01/25/2011

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Hilmer et al. US Patent 7,656,712 (December 28, 2010) to BASF AGMethod for reacting thermoplastic polyurethanes with compounds containing isocyanate groupsAbstractThe invention relates to a process for reacting thermoplastic polyurethanes with compounds having isocyanate groups, where the compounds used having isocyanate groups comprise compounds having at least three isocyanate groups based on aliphatic isocyanates and compounds having two isocyanate groups based on aromatic isocyanates.The invention also relates to polyisocyanate polyaddition products, in particular fibers, hoses, cable sheathing, profiles, moldings, and foils, obtainable by way of the inventive process.Further detailsThe object of the present invention consisted in optimizing the chemical components in such a way that maximum cross-linking can be achieved with very good process reliability.In achieving this object, the compounds used having isocyanate groups comprise compounds having at least three isocyanate groups, preferably three isocyanate groups, based on aliphatic isocyanates, preferably hexamethylene diisocyanate (HDI) and/or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), particularly preferably hexamethylene diisocyanate (HDI), and compounds having two isocyanate groups based on aromatic isocyanates, preferably diphenylmethane 2,2'-, 2,4'-, and/or 4,4'-diisocyanate (MDI), particularly preferably diphenylmethane 4,4'-diisocyanate.Another object underlying the present invention was to develop a process which reacts  thermoplastic polyurethanes with compounds having isocyanate groups, in particular comprising tri- and polyisocyanates, and whose apparatus is designed to permit safe, rapid, and reliable reaction. This process should avoid variations in product properties, and also throughput variations with resultant dimensional variations during extrusion, deposits in the extruder or in the injection molding machine, and premature cross-linking via triisocyanates associated with stoppage of transport (blocking of the plant).This object was achieved by feeding preferably granulated thermoplastic polyurethane by way of a feeding aid, i.e. a feed zone with conveying action, to an extruder or an injection molding apparatus, preferably an extruder, and, in the extruder or in the injection molding apparatus, preferably in the extruder, mixing it with compounds having isocyanate groups, and preferably reacting it before it leaves the extruder.By way of the preferred use of a feeding aid, by way of which and preferably also  are fed to the extruder, it is possible, at the extruder or at the injection molding apparatus, to introduce solid TPU granules together or separately, preferably together with the (ii) compounds having isocyanate groups, these compounds preferably being liquids or normal or high viscosity at 15 °C, preferably of normal viscosity, into the extruder or the injection molding apparatus rapidly and reliably. Since the melt pressure usually rises along the length of the extruder, it is preferable for the compounds having isocyanate groups to be introduced into the extruder at a point at which the melt pressure is less than 200 bar. It is particularly preferable for the compounds having isocyanate groups to be introduced by way of the feeding aid into the extruder or the injection molding apparatus together with thermoplastic polyurethanes, and this means using the same feeding aid for  both substances.The inventive product of the process can be processed by well-known processes to give moldings of any type, foils, hoses, sheathing for cables, injection-molded items, or fibers. The processing temperature in the production of the foils, moldings, or fibers is preferably up to 150-230 °C, particularly preferably 180-220 °C. Processing of the mixture to give the desired foils, moldings, and/or fibers preferably takes place directly after or during the mixing of the components and, because thermoplastic processing of the polyisocyanate polyaddition product to give foils, moldings, or fibers is preferably carried out prior to and/or during the formation of the cross-links.Arriola, et al., US Patent 7,858,707 (December 28, 2010), to Dow Global Technologies IncCatalytic olefin block copolymers via polymerizable shuttling agentAbstractA polymerization process and the resulting polymer composition, said process comprising polymerizing one or more addition polymerizable monomers and a polymerizable shuttling agent in the presence of at least one addition polymerization catalyst comprising a metal compound or complex and a cocatalyst under conditions characterized by the formation of a branched polymer, preferably comprising pseudo-block molecular architecture.Further detailsAccording to the present invention there is now provided a branched copolymer of at least one addition polymerizable monomer having unique morphology. The present polymers are uniquely formed by the polymerization of one or more addition polymerizable monomers under addition polymerization conditions with a composition comprising at least one addition polymerization catalyst, a cocatalyst and a polymerizable shuttling agent (PSA). In a preferred embodiment, the resulting polymer comprises multiple blocks or segments of differentiated polymer composition or properties, especially blocks or segments comprising differing comonomer incorporation levels, in a branched polymer structure. Due to the fact that the blocks are catalytically prepared they possess a random chemical structure and they are randomly assembled in the resulting copolymer structure. Accordingly, the resulting polymers are referred to as "pseudo-block" copolymers. Certain of these branched copolymers may be substantially linear and possess controllable amounts of long chain branching (due to reincorporation of previously prepared polymer segments) through selection of catalyst and process conditions. Highly preferably, the resulting polymers are multiply branched and have a "comb" type of molecular architecture. Additionally, certain of the inventive copolymers may possess a "branch on branch" architecture, wherein some fraction of the long chain branches are themselves branched. In general, the resulting polymers contain reduced incidence of cross-linked polymer formation evidenced by reduced gel fraction. Preferably, the polymers of the invention comprise less than 2 percent of a cross-linked gel fraction, more preferably less than 1 percent cross-linked gel fraction, and most preferably less than 0.5 percent of cross-linked gel fraction.More particularly, the present invention includes an embodiment wherein there is provided a process and the resulting branched copolymer, said process comprising polymerizing one or more olefin monomers in the presence of at least one olefin polymerization catalyst and a PSA in a polymerization reactor thereby causing the formation of a polymer comprising multiple branches. At least some of the branches are ideally long chain branches formed from the polymerization of two or more, more preferably 2 to 100, and most preferably 3-20 monomer units. The polymer preferably is further characterized by the presence of pseudo-block chemical structure resulting from polymerization of different segments of the polymer under differing process conditions.Abraham et al., US Patent 7,858,689 (December 28, 2010) to ExxonMobil Chemical Patents, IncThermoplastic vulcanizates with improved mechanical propertiesAbstractA thermoplastic vulcanizate comprising a dynamically-cured rubber, where the rubber is selected from the group consisting of ethylene-propylene-non-conjugated diene rubber, propylene-based rubbery copolymers with units derived from non-conjugated diene monomers, butyl rubber and styrene-butadiene rubber, where dynamic vulcanization is effected with a phenolic resin or a silicon-containing curative, and where the rubber is dynamically cured to an extent where greater than 94% by weight of the rubber is insoluble in cyclohexane at 23 °C, and from about 25 to about 250 parts by weight of a thermoplastic polymer phase per 100 parts by weight rubber, where about 85% to about 50% by weight of the thermoplastic polymer phase includes a propylene-based polymer, and where from about 15% to about 50% by weight of the thermoplastic polymer phase includes a butene-1-based polymer.Further detailsOne or more embodiments of the present invention are directed toward thermoplastic vulcanizates that include both a propylene-based polymer and a butene-1-based polymer in the thermoplastic phase. The rubber phase of the thermoplastic vulcanizate includes a highly-cured olefinic rubber or highly-cured butyl rubber. In one or more embodiments, dynamic vulcanization of the rubber is advantageously achieved with a phenolic resin or a silane-based curative. In one or more embodiments, the presence of the butene-1-based polymer and propylene-based polymer within the thermoplastic phase advantageously improves the mechanical properties of the thermoplastic vulcanizate over similar thermoplastic vulcanizates that include only either polypropylene or poly(butene-1) as the plastic phase. It is believed that this improvement is caused by a synergy that may exist between a propylene-based and butene-1-based thermoplastic polymer.Accordingly, in one or more embodiments, thermoplastic vulcanizates of the present invention include a rubber phase and a thermoplastic matrix or phase including a propylene-based thermoplastic polymer and a butene-1-based thermoplastic polymer. The thermoplastic vulcanizates of one or more embodiments may also include other constituents that may be employed in the art of making thermoplastic vulcanizates.Datta et al., US Patent 7,855,258 (December 21, 2010) to ExxonMobil Chemical Patents Inc.Propylene olefin copolymersAbstractImproved thermoplastic polymer blend compositions comprising an isotactic polypropylene component and an alpha-olefin and propylene copolymer component, said copolymer comprising crystallizable alpha-olefin sequences. In a preferred embodiment, improved thermoplastic polymer blends are provided comprising from about 35% to about 85% isotactic polypropylene and from about 30% to about 70% of an ethylene and propylene copolymer, wherein said copolymer comprises isotactically crystallizable propylene sequences and is predominately propylene. The resultant blends manifest unexpected compatibility characteristics, increased tensile strength, and improved process characteristics, e.g., a single melting point.Further detailsThe invention relates to a blend of at least two thermoplastic components differing in their crystallinities. The blend has a heterogeneous morphology with distinct phase separated zones of different composition and crystallinity present. The resulting blend with the defined morphology shows dramatic improvements in mechanical deformation recoverability when compared to its individual unblended components. The invention also relates to improvements in the flexibility of the blend. Changes in the relative amounts or the crystallinities of the blend components or the morphology of the blend affect the recoverability and the flexibility of the blend.The inventive blends designed for recoverability contains a dispersed phase of a greater crystallinity and a continuous phase of lesser crystallinity. The sizes of the individual domains of the dispersed phase are very small with the smallest length dimension for the dispersed phase being less than 5 .mu.m. This phase size of the dispersed phase is maintained during processing even without crosslinking. The inventive blends designed for flexibility have a slightly wider range in morphology as the components of greater and lesser crystallinity can also be co-continuous. The components of the blend in both cases are also compatible to the extent that no compatibilizer needs to be added to attain and retain this fine morphology. Furthermore, this invention describes improving the mechanical deformation recoverability of the aforementioned blends by aging the blends and mechanically orienting the articles formed from these blends.One of the components is a polymer comprising predominately stereospecific polypropylene, preferably isotactic polypropylene. This is the component with greater crystallinity. A second component is a copolymer of propylene and a C2, C3-C20 .alpha.-olefin, preferably ethylene. This is the component with lesser crystallinity. In the copolymer the propylene is polymerized substantially stereospecifically. The copolymer has a substantially uniform composition distribution preferably as a result of polymerization with a metallocene catalyst. Most preferably, said second component is an ethylene propylene copolymer, e.g. ethylene propylene semicrystalline elastomer.Abraham, et al. US Patent 7,851,556 (December 14, 2010) to ExxonMobil Chemical Patents Inc.Thermoplastic vulcanizates with low compression setAbstractA thermoplastic vulcanizate comprising a dynamically-cured rubber, where the rubber is selected from the group consisting of ethylene-propylene-non-conjugated diene rubber, propylene-based rubbery copolymers with units derived from non-conjugated diene monomers, and butyl rubber, where dynamic vulcanization is effected with a phenolic resin or a silicon-containing curative, and where the rubber is dynamically cured to an extent where greater than 94% by weight of the rubber is insoluble in cyclohexane at 23 °C., and from about 25 to about 250 parts by weight of a thermoplastic polymer phase per 100 parts by weight rubber, where from about 75% to about 100% by weight of said thermoplastic polymer phase includes a butene-1-based polymer.Further detailsOne or more embodiments of the present invention provide a thermoplastic vulcanizate comprising a dynamically-cured rubber, where the rubber is selected from the group consisting of ethylene-propylene-non-conjugated diene rubber, propylene-based rubbery copolymers with units derived from non-conjugated diene monomers, and butyl rubber, where dynamic vulcanization is effected with a phenolic resin or a silicon-containing curative, and where the rubber is dynamically cured to an extent where greater than 94% by weight of the rubber is insoluble in cyclohexane at 23 °C., and from about 25 to about 250 parts by weight of a thermoplastic polymer phase per 100 parts by weight rubber, where from about 75% to about 100% by weight of said thermoplastic polymer phase includes a butene-1-based polymer.One or more embodiments of the present invention also provides a method for preparing a thermoplastic vulcanizate, the method comprising dynamically curing a rubber in the presence of a thermoplastic polymer phase, where the rubber is selected from the group consisting of ethylene-propylene-non-conjugated diene rubber, propylene-based rubbery copolymers with units derived from non-conjugated diene monomers, and butyl rubber, where said step of dynamically vulcanizing is effected with a phenolic resin or a silicon-containing curative, where the rubber is dynamically cured to an extent where greater than 94% by weight of the rubber is insoluble in cyclohexane at 23 °C., and where from about 75% to about 100% by weight of said thermoplastic polymer phase includes a butene-1-based polymer.One or more embodiments of the present invention further provides thermoplastic vulcanizate comprising a dynamically-cured rubber, where the rubber is selected from the group consisting of ethylene-propylene-non-conjugated diene rubber, propylene-based rubbery copolymers with units derived from non-conjugated diene monomers, and butyl rubber, where dynamic vulcanization is effected with a phenolic resin or a silicon-containing curative, and where the rubber is dynamically cured to an extent where greater than 94% by weight of the rubber is insoluble in cyclohexane at 23.degree. C., and from about 25 to about 250 parts by weight of a thermoplastic polymer phase per 100 parts by weight rubber, where from about 75% to about 100% by weight of said thermoplastic polymer phase includes a butene-1-based polymer.Worley II et al., US Patent 7,847,024 (December 7, 2010) to Teknor ApexCo.Elastomer and vulcanizate compositions having desirable high temperature propertiesAbstractCompositions including a thermoplastic elastomer or thermoplastic vulcanizate derived from a styrenic block copolymer having a reactive or crosslinkable hard block including aromatic vinyl repeat units and also preferably a cross-linkable soft block, and a non-olefin thermoplastic polymer or copolymer and preferably a compatibilizer such as the reaction product of a non-olefin thermoplastic polymer and a functionalized polymer such as a maleic anhydride functionalized styrenic block copolymer that is compatible with the styrenic block copolymer having a reactive or crosslinkable hard block, and optionally a linking compound. The vulcanizates are prepared by cross-linking the styrenic block copolymer in the presence of the non-olefin thermoplastic polymer and a suitable cross-linking agent, and optionally the compatibilizer, preferably utilizing dynamic vulcanization. In a further embodiment, thermoplastic vulcanizate compositions are provided including the styrenic block copolymer, a polyolefin polymer or copolymer, a non-olefin thermoplastic polymer and the compatibilizer.Further detailsIn view of the above considerations, the inventors of the present application have discovered thermoplastic elastomer blend and vulcanizate compositions that exhibit desirable properties, such as chemical resistance and low swelling in fluids at relatively high temperatures. The compositions include a non-olefin thermoplastic polymer or copolymer such as Nylon-6 or Nylon-6,6, or the like, and a styrenic block copolymer having a reactive or cross-linkable moiety/site in at least one hard block and at least one soft block comprising one or more repeat units, which are the same or different repeat units when two or more repeat units are present, that are derived from one or more monomeric units, for example, an olefin monomer, such as ethylene, propylene, or butylene, or a diene monomer such as butadiene, isoprene or combinations thereof, with at least one soft block preferably being cross-linkable. In a preferred embodiment, the composition further includes a compatibilizer.In one embodiment, the composition is a thermoplastic elastomer blend, formed by blending a non-olefin thermoplastic such as polyamide and the styrenic block copolymer having the reactive hard block above the melting point of the non-olefin thermoplastic. Optionally, but preferably, one or more compatibilizers such as a reaction product of polyamide and maleated styrenic block copolymer are incorporated in and/or formed during the formation of the blend.In a further embodiment, the reactive sites on the hard block of the styrenic block copolymer and reactive sites on the soft block when present are reacted in the presence of a molten or melted non-olefin thermoplastic such as polyamide and optionally a compatibilizer utilizing a cross-linking agent to form a thermoplastic vulcanizate. Additional embodiments of the invention include thermoplastic vulcanizates formed from a composition including a styrenic block copolymer having a reactive or cross-linkable moiety/site in at least one hard block, and preferably at least one soft block, preferably being crosslinkable; a polyolefin polymer or copolymer; a non-olefin thermoplastic polymer or copolymer having a higher melting point than the polyolefin, and a compatibilizer, such as formed from the reaction product of a non-olefin thermoplastic, a functional group containing styrenic block copolymer and optionally a linking compound when the non-olefin thermoplastic and functional group containing styrenic block copolymer contain the same functional group or are otherwise non-reactive with each other, wherein the linking compound forms a bridge between the non-olefin thermoplastic and the functional group containing styrenic block copolymer. Vulcanizates are preferably prepared by subjecting the molten blend mixture to vulcanization under dynamic mixing conditions. Both the thermoplastic elastomer blend and thermoplastic vulcanizate compositions are thermoplastic in nature and thus can be molded and remolded or recycled.In one aspect of the invention, a thermoplastic composition, comprising a styrenic block copolymer comprising at least one hard polymer block (A) and at least one soft polymer block (B), wherein at least one unit of the at least one hard polymer block (A) is crosslinkable and independently includes at least one of (i) an alkyl styrene-derived functional unit and (ii) an aromatic vinyl compound unit having a functional group, wherein the soft polymer block (B) includes at least one repeat unit derived from an olefin or a diene; and a non-olefin thermoplastic polymer or copolymer in an amount from about 10 to about 1,500 parts per 100 parts by weight of the styrenic block copolymer, and wherein the composition is substantially free of a polyolefin, wherein the non-olefin thermoplastic includes one or more of polyamide, polyester, poly(phenylene oxide), poly(phenylene sulfide), poly(imide) and poly(sulfone). Optionally, but preferably, one or more compatibilizers such as a reaction product of a non-olefin thermoplastic such as polyamide and maleated styrenic block copolymer are incorporated in the blend or formed in situ during preparation of the blend.In another aspect of the invention, A thermoplastic vulcanizate composition, comprising a styrenic block copolymer comprising at least one hard polymer block (A) and at least one soft polymer block (B), wherein one or more units of the at least one hard polymer block (A) are cros-linkable and independently include at least one of (i) an alkyl styrene-derived functional unit, and (ii) an aromatic vinyl compound unit having a functional group, wherein the soft polymer block (B) includes at least one repeat unit derived from an olefin or a diene; a polyolefin polymer or copolymer; a non-olefin thermoplastic polymer or copolymer polyamide in an amount from about 10 to about 1,500 parts per 100 parts by weight of the styrenic block copolymer, wherein the non-olefin thermoplastic polymer or copolymer is one or more of polyamide, polyester, poly(phenylene oxide), poly(phenylene sulfide), poly(imide) and poly(sulfone); a compatibilizer; and a crosslinking agent, wherein the crosslinking agent crosslinks one or more segments of the styrenic block copolymer. Preferably, the compatibilizer includes a styrenic block copolymer including one or more crosslinkable functional groups independently derived from a compound including a carboxylic acid group and/or an anhydride group.Functional groups in the soft block (B) either introduced during polymerization or later on by reactive extrusion can be used for a cross-linking reaction. Vulcanizates are preferably prepared by subjecting the composition mixture to dynamic vulcanization in the presence of one or more of appropriate curing agents under melted, mixing conditions. Optionally, but preferably, one or more compatibilizers, such as a reaction product of polyamide and maleated styrenic block copolymer, are incorporated in the blend initially or formed during processing or formation of the vulcanizate. The vulcanizate composition can be additionally later melt blended with one or more polymers, such as polyamide, polyester and the like, above their melting temperature.The compatibilizer can have a number of different structures. The compatibilizer is an oligomer, a block copolymer, a graft copolymer, or a reaction product of two or more oligomers or polymers which comprises at least one portion or segment compatible with the styrenic block copolymer having a reactive hard block and at least one portion or segment compatible with a non-olefin thermoplastic polymer such as polyamide, polyester, PPO and the like. In one embodiment, the compatibilizer is the reaction product of a functionalized styrenic block copolymer and a non-olefin functionalized thermoplastic polymer or copolymer. In a further embodiment, the compatibilizer is the reaction product of functionalized styrenic block copolymer, a non-olefin thermoplastic polymer and a linking compound, wherein the functional groups of the styrenic block copolymer and the thermoplastic polymer are the same or are otherwise non-reactive with each other, with the linking compound having two or more functional groups, at least one capable of reacting with functionalized styrenic block copolymer and at least one capable of reacting with the non-olefin functionalized thermoplastic polymer. In one embodiment, the compatibilizer is the reaction product of polyamide and functionalized styrenic block copolymer. The functional group in the styrenic block copolymer is optionally, but preferably, maleic anhydride or a carboxylic acid moiety.The compatibilizer is formed preferably utilizing a melt reaction process. The compatiblizer can be formed via an in situ melt mixing and/or dynamic vulcanization process or through multiple step processes. In multiple step processes, a portion of the compatibilizer can be formed in a first reaction process wherein a linking compound is reacted with either the non-olefin thermoplastic or the functionalized styrenic block copolymer. In the second process the formed reaction product is reacted with the component, non-olefin thermoplastic or functionalized styrenic block copolymer not present in the first reaction product. The formed reaction product compatibilizer can then be melt blended in a desired further composition. In one embodiment, the compatibilizer is preferably formed in situ during dynamic vulcanization through reaction of functional groups present on the styrenic block copolymer and a non-olefin thermoplastic such as a polyamide. Accordingly, the compatibilizer has affinity for both styrenic block copolymer and thermoplastic, such as polyamide, and it, therefore, in a polymer composition improves compatibility between a styrenic block copolymer having at least a reactive hard block and a non-olefin thermoplastic, such as a polyamide.Watkins et al, US Patent 7,842,391 (November 30, 2010) to Nike Inc.Gel reduction in blends of thermoplastic polyurethane and hydroxyl functional polymersAbstractGas barrier layers and composites contain a low gel sheet produced from a composition containing a thermoplastic polyurethane (TPU), a hydroxyl functional copolymer, and a gel reducing additive. The gel reducing additive has functional groups that can react with isocyanate groups to reduce gel formation during the processing of blends of urethane containing polymers and hydroxyl functional polymers. Multilayer composites containing the low gel sheets can be made into inflatable membranes for containing an inflationary gas. In a particularly preferred embodiment, the membranes are used as bladders of cushioning devices in the soles of shoes, particularly athletic shoes.Further detailsImproved gas barrier layers and composites are produced according to the invention by forming a low gel sheet from a composition containing three components. A first component comprises a thermoplastic polyurethane (TPU). A second component comprises a hydroxyl functional copolymer, and the third component is a gel reducing additive. In another aspect, a polymer composition with decreased gel forming tendency when blended with polymers containing urethane linkages is provided. The composition contains a hydroxyl functional polymer as described above and the gel reducing additive. Upon adding a urethane polymer such as a thermoplastic polyurethane to the polymer composition, a composition is obtained that can be formed or extruded into a sheet having desirable properties.In another embodiment, sheets made from the compositions are provided. The sheets are produced by combining the first, second, and third components to form a blend, applying thermal energy, mechanical energy or both to the blend, and producing a sheet from the blend.In another embodiment, a multilayer composite is provided made up of a plurality of flexible layers. At least one of the flexible layers is the product of forming a sheet from a blend of thermoplastic polyurethane, hydroxyl functional copolymer, and gel reducing additives as described above. In a preferred embodiment, the multilayer composite contains alternating layers of thermoplastic polyurethane and hydroxyl functional polymer, for example ethylene vinyl alcohol copolymer (EVOH). In addition, at least one of the flexible layers is produced from a blend of thermoplastic polyurethane and hydroxyl functional copolymer, formed for example by coextrusion in the presence of the gel reducing additive.In a preferred embodiment, the multilayer composite can be made into an inflatable membrane for containing an inflationary gas. The membrane is made of a multilayer composite, wherein the composite contains at least one flexible layer made of a blend of thermoplastic polyurethane, hydroxyl functional copolymer, and a gel reducing additive as described above. In a particularly preferred embodiment, the membranes are used as bladders of cushioning devices in the soles of shoes, particularly athletic shoes.Melanson et al., US Patent 7,842,211 (November 30, 2010) to Callaway Golf CompanyMethod for treating thermoplastic polyurethane golf ball coversAbstractA method of forming a golf ball is disclosed herein. The method includes placing a golf ball precursor product with a thermoplastic polyurethane cover in a solution containing an isocyanate functionality reactive material. The precursor product is then removed from the solution and heated to remove solvent. The precursor product is then placed in an isocyanate solution. The precursor product is then removed and heated to remove solvent to prepare the precursor product for finishing.Further detailsThe present invention provides a method of improving the durability, namely scuff resistance, of a golf ball with a thermoplastic cover. The invention is able to increase the durability of a golf ball with a thermoplastic polyurethane cover through the addition of reactive moieties to the cover prior to subsequent treatment with isocyanate groups.One aspect of the present invention is a method of forming a golf ball with a thermoplastic polyurethane cover. The method includes placing a golf ball precursor product in a solution to create a solution covered golf ball precursor product. The solution includes moieties capable of reacting with isocyanate functionalities. Next, the solution covered golf ball precursor product is removed from the solution. Next, the solution covered golf ball precursor product is heated to remove the solvent to create a heated solution covered golf ball precursor product. Next, the heated solution covered golf ball precursor product is placed in an isocyanate solution to create a isocyanate solution covered golf ball precursor product. Next, the isocyanate solution covered golf ball precursor product is heated to create a final golf ball precursor product.Another aspect of the present invention is a method of forming a golf ball. The method begins with placing a golf ball precursor product in a solution to create a solution covered golf ball precursor product. The golf ball precursor product includes a core, a boundary layer and a cover comprising a thermoplastic polyurethane material. The solution includes a dissolved PTMEG based polyol in an amount of 0.1% to 25% by weight of the solution and a solvent. Next, the solution covered golf ball precursor product is removed from the solution. Next, the solution covered golf ball precursor product is heated to remove the solvent to create a heated solution covered golf ball precursor product, wherein the solution covered golf ball precursor product is heated from two to four hours at a temperature ranging from 125 °F. to 250 °F. Next, the heated solution covered golf ball precursor product is placed in an isocyanate solution to create a isocyanate solution covered golf ball precursor product. The isocyanate solution includes acetone and MDI. Next, the isocyanate solution covered golf ball precursor product is heated to create a final golf ball precursor product, wherein the isocyanate solution covered golf ball precursor product is heated from two to four hours at a temperature ranging from 125 °F. to 250 °F.Another aspect of the invention includes incorporating in the cover an additive which contains moieties capable of reacting with isocyanate functionalities prior to injection molding.US Patent 7,829,923 (November 9, 2010), Ouhadi et al to ExxonMobil Chemical Patents Inc.Thermoplastic vulcanizates having improved fabricabilityAbstractA TPV composition having improved fabricability and surface appearance is achieved by a process for preparing a thermoplastic vulcanizate composition having a dispersed, cross-linked rubber phase in a continuous thermoplastic polypropylene phase comprising: a) providing into melt processing equipment at least the following components; i) at least one thermoplastic polypropylene homopolymer or copolymer having a melt temperature greater than 120 °C; ii) 6-12 wt. %, based on the total weight of the thermoplastic vulcanizate composition, at least one propylene copolymer having from 7 to 30 wt. % ethylene, based upon the weight of the random propylene copolymer, and a melting point less than 120 °C.; iii) at least one cross-linkable rubber, where, if including an ethylene copolymer rubber, said copolymer rubber having equal to or more than 40 wt. % the total copolymer rubber weight; b) melt processing the blend of i), ii), and iii) of a); c) dynamically vulcanizing the cross-linkable rubber iii) in the presence of the thermoplastic i) and random copolymer ii); and d) removing a thermoplastic vulcanizate product of c) from the melt processing equipment, wherein the dispersed, cross-linked rubber phase of the product thermoplastic vulcanizate d) consists of particles having an effective diameter not greater than 2 millimicrons.Further detailsA thermoplastic vulcanizate (TPV) with excellent fabricability while retaining a good elastic recovery has been discovered to be particularly suitable for shaped articles, and as shaped components for composite structures. The invention TPV is achieved by a process for preparing a thermoplastic vulcanizate composition having a dispersed, cross-linked rubber phase in a continuous thermoplastic polypropylene phase comprising: a) providing into melt processing equipment at least the following components; i) at least one thermoplastic polypropylene homopolymer or copolymer having a melt temperature greater than 120 °C.; ii) 6-12 wt. %, based on the total weight of the thermoplastic vulcanizate composition, at least one propylene copolymer having from 7 to 30 wt. % ethylene, based upon the weight of the propylene copolymer, and a melting point less than 120  °C.; iii) at least one cross-linkable rubber, where, if including an ethylene copolymer rubber, said copolymer rubber having equal to or more than 40 wt. % the total copolymer rubber weight; b) melt processing the blend of i), ii), and iii) of a); c) dynamically vulcanizing the cross-linkable rubber iii) in the presence of the thermoplastic i) and copolymer ii); and d) removing a thermoplastic vulcanizate product of c) from the melt processing equipment, wherein the dispersed, cross-linked rubber phase of the product thermoplastic vulcanizate d) consists of particles having an effective diameter not greater than 2 millimicrons.Excellent fabricability for the invention TPVs means excellent processability and parts with no surface imperfection. Further, TPVs prepared by the process have 1) a maximum compression set (CSmax) measured at 100 °C. for 22 hours compression with 25% deformation not greater than that 12 points of a polypropylene-based TPV of the same hardness not containing a propylene copolymer with melting temperature below 120 °C. and 2) exhibit die plug free operation when extruded from an extruder at a pressure of not greater 10 bar for at least 6 hours. Additionally, the surface of shaped parts from the invention compositions showed an unexpectedly high gloss.Also provided is the use of from 6 wt % to 12 wt % based on total weight of the composition a propylene copolymer that (i) has 60 wt % or more units derived from propylene, (ii) includes isotactically arranged propylene derived sequences and (iii) has a heat of fusion less than 45 J/g in a thermoplastic vulcanizate composition comprising of from 10 wt % to 50 wt % based on total weight of the composition, a dispersed, particulate rubber component, and of from 5 wt % to 50 wt % based on total weight of the composition, a polyolefinic thermoplastic resin component for the purpose of improving fabricability and surface appearance.

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