched, copolymers having a Substantially non-crystalline ethylene radial, or a multiarm copolymer. butylene and ethylene-propylene midblock Segments; 8. A gel according to claim 7, wherein Said gel is being wherein Said Selected amount of crystallinity is capable of denoted by G, is physically interlocked with a Selected exhibiting a broad melting endotherm in differential Scan material M forming the combination G.M., G.M.G., ning calorimeter (DCS) curves as seen on heating and a M.G.M., M.G. G.M., G.M.M.G., G.M.G.M.G., Sharp crystallization exotherm as seen on cooling; (iv) 15 M.M.M.G., M.M.M.G.M.M.M. or a permutation of one optionally in combination with a Selected amount of one or or more of Said G, with M, wherein when n is a Subscript more polymer or copolymer of poly(styrene-butadiene of M, n is the same or different selected from the group styrene), poly(styrene-butadiene), poly(styrene-isoprene consisting of paper, foam, plastic, fabric, metal, metal foil, styrene), poly(styrene-isoprene), poly(styrene-ethylene concrete, wood, glass, glass fibers, ceramics, Synthetic resin, propylene), poly(styrene-ethylene-propylene-styrene), poly Synthetic fibers or refractory materials, and wherein when in (styrene-ethylene-butylene-styrene), poly(styrene-ethylene is a Subscript of G, n denotes the same or a different gel butylene), poly(styrene-ethylene-propylene)n, poly(styrene rigidity. ethylene-butylene)n, maleated poly(styrene-ethylene 9. A gel according to claim 6, wherein Said gel being propylene-styrene), maleated poly(styrene-ethylene formed into a shape floSS Suitable for use as a dental floSS. butylene-styrene), maleated poly(styrene-ethylene 25 butylene), maleated poly(styrene-ethylene-propylene)n,