US 20140316041A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0316041 A1 Mehta (43) Pub. Date: Oct. 23, 2014

(54) ALTERNATIVE APPROACH TO Publication Classification TOUGHENING AND FLEXBILIZING AND THERMOSET (51) Int. Cl. POLYMERS COSL 83/04 (2006.01) COSL 2L/00 (2006.01) (71) Applicant: Veerag Mehta, Plainsboro, NJ (US) COSL 77/06 (2006.01) (52) U.S. Cl. (72) Inventor: Veerag Mehta, Plainsboro, NJ (US) CPC ...... C08L 83/04 (2013.01); C08L 77/06 (2013.01); C08L 21/00 (2013.01) (21) Appl. No.: 14/257,032 USPC ...... 524/323: 524/538; 524/506 Filed: Apr. 21, 2014 (22) (57) ABSTRACT Related U.S. Application Data A composition of matter comprising a thermoplastic or ther (60) Provisional application No. 61/814.362, filed on Apr. moset polymer blended with a polysiloxane base and option 22, 2013. ally adjuvents. US 2014/0316041 A1 Oct. 23, 2014

ALTERNATIVE APPROACH TO 0007. This invention describes a novel composition to TOUGHENING AND FLEXBILIZING improve on all aspects of the existing technology of additive THERMOPLASTIC AND THERMOSET to improve flexibility and/or impact strength of a wide range POLYMERS of polymer compositions. This technology is novel because it does not rely on interference of hydrogen bonding between 0001. The present invention deals with a process for pro polymer chains to exhibits its performance properties as does viding a thermoplastic or thermoset resin composition. This the current industrial technologies. Additionally, the invention claims priority from U.S. Provisional Ser. No. described technology can be utilized over a vast range of 61/814,362, filed Apr. 22, 2013. temperatures from leas than-50° C. to greater 400° C. BACKGROUND OF THE INVENTION 0008. An additional aspect is the greatly improved eco toxicological profile. The materials used as an additive in this 0002 There are many obstacles to developing a multi invention are commonly used in a number of applications for purpose flexible polymer composition. Polymers are widely indirect and direct food contact. Due to its high molecular used in many various applications. Through modification, the weight, these additives are not metabolized by various living properties of polymers can be tailored for an intended perfor Creatures. mance. These applications include, but are net limited to, 0009. The purpose of this invention is the use of a modified automotive, construction, oil field, packaging, including tub organo-silicone additive in place of the conventional tech ing, hoses and cable jackets, as well as, a number of other nologies used in a wide range of polymer compositions and applications and compositions. These applications require constructions. This invention is particularly useful in auto high flexibility and/or improved impact strength across a motive, construction, oil field, packaging, including tubing, wide range of temperatures. These attributes are generally hoses, wire and cable, containers for food or general packag attained by the addition of a additive. ing, electrical connectors, protective covers, specialty films, 0003 Traditional provide flexibility in the end automotive components, industrial housings, sporting good, use product. The most common mechanism by which they footwear, fibers, foam, as well as, a number of other applica work is that they have partial solubility in the polymer to tions and compositions. These are all products that can be which they are added, so they blend and disperse easily. Once made by conventional polymer processing. dispersed in the polymer matrix, they create spacing between the polymerchains, lowering the glass transition temperature, and thus increasing the flexibility. THE INVENTION 0004 Plasticizer additives, though they perform well in 0010 Thus, what is disclosed and claimed herein is a many applications, they have any issues, such as a limited composition of matter comprising a blend of 20 to 98 weight performance range and a negative eco-toxicological aspects. percent of a thermoplastic resin and, 2 to 80 weight percent of For example, Sulfonamides, such as N-ethyl-Orthofpara-tolu an ultra-high molecular weight polysiloxane having a enesulfonamide and N-Butylbenzenesulfonamide, are com molecular weight (Mn) of at least 10,000 and not more than monly used in commercial and industrial applications for about 1,000,000 (Mn), wherein the ultra-high molecular imparting flexibility and/or impact strength to various polya weight polydimethylsiloxane has blended with it 3 to 35 mides. Sulfonamides can be used with a number of weight percent of a silica selected from the group consisting compositions across a wider range of temperature than with of precipitated silica and fumed silica. water or N-alkylpyrrolidones. Sulfonamides are suspect for a 0011. The ultra-high molecular weight polydimethylsi wide range to eco-toxicological properties, such as reports of loxane has pendant groups, terminal groups, or mixtures of neurotoxicity and accumulation in Surface waters. In addi pendant groups and terminal groups, selected from the group tion, they are limited in performance below -25° C. and in consisting of hydrogen, trimethyl, dimethyl, methyl, phenyl, temperatures over 150° C. they are known for volatilizing out fluoro, amino, vinyl, hydroxyl, and methacrylate. of the polyamide resin. 0005 Again using a polyamide 6 or polyamide 66 resin as 0012. In another embodiment, there is a composition of an example, water is also used as a plasticizer. Though water matter comprising a blend of 20 to 98 weight percent of a has a good eco-toxicological profile, it is limited in its use thermoset resin and, 2 to 80 weight percent of an ultra-high across a wide range oftemperatures due to its melting point at molecular weight polysiloxane having a molecular weight 0° C. and its boiling point of 100° C.; essentially affecting its (Mn) of at least 10,000 and not more than about 1,000,000 low temperature brittleness performance and its volatility at (Mn), wherein the ultra-high molecular weight polydimeth higher temperature. These aspects greatly affect the perfor ylsiloxane has blended with it 3 to 35 weight percent of a mance properties of the various polyamide compositions silica selected from the group consisting of precipitated silica where is used. Water is also quite limited to use in more and fumed silica. “exotic' polyamide compositions that require higher com 0013 The ultra-high molecular weight polydimethylsi pounding temperatures, thus resulting in significant loss of loxane has pendant groups, terminal groups, or mixtures of the additive. pendant groups and terminal groups, selected from the group 0006. The market requires an improvement on existing consisting of hydrogen, trimethyl, dimethyl, methyl, phenyl, technologies, as well as, potential new applications, such as, fluoro, amino, vinyl, hydroxyl, and methacrylate. automotive, construction oil field, packaging, including tub 0014. In addition there is a composition of matter com ing, hoses and cable jackets, as well as, a number of other prising a blend of 20 to 98 weight percent of a thermoset applications and compositions. This invention, potentially, rubber and 2 to 80 weight percent of an ultra-high molecular will open new avenues for various polymer compositions, in weight polysiloxane having a molecular weight (Mn) of at existing, more technologically difficult areas, as well as new least 10,000 and not more than about 1,000,000 (Mn), market potentials. wherein the ultra-high molecular weight polydimethylsilox US 2014/0316041 A1 Oct. 23, 2014

ane has blended with it 3 to 35 weight percent of a silica 0024. Other materials or adjuvents can be added to the selected from the group consisting of precipitated silica and blends depending on which properties one wishes to enhance. fumed silica. For example, one can add compatibilizer. Such compatibiliz 0015 The ultra-high molecular weight polydimethylsi ers are known in the art and can be selected based on the type loxane has pendant groups, terminal groups, or mixtures of of thermoplastic or thermoset polymer and the kind of func pendant groups and terminal groups, selected from the group tionality it has. Typical compatibilizers include polymers and consisting of hydrogen, trimethyl, dimethyl, methyl, phenyl, oligomers that are block and/or graft co-, tert-, tetra-polymers fluoro, amino, vinyl, hydroxyl, and methacrylate. or oligomers with groups that include, but are not limited to, ethylene, propylene, butylene, butadiene, vinyl, maleic anhy DETAILED DESCRIPTION OF THE INVENTION dride, vinyl acetate, carboxylic acid, acrylic acids, lactic acid, 0016. Thus, the invention herein is a composition that is esters, silanes, dimethylsiloxanes, styrene, ether, acrylates, provided by blending a thermoplastic or thermoset polymer, epoxides, oxides, dienes, cyanurate, urethane, quinone, aza Such as resins or rubbers with an ultra-high molecular weight lactone, Sulfonate, chloride, fluoride, imide, ketones, vinyl, polysiloxane base. phenyl, hydroxyl, epoxy, methoxy, amide, imide, isoprene, 0017. The thermoplastic polymer can be selected from the hexane, octane, decane, and dodecane. The compatibilizer group consisting of , high impact polystyrene, can be added during the blending of the polymer with the , , , poly(phenylene ultra-high molecular weight polysiloxane base. Sulfide), acrylonitrile-butadiene-styrene copolymer, , 0025 Plasticizers can also be added to the blend of the acetal, , polyketones, poly(ethylene terephtha polysiloxane base and the polymer, Such plasticizers can be, late), poly(butylene terephthalate), acrylate, fluoroplastics, for example, Dicarboxylic/tricarboxylic ester-based plasti , phenolics, epoxies, urethanes, , cizers such as, -based plasticizers: Bis(2-ethyl melamine formaldehyde and urea, among others. Blends of hexyl) phthalate (DEHP), Di (2-ethylhexyl) Phthalate, these polymers are contemplated within the scope of this (DINP), Di-n-butyl phthalate (DnBP invention. DBP), Butylbenzyl phthalate (BBZP), 0018 Useful thermoset polymers are polyesters, polyure (DIDP), Di-n-octyl phthalate (DOP or DnOP), Diisooctyl thanes, rubbers, phenol-formaldehyde, urea-formaldehyde, phthalate (DIOP), Diethyl phthalate (DEP), Diisobutyl melamines, epoxy, polyimides and polycyanurates, among phthalate (DIBP), Di-n-hexyl phthalate, di-2-ethylhexyl others. Blends of these polymers are contemplated within the phthalate. Butyl Benzene Phthalate, Di-isoNonyl Phthalate, scope of this inventions. Di-isodecyl Phthalate, Dipropylheptyl phthalate, Diundecyl 0019 Typically, these polymers are used in a ratio of 20 phthalate, Diisoundecyl phthalate, Ditridecyl phthalate, weight percent to 98 weight percent to 80 to 2 weight percent . , Didobutyl phtha of the ultra-high molecular weight polysiloxane base. More late, Diisoheptyl phthalate, Dipropyl phthalate, Dimethyl preferably, the polymers are used at 50 weight percent to 98 phthalate; Trimellitates such as, Trimethyl trimellitate weight percent and most preferably, the polymers are used at (TMTM), Tri-(2-ethylhexyl)trimellitate (TEHTM-MG), Tri 70 to 98 weight percentall based on the weight of the polymer (n-octylin-decyl) trimellitate (ATM), Tri-(heptylnonyl)trim and the polysiloxane base. ellitate (LTM), n-octyl trimellitate (OTM), Trioctyl trimelli 0020. The polymers are blended with 2 to 80 weight per tate/Tris(2-ethylhexyl)trimellitate; , sebacates, cent of ultra-high molecular weight polysiloxane bases. The maleates, such as, Bis(2-ethylhexyl) (DEHA), Dim polysiloxanes in Such bases have pendant groups, terminal ethyl adipate (DMAD), Monomethyl adipate (MMAD), Dio groups, or mixtures of pendant groups and terminal groups ctyladipate (DOA), Dibutyl sebacate (DES), Dibutyl maleate selected from groups such as trimethyl, dimethyl, methyl, (DBM), Diisobutyl maleate (DIBM), di(butoxyethyl)adipate, phenyl, fluoro, amino, vinyl, hydroxyl, and methacrylate to Dibutoxyethoxyethyladipate, Di (2-ethylhexyl) adipate, and, mention a few. /Bis(2-ethylhexyl)adipate. 0021. The silica in such bases consists primarily of pre 0026. Other plasticizers include Benzoates, Terephtha cipitated and fumed silicas. The silica is present in the range lates such as Dioctyl terephthalate/DEHT, Glyceryl triben of 3 to 35 weight percent based on the weight of the silica and Zoate, 1,4-cyclohexanedimethanol dibenzoate, Polypropy the polysiloxane. A more preferred range for the silica is 15 to lene glycol dibenzoate, Neopentyl glycol dibenzoate, 1.2- 25 weight percent. Cyclohexane dicarboxylic acid diisononyl ester, Epoxidized 0022. The preferred polysiloxanes for this invention are vegetable oils, alkyl sulphonic acid phenyl ester (ASE), Sul polydimethyl-siloxanes having either hydroxydimethyl ter fonamides, N-ethyl toluene sulfonamide (o?p ETSA), ortho mination, vinyldimethyl termination, trimethylsiloxy termi and paraisomers, N-(2-hydroxypropyl)benzene Sulfonamide nation or, the above-mentioned materials wherein there are (HP BSA). N-Ethyl-o/p-toluene sulfonamide, N-(n-butyl) pendant groups as set forth Supra. What is meant by “ultra benzene sulfonamide (BBSA-NBBS), N-butylbenzene sul high molecular weight' is that the polysiloxanes have a fonamide, , Dipropylene glycol diben molecular weight (Mn) of at least 10,000 and not more than Zoate, dipropylene glycol 1,4-cyclohexane dimethanol diben about 1,000,000 (Mn). Preferred is an Mn of 50,000 to 500, Zoate, triethyl phosphate, triisopropyl phenyl phosphate, 000 and most preferred is an Mn of 250,000 to 350,000. When Tricresyl phosphate (TCP), Tributyl phosphate (TEP), e-eth the molecular weight is below 10,000, the resultant silicone ylhexyldiphenyl phosphate, Dioctyl phosphate, isol Decyl base may not be as effective. When the molecular weight is diphenyl phosphate, triphenyl phosphate, triaryl phosphate above 1,000,000, blending the polysiloxane with silica synthetic, tributoxyethyl phosphate, tris-(chloroethyl) phos becomes difficult to disperse, but such a polysiloxane can still phate, buty phenyl diphenyl phosphate, chlorinated organic be employed. phosphate, cresyl diphenyl phosphate, tris-(dichloropropyl) 0023 The blends are prepared by known methods in the phosphate, isopropylphenyl diphenyl phosphate, trixenyl industry and do not entail complex manufacturing. phosphate, tricresyl phosphate, diphenyl octyl phosphate, US 2014/0316041 A1 Oct. 23, 2014

Glycols/polyethers, Triethylene glycol dihexanoate (3G6, mer with a melt flow index of 9 g/10 min. A Thermoplastic 3GH), Tetraethylene glycol diheptanoate (4G7), Polymeric Elastomer () (TPU-Polyester) mate plasticizers, Polybutene, N-n-butylbenzenesulphonamide, rial with a specific gravity of 1.20. A random copolymer of Triethyleneglycol bis (2-ethylhexanoate), N-ethyl of p-tolu Ethylene and Methyl Acrylate with a melt flow index of 8 g/10 ene sulfonamide, PEG di-2-ethylhexoate, PEG di laurate, 1. Triethyl acetylcitrate, Acetyl tributyl citrate, Triethylene gly col bis(2-ethylhexanoate), Dioctyl terephthalate/Bis(2-ethyl Example 1: Polyamido 12 Blends hexyl)-1,4-benzenedicarboxylate, Dioctyl succinate/Bis(2- 0032. The material can be prepared in two steps. In the first ethylhexyl)succinate, Dioctyl succinate/Bis(2-ethylhexyl) step the precipitated silica was blended into the ultra-high Succinate and Biodegradable plasticizers such as Acetylated molecular weight polysiloxane. This base was prepared at monoglycerides, Alkylcitrates, Triethylcitrate (TEC), Acetyl room temperature in a 25mm twin screw extruder wherein 25 triethylcitrate (ATEC), Tributylcitrate (TBC), Acetyltributyl weight percent silica, and 75% silicone gum. This blend citrate (ATBC), Trioctyl citrate (TOC), Acetyl trioctyl citrate (Blend 1) is then used in the next step. (ATOC), Trihexyl citrate (THC), Acetyl trihexyl citrate 0033. In the second step, the twin screw extruder was (ATHC), Butyryl trihexylcitrate (BTHC, trihexyl o-butyryl heated to 250° C. and used to mix the 12% of the silicone base citrate), Trimethyl citrate (TMC). Plasticizers for energetic from step 1.3% ionomer, and 85% polyamide 12. The result materials such as Nitroglycerine (NG, aka “nitro, glyceryl ing material had 412% elongation and 756.8 MPa flexural trinitrate), Butanetriol trinitrate (BTTN), Dinitrotoluene (DNT), Trimethylolethane trinitrate (TMETN, aka Metriol modulus compared to the natural polyamide 12 that had an trinitrate, METN), Diethylene glycol dinitrate (DEGDN, less elongation of 125% and a flexural modulus of 1103 MPa. commonly DEGN), Triethylene glycol dinitrate (TEGDN, Example 12: Polyamide 66 Blends less commonly TEGN), Bis(2,2-dinitropropyl)formal (BD NPF), Bis (2,2-dimitropropyl)acetal (BDNPA), 2.2.2-Trini 0034. This material was prepared in 2 steps. In step one troethyl 2-nitroxyethyl ether (TNEN), Epoxy esters, Phos 22% of the precipitated silica was blended along with 0.5% of phate Esters, Secondary Plasticizers, Epoxidized soybean oil the phenolic antioxidant and 77.5% of the ultra-high molecu (ESBO) and Epoxidized linseed oil (ELO), Cyclohexane lar weight polysiloxane using a twin screw extruder. diacids esters: Di-isononyl cyclohexane dicarboxylate, Trig 0035. In the second step, the base from step one was lyceride plasticizers: Tris-2-ethylhexyl trimellitate (Tri-octyl blended on a twin screw extruder with the polyamide 66 resin Trimellitate TOTM), Tri (2-ethylhexyl) trimellitate, Glyc to make a composition of 20% polysiloxane base and 80% erol Acetylated esters, Di-(2-ethylhexyl terephthalate), Di polyamide 66. The resulting material has 51.7% elongation (iso nonyl)cyclohexane 1-2 di carboxylic acid ester, Di-(2- and 1545.6 MPa flexural modulus. ethylhexyl)acetate, and 2-Ethylhexyl adipates. 0027. Other adjuvents that can be added as desired by the Example 3: Acetal Blends user include glass fibers, glass beads, mineral fillers, flame 0036. This material was prepared in 2 steps. In step one, retardants, stabilizers, antioxidants, glass bubbles, polymeric 18% of the precipitated silica was blended along with 0.5% of fibers, carbon fibers, pigments, process aids, lubricants, and the phenolic antioxidant and 81.5% of the ultra-high molecu mixtures of any of the adjuvents. lar weight polysiloxane using a twin screw extruder. 0028. The adjuvents can be blended with the ultra-high 0037. The polysiloxane base from step one was blended molecular weight polysiloxanes and silicablend prior to addi on a twin screw extruder at 190° for a composition of 15% tion to the thermoplastic polymer or they can added directly to polysiloxane base, 1.25% ethylene methyl acrylate copoly the combination of polymer and polysiloxane base. mer, 3.75% thermoplastic polyurethane, 0.5% phenolic anti 0029. The polysiloxane base and the polymer are inti oxidant, and 78.5% copolymer acetal. The resulting material mately blended and the blend can be applied, for example, as had a flexural modulus of 1651 MPa compared to 2595 MPa a coating to the outside of a wire or covered metal strand and of the original acetal copolymer resin. then cured through known methods. What is claimed is: 0030 The materials are formulated, for example using 1. A composition of matter comprising a blend of: polyamide 6 resin, which renders the resin flexible enough for i. 20 to 98 weight percent of a thermoplastic resin and, use in THFHN wire and cable and can be used instead of ii 2 to 80 weight percent of an ultra-high molecular weight relying on caprolactam as an additive in nylon resins, to make polysiloxane having a molecular weight (Mn) of at least the product acceptable. The additional benefit of this 10,000 and not more than about 1,000,000 (Mn), approachallows the material to be flexible regardless of mois wherein the ultra-high molecular weight polydimethyl ture content in the polymer. Also, it allows it to be flexible siloxane has blended with it 3 to 35 weight percent of a down to -40°C. silica selected from the group consisting of 0031. The following examples are presented to better a. precipitated silica and, illustrate the method of the present invention. The materials b. fumed silica, used in the following examples were: precipitated silica with wherein the ultra-high molecular weight polydimethylsilox a surface area of 250 g/m and average particle size of 9 ane has pendant groups, terminal groups or mixtures of pen microns: An ultra high molecular weight polysiloxane with a dant groups and terminal groups selected from the group mn of 55,000 and a 100 pm level of vinyl termination. A consisting of hydrogen, trimethyl, dimethyl, methyl, phenyl, general purpose Nylon 66 resin with a viscosity value of 150. fluoro, amino, vinyl, hydroxyl, and methacrylate. Polyamide 12 with a melt volume rate of 0.15 in/10 min. A 2. A composition of matter as claimed in claim 1 wherein Zinc based ionomer based on ethylene acrylic acid. A steri the silica is present in the range of 15 to 25 weight percent. cally hindered phenolic primary antioxidant for processing 3. A composition of matter as claimed in claim 1 wherein and long-term thermal stabilization, a natural acetal copoly the thermoplastic resin is present at 50 to 98 weight percent. US 2014/0316041 A1 Oct. 23, 2014

4. A composition of matter as claimed in claim 1 wherein 16. The composition of claim 13 wherein the plasticizer is the thermoplastic resin is present at 70 to 95 weight percent. present at 2 to 8 weight percent. 5. A composition of matter as claimed in claim 1 wherein 17. A composition of matter comprising a blend of: the ultra-high molecular weight polysiloxane is a hydroxyl i. 20 to 98 weight percent of a thermoset resin and, terminated polydimethylsiloxane. ii. 2 to 80 weight percent of an ultra-high molecular weight 6. A composition of matter as claimed in claim 1 wherein polysiloxane having a molecular weight (Mn) of at least the ultra-high molecular weight polysiloxane is a trimethyl 10,000 and not more than about 1,000,000 (Mn), siloxy terminated polydimethylsiloxane. wherein the ultra-high molecular weight polydimethyl 7. A composition of matter as claimed in claim 1 wherein siloxane has blended with it 3 to 35 weight percent of a the composition of matter contains, in addition, a compatibi silica selected from the group consisting of lizer. a. precipitated silica and, 8. A composition of matter as claimed in claim 7 wherein b. fumed silica, the compatibilizer is added during the blending of the ther wherein the ultra-high molecular weight polydimethylsilox moplastic polymer with the ultra-high molecular weight pol ane has pendant groups, terminal groups or mixtures of pen ysiloxane. dant groups and terminal groups selected from the group 9. A composition of matter as claimed in claim 1 wherein, consisting of hydrogen, trimethyl, dimethyl, methyl, phenyl, in addition, there is also present in the composition an adjunct fluoro, amino, vinyl, hydroxyl, and methacrylate. selected from the group consisting of: 18. A composition of matter comprising a blend of: i. glass fiber, i. 25 to 98 weight percent of a thermoset rubber and, ii. glass beads, ii. 2 to 75 weight percent of an ultra-high molecular weight iii. mineral fillers, polysiloxane having a molecular weight (Mn) of at least iv. flame retardant, 10,000 and not more than about 1,000,000 (Mn), V. stabilizer, wherein the ultra-high molecular weight polydimethyl vi. antioxidant, siloxane has blended with it 3 to 35 weight percent of a vii. glass bubbles, silica selected from the group consisting of viii. polymeric fibers, a. precipitated silica and, ix. carbon fibers, b. fumed silica, X. pigments, wherein the ultra-high molecular weight polydimethylsilox Xi. process aids, ane has pendant groups, terminal groups or mixtures of pen xii. lubricants, and, dant groups and terminal groups selected from the group xiii. mixtures of any of i. to Xii. consisting of hydrogen, trimethyl, dimethyl, methyl, phenyl, 10. A composition as claimed in claim 9 wherein said fluoro, amino, vinyl, hydroxyl, and methacrylate. adjuvents are blended with the ultra-high molecular weight 19. In combination, a composition as claimed in claim 1 polysiloxane and silicablend prior to addition to the thermo and a wire. polymer. 20. In combination, a composition as claimed in claim 1 11. A composition of matter as claimed in claim 1 wherein and a cable. the thermoplastic polymer is selected from the group consist 21. In combination, a composition as claimed in claim 1 ing of polystyrene, high impact polystyrene, polypropylene, and a film. polycarbonate, polysulfone, poly(phenylene Sulfide), acry 22. In combination, a composition as claimed in claim 1 lonitrile-butadiene-styrene copolymer, nylon, acetal, poly and a fiber. ethylene, poly(ethylene terephthalate), poly(butylene tereph 23. In combination, a composition as claimed in claim 1 thalate), polyketone, acrylate, fluoroplastics, polyesters, and a molded container or housing. phenolics, epoxies, urethanes, polyimides, melamine formal 24. In combination, a composition as claimed in claim 1 dehyde and urea. and a extruded sheet. 12. A composition of matter as claimed in claim 11 wherein 25. In combination, a composition as claimed in claim 1 the thermoplastic polymer is selected from a blend of one or and a hose. more thermoplastic polymers. 26. In combination, a composition as claimed in claim 1 13. A composition of matter as claimed in claim 1 wherein, and a tube. in addition, there is present a plasticizer. 27. In combination, a composition as claimed in claim 1 14. A composition of matter claimed in claim 13 wherein and a fiber. there is a blend of plasticizers. 28. In combination, a composition as claimed in claim 1 15. The composition of claim 13 wherein the plasticizer and an article used in sporting goods. compound is present at 1 to 30 weight percent. k k k k k