WO2022093448A1 - Compositions de vulcanisat thermoplastique et articles contenant celles-ci - Google Patents

Compositions de vulcanisat thermoplastique et articles contenant celles-ci Download PDF

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WO2022093448A1
WO2022093448A1 PCT/US2021/051696 US2021051696W WO2022093448A1 WO 2022093448 A1 WO2022093448 A1 WO 2022093448A1 US 2021051696 W US2021051696 W US 2021051696W WO 2022093448 A1 WO2022093448 A1 WO 2022093448A1
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group
polyolefin
silyl
thermoplastic vulcanizate
thermoplastic
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PCT/US2021/051696
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English (en)
Inventor
Vincent F. RERAT
Wanli WANG
Paul Tu Quang NGUYEN
Jianya Cheng
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Celanese International Corporation
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Publication of WO2022093448A1 publication Critical patent/WO2022093448A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • C09J123/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer

Definitions

  • thermoplastic vulcanizates that have improved adhesion to non-polymeric polar surface, such as metals, alloys, concretes, ceramics, glasses etc., methods of making such thermoplastic vulcanizates, and articles comprising such thermoplastic vulcanizates, in particular to such the thermoplastic vulcanizates are directly contacted with a non-polymeric polar surface.
  • Thermoplastic elastomers are both elastomeric and thermoplastic.
  • Thermoplastic vulcanizates are a class of TPE in which cross-linked rubber forms a dispersed, particulate, elastomeric phase within a thermoplastic phase of a stiff thermoplastic such that TPE properties are achieved.
  • TPVs or TPV compositions are conventionally produced by dynamic vulcanization.
  • Dynamic vulcanization is a process whereby a rubber component is cross-linked, or vulcanized, under intensive shear and mixing conditions within a blend of at least one non-vulcanizing thermoplastic polymer component at or above the melting point of that thermoplastic.
  • the rubber component forms cross-linked, elastomeric particles dispersed uniformly in the thermoplastic.
  • Dynamically vulcanized thermoplastic elastomers consequently have a combination of both thermoplastic and elastic properties.
  • Conventional plastic processing equipment can extrude, inject, or otherwise mold, and thus press and shape TPV compositions into useful products alone or in composite structures with other materials.
  • TPV are generally non-polar, but it is often desired to apply TPVs onto polar substrates or polar surfaces, e.g., metals, woods, glasses etc.
  • a method of using primers and adhesion promoters to improve the adhesion between non-polar polymers and non-polymeric polar surfaces, e.g., glasses in an over-molding process can comprise the steps of: (i) cleaning of the glass, typically using a solvent, (ii) activating the glass by means of the application of a primer comprising pre -hydrolyzed silanes; (iii) drying and curing of an adhesion promoter; (iv) applying the adhesion promoter which can be either solvent or aqueous based solutions containing various pre-polymers and oligomers of polyurethane; (v) drying and curing of the primer; and (vi) over-molding the glass by means of injection molding.
  • thermoplastic elastomer compositions comprising an amine-containing silsesquioxane or an amine- containing alkyltrialkoxysilane, and use of such compositions as an adhesive layer bonding to a polar layer.
  • U.S. Patent No. 8,569,417 B2 describes a process for grafting hydrolysable silyl groups to a polyolefin, comprising reacting the polyolefin with an unsaturated silane, which comprise at least one hydrolysable group bonded to Si atom, or a hydrolysate thereof.
  • the grafting is carried out in the presence of co-agents, for example, styrene, a sorbate ester, a 2,4- pentadienoate.
  • a co-agent as said inhibits polymer degradation by beta scission in the presence of means capable of generating free radical sites in the polymer.
  • Adhesion of non-polar polymers such as TPV onto a non-polymeric polar surface is a very complex physico-chemical phenomenon including surface energy and miscibility factors as well as selective interface chemical reactivity.
  • the above effects are achieved by including a silyl-functionalized polyolefin in thermoplastic vulcanizates (TPVs).
  • TPVs thermoplastic vulcanizates
  • the silyl- functionalized polyolefin means a polyolefin bearing a hydrolysable silyl group, for example, silyl-alkoxy or silyl-acethoxy group.
  • the present invention in some aspects includes TPV compositions, and methods of making such TPV compositions that provide strong adhesion to non-polymeric polar surfaces and can be applied thereon without need of pre-treatment to the polar surface.
  • thermoplastic vulcanizate compositions of the present invention provide at least 70%, mostly preferably 100% of cohesive failure, both before and after cataplasma aging.
  • the present TPV compositions comprise (i) 5 wt.% to 85 wt.% of a thermoplastic resin component and 15 wt.% to 95 wt.% at least partially vulcanized rubber component dispersed in the thermoplastic resin component, based on the total weight of the thermoplastic resin component and the rubber component; and (ii) 1 wt.% to 25 wt.% silyl-functionalized polyolefin containing a hydrolysable silyl group at least 3 atoms, or at least 4 atoms, preferably at least 5 atoms distanced from the polyolefin backbone, based on the weight of the thermoplastic vulcanization composition.
  • Y can be preferably an alkyl, aryl or arylalkyl moiety having a chain length of at least three atoms, for example from 3 to 8 atoms.
  • the method of forming the silyl-functionalized polyolefin is carried out in the absence of any co-agent that is dedicated for inhibiting degradation of the polyolefin, for example aromatics including styrene, sorbates, 2, 4-pentadienoate, and cyclic derivatives thereof, as such described in U.S. Patent No. 8,569,417 B2.
  • the method of making the present TPV compositions comprises the steps of mixing a TPV with the silyl-functionalized polyolefin, in particular the method comprises the steps of (a) forming the silyl-functionalized polyolefin, (b) forming a TPV, and (c) mixing the silyl-functionalized polyolefin with the TPV, and in some embodiments the steps (a) and (c), the steps (b) and (c), and steps (a), (b) and (c) can be carried out simultaneously.
  • the present invention also provides articles and methods of making the articles, which comprise a non-polymeric polar surface and the present TPV compositions applied thereon, by any known methods, for example, compression molding, injections molding, and extrusion molding.
  • a “polymer” may be used to refer to homopolymers, copolymers, interpolymers, and terpolymers.
  • Homopolymers are polymers made from a single type of monomer (e.g., homopolypropylene, made from propylene).
  • copolymers may refer to polymers made from two or more types of monomers (including both, e.g., ethylene -propylene copolymers and ethylene-propylene-polyene terpolymers, as well as tetrapolymers, and polymers made from 5 or more monomer types); and “terpolymers” refer to a sub-set of copolymers made from three monomer types (e.g., ethylene-propylene-polyene terpolymers) .
  • a polymer when referred to as comprising a monomer, the monomer is present in the polymer in the polymerized form of the monomer or in the derivative form of the monomer.
  • a polymer composition or blend is said herein to comprise a certain percentage, wt%, of a monomer, that percentage of monomer is based on the total amount of monomer units in all the polymer components of the composition or blend, unless otherwise stated.
  • Elastomer or “elastomeric composition” refers to any polymer or composition of polymers (such as blends of polymers) consistent with the ASTM D1566 definition. Elastomer includes mixed blends of polymers such as melt mixing and/or reactor blends of polymers. The terms may be used interchangeably with the term “rubber(s),” unless noted otherwise.
  • a Ce a-olefin is an a-olefin having 6 carbon atoms (with a double bond connecting the 1 and 2 carbons).
  • a “C x - C y a-olefin” or a “C x y a-olefin” is an a-olefin having from x to y carbon atoms, inclusive (e.g., a Ce - Cio or Ce-io a-olefin is an a-olefin having 6, 7, 8, 9, or 10 carbon atoms).
  • a composition "free of” or “without presence of’ a component refers to a composition substantially devoid of the component, or comprising the component in an amount of less than about 0.01 wt.%, by weight of the total composition.
  • thermoplastic vulcanizate is broadly defined as any material that includes a dispersed, at least partially vulcanized, rubber component within a thermoplastic resin component.
  • a thermoplastic vulcanizate material can further include additive oil, other ingredients, other additives, or combinations thereof.
  • vulcanizate means a composition that includes some component (e.g., rubber) that has been vulcanized.
  • vulcanized is defined herein in its broadest sense, as reflected in any issued patent, printed publication, or dictionary, and refers in general to the state of a composition after all or a portion of the composition (e.g., cross-linkable rubber) has been subjected to some degree or amount of vulcanization.
  • the term encompasses both partial and total vulcanization.
  • a preferred type of vulcanization is "dynamic vulcanization," discussed below, which also produces a “vulcanizate.”
  • vulcanized refers to more than insubstantial vulcanization, e.g., curing (cross-linking) that results in a measurable change in pertinent properties, e.g., a change in the melt flow index (MFI) of the composition by 10% or more (according to any ASTM- 1238 procedure).
  • MFI melt flow index
  • the term vulcanization encompasses any form of curing (cross-linking), both thermal and chemical, which can be utilized in dynamic vulcanization.
  • dynamic vulcanization means vulcanization or curing of a curable rubber component blended with a thermoplastic resin component under conditions of shear at temperatures sufficient to plasticize the mixture.
  • the rubber component is simultaneously cross-linked and dispersed as micro-sized particles within the thermoplastic resin component.
  • the rubber component to thermoplastic resin component ratio, compatibility of the rubber component and thermoplastic resin component, the kneader type and the intensity of mixing (shear rate), other morphologies, such as co-continuous rubber phases in the plastic matrix, are possible.
  • a “partially vulcanized” rubber is one wherein more than 5 weight percent (wt%) of the cross-linkable rubber is extractable in boiling xylene, subsequent to vulcanization (preferably dynamic vulcanization), e.g., cross-linking of the rubber phase of the TPV.
  • a TPV comprising a partially vulcanized rubber at least 5 wt% and less than 10, 20, 30, or 50 wt% (in varying embodiments) of the cross-linkable rubber is extractable from the specimen of the TPV in boiling xylene (said wt% based upon the total weight of rubber present in the TPV specimen).
  • the percent of soluble rubber in the cured composition is determined by refluxing a specimen in boiling xylene, weighing the dried residue and making suitable corrections for soluble and insoluble components based upon knowledge of the composition.
  • corrected initial and final weights are obtained by subtracting from the initial weight of the soluble components, other than the rubber to be vulcanized, such as extender oils, plasticizers, and components of the compositions soluble in organic solvent, as well as thermoplastic resin components that are not intended to cure. Any insoluble pigments, fillers, etc., are subtracted from both the initial and final weights. Any materials in the uncured rubber that are soluble in refluxing xylene are subtracted from the rubber when calculating the percent of soluble rubber in a cured composition.
  • a further description of the technique for determining the percentage of extractable rubber is set forth in Column 4, lines 19-50 of U.S. Patent No. 4,311,628, which description is hereby incorporated by reference.
  • a “fully vulcanized” (or fully cured or fully cross-linked) rubber is one wherein less than 5 wt% of the cross-linkable rubber is extractable in boiling xylene, subsequent to vulcanization (preferably dynamic vulcanization), e.g., cross-linking of the rubber phase of the TPV.
  • vulcanization preferably dynamic vulcanization
  • cross-linking of the rubber phase of the TPV e.g., cross-linking of the rubber phase of the TPV.
  • a TPV comprising a fully vulcanized rubber
  • less than 4, 3, 2, or even 1 wt% of the cross-linkable rubber is extractable from the specimen of the TPV in boiling xylene.
  • a TPV comprising a fully vulcanized rubber
  • from 0.5 to 2.0 wt%, such as from 0.1 to 2.0 wt%, of the cross-linkable rubber is extractable from the specimen of the TPV in boiling xylene.
  • “extender oil” and “processing oil” may have similar compositions, or be selected from the same or similar compounds. The terms are used to distinguish the timing in the manufacturing cycle of elastomeric compositions (including TPVs) at which the oil is introduced.
  • “Extender oil” is oil that is added to or otherwise incorporated with an elastomer following its polymerization, e.g., incorporated (along with any other desired additives) as part of the elastomer pellets, bales, or the like that are shipped or otherwise provided to downstream manufacturers, who in turn process the elastomer into intermediate products (including TPVs) and/or finished goods.
  • “Processing oil” or “process oil” is formulated with the elastomer during such downstream manufacturing (e.g., during extrusion, mixing, or other processing of the elastomer, including formation into a TPV).
  • “extender oil” may be present in a rubber component used in manufacturing the TPV ;
  • “process oil” is oil that is added during the TPV manufacturing process.
  • the total of both extender oil and process oil may be cumulatively referred to as “additive oil.”
  • a “Group I oil”, a “Group II oil”, a “Group III oil”, a “Group IV oil” (also referred to as a polyalphaolefin or “PAG”) and a “Group V oil” refer to the respective base stock oil group as understood in accordance with the American Petroleum Institute (API)’s categorization of base stock oils (set forth in Annex E of API 1509, 17th Edition, Addendum 1 (March 2015), incorporated herein by reference).
  • API American Petroleum Institute
  • a Group I oil is a petroleum- derived base oil or basestock oil having less than 90 wt% saturates (as determined in accordance with ASTM D2007), greater than 300 wppm sulfur (as determined in accordance with ASTM D1552, ASTM D2622, ASTM D3120, ASTM D4294, or ASTM D4297, with ASTM D4294 prevailing in case of conflicting results among those methods), and having a viscosity index ranging from 80 to 120 (as determined by ASTM D2270).
  • a Group II oil is a petroleum-derived base oil or basestock oil having greater than or equal to 90 wt% saturates, less than or equal to 300 wppm sulfur content, and a viscosity index ranging from 80 to 120 (each property determined by the same methods identified for Group I oils).
  • Group III, IV, and V oils are similarly in accordance with their description in Annex E of API 1509.
  • hydrolysable silyl group refers to a group containing a silicon atom bearing a hydroslysable group, and can be referred to as -SiR a R3, where groups Ri, R2 and R3 each independently is a hydrogen or a substituted group and at least one of groups Ri, R2 and R3 comprises a hydrolysable group, i.e., a group being capable of undergoing hydrolysis at certain circumstance.
  • the TPV compositions may be made by mixing or coextruding or otherwise combining (i) a TPV or TPV- containing composition and (ii) a silyl-functionalized polyolefin, preferably the polyolefin is miscible with the TPV or TPV-containing composition.
  • the distance between the polyolefin backbone and hydrolysable silyl group can have an impact on the adhesion performance of resulting functionalized polyolefin. It has been found that at least 3, typically 5 atoms distance between the hydrolysable silyl group and the polyolefin backbone would lower the steric hindrance effects between the polyolefin matrix and the non-polymeric polar surface, resulting an improved adhesion to the non-polymeric polar surface.
  • a silyl-functionalized polyolefin prepared from use of a co-agent that is dedicated to inhibit degradation of polyolefin shows lowered cataplasma aging resistance, compared with such prepared without use of such degradation inhibiting co-agent. It is believed that, but not to be bound by any theory, when in use of such co-agent, copolymerization of the co-agent with the silane, e.g., acryloxy-silanes on the side grafting chain may occur, which increases the grafting level while in the meantime limits the number of grafting sites onto the polyolefin backbone.
  • a high flowability of the functionalized polyolefin for example, with a MFR of greater than 100, or greater than 150, or greater than 200, such as from 100 -2000 g/lOmin, or from 200 to 800 g/10 min, can be obtained. It’s believed, but not to be bound by any theory, that is attributed to the degradation of the polyolefin backbone. The higher flowability allows a better mobility and wetting of the hydrolysable groups till the polar surface, resulting an improved adhesion performance of TPV compositions to polar surface.
  • Thermoplastic vulcanizate (TPV) of various embodiments may comprise, consist essentially of, or consist of: (a) an at least partially vulcanized rubber component dispersed within a continuous thermoplastic matrix; (b) oil; and, optionally, (c) one or more additives (e.g., one or more fillers, foaming agents, or the like).
  • TPV polypropylene
  • additives e.g., one or more fillers, foaming agents, or the like.
  • “consist essentially of’ means that the TPV composition is free of other materials except those minor impurities (e.g., 0.1 wt% or less) that one would typically expect in normal commercial operations.
  • a single process line may be used to in a continuous process to create multiple different types of materials in series, and some residuals (e.g., residual polymer, monomer, curative, additives, or other material) from previous product campaigns may acceptably be left in such equipment.
  • some residuals e.g., residual polymer, monomer, curative, additives, or other material
  • Such TPVs are formed by dynamically vulcanizing a TPV formulation.
  • the TPV formulation of various embodiments comprises (i) a rubber component (which may or may not be oil-extended), (ii) a thermoplastic resin (iii) a vulcanizing agent or curative; (iv) processing oil; and (v) optionally, one or more additives (including, e.g., cure accelerators, metal oxides, acid scavengers, flame retardants, fillers, stabilizers, antioxidant slurry, color masterbatch etc.).
  • the TPV may therefore alternatively be considered the product of dynamic vulcanization of the TPV formulation.
  • a TPV composition may instead be referred to as a composition comprising the TPV and other components, for example the silyl functionalized polyolefin and optionally other additives.
  • dynamic vulcanization includes a process whereby a rubber that is undergoing mixing with a thermoplastic resin is cured (i.e., crosslinked, or vulcanized).
  • the rubber is cross-linked or vulcanized under conditions of high shear at a temperature above the melting point of the thermoplastic resin.
  • the thermoplastic resin becomes the continuous phase of the mixture and the rubber becomes dispersed as a discontinuous phase within the continuous thermoplastic phase.
  • the mixture (e.g., the TPV formulation) undergoes a phase inversion during dynamic vulcanization, where the blend, which initially includes a major volume fraction of rubber, is converted to a blend where the plastic phase is the continuous phase and the rubber is simultaneously cross-linked and dispersed as fine particles within the thermoplastic matrix.
  • the dynamic vulcanization of the TPV formulation takes place within a reactor, such as an extruder, melt-mixer, or other reactive mixing device (described in more detail below).
  • a reactor such as an extruder, melt-mixer, or other reactive mixing device (described in more detail below).
  • not all components of the TPV formulation need necessarily be introduced to the reactor at the same time.
  • dynamic vulcanization proceeds as follows: The rubber component and thermoplastic resin component are mixed to form a blend, which may be referred to as a solids blend (although not all components of the blend need necessarily be in the solid state).
  • Optional solid additives such as cure accelerator, fillers, zinc oxide, and miscellaneous solids such as pigments and antioxidants, may be added to the solids blend.
  • the blend is continually mixed at a temperature above the melt temperature of the thermoplastic resin to form a molten blend.
  • the vulcanizing agent e.g., curative
  • Heating and mixing continues in order to effect dynamic vulcanization.
  • Processing oil can be introduced at any stage, or in multiple stages, of the process.
  • oil can be added to the solids blend, to the molten blend, together with the curative, or after dynamic vulcanization, or at any two or more of the foregoing points in the process.
  • Methods according to particular embodiments include “preloading” process oil — meaning that a portion of the process oil is introduced to the TPV formulation before the curative is introduced. Surprisingly, it has been found that some degree of oil preloading may result in increased tensile properties of the resulting TPV, without increasing hardness, which may be desired in some foaming applications.
  • the preloaded oil e.g., a first portion of process oil
  • the preloaded oil is introduced into the molten blend of TPV formulation components before introducing the curative.
  • at least 15 wt%, more preferably at least 30 wt%, such as at least 40 wt%, or at least 50 wt%, of the total process oil used in forming the TPV is preloaded (i.e., introduced before the curative).
  • the amount of preloaded process oil is within the range from 15 to 60 wt%, such as 20 to 60 wt%, preferably 25 to 60 wt%, such as 25 to 55 wt%, 30 to 50 wt%, or 35 to 45 wt%, with ranges from any of the foregoing low ends to any of the foregoing high ends also contemplated in various embodiments.
  • These wt%s are based on total weight of process oil added to the TPV (which is exclusive of any extender oil that may be present in the rubber component, but which includes process oil that might be added to the process with the curative, as is the case with phenolic resin-in-oil curatives).
  • molten thermoplastic vulcanizate a molten thermoplastic vulcanizate
  • post- vulcanization additives such as acid scavengers (and additional process oil, as noted)
  • acid scavengers and additional process oil, as noted
  • the product can then be extruded through an extruder die, or otherwise fabricated, and ultimately cooled for handling and/or further processing.
  • the molten thermoplastic vulcanizate composition may be cooled and/or solidified and subsequently pelletized for future storage and/or shipment.
  • Practice of such embodiments of the present invention is not necessarily limited by the manner in which the thermoplastic vulcanizate composition is subsequently solidified or fabricated.
  • Continuous mixing reactors may include those reactors that can be continuously fed ingredients and that can continuously have product removed therefrom.
  • continuous mixing reactors include twin screw or multi-screw extruders (e.g., ring extruders). Methods and equipment for continuously preparing thermoplastic vulcanizates are described in U.S. Patent Nos. 4,311,628; 4,594,390; 5,656,693; 6,147,160; and 6,042,260, as well as WIPO Patent Publication No.
  • WO 2004/009327 Al which are incorporated herein by reference, although methods employing low shear rates can also be used.
  • the temperature of the blend as it passes through the various barrel sections or locations of a continuous reactor can be varied as is known in the art. In particular, the temperature within the cure zone may be controlled or manipulated according to the half-life of the curative employed.
  • the rubber component of TPV formulations of various embodiments is preferably a cross-linkable (vulcanizable) rubber component, such that upon dynamic vulcanization, the rubber component in the resulting TPV composition (i.e., resulting from processing, including by dynamic vulcanization, of the TPV formulation) of such embodiments is at least partially cross-linked, preferably fully cross-linked.
  • a cross-linkable (vulcanizable) rubber component such that upon dynamic vulcanization, the rubber component in the resulting TPV composition (i.e., resulting from processing, including by dynamic vulcanization, of the TPV formulation) of such embodiments is at least partially cross-linked, preferably fully cross-linked.
  • any rubber suitable for use in the manufacture of TPVs can be used to manufacture (and be present in) the TPV compositions of some embodiments of the present invention.
  • the term “rubber” refers to any natural or synthetic polymer exhibiting elastomeric properties, any may be used herein synonymously with “elastomer.”
  • the rubber component may comprise one rubber, or a mix of two or more rubbers.
  • the rubber component can be any olefin-containing rubber such as ethylene-propylene copolymers (EPM), including in particular saturated compounds that can be vulcanized using free radical generators such as organic peroxides, as described in U.S. Patent No. 5,177,147.
  • EPM ethylene-propylene copolymers
  • EPDM ethylene -propylene-diene
  • EPDM-type rubber can be a terpolymer derived from the polymerization of at least two different monoolefin monomers having from 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, and at least one poly-unsaturated olefin having from 5 to 20 carbon atoms.
  • the rubber component can also be a butyl rubber.
  • butyl rubber includes a polymer that predominantly includes repeat units from isobutylene, but also includes a few repeat units of a monomer that provides a site for cross-linking. Monomers providing sites for cross-linking include a polyunsaturated monomer such as a conjugated diene or divinyl benzene.
  • the butyl rubber polymer can be halogenated to further enhance reactivity in cross-linking. Those polymers are referred to as "halobutyl rubbers.”
  • the rubber component can be homopolymers of conjugated dienes having from 4 to 8 carbon atoms and rubber copolymers having at least 50 wt% repeat units from at least one conjugated diene having from 4 to 8 carbon atoms.
  • the rubber component can also be synthetic rubber, which can be nonpolar or polar depending on the comonomers. Examples of synthetic rubbers include synthetic polyisoprene, polybutadiene rubber, styrene-butadiene rubber, butadiene-acrylonitrile rubber, etc. Amine-functionalized, carboxy-functionalized or epoxy-functionalized synthetic rubbers can also be used. Examples of those include maleated EPDM, and epoxy-functionalized natural rubbers.
  • a list of preferred rubber component include, but are not limited to, ethylenepropylene rubber, ethylene-propylene-diene rubber, natural rubber, butyl rubber including halobutyl rubber, halogenated rubber copolymer of p-alkystyrene and at least one isomonoolefin having 4 to 7 carbon atoms, a copolymer of isobutylene and divinyl-benzene, a rubber homopolymer of a conjugated diene having from 4 to 8 carbon atoms, a rubber copolymer having at least 50 wt.% repeat units from at least one conjugated diene having from 4 to 8 carbon atoms and a vinyl aromatic monomer having from 8 to 12 carbon atoms, or acrylonitrile monomer, or an alkyl substituted acrylonitrile monomer having from 3 to 8 carbon atoms, or an unsaturated carboxylic acid monomer, or an unsaturated anhydride of a dicarboxylic acid,
  • the rubber component may be present in TPV formulation and/or TPV and/or TPV composition in the amount of from about 15 wt.% to about 95 wt.%, based upon the total weight of rubber component and thermoplastic resin component. In one or more embodiments, the rubber component is present in the amount of from about 45 wt.% to about 90 wt.%, or 60 wt.% to 88 wt.%, based upon the total weight of rubber component and thermoplastic resin component.
  • the rubber component is preferably present in the TPV formulation (and/or present in the resulting TPV) in an amount within the range from 10 wt% to 40 wt%, preferably 15 wt% to 30 wt%, such as 16 to 28 wt%, based on total weight of the TPV, with ranges from any of the foregoing low ends to any of the foregoing high ends also contemplated in various embodiments.
  • these wt% values for rubber component are exclusive of any extender oil that may be formulated with the rubber component (e.g., for ease of processing).
  • the TPV formulations of various embodiments include a thermoplastic resin component comprising at least one olefinic thermoplastic resin.
  • the thermoplastic resin may be a polymer or polymer blend considered by persons skilled in the art as being thermoplastic in nature, e.g., a polymer that softens when exposed to heat and returns to its original condition when cooled to room temperature.
  • the olefinic thermoplastic resin component may contain one or more polyolefins, including polyolefin homopolymers and polyolefin copolymers.
  • thermoplastic resins suitable for inclusion in the thermoplastic resin component may be prepared from mono-olefin monomers including, but not limited to, monomers having 2 to 7 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene, 3 -methyl- 1 -pentene, 4- methyl-1 -pentene, 5-methyl- 1-hexene, mixtures thereof, and copolymers thereof.
  • mono-olefin monomers including, but not limited to, monomers having 2 to 7 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene, 3 -methyl- 1 -pentene, 4- methyl-1 -pentene, 5-methyl- 1-hexene, mixtures thereof, and copolymers thereof.
  • the olefinic thermoplastic resin is unvulcanized or non cross-linked in the resulting TPV (i.e., it is non-vulcanizable or non-cross-linkable as present in the TPV formulation, prior to dynamic vulcanization).
  • the thermoplastic resin is an olefinic thermoplastic resin that comprises, or consists of, polypropylene.
  • polypropylene as used herein broadly means any polymer that is considered a "polypropylene” by persons skilled in the art and includes homopolymers as well as impact, random, and other copolymers of propylene.
  • the polypropylene used in the TPVs described herein has a melting point above 110°C and includes at least 90 wt% propylene-derived units.
  • the polypropylene may also include isotactic, atactic or syndiotactic sequences, and preferably includes isotactic sequences.
  • the polypropylene can either derive exclusively from propylene monomers (i.e., having only propylene-derived units) or comprises at least 90 wt%, or at least 93 wt%, or at least 95 wt%, or at least 97 wt%, or at least 98 wt%, or at least 99 wt% propylene-derived units, with the remainder derived from one or more olefins selected from the group consisting of ethylene and C4 to C10 a-olefins.
  • the thermoplastic resin may have a melting temperature of at least 110°C, or at least 120°C, or at least 130°C, and may range from 110°C to 170°C or higher as measured by Differential Scanning Calorimetry (DSC).
  • DSC Differential Scanning Calorimetry
  • the procedure for DSC is described as follows: 6 to 10 mg of a sheet of the resin pressed at approximated 200°C to 230°C is removed with a punch die and then annealed at room temperature (about 23 °C) for 240 hours. At the end of this period, the sample is placed in a Differential Scanning Calorimeter (Perkin Elmer 7 Series Thermal Analysis System) and cooled at a rate of 10°C/min to -50°C to -70°C.
  • the sample is then heated at a rate of 20°C/min to attain a final temperature of 200°C to 220°C.
  • the thermal output during this heating cycle is recorded as the area under the melting peak of the sample and is measured in Joules as a measure of the heat of fusion.
  • the melting temperature is recorded as the temperature of the greatest heat absorption within the range of melting of the sample.
  • the olefinic thermoplastic resin component has MFR of 0.1, 0.5, 1, 5, 10, 15, 20, 30, 50, 100, 200, 500, 800, 1000, 1200, 1500 or even 1800 g/lOmin or greater, measured per ASTM D-1238, at 230°C and 2.16 kg mass.
  • MFR of the thermoplastic resin component may be within the range from a low of any one of 1, 10, 20, 50, 100, 200, 500, 800, 1000, 1200, and 15000 g/10 min to a high of any one of 5000, 4000, 3000, 2500, 2000, 1800, 1500, 1200, 100, 800, 600, 400 and 300 g/10 min (ASTM D-1238, 230°C and 2.16 kg) as long as the upper limit value is not lower than the lower limit value, for example from 100 to 5000 g/ 10 min, from 200 to 2000 g/lOmin, or from 300 to 800 g/lOmin, or a range between any two values as above described.
  • the TPV and/or the TPV formulation may comprise two or more thermoplastic resin components.
  • the TPV may comprise (i) a thermoplastic resin having high MFR of 100 g/10 min or greater (or other MFR per the just- given description); and (ii) a low-MFR thermoplastic resin having MFR of less than 100 g/10 min, for instance, within the range from greater than 1 to 100 g/10 min, preferably within the range from greater than 15 to 100 g/10 min,.
  • the high-MFR thermoplastic resin may otherwise be in accordance with the above-given descriptions of suitable thermoplastic resins (e.g., with respect to monomeric constituents, melting temperature, and the like).
  • the TPV composition and/or formulation preferably includes more high-MFR thermoplastic resin than low-MFR thermoplastic resin.
  • 51 to 99 wt% is high-MFR, such as 55 to 95 wt%, or 55 wt% to 75 wt%, with the balance being the low-MFR thermoplastic resin.
  • the thermoplastic resin component(s) in TPV formulation and/or TPV an/or TPV composition is present in an amount from about 5 wt% to about 85 wt%, or from about 10 wt% to about 55 wt%, or from about 12 wt% to about 40 wt% of the total weight of rubber component(s) and thermoplastic resin component(s), and/or in an amount from about 10 wt% to about 40 wt%, or about 15 wt% to about 30 wt%, or about 17 wt% to about 25 wt%, based on the total weight of the TPV formulation, as applicable.
  • Other ranges of the amount of thermoplastic resin component(s) include ranges between any the foregoing two amount values as long as the low end is not greater than the high end in various embodiments.
  • TPVs and TPV formulations used in making the TPVs may further comprise oil, including process oil (added to the TPV formulation, as described previously) and/or extender oil (which may be present in the rubber component included in the TPV formulation, also as described previously).
  • oils that may be used include hydrocarbon oils and plasticizers, such as organic esters and synthetic plasticizers.
  • Many additive oils are derived from petroleum fractions, and have particular ASTM designations depending on whether they fall into the class of paraffinic, naphthenic, or aromatic oils.
  • Other types of additive oils include alpha olefinic synthetic oils, such as liquid polybutylene.
  • Additive oils other than petroleum based oils can also be used, such as oils derived from coal tar and pine tar, as well as synthetic oils, e.g., polyolefin materials.
  • oil included in the TPV is selected based on API groupings (e.g., an API Group I, Group II, Group III, Group IV, or Group V base stock oil may be used as the oil in the TPV).
  • oil included in the TPV comprises Group II or higher oil, such as Group II oil (e.g., ParaLuxTM 6001R process oil, available from ChevronTexaco Corp.).
  • the oil could include white oil (e.g., pharmaceutical grade oil, such as PrimolTM 542 medicinal grade white oil, available from ExxonMobil Chemical Company, Baytown, Texas).
  • Process oil may be added to a TPV formulation and/or may be present in a resulting TPV in total amounts ranging from 5 to 200 phr (parts by weight per 100 parts by weight rubber component), preferably 50 to 150 phr, such as 75 to 125 phr, with ranges from any of the foregoing lows to any of the foregoing highs also contemplated in various embodiments.
  • process oil may be added to the TPV formulation and/or present in the TPV in amounts within the range from 5 to 80 wt%, preferably 20 to 70 wt%, such as 30 to 60 wt%, or 40 to 55 wt%, such wt%s based on total weight of the TPV formulation or TPV, as applicable, and with ranges from any of the foregoing lows to any of the foregoing highs also contemplated in various embodiments.
  • Extender oil may be present in the rubber component in amounts within the range from 0 phr to 150 phr, such as 25 to 125 phr, or 50 to 100 phr (0 to 30 wt%, preferably 10 to 25 or 12 to 20 wt%, based on total weight of the TPV formulation or TPV, as applicable), with ranges from any of the foregoing lows to any of the foregoing highs also contemplated.
  • Total additive oil may therefore be within the range from 5 to 350 phr (or 5 to 70 wt% based on total weight of TPV formulation or TPV, as applicable); preferably within the range from 150 to 250 phr (or 30 to 45 wt% based on total weight of TPV formulation or TPV).
  • the TPV formulation also includes a vulcanizing agent, which may be at least in part consumed during dynamic vulcanization of the TPV formulation.
  • a vulcanizing agent that is capable of curing or cross-linking the rubber employed in preparing the TPV may be used.
  • the cure system may include sulfur, peroxides, phenolic resins, free radical curatives, and/or other curatives conventionally employed.
  • the vulcanizing agent comprises a phenolic resin, and may be, for instance, a phenolic resin-in-oil cure agent (where the oil added with the resin forms part of the process oil added to the TPV formulation during processing).
  • Cure accelerators e.g., metal halides such as stannous chloride, zinc oxide, and the like
  • metal halides such as stannous chloride, zinc oxide, and the like
  • Particularly useful vulcanizing agents, including phenolic resins, and cure accelerators, including stannous chloride, are described in Paragraphs [0046] to [0054] of PCT Application No. PCT/US 15/65048, filed December 10, 2015, which description is herein incorporated by reference.
  • hydrosilation cure systems may include silicon hydride reducing agent compounds having at least two Si-H groups, such as polysiloxanes and polyorganosiloxanes.
  • Silicon hydride compounds that are useful in practicing the present disclosure include methylhydrogenpoly siloxanes, methylhydrogendimethylsiloxane copolymers, alkylmethyl-co-methylhydrogenpolysiloxanes, bis(dimethylsilyl)alkanes, bis(dimethylsilyl)- benzene, and mixtures thereof.
  • multi-functional organosilicon compounds include polymethylhydrodimethylsiloxane copolymers terminated with trimethylsiloxy groups or alkoxy groups; polymethylhydrosiloxane polymers similarly terminated.
  • the silicon hydride reducing agent compound is a trimethyl silyl terminated methyl hydrogen methyloctyl siloxane.
  • the silicon hydride reducing agent compounds also act as an effective abrasion resistance enhancing agent or slip agent as wells as acting as a hydrosilation based crosslinking agent.
  • these hydrosilating agents may be characterized by a molecular weight in a range from about 200 g/mole to about 800,000 g/mole, in other embodiments in a range from about 300 g/mole to about 300,000 g/mole, and in other embodiments in a range from about 400 g/mole to about 150,000 g/mole.
  • a silicon hydride compound includes Xiameter OFX-5084 available from Dow Corning of Midland, MI.
  • hydrosilating agents which may also be referred to as HQ- type resins or hydride-modified silica Q resins, include those compounds that are commercially available under the trade name MQH-9TM (available from Clariant of Muttenz, Switzerland), which is a hydride-modified silica Q resin characterized by a molecular weight of 900 g/mole and an activity of 9.5 equivalents/kg; HQM 105TM (available from Gelest of Morrisville, PA), which is a hydride modified silica Q resin characterized by a molecular weight of 500 g/mole and an activity of 8-9 equivalents/kg; and HQM 107TM (available from Gelest of Morrisville, PA), which is a hydride-modified silica Q resin characterized by a molecular weight of 900 g/mole and an activity of 8-9 equivalents/kg.
  • MQH-9TM available from Clariant of Muttenz, Switzerland
  • MQH-9TM available from Clariant
  • the rubber employed with the hydrosilation curatives includes diene units deriving from 5- vinylidene-2-norbomene.
  • Useful catalysts include those compounds or molecules that can catalyze the hydrosilation reaction between a reactive SiH-containing moiety or substituent and a carboncarbon bond such as a carbon-carbon double bond. Also, in one or more embodiments, these catalysts may be soluble within the reaction medium. Types of catalysts include transition metal compounds including those compounds that include a Group VIII metal. Exemplary Group VIII metals include palladium, rhodium, germanium, and platinum.
  • Exemplary catalyst compounds include chloroplatinic acid, elemental platinum, chloroplatinic acid hexahydrate, complexes of chloroplatinic acid with sym-divinyltetramethyldisiloxane, dichloro- bis (triphenylphosphine) platinum (II), cis-dichloro-bis(acetonitrile) platinum (II), dicarbonyldichloroplatinum (II), platinum chloride, and platinum oxide, zero valent platinum metal complexes such as Karstedt's catalyst, solid platinum supported on a carrier (such as alumina, silica or carbon black), platinum-vinylsiloxane complexes ⁇ for instance: Pt n (ViMe2 SiOSiMe2 Vi) n and Pt[(MeViSiO)4]m], platinum-phosphine complexes ⁇ for example: Pt(PPh3)4 and Pt(PBU3)4 ⁇ , and platinum-phosphi
  • the catalysts may be employed in conjunction with a catalysts inhibitor.
  • a catalysts inhibitor may be particularly advantageous where thermoplastic vulcanizates are prepared by using dynamic vulcanization processes.
  • Useful inhibitors include those compounds that stabilize or inhibit rapid catalyst reaction or decomposition
  • Exemplary inhibitors include olefins that are stable above 165° C. Other examples include 1, 3,5,7, - tetravinyltetramethylcyclotetrasiloxane.
  • the amount of hydrosilating agent employed may be expressed in terms of the ratio of silicon hydride equivalents (i.e., number of silicon hydride groups) to the equivalents of vinyl double bonds (e.g. number of diene-derived units on the polymer).
  • a deficiency of silicon hydride is employed.
  • an excess of silicon hydride is employed.
  • the ratio of equivalents of silicon hydride to equivalents of vinyl bonds on the rubber is in a range from about 0.7: 1 to about 10: 1, in other embodiments in a range from about 0.95: 1 to about 7: 1, in other embodiments in a range from 1 : 1 to 5: 1, and in other embodiments in a range from 1.5: 1 to 4: 1.
  • the silicon hydride reducing agent compounds may be employed in an amount in a range from about 0.5 parts by weight to about 5.0 parts by weight per 100 parts by weight of rubber (such as from about 1.0 parts by weight to about 4.0 parts by weight or from about 2.0 parts by weight to about 3.0 parts by weight).
  • a complementary amount of catalyst may include metal in a range from about 0.5 parts to about 20.0 parts per million parts by weight of the rubber (such as from about 1.0 parts to about 5.0 parts or from about 1.0 parts to about 2.0 parts).
  • the silicon hydride reducing agent compounds may be employed in an amount in with the molar equivalent of the Sill groups per kilogram of the reducing agent is in a range from 0.1 to 100 In certain embodiments of a hydrosilation cure system, the silicon hydride reducing agent compounds have a number average molecular weight in a range from about 0.2 kg/mol to about 100 kg/mol.
  • the cure system comprises a moisture-curable silane compound cured by exposing the blend to moisture (such a steam, hot water, cold water, or ambient moisture).
  • the silane compound can be grafted onto the polyethylene resin by reactive extrusion, and the graft resin can be mixed with a masterbatch comprising moisturecuring catalyst.
  • a moisture-cure catalyst is Silfin 63 available from Evonik of Parsippany, NJ.
  • the TPV formulations and/or TPV of various embodiments may also include one or more additives, including metal oxides, acid scavengers, reinforcing and non-reinforcing fillers and/or extenders, antioxidants, stabilizers (e.g., UV stabilizers), antiblocking agents, anti-static agents, waxes, foaming agents, pigments, flame retardants, and any other additive, such as processing aids known in the rubber compounding art.
  • the composition further comprises at least one additive selected from fillers, processing aids, curing accelerators, or combinations thereof.
  • the TPVs and/or TPV formulations may include reinforcing and nonreinforcing fillers, antioxidants, stabilizers, antiblocking agents, anti-static agents, waxes, foaming agents, pigments, flame retardants and other processing aids (other than the process oils described above) known in the rubber compounding art.
  • Fillers and extenders that can be utilized include conventional inorganics such as calcium carbonate, clays, silica, talc, titanium dioxide, carbon black, as well as organic and inorganic nanoscopic fillers. Fillers, such as carbon black, may be added as part of a masterbatch, and for example may be added in combination with a carrier such as polypropylene.
  • the TPV formulation and/or TPV includes at least 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt% of one or more fillers, such as calcium carbonate, clays, silica, talc, titanium dioxide, carbon black, and blends thereof, based on the weight of the TPV formulation or TPV, as applicable.
  • the TPV formulation and/or TPV includes clay and/or carbon black in an amount ranging from a low of any one of 5, 6, 7, 8, 9, or 10 to a high of any one of 15, 16, 17, 18, 19, or 20 wt% based on the total weight of the TPV formulation or TPV, as applicable.
  • the TPV formulation and/or TPV includes clay in an amount ranging from a low of any one of 0.5, 1, 1.5, 2, 2.5, 3, to a high of any one of 10, 8, 7, 6, 5, or 4 wt%, for example, from 2.5 to 5 wt%, based on the total weight of the TPV formulation or TPV, as applicable.
  • the TPV or TPV formulation or TPV composition comprises antioxidants in an amount less than or equal to 5 wt%, or 4 wt%, or 3 wt%, or 2 wt%, or 1 wt%, or 0.5 wt%, based on the total weight of the TPV formulation or TPV or TPV composition.
  • the present TPV compositions comprise a silyl-functionalized polyolefin, in which a silane unit containing a hydrolysable silyl group, as used herein, is grafted onto the polyolefin backbone and the hydrolysable silyl group is distanced at least three atoms, for example, at least four atoms, such as from 5 to 10 atoms, from the polyolefin backbone.
  • a silane unit containing a hydrolysable silyl group as used herein
  • the hydrolysable silyl group is distanced at least three atoms, for example, at least four atoms, such as from 5 to 10 atoms, from the polyolefin backbone.
  • distancing feature is important to achieve the present TPV compositions that exhibit strong adhesion to non-polymeric polar surfaces and can be directly applied onto such polar surfaces.
  • the polyolefin can be functionalized by combining with a free radical initiator and a grafting monomer and/or other functional group (such as silanes having hydrolysable silyl group as indicated in formulas (I) to (III)), and heating to react the grafting monomer with the polyolefin to form the grafted polyolefin containing functional groups.
  • a free radical initiator such as silanes having hydrolysable silyl group as indicated in formulas (I) to (III)
  • the free radical initiator may not be present in the reaction.
  • Multiple methods exist in the art for functionalizing polymers may be used to prepare the silyl-functionalized polyolefins.
  • Polyolefin useful in the present invention can be a homopolymer or copolymer of an olefin having 3 to 18 carbon atoms, preferably alpha-olefin, including but are not limited to propene (propylene), 1-butene, 1-hexene, 1-octene, 4-methyl-pentene- 1 or 2-methyl-propene- 1 (isobutylene).
  • propene propylene
  • 1-butene 1-hexene
  • 1-octene 4-methyl-pentene- 1 or 2-methyl-propene- 1 (isobutylene).
  • Particularly useful polyolefin to prepare the functionalized polyolefin can be any of such polyolefins described as the foregoing olefinic thermoplastic resin components of the TPV formulation, such as polypropylene, polyethylene, propylene-ethylene copolymer, and propylene-ethylene-diene terpolymer.
  • the polyolefin to be functionalized is the same as that of the olefin thermoplastic resin components.
  • the polyolefin useful in the present invention can be a homopolymer, such as homopolypropylene. Most commercially available polypropylene is isotactic polypropylene, but the present invention is applicable to atactic and syndiotactic polypropylene as well as to isotactic polypropylene. Isotactic polypropylene can be prepared for example by polymerization of propene using a Ziegler-Natta catalyst or a metallocene catalyst.
  • the polyolefin can alternatively be a polymer of a diene, such as a diene having 4 to 18 carbon atoms and at least one terminal double bond, for example butadiene or isoprene.
  • the polyolefin can be a copolymer, particularly a copolymer comprising at least 50% by weight units of an olefin having 3 to 18 carbon atoms, for example a copolymer of at least 50% by weight propylene with ethylene or an alpha-olefin having 4 to 18 carbon atoms, or with an acrylic monomer such as acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile or an ester of acrylic or methacrylic acid and an alkyl or substituted alkyl group having 1 to 16 carbon atoms, for example ethyl acrylate, methyl acrylate or butyl acrylate, or a copolymer with vinyl acetate
  • the polyolefin can be a terpolymer for example a propylene ethylene diene terpolymer.
  • the polyolefin can be a diene polymer such as polybutadiene, polyisoprene or a copolymer of butadiene with styrene, or a terpolymer of butadiene with ethylene and styrene or with acrylonitrile and styrene.
  • the polyolefin can be heterophasic, for example a propylene ethylene block copolymer.
  • the polyolefin may have MFR of 0.1 g/ 10 min or greater, more preferably 0.5 g/10 min or greater, 1 g/10 min or greater or less, 3 g/10 min or greaterl g/10 min or greater, 5 g/10 min or greater, 10 g/10 min or greater, 12 g/10 min or greater in some embodiments (measured per ASTM D-1238, at 230°C and 2.16 kg mass).
  • MFR of the thermoplastic resin may be within the range from a low of any one of 0.1, 0.5, 1, 2, 3, 5, 8., and 10 g/10 min to a high of any one of 50, 40, 30, 20, and 15 g/10 min (ASTM D-1238, 230°C and 2.16 kg), for example from 0.1 to 50 g/ lOmin, or from 5 to 25 g/ lOmin, or from 10 - 20 g/10 min.
  • a mixture of different polyolefins can be used.
  • microporous polypropylene is very effective in mixing with liquid additives to form a masterbatch, which can be mixed with bulk polypropylene or with a different alpha-olefin polymer.
  • Microporous polyethylene is also very effective in mixing with liquid additives to form a masterbatch, and such a masterbatch can be mixed with an alpha-olefin polymer such as polypropylene in the process of the invention provided that the polyethylene is miscible with the polyolefin and the proportion of ethylene units in the resulting polyolefin composition is less than 50% by weight.
  • Useful unsaturated silanes in the present invention include unsaturated silanes having one of the following structures:
  • Y is preferably an alkyl, aryl or arylalkyl moiety having a chain length of at least three atoms, for example from 3 to 8 atoms.
  • the moiety Y in the above structures is a chemical linkage between X and the hydrolysable silyl group -SiR n R'(3-n)
  • the linkage moiety Y can in general be a divalent organic group having a chain length of at least 2, 3, 4, 5 or 6 atoms, and up to 10, 9, 8, 7, or 6 atoms, such as alkyl, aryl, or arylalkyl group, for example a propyl, butyl, phenyl, hexyl, phenethyl, and decyl group.
  • the linkage moiety Y can comprise a straight or branched chain as long as the chain length comprises at least 2 atoms.
  • the “chain length” of moiety Y represents the length by atoms between the atom (inclusive) linking to the silyl group and the atom (inclusive) linking to X moiety.
  • the hydrolysable group R can be preferably an alkoxy group, though other hydrolysable groups such as acryloxy, for example acetoxy, ketoxime, for example methylethylketoxime, alkyllactato, for example ethyllactato, amino, amido, aminoxy or alkenyloxy groups can be used.
  • Alkoxy groups R preferably each comprises a linear or branched alkyl chain of 1 to 10 carbon atoms, for example, methoxy, ethoxyl, propyoxy, butoxy, and pentoxy groups, and more preferably are methoxy or ethoxy groups.
  • the value n in the silane structures can for example be 3, for example the silane can be a trimethoxy silane, to give the maximum number of hydrolysable and/or crosslinking sites.
  • the hydrolysable groups for example silyl-alkoxy groups grafted to the polyolefin can react with polar groups, for example hydroxyl groups present on the surface of many fillers and substrates to form Si — O — Si linkages between polymer chains, which offers adhesion when being applied.
  • the group R' if present is preferably a hydrogen or an alkyl chain of 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, butyl, and pentyl groups, and more preferably methyl or ethyl group.
  • Preferred examples of useful silane in the present invention can include acryloxylpropyltrimethoxysilane, methacryloxybutyltrimethoxysilane, acryloxylpropyltriethoxysilane, methacryloxybutyltriethoxysilane, acryloxylpropylmethyldimethoxysilane, methacryloxylpropylmethyldimethoxysilane, acryloxylbutylmethyldimethoxysilane, methacryloxylbutylmethyldimethoxysilane, acryloxypropyltributoxysilane, methacryloxypropyltributoxysilane, acryloxypropyltripentoxysilane, or methacryloxypropyltripentoxysilane,
  • silanes are such having an acryloxy terminal in the above structures, i.e., where R" and R'" are both hydrogen, for example, acryloxylpropyltrimethoxysilane and acryloxylpropyltriethoxysilane.
  • Blends of unsaturated silanes can be used, for example a blend of acryloxypropyltrimethoxysilane with acryloxylpropyltriethoxysilane.
  • Useful silanes can be prepared by any known methods in the art, for example such as described in U.S. Patent No. 3179612.
  • Commerically available silanes can be those obtained from Shin-Etsu Chemical Co., Ltd., Japan under series name of KBM such as grades 5103 and 503, those from PCC Group under trade name of SiSiB® PC4600, and those from Wacker Chemical Corporation under the tradename of Geniosil® GF31.
  • the unsaturated silane and free radical initiator i.e., a compound capable of generating free radical sites in the polyolefin
  • the silane and the free radical initiator and optional other additives, if desired, are first mixed to form a mixture.
  • the free radical initiator in the polyolefin is preferably an organic peroxide, for example, hydroperoxides, carboxylic peroxyesters, peroxyketals, dialkyl peroxides and diacyl peroxides, ketone peroxides, diaryl peroxides, arylalkyl peroxides, peroxy di carbonates, peroxyacids, acyl alkyl sulfonyl peroxides and monoperoxydicarbonatesalthough other free radical initiators such as azo compounds can be used.
  • organic peroxide for example, hydroperoxides, carboxylic peroxyesters, peroxyketals, dialkyl peroxides and diacyl peroxides, ketone peroxides, diaryl peroxides, arylalkyl peroxides, peroxy di carbonates, peroxyacids, acyl alkyl sulfonyl peroxides and monoperoxydicarbonates although other free radical initiators such as azo
  • peroxides examples include dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert- butylperoxy)hexane, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne- 3,3,6,9-triethyl-3,6,9-trimethyl-l,4,7-triperoxonane, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxy acetate, tert-butyl peroxybenzoate, tert-amylperoxy-2-ethylhexyl carbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, 2,2-di(tert-butylperoxy)butane, tertbutylperoxy isopropyl carbonate, tert-buylperoxy-2-ethyl
  • reaction of the unsaturated silane, or the mixture comprising the unsaturated silane and optionally peroxides, and the polyolefin is preferably carried out without presence of a co-agent that inhibits degradation of polyolefin, or called degradation inhibiting agent as used herein.
  • a co-agent that inhibits degradation of polyolefin or called degradation inhibiting agent as used herein. It has been disclosed in the art that the grafting of silane onto polyolefin can be accompanied by degradation of the polyolefin by chain scission in the beta-position or so-called beta-scission, which as said may result in decrease of viscosity of the material to be processed.
  • co-agents capable of inhibiting the degradation of polyolefin for example an aromatic compound as described in JP-A-1994-172459, styrene, sorbate, 2, 4-pentadienoate and cyclic derivatives thereof as described in U.S. Patent No. 8,569,417.
  • an degradation inhibiting agent is suggested for increasing the grafting level
  • the preparation of the silanes useful in the present invention does not include use of such degradation inhibiting coagent, and the inventors have found surprisingly that certain level of degradation of the polyolefin may actually improve the adhesion of the present TPV composition onto the non- polymeric polar surface, especially after cataplasma aging.
  • the grafting reaction between the polyolefin and the unsaturated silane can be carried out as a batch process or as a continuous process using any suitable apparatus as already known in the art.
  • a batch process can for example be carried out in an internal mixer such as a Brabender mixer or a Banbury mixer.
  • a continuous processing is generally preferred, for example an extruder adapted to mechanically pass while kneading or compounding the raw materials through it, for example a twin screw extruder or a Farrel Continuous Mixer.
  • the extruder preferably includes a vacuum port before the extrusion die to remove any volatiles including unreacted silane.
  • the reaction temperature is generally above 120 °C, usually above 140 °C, and is sufficiently high to melt the polyolefin and to decompose the free radical initiator.
  • a temperature in the range 170 °C to 220 °C is usually preferred.
  • the peroxide in the polyolefin preferably has a decomposition temperature in a range between 120 - 220 °C, most preferably between 160 -190 °C.
  • All or a portion of the polyolefin may be premixed with the unsaturated silane and/or the compound capable of generating free radical sites (free radical initiator) in the polyolefin before being fed to the extruder, but such premixing is generally at below 120 °C, for example at ambient temperature, to avoid the decomposition of peroxides.
  • up to 20 % s, 15% or 10% of the total polyolefin that is used for the functionalization may be added, without being pre-mixed, into the extruder in a solid and/or molten state so as to adjust the melt flow rate of the resulting silyl-functionalized polyolefin.
  • the free radical initiator can be added during the reaction of the polyolefin and the unsaturated silanes to create free radical sites, for example, by shearing, for further grafting the unsaturated silanes onto the polyolefins.
  • the free radical initiator can be added in an amount of at least 0.01% by weight of the total amount of the present TPV compositions, and can be present in an amount of up to 10%.
  • An organic peroxide for example, is preferably present at 0.01 to 10% by weight based on the polyolefin during the grafting reaction. Most preferably, the organic peroxide is present at 0.1% to 1 % by weight of the total amount of the present TPV compositions.
  • such free radical initiator can be absent from addition into the reaction of the polyolefin and unsaturated silanes as the azido silanes can be grafted onto polyolefin backbones by radical insertion.
  • the silyl-functionalized polyolefin is formed in the process of making TPV compositions, as described below, for example, by adding the silanes into the process of making the TPVs or by processing the silanes directly with TPVs .
  • additives such as fillers, antioxidants, UV stabilizers, flame retardants, and other processing aids known in the thermoplastic resin processing industry, for example such as described herein, can be added optionally and desirably during the reaction of the unsaturated silanes and the polyolefins.
  • the silyl-functionalized polyolefin can comprise from about 0.1, 0.5, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0 wt% or greater and up to about 10, 9, 8, 7, 6, 5 wt% of the silane-derived unit based on the weight of the silyl-functionalized polyolefin.
  • the silane-derived units in the silyl- functionalized polyolefin can be present, or in any ranges between the above amount values as long as the low end value is not greater than the high end value, for example, from 0.1 wt% to 10 wt%, or from 1 wt% to 10 wt%, or from 2 wt% to 8 wt% based on the weight of the silyl- functionalized polyolefin.
  • the silyl-functionalized polyolefin can have an melt flow rate (MFR) of 100, 200, 500, 800, 1000, 1200, 1500 or even 1800 g/lOmin or greater, measured per ASTM D-1238, at 230°C and 2.16 kg mass.
  • MFR melt flow rate
  • MFR of the thermoplastic resin component may be within the range from a low of any one of 100, 150, 200, 300, 500 g/10 min to a high of any one of 5000, 4000, 3000, 2500, 2000, 1800, 1500, 1200, 100, 800, 600, 400 and 300 g/10 min as long as the upper limit value is not lower than the lower limit value, for example from 100 to 2000 g/lOmin, or from 200 to 800 g/lOmin, or a ranges between any two values as above described.
  • Also provided includes a process for making the TPV compositions (e.g., to make a reaction product).
  • the method may comprise the steps of: (a) forming a silyl-functionalized polyolefin, (b) forming a TPV, and (c) blending the TPV, the silyl-functionalized polyolefin, and optionally other additives, to form a TPV composition.
  • the thermoplastic vulcanizate(s), silyl-functionalized polyolefin, and other optional additives such as antioxidant, if present, can be blended by any suitable means.
  • blending can include dry blending, though more preferably melt-blending in a batch mixer or in a continuous mixer, such as extruder or Farrel mixer, or by a combination thereof.
  • the TPV composition is prepared by blending the components in a batch mixer, such as a twin rotor internal mixer equipped with a temperature and/or pressure ram. Mixing can be performed at pressures and temperatures such that the filler and other components are finely incorporated and become uniformly dispersed within the thermoplastic vulcanizate and silyl-functionalized polyolefin.
  • a batch mixer such as a twin rotor internal mixer equipped with a temperature and/or pressure ram. Mixing can be performed at pressures and temperatures such that the filler and other components are finely incorporated and become uniformly dispersed within the thermoplastic vulcanizate and silyl-functionalized polyolefin.
  • the preferred polyolefin are miscible with the thermoplastic resin component of the TPV and accordingly the resulting TPV composition becomes a mixture of finely incorporated and dispersed TPV and the silyl-functionalized polyolefin, for example, in a way that the thermoplastic resin component in the TPV and the silyl-functionalized polyolefin are fully and uniformly incorporated into each other, forming a uniform continuous thermoplastic phase.
  • the TPV and the silyl-functionalized polyolefin can be blended gradually by first adding and blending a portion of the TPV and/or the silane- functionalized polyolefin into a mixer with internal blending elements such as bladders, for example an extruder or a Farrel mixer, and then adding and blending the remaining or another portion of the material.
  • a mixer with internal blending elements such as bladders, for example an extruder or a Farrel mixer
  • the temperature of the blending TPV and the silane-functionalized polyolefin is not particular limited as long as it is higher than the melting points of the TPV and the silane- functionalized polyolefin during the blending process, for example in a range from 140 °C to 250 °C, or from 170 °C to about 220 °C.
  • the blending comprises a gradually increasing temperature profile from the beginning to the end of such blend, for example by changing the rotating speeds of the internal blending elements.
  • the steps (b) and (c) can be carried out simultaneously.
  • the silyl-functionalized polyolefin formed in step (a) can used as the thermoplastic resin in the dynamically vulcanization process and accordingly the silyl- functionalized polyolefin, the rubber component, and optionally the thermoplastic resin component and other fillers and additives are subjected to the dynamic vulcanization process in the presence of a curing system, for example, a hydrosilation cure system as described herein, to form the TPV compositions.
  • the silyl-functionalized polyolefin serves as a portion or all of the thermoplastic resin component.
  • the silyl-functionalized polyolefin formed in step (a) can be added in a solid and/or molten state after the rubber component is partially cured in a dynamic vulcanization process.
  • the steps (a) and (c) can be carried out simultaneously.
  • the hydrolysable unsaturated silane, and optionally the polyolefin, and the TPV formed in step (b) can be blended and processed such that the silanes are grafted onto the thermoplastic resin component and/or the polyolefin, if present, with or without the presence of a radical generating compounds, for example, peroxide.
  • the steps (a), (b) and (c) are combined and carried out simultaneously in one step, i.e., in-situ formation of the TPV composition.
  • the thermoplastic resin component, the rubber component, the polyolefin, and hydrolysable unsaturated silane can be added into the dynamically vulcanization process where for example, a peroxide and/or a hydrosilation cure system is used.
  • the hydrolysable unsaturated silane is added after the rubber is at least partially cured.
  • the polyolefin is the same as the thermoplastic resin component.
  • the silane-functionalized polyolefin can be present in the present TPV composition in an amount of at least 0.1 wt%, 1 wt%, 3 wt%, 5 wt% and up to 25 wt%, 20 wt%, 15 wt%, 12 wt%, 10 wt%, 8 wt%, or 5 wt% based on the weight of the TPV and the silane-functionalized polyolefin, or in any ranges between the above amount values as long as the low end value is not greater than the high end value, for example, from 0.1 wt% to 25 wt%, or from lwt% to 15 wt%, or from 2 wt% to 10 wt% based on the weight of the TPV and the silyl-functionalized polyolefin.
  • a hydrolysis-condensation catalyst can also be incorporated into the present TPV composition.
  • the hydrolysis-condensation catalyst may further accelerate the adhesion of the TPV composition to the polar surface and reduce the application temperature (interface temperature).
  • Those catalyst can be such known in the art and can comprise for example titanate and stannate derivatives such as dimethyl-tin-dineodecanoate (DMTDN).
  • the TPV and/or formed TPV composition of the present invention may have a Laboratory Capillary Rheometer (“LCR”) viscosity at 1200/s, as measured based on method ASTM D-3835, of 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100 Pa-s or greater, and/or up to 300, 250, 220, 200, 180, 160, 150, 130, 120, 100 Pa-s or less, or be in a range between any two of the above values as long as the low end value is not greater than the high end value, for example, from 30 Pa- s to 200 Pa-s, or from 50 Pa-s to 160 Pa- s, or from 70 Pa- s to 120 Pa- s, wherein a desirable range may comprise any combination of any lower limit with any upper limit described herein.
  • LCR Laboratory Capillary Rheometer
  • high flowability of the TPV composition can create more interactions between the hydrolysable groups with a polar surface in the present of moisture, and a high flowability of the present TPV composition could reduce the internal stress of material that could be less shrinkage/deformation after being solidified, which would result less deformation of the bonding between functional groups and polar surface.
  • the useful TPV and/or formed TPV compositions of the present invention can have a Shore A hardness of 25 or greater, 30 or greater, 35 or greater, 40 or greater, 50 or greater, or greater than 60, and can have a Shore D hardness of 60 or less, 50 or less, 40 or less, preferably a Shore A hardness from 25 to 90, or from 60 to 80.
  • the hardness values are measured according to ASTM D-2240.
  • the TPV composition of the present invention when applied onto a polar surface, can have a cohesive failure of at least 70%, at least 80%, at least 90%, at least 95%, at least 98%, at least 99, or 100%, both before and after cataplasma.
  • the present invention also encompasses an article comprising a non-polymeric polar surface and the present TPV composition applied onto the polar surface.
  • the non- polymeric polar surface can be such surface of or containing a polar substrate, for example, glass, metal, metal alloys, woods, paper, concrete, ceramics, foil and the like.
  • the process for applying the present TPV composition can be any such known in the art to process TPV or TPV compositions, for example, by means of injection molding, compression molding, profile extrusion, robotical extrusion, casting, etc.
  • the non-polymeric polar surface can be applied with the present TPV composition without being prior treated, e.g., cleaning of the surface by a solvent, or incorporation of a primer and/or adhesion promoter etc.
  • the TPV composition is applied and directly contacted with the non-polymeric polar surface. This significantly simplifies the application process.
  • the polar surface can be pre-heated till 100 °C or above before applying the present TPV composition onto such polar surface, for example by means of injection molding.
  • the present invention does not preclude the treatment of the polar surface using primer and/or adhesion promoter before applying the present TPV composition onto a non-polymeric polar surface.
  • a primer and/or adhesion promoter can be used on the polar surface as such described in the prior art.
  • the non-polymeric polar surface can be treated with both primer and an adhesion promoter as such known in the adhesive industry with various chemistries such as silanes and polyurethanes, and in some other embodiments the polar surface can be treated with only adhesion promoter, without use of a primer (i.e., using the present TPV composition to replace the primer). Accordingly, the present invention provides flexibilities on application of the TPV compositions onto a non-polymeric polar surface for desired properties.
  • Embodiment A A thermoplastic vulcanizate composition, comprising (i) a thermoplastic vulcanizate containing 5 wt.% to 85 wt.% of a thermoplastic resin component and 15 wt.% to 95 wt.% at least partially vulcanized rubber component dispersed in the thermoplastic resin component, based on the total weight of the thermoplastic resin component and the rubber component; and (ii) 0.1 wt.% to 25 wt.% silyl-functionalized polyolefin containing a hydrolysable silyl group being at least three atoms distanced from the polyolefin backbone, based on the weight of the thermoplastic vulcanizate composition.
  • Embodiment B The thermoplastic vulcanizate composition of Embodiment A, wherein the hydrolysable silyl group is at least 4, or at least 5 atoms distanced from the polyolefin backbone.
  • Embodiment C The thermoplastic vulcanizate composition of Embodiments A or B wherein the silyl-functionalized polyolefin is a reaction product of a polyolefin and a silane having at least one of the following structures:
  • X represents a moiety comprising carboxyl group, carbonyl group, amide group or sulfonyl group
  • Y represents a moiety having a chain length of at least two atoms
  • R represents a hydrolysable group selected from the group consisting of alkoxy, acethoxy, aminoxy, alkenyloxy, hydroxyl, and combinations thereof
  • R' represents a hydrogen or a hydrocarbyl group having 1 to 10 carbon atoms
  • n has a value of 1, 2, or 3.
  • Embodiment D The thermoplastic vulcanizate composition of Embodiment C, wherein X is a carboxyl or sulfonyl group, Y is an alkyl group having a chain length of from 3 to 8 atoms, and R is an alkoxy group having 1 to 6 carbon atoms; R' is a hydrogen or a hydrocarbyl group having 1 to 6 carbon atoms; and n is 2 or 3.
  • Embodiment E The thermoplastic vulcanizate composition of Embodiments C or D, in which X is a carboxyl, Y is an alkyl group having a chain length of from 3 to 6 atoms, and R is an alkoxy group having 1 to 3 carbon atoms; and n is 3.
  • Embodiments F The thermoplastic vulcanizate composition of any one of Embodiments C to E, wherein the silane is at least one of the following:
  • Embodiments G The thermoplastic vulcanizate composition of Embodiment F, wherein the R" and R'" are hydrogen.
  • Embodiment H The thermoplastic vulcanizate composition of any one of Embodiments C to G, wherein the silane comprises acryloxylpropyltrimethoxysilane, acryloxylpropyltriethoxysilane, methacryloxybutyltrimethoxysilane, methacryloxybutyltriethoxysilane, acryloxylpropylmethyldimethoxysilane, acryloxylbutylmethyldimethoxysilane, acryloxypropyltributoxysilane, methacryloxypropyltripentoxysilane, (azidomethyl)ohenethyltrimethoxysilane, p- azidomethylphenyltrimethoxysilane, 3 -azidopropyl triethoxysilane, 6- azidosulfonylhexyltriethoxysilane, 4-(azidosulfonyl)phenethyltrimethoxys
  • Embodiment I The thermoplastic vulcanizate composition of any one of Embodiments C to H, wherein the silane comprises acryloxylpropyltrimethoxysilane, acryloxylpropyltriethoxysilane, acryloxylpropylmethyldimethoxysilane, acryloxylbutylmethyldimethoxysilane, acryloxypropyltributoxysilane,
  • Embodiment J The thermoplastic vulcanizate composition of any one of Embodiments A to I, wherein the silyl-functionalized polyolefin is a reaction product of a polyolefin and an unsaturated silane without presence of a degradation inhibiting co-agent.
  • Embodiment K The thermoplastic vulcanizate composition of Embodiment J, wherein the degradation inhibiting co-agent comprises aromatics, sorbates, 2, 4-pentadienoate, and cyclic derivatives thereof.
  • Embodiments L The thermoplastic vulcanizate composition of any one of Embodiments A to K comprising from about 0.1 to 25 wt%, from 1 to 15 wt%, or from 2 to 10 wt% the silyl-functionalized polyolefin based on the total weight of the thermoplastic vulcanizate and the silyl-functionalized polyolefin.
  • Embodiment M The thermoplastic vulcanizate composition of any one of Embodiments A to L, wherein the silyl-functionalized polyolefin comprises from 0.1 to 10 wt%, 1 to 10 wt%, or 2 to 8 wt% of the silane-derived units based on the weight of the silyl- functionalized polyolefin.
  • Embodiment N The thermoplastic vulcanizate composition of any one of Embodiments A to M, wherein the thermoplastic resin component comprises a polyethylene homopolymer, a polypropylene homopolymer, an ethylene-propylene copolymer, or any combination thereof.
  • Embodiment O The thermoplastic vulcanizate composition of any one of Embodiments A to N, wherein the thermoplastic component resin has melt flow rate of from 100 to 5000 g/ 10 min, from 200 to 2000 g/lOmin, or from 300 to 800 g/lOmin, as measured based on method ASTM D-1238 at 230 °C and 2.16 kg.
  • Embodiment P The thermoplastic vulcanizate composition of any one of Embodiments A to O, the polyolefin is the same as the thermoplastic resin component.
  • Embodiment Q The thermoplastic vulcanizate composition of any one of Embodiments A to P, wherein the polyolefin is homopolypropylene.
  • Embodiment R The thermoplastic vulcanizate composition of any one of Embodiments A to Q, wherein the rubber component is selected from the group consisting of an ethylene-propylene rubber, ethylene-propylene-diene rubber, butyl rubber and natural rubber.
  • Embodiment S The thermoplastic vulcanizate composition of any one of Embodiments A to R, wherein the silyl-functionalized polyolefin has a melt flow rate of from 100 to 2000 g/10 min, or from 200 to 800 g/10 min, as measured based on method ASTM D- 1238 at 230 °C and 2.16 kg.
  • Embodiment T The thermoplastic vulcanizate composition of any one of Embodiments A to S, having one or more of the following properties:
  • Embodiment U A method of making a silyl-functionalized polyolefin, comprising the step of reacting a polyolefin and an unsaturated silane having at least one of the following structures to form the silyl-functionalized polyolefin without presence of a degradation inhibiting co- agent,
  • X represents a moiety comprising carboxyl group, carbonyl group, amide group or sulfonyl group
  • Y represents a moiety having a chain length of at least two atoms
  • R represents a hydrolysable group selected from the group consisting of alkoxy, acethoxy, aminoxy, alkenyloxy, hydroxyl, and combinations thereof
  • R' represents a hydrogen or a hydrocarbyl group having 1 to 10 carbon atoms
  • n has a value of 1, 2, or 3
  • the degradation inhibiting co-agent comprises aromatics, sorbates, 2, 4-pentadienoate, and cyclic derivatives thereof
  • the silyl-functionalized polyolefin has a melt flow rate of from 100 to 2000 g/10 min, or from 200 to 800 g/10 min, as measured based on method ASTM D-1238 at 230 °C and 2.16 kg.
  • Embodiment V A method of making the thermoplastic vulcanizate composition, comprising the steps of:
  • thermoplastic vulcanizate comprising 5 wt.% to 85 wt.% of a thermoplastic resin component and 15 wt.% to 95 wt.% at least partially vulcanized rubber component dispersed in the thermoplastic resin component, based on the total weight of the thermoplastic resin component and the rubber component;
  • thermoplastic vulcanizate composition (c) mixing the thermoplastic vulcanizate with 0.1 wt% to 25 wt% the silyl- functionalized polyolefin based on the weight of thermoplastic vulcanizate and the silyl-functionalized polyolefin; to form the thermoplastic vulcanizate composition.
  • Embodiment W The method of Embodiment V, wherein step (a) comprising the method of Embodiment U.
  • Embodiment X The method of Embodiments V or W, wherein steps (a) and (c) are carried out simultaneously, wherein the unsaturated silane, the TPV, and optionally a polyolefin are mixed.
  • Embodiment Y The method of Embodiments V or W, wherein steps (b) and (c) are carried out simultaneously, and wherein the silyl-functionalized polyolefin, the rubber component, and optionally a thermoplastic resin component are subject to a dynamic vulcanization in the presence of a cure system.
  • Embodiment Z The method of Embodiments V or W, wherein steps (a), (b) and (c) are carried out simultaneously, and wherein the unsaturated silane, the polyolefin and/or the thermoplastic resin component, the rubber component are subject to a dynamic vulcanization in the presence of a cure system.
  • Embodiment AA The method of Embodiments Y or Z, wherein the cure system comprising a hydrosilation cure system.
  • Embodiment AB The method of any one of Embodiment V to AA, wherein the polyolefin is the same as the thermoplastic resin component.
  • Embodiment AC The method of any one of Embodiments V to AB, the polyolefin and the thermoplastic resin component are the same homopolypropylene.
  • Embodiment AD An article comprising a non-polymeric polar surface and the thermoplastic vulcanization composition of any one of Embodiments A to T, wherein the thermoplastic vulcanizate composition is directly contacted with the non-polymeric polar surface.
  • Embodiment AE The article of claim Embodiment AD, wherein the thermoplastic vulcanization composition is applied directly onto the non-polymeric polar surface by compression molding, injection molding, or extrusion molding.
  • Embodiment AF The article of any one of Embodiment AD or AE, wherein the non-polymeric polar surface is not pre-treated with an adhesion promoter before being applied with the thermoplastic vulcanizate composition.
  • the cohesive failure is measured by mean of peeling test.
  • a tensile traction bank was used to held the samples of glasses on which the TPV compositions were applied.
  • the over-molded TPV compositions were pulled vertically, i.e., with an angle of 90 degree relative to the glass surface at a speed of about 50 mm/min.
  • regular incisions are made at the interface to force interface rupture.
  • the cohesive failure was observed, after the peeling test, by percentage of the area having the TPV compositions residues relative to the areas that the TPV compositions were initially applied.
  • a 100% cohesive failure represents that all the areas of the glass surface where the TPV composition was applied contained residues of TPV compositions after the peeling test, indicating a very strong adhesion to the glass.
  • Adhesion performance of the modified TPV compositions are tested by pulling the applied TPV compositions at a thickness of 2 or 4 cm on a traction bank perpendicular to the surface as per drawing 1 at a speed of 50mm/min after a pre-conditioning of the samples at 23 °C and 50% relative humidity for a minimum of 48 hours. Samples showing cohesive failure were systematically cut with a cutter blade at the interface to force the interface cleavage and avoid bulk material rupture. To ensure proper adhesion data, samples were pulled on an adhesion length of 150 mm where maximum adhesion force and average adhesion forces were measured. Compiled data in the application are mean average of 5 experiments to ensure meaningful statistical data.
  • the maximum force is defined as the highest force that has been measured during the peeling testing on the peeling range from 10 to 150mm.
  • the average force is the average of the forces recorded between 10 and 150mm peeling.
  • Aging cataplasma tests are performed by wrapping the samples inside a water soaked cotton pad. Wrapped samples are then placed inside a hermetic plastic bag and the whole placed in an oven at 70 °C for 168 hrs. After aging, samples are unwrapped and conditioned at 23 °C and 50% relative humidity for minimum 48 hours at a traction speed of 50 mm/min. Samples are then tested for adhesion following aforementioned protocol.
  • TPV used in examples was commercially available from ExxonMobil Chemical Company, U.S.A, under trade name SantopreneTM 121-60M200, having a shore A hardness of 61 at 15 second and temperature of 23 °C, a maximum tensile strength and elongation at break at 23 °C of 4.1 MPa and 380% respectively, and LCR of 40.
  • PP used in examples was homopolymer polypropylene having a melt index (2.16 kg, 230 °C) of 12 g/10 min and being commercially available from Total SE, France under trade name PPH 7060.
  • Silane used in examples was an acryloxypropyltrimethoxysilane commercially available from Shin-Etsu Chemical Co., Ltd., Japan, under trade name KBM-5103, methacryloxypropyltrimethoxysilane commercially available from Shin-Etsu under the tradename of KBM-503.
  • Co-Agent used in examples was divinyl-benzene was obtained from Sigma- Aldrich.
  • Peroxide used in examples was 2,5-Dimethyl-2,5-di-(tert-butylperoxy)-hexane commercially available from Pergan GmbH, under the commercial name Peroxan® HX.
  • Antioxidant used in examples was a mixture of Irgafos® 168 and Irganox® 1010 in a 1:1 ratio, which was commercially available from BASF under the commercial name of Irganox® B225.
  • Vestoplast® 206 was vinylsilyl-functionalized poly-a-olefin and was commercially available from Evonik Corporation.
  • PP and antioxidant were added in 0D (cooled main throat).
  • Table 2 Ingredients of silyl-functionalized polyolefin, parts by weight
  • Table 3 TPVs compositions, parts by weight
  • modified TPV compositions were applied onto glass surfaces by means of compression molding with Collin 300P press. Glass surfaces were cleaned by means of isopropanol to remove any grease contaminants.
  • the glasses were pre-heated for 2 minutes at a temperature of 200 °C, and the modified TPV compositions were pre-melted for 1 min at 5 bars, followed by a compression for 4 minutes at 40 bars.
  • a cooling was applied with a temperature reducing rate of 1°C per 4 seconds and a final de-compression was performed for Imin at 5 bars at 40 °C.
  • the thickness of TPV compositions applied onto glass were 2mm (examples 1 to 7 and 12 to 21) or 4mm (examples 8 to 11). Adhesion performance of the TPV compositions are tested and shown in Table 4. Table 4: Adhesion Test Results
  • silyl-functionalized PP prepared in the presence of a degradation inhibiting co-agent which was dedicated for improving grafting efficiency and reducing degradation of the polypropylene backbone by beta-scission (examples 3 to 5), showed some strong initial adhesion with significantly reduced cohesive failure after cataplasma aging and such reduction being increased along with increasing of the addition level of such co-agent, whereas the use of present silyl-functionalized PP prepared without the presence of any degradation inhibiting agent resulted 100% cohesive failure indicating strong adhesion to the non-polymeric polar material after cataplasm.
  • a degradation inhibiting co-agent which was dedicated for improving grafting efficiency and reducing degradation of the polypropylene backbone by beta-scission
  • Examples 8-9 are repeats of the Example 6-7 where the thickness of the TPV was increased from 2 to 4mm to reach higher peeling forces and check robustness. In those cases, excellent adhesions were observed reaching full cohesive failure mode. The results obtained after the cataplasma aging did show minor effect on the adhesion profile, still reaching high peeling values and cohesive failure.
  • Examples 10-11 are demonstrating the possibility to further decrease the level of hydrolysable groups on the PO backbone by 33% vs Examples 8 and 9 and still delivering strong adhesion profiles onto the non-polymeric polar surface. Strong Cohesive failure mode is still observed even after the cataplasma aging.
  • the comparative data obtained when replacing the acryloxy-functional silane by a methacryloxyfunctional silane did show a relatively high decrease in the adhesion onto the non-polymeric polar surface. None of the examples 12 to 17 showed any adhesion after aging. It is believed, without being binded to any theory, that the grafting efficiency onto polypropylene backbone of the methacryloxy compared to the acryloxy is lower, hence delivering a polyolefin having less anchoring points to trigger the adhesion.

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Abstract

La présente invention concerne une composition de vulcanisat thermoplastique qui comprend un vulcanisat thermoplastique et une polyoléfine fonctionnalisée par silyle. La polyoléfine fonctionnalisée par silyle contient un groupe silyle hydrolysable qui est située à distance du squelette de polyoléfine équivalente à au moins 3 atomes. La présente composition de vulcanisat thermoplastique fournit une rupture cohésive d'au moins 70 %, aussi bien avant et après vieillissement par cataplasme, et peut être appliquée sur une surface polaire non polymère sans qu'un pré-traitement soit nécessaire.
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WO2004009327A1 (fr) 2002-07-22 2004-01-29 3+Extruder Gmbh Extrudeuse destinee au traitement continu de materiaux coulants
US20090162664A1 (en) 2007-12-21 2009-06-25 Duan Li Ou Preparation of a self-bonding thermoplastic elastomer using an in situ adhesion promoter
US8569417B2 (en) 2008-07-03 2013-10-29 Dow Corning Corporation Modified polyolefins

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115058086A (zh) * 2022-05-09 2022-09-16 宁波信泰机械有限公司 一种挤出级热塑性硫化橡胶及其制备方法
CN115058086B (zh) * 2022-05-09 2024-01-23 宁波信泰机械有限公司 一种挤出级热塑性硫化橡胶及其制备方法

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