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WO2025106160A1 - Fabrication de matériaux hybrides de silicone-polyoléfine - Google Patents

Fabrication de matériaux hybrides de silicone-polyoléfine Download PDF

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Publication number
WO2025106160A1
WO2025106160A1 PCT/US2024/048266 US2024048266W WO2025106160A1 WO 2025106160 A1 WO2025106160 A1 WO 2025106160A1 US 2024048266 W US2024048266 W US 2024048266W WO 2025106160 A1 WO2025106160 A1 WO 2025106160A1
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Prior art keywords
silicone
polyolefin
group
reactive
hybrid material
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Inventor
Ryan Zowada
Jason CATER
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Dow Silicones Corp
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Dow Silicones Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/41—Intermeshing counter-rotating screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/52—Screws with an outer diameter varying along the longitudinal axis, e.g. for obtaining different thread clearance
    • B29C48/525—Conical screws
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/52—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices with rollers or the like, e.g. calenders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/584—Component parts, details or accessories; Auxiliary operations for mixers with rollers, e.g. wedges, guides, pressing means, thermal conditioning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/425—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders using three or more screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/465—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using rollers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • silicone-polyolefin hybrid material using silicone rubber bases comprising high viscosity (i.e., greater than 1 million mPa.s at 25 o C) silicone polymers, fillers, and suitable polyolefin materials.
  • high viscosity silicone polymers are often referred to in the industry as silicone polymer gums or silicone gums.
  • the disclosure also relates to the resulting silicone-polyolefin hybrid materials, their uses and products made therefrom. Silicones are polymeric materials used in numerous commercial applications, primarily due to significant advantages they possess over their carbon-based analogues.
  • silicones include an inorganic silicon-oxygen backbone chain ( ⁇ –Si–O–Si–O–Si–O– ⁇ ) having organic side groups attached to the silicon atoms. Organic side groups may be used to link two or more of these backbones together.
  • silicones can be synthesized with a wide variety of properties and compositions, with silicone networks varying in consistency from liquid to gel to rubber to hard plastic. Cured silicone and siloxane-based materials are utilized in myriad end use applications and environments, including as components in a wide variety of industrial, home care, and personal care formulations.
  • silicone-polyolefin hybrid compositions however conventional siloxanes are incompatible with most carbon-based polymers, typically due to immiscibility and/or exhibiting antagonistic properties with respect to one another.
  • Such hybrid materials e.g., silicone-polyolefin (SiPO) hybrid materials are typically produced though a reactive compatibilization of the dissimilar materials during a mixing process. The mixing process generates a dispersed phase and a continuous or bulk phase which contains the disperse phase and a chemical reaction occurs at the surface of the dispersed phase which compatibilises and/or binds the disperse phase into the continuous material.
  • the mixing process is typically a form of reactive extrusion (REX) on continuous high-shear equipment such as twin-screw extruders (TSE).
  • REX reactive extrusion
  • TSE twin-screw extruders
  • the high temperatures used for REX facilitate the heat of reaction needed for compatibilization.
  • the hybrid material’s resulting mechanical properties and dispersed polyolefin domain morphology are not influenced by change in mixing operations using a TSE, such as mixing speed or temperature.
  • a TSE would be the obvious choice of mixing a polyolefin-in-silicone hybrid material since silicone requires a higher amount of heat and shearing for a reduction in viscosity to allow dispersion as well as facilitating the REX reaction.
  • a process for the preparation of a silicone-polyolefin hybrid material which is prepared by mixing a silicone polymer base (A) comprising one or more silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08 with one or more functionalised polyolefins (B) and a reactive compatibiliser (C) which process comprises the steps of: (i) Introducing said silicone polymer base (A) comprising one or more silicone polymers and/or copolymers, in each instance having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08 into a mixing chamber of a mixer, and mixing while heating to a predetermined temperature of from 100 o C to 200 o C; (ii) Either simultaneously with step (i) or silicone polymer base (A) has reached said predetermined temperature of from 100 o C to 200 o C, introducing one or more functionalised polyolefins (B) into the mixing chamber
  • a silicone-polyolefin hybrid product obtained or obtainable by the above process.
  • a conical screw dump extruder as a means of preparing a silicone- polyolefin hybrid composition product which is prepared by mixing a silicone polymer base (A) comprising one or more silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08, one or more functionalised polyolefins (B) and a reactive compatibiliser (C) which process comprises the steps of: (i) Introducing, silicone polymer base (A) into a mixing chamber of a mixer, and mixing while heating to a predetermined temperature of from 100 o C to 200 o C; (ii) Either simultaneously with step (i) or once the silicone polymer base (A) has reached said predetermined temperature of from 100 o C to 200 o C, introducing one or more functionalised polyolefins (B) into the mixing chamber of the mixer whils
  • a hybrid material is a combination of two dissimilar materials that are compatibilized to form a stable heterogenous substance with synergistic properties.
  • the purpose of the current disclosure is to provide a suitable method which is able to efficiently reactively compatibilise a silicone polymer base comprising one or more silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08, with one or more functionalised polyolefins (B) into an acceptable a silicone-polyolefin hybrid material utilising the reactive compatibiliser (C) to generate a dispersed phase e.g., the functionalised polyolefins (B) with a continuous or bulk phase e.g., the one or more silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08 (or vice versa) utilising the said reactive compatibiliser (C) comprising or consisting of a silicone
  • the silicone polymer base (A) described herein comprises one or more silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08 (A)(1) in combination with one or more fillers (A)(2) selected from reinforcing fillers such as fumed silica and precipitated silica and the like, non-reinforcing fillers, and a combination of reinforcing fillers and non-reinforcing fillers.
  • a silicone polymer base does not contain any curatives and/or cross- linkers, i.e., it is uncatalyzed and therefore cannot cure into an elastomer or the like until it is transformed into a curable compound composition containing curatives and/or cross-linkers (if required) as well as other additives.
  • Fillers, especially reinforcing fillers are incorporated into silicone rubber materials to enhance strength and toughness in a cured elastomeric material. Reinforcing fillers are highly surface active and have a high surface area, which reinforces the cured siloxane polymer matrix through hydrogen bonding and other means.
  • Non-reinforcing fillers are generally lower surface area and are provided mainly to decrease the cost of the silicone rubber.
  • Reinforcing fillers usually enhance at least one of the following mechanical properties tensile-strength, tear-strength and flex-fatigue resistance crepe hardening, improve compression-set resistance and can provide silicone elastomers with e.g., exceptional resistance to heat-aging.
  • silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08 are silicon- based compounds comprising a siloxane backbone, i.e., and at least a semi-contiguous chain composed of inorganic silicon-oxygen-silicon groups (i.e., -Si-O-Si-), with organosilicon and/or organic side groups attached to the silicon atoms.
  • Such siloxanes are typically characterized in terms of the number, type, and/or proportion of [M], [D], [T], and/or [Q] units/siloxy groups, which each represent structural units of individual functionality present in polysiloxanes, such as organosiloxanes and organopolysiloxanes.
  • [M] represents a monofunctional unit of general formula R ⁇ 3 SiO 1/2
  • [D] represents a difunctional unit of general formula R ⁇ 2 SiO 2/2
  • [T] represents a of general formula R ⁇ SiO 3/2
  • [Q] represents a tetrafunctional unit of general formula SiO 4/2 , as shown by the general structural moieties below: . lent substituent.
  • each R ⁇ is independently selected from hydrocarbyl groups, alkoxy and/or aryloxy groups, and siloxy groups.
  • hydrocarbyl groups suitable for R ⁇ examples generally include monovalent hydrocarbon moieties, as well as derivatives and modifications thereof, which may independently be substituted or unsubstituted, linear, branched, cyclic, or combinations thereof, and saturated or unsaturated.
  • the term “unsubstituted” describes hydrocarbon moieties composed of carbon and hydrogen atoms, i.e., without heteroatom substituents.
  • substituted describes hydrocarbon moieties where either at least one hydrogen atom is replaced with an atom or group other than hydrogen (e.g., a halogen atom, an alkoxy group, an amine group, etc.) (i.e., as a pendant or terminal substituent), a carbon atom within a chain/backbone of the hydrocarbon is replaced with an atom other than carbon (e.g., a heteroatom, such as oxygen, sulfur, nitrogen, etc.) (i.e., as a part of the chain/backbone), or both.
  • a heteroatom such as oxygen, sulfur, nitrogen, etc.
  • suitable hydrocarbyl groups may comprise, or be, a hydrocarbon moiety having one or more substituents in and/or on (i.e., appended to and/or integral with) a carbon chain/backbone thereof, such that the hydrocarbon moiety may comprise, or otherwise be referred to as, an ether, an ester, etc.
  • Linear and branched hydrocarbyl groups may independently be saturated or unsaturated and, when unsaturated, may be conjugated or nonconjugated.
  • Cyclic hydrocarbyl groups may independently be monocyclic or polycyclic, and encompass cycloalkyl groups, aryl groups, and heterocycles, which may be aromatic, saturated and nonaromatic and/or non-conjugated, etc.
  • Examples of combinations of linear and cyclic hydrocarbyl groups include alkaryl groups, aralkyl groups, etc.
  • General examples of hydrocarbon moieties suitably for use in or as the hydrocarbyl group include alkyl groups, aryl groups, and the like, as well as derivatives, modifications, and combinations thereof.
  • alkyl groups include methyl, ethyl, propyl (e.g., iso-propyl and/or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and/or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and/or tert-pentyl), hexyl, and the like (i.e., other linear or branched saturated hydrocarbon groups, e.g., having greater than 6 carbon atoms).
  • propyl e.g., iso-propyl and/or n-propyl
  • butyl e.g., isobutyl, n-butyl, tert-butyl, and/or sec-butyl
  • pentyl e.g., isopentyl, neopentyl, and/or tert-
  • aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, dimethyl phenyl, and the like, as well as derivatives and modifications thereof, which may overlap with alkaryl groups (e.g., benzyl) and aralkyl groups (e.g., tolyl, dimethyl phenyl, etc.).
  • alkaryl groups e.g., benzyl
  • aralkyl groups e.g., tolyl, dimethyl phenyl, etc.
  • the silicone polymers, and/or copolymers of component (A)(1) may also contain substituted alkyl groups such as halocarbon groups and reactive groups such as alkenyl groups, alkynyl groups, alkoxy groups, aryloxy groups and hydroxyl groups, however, it is desired in this instance that any such reactive groups present are unreactive with the Y groups of functionalized polyolefin (B) and the X groups of reactive compatibiliser (C).
  • non-reactive or unreactive groups should be considered to include reactive groups present which do not react with either X or Y at a competitive rate under the conditions of the reaction of X and Y.
  • the terms non-reactive and unreactive used herein are interchangeable and are intended to have the same meaning.
  • halocarbon groups include halogenated derivatives of the hydrocarbon moieties above, such as halogenated alkyl groups (e.g., any of the alkyl groups described above, where one or more hydrogen atoms is replaced with a halogen atom such as F or Cl), aryl groups (e.g., any of the aryl groups described above, where one or more hydrogen atoms is replaced with a halogen atom such as F or Cl), and combinations thereof.
  • halogenated alkyl groups e.g., any of the alkyl groups described above, where one or more hydrogen atoms is replaced with a halogen atom such as F or Cl
  • aryl groups e.g., any of the aryl groups described above, where one or more hydrogen atoms is replaced with a halogen atom such as F or Cl
  • halogenated alkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, 3,4-difluoro-5- methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl, and the like, as well as derivatives and modifications thereof.
  • halogenated aryl groups include chlorobenzyl, pentafluorophenyl, fluorobenzyl groups, and the like, as well as derivatives and modifications thereof.
  • alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, cyclohexenyl groups, and the like, as well as derivatives and modifications thereof;
  • alkynyl groups may be exemplified by, but not limited to, ethynyl, propynyl, and butynyl groups.
  • examples generally include hydrocarbyl (e.g., alkyl, aryl, etc.) groups bonded to the silicon atom via an oxygen atom (i.e., forming a silyl ether).
  • the hydrocarbyl groups in these examples may include any of the hydrocarbyl groups described above.
  • examples generally include siloxy groups represented by a combination, of [M], [D], [T], and/or [Q] units described above.
  • silicone polymers, and/or copolymers of component (A)(1) are substantially linear i.e., substantially free from branching attributable to [T] units and/or [Q] units are typically referred to as “linear” although it will be appreciated that a linear (i.e., MDM-type) siloxane may comprise individual molecules having T and/or Q units and still be considered “linear” based on the average unit formula of the siloxane as a whole and further more they preferably do not contain any halocarbon groups.
  • each of the one or more silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08 in (A)(1) may, for example, be selected from polydimethylsiloxanes, alkylmethylpolysiloxanes, alkylarylpolysiloxanes or copolymers thereof (where reference to alkyl means any suitable alkyl group, alternatively an alkyl group having two or more carbons) and as such may, for the sake of example, be: a trialkyl terminated polydimethylsiloxane, a trialkyl terminated dimethylmethylphenylsiloxane, a dialkylalkenyl terminated polydimethylsiloxane, e.g., dimethylvinyl terminated polydimethylsiloxane; a dialkylalkenyl terminated dimethylmethylphenylsiloxane, e.g., dimethylvinyl terminated dimethyl
  • the one or more silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08, (A)(1) are trialkyl terminated polydimethylsiloxane or a trialkyl terminated dimethylmethylphenylsiloxane.
  • Such one or more silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08, (A)(1) are organopolysiloxane polymer gums.
  • Organopolysiloxane polymer gums have viscosity values of at least 1,000,000mPa.s at 25 o C and often many millions of mPa.s at 25 o C.
  • the organopolysiloxane gum has a Williams plasticity of from 75mm/100 to 500mm/100 measured in accordance with ASTM D-926-08, alternatively from 100mm/100 to 450mm/100 measured in accordance with ASTM D-926-08, alternatively from 120mm/100 to 400mm/100 measured in accordance with ASTM D-926-08, alternatively from 120mm/100 to 375mm/100 in accordance with ASTM D-926-08.
  • the alkenyl and/or alkynyl content, e.g., vinyl content of the polymer is from 0.01 to 3 wt. % for each organopolysiloxane polymer containing at least two silicon-bonded alkenyl groups per molecule of component (a), alternatively from 0.01 to 2.5 wt. % of component (a), alternatively from 0.001 to 2.0 wt. %, alternatively from 0.01 to 1.5 wt. % of component (a) of the or each organopolysiloxane polymer containing at least two unsaturated groups per molecule, which unsaturated groups are selected from alkenyl or alkynyl groups per molecule of component (a).
  • the alkenyl/alkynyl content of component (a) is determined using quantitative infra-red analysis in accordance with ASTM E168.
  • (A)(2) Fillers Component (A)(2) comprises at least one reinforcing filler, non-reinforcing filler or a combination thereof. Fillers (A)(2) may be at least one reinforcing filler. Preferably said reinforcing fillers are in a finely divided form.
  • the reinforcing fillers of fillers (A)(2) may be exemplified by fumed silica, colloidal silicas and/or a precipitated silica.
  • Precipitated silica, fumed silica and/or colloidal silicas are particularly preferred because of their relatively high surface area, which is typically at least 50 m2/g (BET method in accordance with ISO 9277: 2010); alternatively, having surface areas of from 50 to 450 m2/g (BET method in accordance with ISO 9277: 2010), alternatively having surface areas of from 50 to 300 m2/g (BET method in accordance with ISO 9277: 2010), are typically used. All these types of silica are commercially available. Reinforcing filler(s) of component (A)(2) are naturally hydrophilic and are preferably treated with one or more treating agents to render them hydrophobic.
  • Such surface modified reinforcing fillers are finely divided in that they do not clump and can be homogeneously incorporated into component (A)(1) to generate the silicone polymer base (A) described herein.
  • silica reinforcing filler is naturally hydrophilic, unless it has been pre-treated to render the surface suitably hydrophobic, it is typically treated in situ during the silicone polymer base manufacturing process with a hydrophobing treating agent. Any suitable treating agent able to render the surface of the silica hydrophobic may be utilised.
  • organosilanes may be selected from suitable organosilanes, polydiorganosiloxanes, or organosilazanes e.g., hexaalkyl disilazane, short chain siloxane diols and/or short chain fluorosiloxane diols.
  • hydrophobing treating agents include, but are not restricted to, silanol terminated trifluoropropylmethylsiloxane, silanol terminated vinyl methyl (ViMe) siloxane, silanol terminated methyl phenyl (MePh) siloxane, liquid hydroxyldimethyl-terminated polydiorganosiloxane containing an average from 2 to 20 repeating units of diorganosiloxane in each molecule, hydroxyldimethyl terminated Phenylmethyl Siloxane, hexaorganodisiloxanes, such as hexamethyldisiloxane and divinyltetramethyldisiloxane; hexaorganodisilazanes, such as hexamethyldisilazane (HMDZ), divinyltetramethyldisilazane and tetramethyldi(trifluoropropyl)disilazane; hydroxyld
  • Fillers (A)(2) may also comprise or consist of one or more non-reinforcing fillers.
  • the non-reinforcing fillers suitable to be used in silicone polymer base (A) may include crushed quartz, diatomaceous earths, barium sulphate, iron oxide, titanium dioxide, precipitated calcium carbonate, ground calcium carbonate, zinc oxide and carbon black, talc, hydroxyapatite, wollastonite.
  • fillers which might be used in addition to the above include aluminite, calcium sulphate (anhydrite), gypsum, calcium sulphate, magnesium carbonate, clays such as kaolin, magnesium hydroxide e.g., brucite, graphite, copper carbonate, e.g., malachite, nickel carbonate, e.g., zarachite, barium carbonate, e.g., witherite and/or strontium carbonate e.g., strontianite.
  • Other fillers may include silicates from the group consisting of olivine group; garnet group; aluminosilicates; ring silicates; chain silicates; and sheet silicates.
  • the olivine group comprises silicate minerals, such as but not limited to, forsterite and Mg 2 SiO 4 .
  • the garnet group comprises ground silicate minerals, such as but not limited to, pyrope; Mg 3 Al 2 Si 3 O 12 ; grossular; and Ca2Al2Si3O12.
  • Aluminosilicates comprise ground silicate minerals, such as but not limited to, sillimanite; Al2SiO5; mullite; 3Al2O3.2SiO2; kyanite; and Al2SiO5.
  • Ring silicates may be utilized as non-reinforcing fillers, these include silicate minerals, such as but not limited to, cordierite and Al3(Mg,Fe)2[Si4AlO18].
  • the chain silicates group comprises ground silicate minerals, such as but not limited to, wollastonite and Ca[SiO 3 ].
  • Sheet silicates may alternatively or additionally be used as non-reinforcing fillers where appropriate group comprises silicate minerals, such as but not limited to, mica; K 2 AI 14 [Si 6 Al 2 O 20 ](OH) 4 ; pyrophyllite; Al 4 [Si 8 O 20 ](OH) 4 ; talc; Mg 6 [Si 8 O 20 ](OH) 4 ; serpentine for example, asbestos; Kaolinite; Al4[Si4O10](OH)8; and vermiculite.
  • silicate minerals such as but not limited to, mica; K 2 AI 14 [Si 6 Al 2 O 20 ](OH) 4 ; pyrophyllite; Al 4 [Si 8 O 20 ](OH) 4 ; talc; Mg 6 [Si 8 O 20 ](OH) 4 ; serpentine for example, asbestos; Ka
  • non-reinforcing fillers may also be treated with a hydrophobing agent as discussed above for reinforcing fillers.
  • component (A)(2) comprises one or more reinforcing fillers and optionally one or more non-reinforcing fillers.
  • the surface treatment of filler (A)(2) may be undertaken prior to introduction in the composition or in situ (i.e., in the presence of at least a portion of the other ingredients of the composition herein by blending these ingredients together at approximately 25 o C or above until the filler is completely treated.
  • untreated filler (A)(2) is treated in situ with a treating agent in the presence of component (A)(1) which results in the preparation of an uncatalyzed silicone polymer base as hereinbefore described.
  • the filler or fillers (A)(2) are present in silicone polymer base (A) in an amount of from 5 to 55 wt. % of the combined weight of (A)(1) + (A)(2), alternatively from 5 to 50 wt. % of the combined weight of (A)(1) + (A)(2), alternatively from 5 to 45 wt. % of the combined weight of (A)(1) + (A)(2), alternatively from 5 to 40 wt.
  • silicone polymer base (A) forms a continuous phase in the silicone-polyolefin hybrid material
  • silicone polymer base (A) is present in an amount of at least 55 wt. % of the starting ingredients for making the silicone-polyolefin hybrid material, alternatively at least 60 wt. % of the starting ingredients for making the silicone-polyolefin hybrid material.
  • One or more functionalized polyolefins (B) As indicated above, the silicone-polyolefin composition also comprises the functionalized polyolefin (B).
  • the functionalized polyolefin (B) comprises an average of at least one functional group Y per molecule, e.g., as a substituent on a polyolefin backbone.
  • the functionalized polyolefin (B) comprises an average of at least two functional groups Y per molecule.
  • the functional groups Y are reactable with the functional groups X of reactive compatibiliser (C) and bonds are formed therebetween.
  • component (B) of the silicone-polyolefin composition generally comprises a polyolefin that is prepared with, obtained with, or otherwise functionalized to include the functional groups Y as substituents.
  • the functionalized polyolefin (B) may comprise, alternatively may be, a terminally substituted (i.e., a functional group-terminated) polyolefin, a pendently-substituted polyolefin, or a combination thereof.
  • polyolefins suitable for the functionalized polyolefin (B) are exemplified by polymers prepared from olefinic monomers, olefinic macromonomer and oligomers, and combinations thereof. Regardless of the actual synthetic route by which the functionalized polyolefin (B) is prepared, one of skill in the art will readily appreciate the scope of the polyolefin component of the functionalized polyolefin (B) in terms of its constituent parts (or theoretical constituent parts), i.e., the olefinic base monomers polymerized to prepare the polyolefin.
  • olefinic used in the context of the base monomers composing the functionalized polyolefin (B) refers to the presence of an ethylenically unsaturated end group, i.e., which is polymerizable with an ethylenically unsaturated group of other olefinic monomer to provide a polyolefin.
  • a “polyethylene” is a polyolefin derived, or theoretically derivable, from the monomer ethene (ethylene), which is the smallest ethylenically unsaturated compound.
  • the functionalized polyolefin (B) comprises a poly-alpha-olefin backbone.
  • one R 2 is methyl and the other R 2 is an esteric carbon, such that the alpha olefin is a methacrylate (e.g., a methyl or ethyl methacrylate, where the other R 2 is a methyl ester or ethyl ester, respectively).
  • hydrocarbyl groups may be substituted or unsubstituted and are exemplified above with regards to the appropriate descriptions of hydrocarbyl groups for R ⁇ and R 1 .
  • oligomers of such alpha olefins may also be utilized in the preparation of the poly-alpha-olefin backbone.
  • polyethylene (PE) oligomers may be utilized to prepare a polyethylene polymer, which may also be prepared using ethene as the sole monomer.
  • polyethylene (PE) and polypropylene (PP) oligomers may be copolymerized to prepare a polyethylene-polypropylene (PE-PP) copolymer, such as a PE-PP block copolymer.
  • PE-PP polyethylene-polypropylene
  • Examples of other oligomers that may be used to prepare poly-alpha-olefin backbone of the functionalized polyolefin (B) include polypropylene oligomers, polybutylene oligomers, polyisobutylene oligomers, polyisoprene oligomers, polybutadiene oligomers, as well as combinations thereof, such as polyethylene/polypropylene oligomers and copolymers, polyethylene/polybutylene oligomers and copolymers, poly(ethylene/butylene)-polyisoprene oligomers and copolymers, etc.
  • the functionalized polyolefin (B) comprises a poly-alpha-olefin backbone comprising monomeric units selected from ethylene, propylene, butylene, and 2-methyl-propylene (i.e., isobutylene).
  • the poly-alpha-olefin backbone comprises monomeric units derived (or theoretically derivable) from alpha-olefins exemplified by hexene, heptene, octene, styrene, an acrylate or methacrylate compound (e.g., acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, an acrylic or methacrylic ester such as a C 1 -C 12 alkyl ester of acrylic or methacrylic acid, etc.), dienes such as butadiene, etc., or combinations thereof.
  • alpha-olefins exemplified by hexene, heptene, octene, styrene
  • an acrylate or methacrylate compound e.g., acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, an acrylic or methacrylic ester such as a C 1 -C
  • the functionalized polyolefin (B) may comprise, alternatively may be, a homopolymer (i.e., having but one type of monomeric unit, or prepared from but one monomer or oligomers of but one monomer) or an interpolymer (i.e., having at least two different monomeric subunits, typically prepared from at least two monomers or oligomers comprising two or more monomeric subunits).
  • an interpolymer encompasses copolymers and terpolymers, i.e., polymers comprising two, or three, different monomeric units, respectively, as well as polymers prepared from four, five, six, or more monomers.
  • the functionalized polyolefin (B) comprises a functionalized polyethylene, polypropylene, or polyethylene-alpha olefin copolymer.
  • the polyethylene-alpha olefin copolymer is selected from copolymers and terpolymers comprising polyethylene and at least one of polypropylene and polybutylene.
  • Various forms of such polyolefins may also be utilized.
  • HDPE high density
  • MDPE medium density
  • LDPE low density
  • ULDPE ultra-low density
  • LLDPE linear- low density polyethylene
  • the functionalized polyolefin (B) comprises an average of at least one, alternatively at least two functional groups Y per molecule.
  • the functionalized polyolefin (B) may be represented by the general formula L(-Y) l, where L is the polyolefin backbone, each Y is a functional group as introduced above, and subscript l ⁇ 1.
  • each functional group Y may be independently selected in each moiety indicated by subscript I, which is at least one, alternatively at least two, but may theoretically be much larger, as will be understood in view of the description of the degree of substitution of the functionalized polyolefin (B).
  • the location of each functional group Y along the polyolefin backbone L is not particularly limited, such that any functional group Y may represent a terminal or pendant group.
  • the group R 3 is generally selected or otherwise controlled based on the particular alpha-olefin monomers used to prepare the functionalized polyolefin (B), or at least the backbone thereof.
  • the functionalized polyolefin (B) is a functionalized polypropylene
  • R 3 is methyl in each moiety indicated by subscript k.
  • the nature of R 3 in the indicated by subscript j will depend on how the functionalized polyolefin (B) was prepared.
  • R 3 will be H in each moiety indicated by subscript o (as opposed to the methyl groups R 3 in the moieties indicated by subscript p).
  • R 3 will typically be a methyl group throughout the functionalized polyolefin (B).
  • any R 3 may be selected such that any one moiety indicated by subscript p may reflect a polymerization product of any of the alpha-olefin monomers described herein or, alternatively, a grafting-functionalization onto a polymer prepared from such alpha-olefins.
  • each R 3 may be the same as or different from any other R 3 of the functionalized polyolefin (B).
  • each R 3 is the same as each other R 3 of the functionalized polyolefin (B).
  • each R 3 is methyl.
  • At least one R 3 is different from at least one other R 3 of the functionalized polyolefin (B).
  • R 3 is predominantly hydrogen throughout the functionalized polyolefin (B) (i.e., from ethene monomer), with a minor proportion of R 3 being selected from alkyl groups (i.e., from propene or higher-order alpha-olefin monomer).
  • each R 4 is an independently selected terminal group.
  • each R 4 generally represents a terminally reacted monomer from the polymerization of the functionalized polyolefin (B), the byproduct of polymerization (i.e., from a radial initiation, propagation, and/or termination step, etc.), or simply a hydrogen atom.
  • the R 4 is thus not particularly limited, will generally be selected by virtue of the route by which the functionalized polyolefin (B), and is typically present in the functionalized polyolefin (B) in such minor amounts as to not substantively impact the average unit formula indicated by subscripts o and p.
  • R 4 generally represents an unreactive group with regards to the compositions and methods provided herein.
  • the functionalized polyolefin (B) comprises at least one, alternatively at least two functional groups per molecule, which are represented by moiety Y in the general unit formula of the functionalized polyolefin (B) above.
  • the functional groups Y are selected based on the functional group X of the reactive compatibiliser (C), such that the functionalized polyolefin (B) is reactive with the reactive compatibiliser (C) in a coupling reaction involving functional group X and functional group Y. More specifically, as introduced above, the functional groups Y of the functionalized polyolefin (B) is reactable with the functional group X of the reactive compatibiliser (C) and a bond is formed therebetween after the reaction.
  • each functional group Y and one functional group X are capable of reacting together (i.e., via additive coupling/cross-linking reaction), to covalently bond together the functionalized polyolefin (B) and the reactive compatibiliser (C).
  • each functional group Y comprises a functional group that may participate in the coupling/cross-linking reaction described above, such as a functional group reactive via substitution reaction, addition reaction, coupling reaction, or combinations thereof, as well as any of the specific variants described above with respect to the functional groups X.
  • functional group Y may comprise, or be, a functional group that is hydrosilylable, condensable, displaceable, nucleophilic, or otherwise reactable (e.g., graftable, linkable, etc.) with the functional group X, or various combinations thereof.
  • functional group Y may comprise, or be, a functional group that is hydrosilylable, (e.g., a silicon-bonded hydrogen atom, an olefinically (i.e., ethylenically) unsaturated group, such as an alkenyl group, alkynyl group, etc.), condensable (e.g., a hydroxyl group, a carboxyl group, a carbinol group, an alkoxysilyl group, a silanol group, an amide group, an anhydride group, etc., or a group that may be hydrolyzable and subsequently condensable), displaceable (e.g., a “leaving group” as understood in the art, such as a halogen atom, or other group stable in an ionic form once displaced, or a functional group comprising such a leaving group, such as esters, anhydrides, amides, epoxides, etc.), nucleophilic (e.
  • each functional group Y is a hydrosilylable, group.
  • hydrosilylable, groups include the olefinically-unsaturated groups (e.g., ethylenically unsaturated groups) described above with respect to the hydrosilylable, groups suitable for functional group X.
  • each functional group Y comprises, alternatively is, a vinyl-substituted organosilicon group (e.g., comprises a vinylsilyl group).
  • each functional group Y comprises, alternatively is, a methacryloyl group, methacryloxy group, or a methacrylate group.
  • hydrosilylable groups suitable for functional group Y include hydridosilyl groups.
  • Examples of such hydridosilyl groups may be generally represented by the subformula – [Z 3 ] q –Si(R 5 ) 2 H, where Z 3 is a divalent linking group, subscript q is 0 or 1, and each R 5 is group.
  • Such moieties may be selected, or otherwise provided, olefin-functional organosilicon compound polymerized in the preparation of the functionalized polyolefin (B).
  • the functionalized polyolefin (B) comprises a copolymer of ethylene and 7-octenyldimethylsilane, such that, with regards to the preceding general unit formula of the functionalized polyolefin (B) and subformula of the functional group Y, each R 3 is H, each subscript q is 1, each linking group Z 3 is – (CH 2 ) 6 –, and each R 5 is methyl.
  • the functionalized polyolefin (B) comprises the polymerization reaction product of ethylene, an alkenyl-functional silane compound, and optionally one or more additional alpha-olefins (e.g., propene, butene, etc.).
  • alkenyl-functional silane compounds include 7- octentyldimethylsilane (ODMS), 5-hexenyldimethylsilane (HDMS), allyldimethylsilane (ADMS), and the like, as well as combinations thereof. It will be appreciated that such alkenyl-functional silane compounds may also be grafted onto a polyolefin polymer to prepare the functionalized polyolefin (B).
  • the particular method used to prepare the functionalized polyolefin (B) is not particularly limited, and numerous examples of such methods are known in the art.
  • each functional group Y is a condensable group, i.e., capable of participating in a condensation reaction.
  • each functional group Y comprises condensable group selected from anhydride groups, amine groups, silanol groups, carbinol groups, and alkoxysilyl groups. Examples of suitable anhydrides and amines for functional group Y generally include those described above with respect to condensable groups suitable for functional group X.
  • anhydrides available from anhydride-functional compounds with olefinic unsaturation will be particularly suitable for use in some embodiments, such as where the anhydride- functional compound can be readily copolymerized with an alpha-olefin monomer (e.g., ethene), or grafted onto an alpha-olefin homopolymer (e.g., via radical grafting, metathesis, etc.).
  • suitable amines for functional group Y generally include primary amino-substituted derivatives of the hydrocarbyl groups described above, as the aminoalkyl groups described above with respect to the functional group X.
  • At least one, alternatively at least two, alternatively functional group Y comprises, alternatively is, a silanol group.
  • at least one functional group Y comprises, alternatively is, a moiety of formula –Z-SiR 1 3-c (OH) c , where each D, R 1 , and subscript c is independently selected and defined above.
  • Z is an oxygen atom.
  • Z is a divalent hydrocarbon from 2 to 18, alternatively from 2 to 16, alternatively from 2 to 14, alternatively from 2 to 16, alternatively from 2 to 12, alternatively from 2 to 10, alternatively from 2 to 8, alternatively from 2 to 6, alternatively from 2 to 4, carbon atoms.
  • At least one, alternatively at least two, alternatively each functional group Y comprises, alternatively is, a carbinol group.
  • the carbinol functional groups can be the same as or different from one another.
  • the carbinol functional groups independently include a moiety having the general formula –Z 1 –O d –(C e H 2e O) f –H, where Z 1 is a covalent bond or a divalent hydrocarbon linking group having from 2 to 18 carbon atoms, subscript d is 0 or 1, subscript e is independently selected from 2 to 4 in each moiety indicated by subscript f, and subscript f is from 0 to 500, with the proviso that subscripts d and f are not simultaneously 0.
  • subscript f is at least 1, such that at least one of the carbinol functional groups includes a moiety having the general formula: –Z1–O d –[C 2 H 4 O] g [C 3 H 6 O] h [C 4 H 8 O] i –H; where Z 1 and subscripts d, g, h, and i are independently selected and defined above.
  • subscript f is 0 and subscript d is 1 such that at least one of the carbinol functional groups includes a moiety having the general formula: –Z 1 -OH, where Z 1 is described above.
  • the carbinol functional groups having this general formula are not polyether groups or moieties.
  • Z 1 may be a covalent bond when functional group Y is bonded directly to a carbon atom in the functionalized polyolefin (B).
  • at least one, alternatively at least two, alternatively each functional group Y comprises, alternatively is, an alkoxysilyl group.
  • each alkoxysilyl group may independently comprise or be a monoalkoxysilyl group, dialkoxysilyl group, or trialkoxysilyl group, respectively.
  • the alkoxysilyl group comprises, alternatively is, a monoalkoxysilyl group.
  • the alkoxy group comprise, alternatively is, a dialkoxysilyl group. In yet other embodiments, the alkoxysilyl group comprises, alternatively is, a trialkoxysilyl group.
  • at least one functional group Y comprises, alternatively is, a moiety of formula –Z 2 -SiR 1 3-j (OR 6 ) j , where each Z 2 is a covalent bond, an oxygen atom, or a divalent hydrocarbon and defined above, subscript j is 1, 2, or 3, and each R 6 is an selected alkyl group having from 1 to 12 carbon atoms.
  • each R 6 independently selected alkyl group having from 1 to 10, alternatively from 1 to 8, from 1 to 6, alternatively from 1 to 4, alternatively 1 to 3, alternatively 1 or 2, alternatively 1, carbon atoms.
  • each R 6 is an independently selected alkyl group having from 1 to 10, alternatively from 1 to 8, alternatively from 1 to 6, alternatively from 1 to 4, alternatively 1 to 3, alternatively 1 or 2, alternatively 1, carbon atoms.
  • suitable alkoxysilyl groups include those comprising trimethoxysilyl groups, triethoxysilyl groups, dimethoxyethoxysilyl groups, dimethoxymethyl groups, diethoxymethyl groups, methoxyethoxymethyl groups, dimethylmethoxy groups, dimethylethoxy groups, etc.
  • At least one, alternatively at least two, alternatively each functional group Y comprises, alternatively is, an epoxy group.
  • suitable epoxy groups include a 3- glycidoxypropyl group, a 4-glycidoxybutyl group, or similar glycidoxyalkyl (i.e., glycidyloxyalkyl) groups; a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-epoxycyclohexyl)propyl group, or similar epoxycyclohexylalkyl groups; a 4-oxiranylbutyl group, and an 8-oxiranyloctyl group.
  • Such epoxy groups may be bonded directly to the functionalized polyolefin (B).
  • a divalent hydrocarbon group may be present in the functional group Y between the epoxide group and the atom to which the functional group Y is bonded.
  • the divalent hydrocarbon group comprises, alternatively is, an alkylene group having the general formula – (CH 2 ) k –, where subscript k is as defined above.
  • the divalent hydrocarbon group comprises from 2 to 10 carbon atoms and includes at least one ether moiety, i.e., at least one oxygen heteroatom.
  • the functionalized polyolefin (B) may comprise at least one functional group Y, and theoretically many of such groups, but is not fully substituted in terms of each olefin subunit present in the functionalized polyolefin (B) (e.g., as indicated by subscript p>0.
  • the moieties indicated by subscript o comprise from 0.01 to 5%, alternatively from 0.01 to 2.5% of the total number of olefin subunits in the functionalized polyolefin (B) (e.g., o + p). In these of other embodiments, the moieties indicated by subscript o may comprise from 0.05 to 10 wt.% of the functionalized polyolefin (B) (e.g., by total weight). The particular properties and physical characteristics of the functionalized polyolefin (B) may be varied.
  • the functionalized polyolefin (B) comprises a number average molecular weight of from 10 to 100 kDa, such as from 10 to 90, alternatively from 15 to 90, alternatively from 15 to 80, alternatively from 20 to 80, alternatively from 20 to 70, alternatively from 20 to 65 kDa.
  • the functionalized polyolefin (B) comprises a molecular weight distribution, as represented by the polydispersity index (PDI) (e.g., as determined by gel permeation chromatography (GPC)), of from 1 to 12, such as from 1 to 10.
  • PDI polydispersity index
  • GPC gel permeation chromatography
  • the functionalized polyolefin (B) exhibits a PDI of from 1 to 5, such as from 1 to 4, alternatively from 1.5 to 3.5, from 1.75 to 3.25, alternatively from 2 to 3. In some embodiments, the functionalized polyolefin (B) exhibits a PDI of from 3 to 6, such as from 3.5 to 5.5, alternatively from 4 to 5. In certain embodiments, the functionalized polyolefin (B) is anhydride functional. In these or other embodiments, the functionalized polyolefin (B) comprises functional group Y in an amount of from 0.5 to 2.0 wt.%. The functionalized polyolefin (B) typically has a melt flow index (MFI) of from 1 to 49 g/10 min.
  • MFI melt flow index
  • the functionalized polyolefin (B) may be introduced into the mixer in any suitable form, for example the functionalized polyolefin (B) may be provided and introduced onto the mixer in the form of pellets.
  • Reactive compatibiliser (C) is a polysiloxane polymer having at least one group X which is reactive with group Y of functionalized polyolefin (B). It can be defined as being structurally similar in structure to component (A) described above. In general, the reactive compatibiliser (C) comprises a polydiorganosiloxane-containing backbone having at least one functional group X per molecule.
  • the reactive compatibiliser (C) is substantially linear, alternatively is linear.
  • the reactive compatibiliser (C) is typically free from [T] siloxy units and/or [Q] siloxy units, as described above.
  • each R 1 is a substituted or unsubstituted hydrocarbyl group having from 1 to 30 carbon atoms.
  • each R 1 is an independently selected hydrocarbyl group having from 1 to 12, alternatively from 1 to 8, alternatively from 1 to 6, carbon atoms.
  • each R 1 is further defined as an alkyl group, aryl group, or combination thereof.
  • R 1 represents an independently selected substituted or unsubstituted alkyl group.
  • alkyl groups include methyl groups, ethyl groups, propyl groups (e.g., n- propyl and iso-propyl groups), butyl groups (e.g., n-butyl, sec-butyl, iso-butyl, and tert-butyl groups), pentyl groups, hexyl groups, etc., and the like, as well as derivatives and/or modifications thereof.
  • Examples of derivatives and/or modifications of such alkyl groups include substituted versions thereof, e.g., where a hydroxyl ethyl group will be understood to be a derivative and/or a modification of the ethyl groups described above.
  • Each R 1 may be the same as or different from any other R 1 of the reactive compatibiliser (C).
  • each R 1 is the same as each other R 1 of the reactive compatibiliser (C).
  • each R 1 is methyl.
  • at least one R 1 is different from at least one other R 1 of the reactive compatibiliser (C).
  • R 1 is predominantly methyl throughout the reactive compatibiliser (C), with one or more other groups pending from the polydiorganosiloxane backbone in minor amounts (e.g., from the preparation of the reactive compatibiliser (C), environmental reactions or impurities, etc.).
  • each R 1 is a fluoroalkyl group, i.e., such that the reactive compatibiliser (C) may be further defined or referred to as a fluorosilicone or fluoropolysiloxane.
  • the reactive compatibiliser (C) comprises, on average, at least one functional group per molecule, as represented by moiety X in the general formula of the reactive compatibiliser (C) above. In some embodiments, however, the reactive compatibiliser (C) comprise an average of at least two functional groups X per molecule. As described in herein, the functional groups X of the reactive compatibiliser (C) are reactable with the functional groups Y of the functionalized polyolefin (B) to form a bond therebetween.
  • one functional group X and one functional group Y are capable of reacting together (i.e., via a coupling reaction, cross-linking reaction, etc.), to covalently bond together the reactive compatibiliser (C) and the functionalized polyolefin (B).
  • C reactive compatibiliser
  • B functionalized polyolefin
  • the average molecules of components (B) and/or (C) have at least two groups capable of participating in the coupling reaction, such that a single molecule of the reactive compatibiliser (C) may be, on average, capable of being coupled at least once to two or more molecules of the functionalized polyolefin (B) or, likewise, at least twice to a single molecule of the functionalized polyolefin (B).
  • each functional group X comprises, alternatively is, a functional group that may participate in the coupling/cross-linking reaction described above. Examples of such functional groups are typically reactive via substitution reaction, addition reaction, coupling reaction, or combinations thereof.
  • reactions include nucleophilic substitutions, ring- opening additions, alkoxylations and/or trans alkoxylations, hydrosilylations, olefin metatheses, condensations, radical couplings and/or polymerizations, and the like, as well as combinations thereof.
  • functional groups X may comprise, or be, a functional group that is hydrosilylable (e.g., a silicon-bonded hydrogen atom, an olefinically (i.e., ethylenically) unsaturated group, such as an alkenyl group, alkynyl group, etc.), condensable (e.g., a hydroxyl group, a carboxyl group, a carbinol group, an alkoxysilyl group, a silanol group, an amide group, an anhydride group, etc., or a group that may be hydrolyzable and subsequently condensable), displaceable (e.g., a “leaving group” as understood in the art, such as a halogen atom, or other group stable in an ionic form once displaced, or a functional group comprising such a leaving group, such as esters, anhydrides, amides, epoxides, etc.), nucleophilic (e.g
  • each functional group X is a hydrosilylable group, and thus selected from olefinically-unsaturated groups (e.g., ethylenically unsaturated groups) and H.
  • each hydrosilylable group represented by X is H, such that the reactive compatibiliser (C) is silicon hydride functional.
  • each hydrosilylable group represented by X is an ethylenically unsaturated group. Examples of ethylenically unsaturated groups generally include substituted or unsubstituted hydrocarbon groups having at least one alkene or alkyne functional group.
  • each functional group X comprises, alternatively is, an alkenyl group or an alkynyl group.
  • each functional group X comprises, alternatively is, a vinyl group.
  • the functional group X may also comprise a divalent linking group between the ethylenically unsaturated group and a silicon atom of the reactive compatibiliser (C).
  • divalent linking groups include divalent versions of the hydrocarbyl groups described above, such as alkyl groups.
  • each functional group X comprises, alternatively is a methacryloxy group, such as a silicon-bonded methacryloxyalkyl group.
  • at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is, a condensable group, i.e., is capable of participating in a condensation reaction.
  • each functional group X comprises a condensable group selected from anhydride groups, amine groups, silanol groups, carbinol groups, and alkoxysilyl groups.
  • suitable anhydrides for functional group X generally include anhydrides of monocarboxylic acids (e.g., acetic acid, lactic acid, propanoic acid, pentanoic acid, methacrylic acid, etc.), which may be homoanydrides or mixed anhydrides, as well as polycarboxylic acids such as succinates (i.e., succinic anhydrides), maleates (i.e., maleic anhydrides), phthalates, etc.
  • anhydrides in terms of linking the same to the silicon atom of the reactive compatibiliser (C).
  • such anhydrides may be grafted onto a siloxane polymer to prepare the reactive compatibiliser (C), and thus one of skill in the art will understand the applicability of other anhydrides, and carboxylic acids/carboxylates that may also be utilized, e.g., via grafting directly to the reactive compatibiliser (C) or instead via an initial grafting and subsequent reaction to prepare the anhydride.
  • anhydrides containing at least one olefinically unsaturated group such as alkenylsuccinic anhydrides, bromomaleic anhydride, chloromaleic anhydride, citraconic anhydride, methylnadic anhydride, nadic anhydride, tetrahydrophthalic anhydride, and the like, may be grafted onto a siloxane (e.g., via hydrosilylation).
  • Free radical based grafting schemes may also be used to produce anhydride functional siloxanes from reagents such as maleic anhydride and vinylsiloxanes.
  • suitable amines for functional group X generally include primary amino-substituted derivatives of the hydrocarbyl groups described above.
  • functional group X may comprise, alternatively may be, an aminoalkyl group, such as an amino-substituted alkyl group having from 1 to 20 carbon atoms (e.g., aminomethyl, 2-aminoethyl, 3-aminopropyl, 6-aminohexyl, an aminoaryl group (e.g., 4-aminophenyl, 3-(4-aminophenyl) propyl, etc.), or an aminoalkylamino group (e.g., N-(2-aminoethyl)-3-aminopropyl, N-(2-aminoethyl)-3-aminoisobutyl, etc.).
  • an aminoalkyl group such as an amino-substituted alkyl group having from 1 to 20 carbon atoms (e.g., aminomethyl, 2-aminoethyl, 3-aminopropyl, 6-aminohexyl, an aminoaryl group (e.g., 4-a
  • the reactive compatibiliser (C) includes only amino functionality as the functional group X.
  • at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is, a silanol group.
  • the silicon atom of the silanol group is a silicon atom of the backbone of the reactive compatibiliser (C).
  • at least one X comprises, alternatively is, a moiety of formula –Z-SiR 1 3-c (OH) c , where each Z is a covalent bond, an oxygen atom, or a divalent hydrocarbon group, R 1 is independently selected and defined above, and subscript c is 1, 2, or 3.
  • the silicon atom of the silanol group includes three silicon-bonded hydroxyl groups; when subscript c is 2, the silicon atom of the silanol group includes two silicon-bonded hydroxyl groups; when subscript c is 1, the silicon atom of the silanol group includes two silicon-bonded hydroxyl groups.
  • Z is an oxygen atom.
  • Z is a divalent hydrocarbon group having from 2 to 18, alternatively from 2 to 16, alternatively from 2 to 14, alternatively from 2 to 16, alternatively from 2 to 12, alternatively from 2 to 10, alternatively from 2 to 8, alternatively from 2 to 6, alternatively from 2 to 4, carbon atoms.
  • each functional group X comprises, alternatively is a silicon-bonded hydroxyl group. In some embodiments, at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is, a carbinol group.
  • Carbinol functional groups bonded to silicon atoms in organopolysiloxanes are distinguished from silanol groups. Specifically, carbinol functional groups include a carbon-bonded hydroxyl group, and silanol functional groups include a silicon-bonded hydroxyl group. Said differently, carbinol functional groups include at least one moiety of formula – COH, whereas silanol functional groups are of formula –SiOH.
  • silanol functional groups can readily condense, which generally does not occur with carbinol functional groups (at least under the same catalysis of hydrolysis/condensation of silanol functional groups).
  • carbinol functional groups can be the same as or different from one another.
  • the carbinol functional groups independently include a moiety having the general formula –Z 1 –O d –(C e H 2e O) f –H, where Z 1 is a covalent bond or a divalent hydrocarbon linking group having from 2 to 18 carbon atoms, subscript d is 0 or 1, subscript e is independently selected from 2 to 4 in each moiety indicated by subscript f, and subscript f is from 0 to 500, with the proviso that subscripts d and f are not simultaneously 0.
  • subscript f is at least one, such that at least one of the carbinol functional groups includes a moiety having the general formula: –Z1–O d –[C 2 H 4 O] g [C 3 H 6 O] h [C 4 H 8 O] i –H; where Z 1 and subscript d are defined above, 0 ⁇ g ⁇ 500, 0 ⁇ h ⁇ 500, and 0 ⁇ i ⁇ 500, with the proviso that 1 ⁇ g + h + I ⁇ 500.
  • the carbinol functional group may alternatively be referred to as a polyether group or moiety, although the polyether group or moiety terminates with —COH, rather than –COR, where R is a monovalent hydrocarbon group, which is the case with certain conventional polyether groups or moieties.
  • R is a monovalent hydrocarbon group, which is the case with certain conventional polyether groups or moieties.
  • moieties indicated by subscript g are ethylene oxide (EO) units
  • moieties indicated by subscript h are propylene oxide (PO) units
  • moieties indicated by subscript i are butylene oxide (BO) units.
  • the EO, PO, and BO units if present, may be in block or randomized form in the polyether group or moiety.
  • the relative amounts of EO, PO, and BO units, if present, can be selectively controlled based on desired properties, e.g., hydrophilicity and other properties.
  • subscript f is 0 and subscript d is 1 such that at least one of the carbinol functional groups includes a moiety having the general formula: –Z 1 -OH, where Z 1 is described above.
  • the carbinol functional groups having this general formula are not polyether groups or moieties.
  • at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is, an alkoxysilyl group.
  • each alkoxysilyl group may independently comprise or be a monoalkoxysilyl group, dialkoxysilyl group, or trialkoxysilyl group, respectively.
  • the alkoxysilyl group comprises, alternatively is, a monoalkoxysilyl group.
  • the alkoxy group comprise, alternatively is, a dialkoxysilyl group.
  • the alkoxysilyl group comprises, alternatively is, a trialkoxysilyl group.
  • the silicon atom of the alkoxysilyl group is a silicon atom of the backbone of the reactive compatibiliser (C).
  • At least one X comprises, alternatively is, a moiety of formula –Z 2 -SiR 1 3-j (OR 6 ) j , where each Z 2 is a covalent bond, an oxygen atom, or a divalent hydrocarbon group, R 1 is independently selected and defined above, subscript j is 1, 2, or 3, and each R 6 is an independently selected alkyl group having from 1 to 12 carbon atoms.
  • each R 6 is an independently selected alkyl group having from 1 to 10, alternatively from 1 to 8, alternatively from 1 to 6, alternatively from 1 to 4, alternatively 1 to 3, alternatively 1 or 2, alternatively 1, carbon atoms.
  • alkoxysilyl groups include those comprising trimethoxysilyl groups, triethoxysilyl groups, dimethoxyethoxysilyl groups, dimethoxymethyl groups, diethoxymethyl groups, methoxyethoxymethyl groups, dimethylmethoxy groups, dimethylethoxy groups, etc.
  • at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is, an epoxy group.
  • suitable epoxy groups include a 3- glycidoxypropyl group, a 4-glycidoxybutyl group, or similar glycidoxyalkyl (i.e., glycidyloxyalkyl) groups; a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-epoxycyclohexyl)propyl group, or similar epoxycyclohexylalkyl groups; a 4-oxiranylbutyl group, and an 8-oxiranyloctyl group.
  • Such epoxy groups may be bonded directly to the reactive compatibiliser (C).
  • a divalent hydrocarbon group may be present in X between the epoxide group and the silicon atom to which X is bonded.
  • the divalent hydrocarbon group comprises, alternatively is, an alkylene group having the general formula –(CH 2 ) k –, where subscript k is from 2 to 10.
  • the divalent hydrocarbon group comprises from 2 to 10 carbon atoms and includes at least one ether moiety, i.e., at least one oxygen heteroatom.
  • Such divalent hydrocarbon groups may also be suitable for use as the divalent linking groups described herein (e.g., Z, Z 1 , Z 2 , etc.).
  • subscript m is independently 1 or 0 in each moiety indicated by subscript a
  • subscript n is independently 1 or 0 in each moiety indicated by subscript b.
  • subscripts m and n merely indicate the presence of the functional group X in any particular [M] unit (i.e., as indicated by subscript a) or [D] unit (i.e., as indicated by subscript b).
  • the reactive compatibiliser (C) comprises at least one pendant functional X (i.e., bonded to a [D] unit).
  • the reactive compatibiliser (C) comprises at least one terminal functional X (i.e., bonded to an [M] unit). In some embodiments, the reactive compatibiliser (C) is only terminally functional with respect to the functional groups X, such that subscript n is 0 in each moiety indicated by subscript b. In some such embodiments, the reactive compatibiliser (C) comprises at least two moieties indicated by subscript a, and subscript m is 1 in at least two moieties indicated by subscript a. In other embodiments, the reactive compatibiliser (C) comprises at least one terminal functional group X.
  • the reactive compatibiliser (C) comprises only pendant functionality with respect to the functional groups X, such that subscript m is 0 in each moiety indicated by subscript a, the reactive compatibiliser (C) comprises at least two moieties indicated by subscript b, and subscript n is 1 in at least two moieties indicated by subscript b.
  • the reactive compatibiliser (C) may be defined as an MDM-type polysiloxane. Accordingly, in such embodiments, the reactive compatibiliser (C) may be defined as a linear polysiloxane (or, more simply, “linear siloxane”). Nonetheless, it is to be appreciated that the general formula above may be an average unit formula, i.e., the average formula based on all molecules in the reactive compatibiliser (C).
  • the reactive compatibiliser (C) may comprise a limited amount of branching (e.g., attributable to [T] and/or [Q] units) without departing from the scope of linearity understood by those of skill in the art, even though such units are not included in the general unit formula above.
  • the reactive compatibiliser (C) is substantially free from, alternatively free from, [T] and/or [Q] units.
  • each of the units represented by subscripts a and b are independently selected, and at least two units of the reactive compatibiliser (C) comprise the functional group X.
  • the preceding general formula for the reactive compatibiliser (C) may be rewritten as the following expanded average unit formula: [XR1 2 SiO 1/2 ] a’ [XR1SiO 2/2 ] b’ [R 1 2 SiO 2/2 ] b’’ [R 1 3 SiO 1/2 ] a’’ , where each X and R 1 is as defined above, subscripts a’, a’’, b’, and b’’ each indicate the number of corresponding moieties present in the reactive compatibiliser (C).
  • a’ + a’’ is equal to number of [M] siloxy units present in the mole fraction represented by subscript a in the general formula above
  • b’ + b’’ is equal to number of [D] siloxy units present in the mole fraction represented by subscript b in the general formula above.
  • the reactive compatibiliser (C) may have a number average degree of polymerization (DP) of from 10 to 10,000.
  • a’ +a’’+ b’ + b’’ is generally from 10 to 10,000.
  • the reactive compatibiliser (C) has a DP of from 10 to 1200, alternatively from 50 to 1200.
  • a’ +a’’+ b’ + b’’ is generally from 10 to 1200, alternatively from 20 to 1200, alternatively from 50 to 1200.
  • the reactive compatibiliser (C) has a DP of from 50 to 1100, alternatively from 50 to 1000, alternatively from 100 to 1000.
  • Subscript b’’ may be from 0 to 10,000, such as from 5 to 5,000, alternatively from 50 to 1200, alternatively from 50 to 1100, alternatively from 50 to 1000, alternatively from 100 to 1000.
  • subscript b’ is from 0 to 200, such as from 0 to 10, alternatively from 1 to 10, alternatively from 1 to 8.
  • the reactive compatibiliser (C) has a degree of substitution (DS) of from 1 to 200.
  • the DS of the reactive compatibiliser (C) may be represented by the sum of subscripts a’ and b’ in the expanded formula above, i.e., which indicates the number of functional groups X.
  • the reactive compatibiliser (C) has a DS of from 1 to 100, alternatively from 1 to 50, alternatively from 1 to 20, alternatively from 1 to 10, alternatively from 2 to 10.
  • the reactive compatibiliser (C) comprises a molecular weight distribution, as represented by polydispersity index (PDI) (i.e., the weight average molecular weight/number average molecular weight (Mw/Mn), of less than 3, alternatively less than 2.5, alternatively less than 2.25, and at the same time greater than or equal to 1.
  • PDI polydispersity index
  • the reactive compatibiliser (C) may comprise a PDI of from 1 to 3, such as from 1 to 2.5, alternatively from 1.5 to 2.5, alternatively from 1.5 to 2.2, alternatively from 1.8 to 2.2, alternatively of about 2.
  • Methods of determining the PDI for the reactive compatibiliser (C) are known in the art, and generally include weight determinations via rheology, solution viscosity, gel permeation chromatography (GPC), etc., with standards and procedures readily understood and available.
  • the reactive compatibiliser (C) utilized in the silicone-polyolefin composition is flowable, i.e., comprises a viscosity low enough to exhibit flow under ambient conditions (e.g., at 25 °C).
  • the reactive compatibiliser (C) is a liquid at room temperature. In certain embodiments, the reactive compatibiliser (C) exhibits a zero-shear viscosity of at least 1000 mPa.s, alternatively of at least 3500mPa.s, at 25 °C up to a maximum viscosity of about 25,000 mPa.s at 25 °C.
  • viscosity measurement given are zero-shear viscosity ( ⁇ o ) values, obtained by extrapolating to zero the value taken at low shear rates (or simply taking an average of values) in the limit where the viscosity-shear rate curve is rate-independent, which is a test-method independent value provided a suitable, properly operating rheometer is used.
  • the zero- shear viscosity of a substance at 25 °C may be obtained by using commercial rheometers such as an Anton-Parr MCR-301 rheometer or a TA Instruments AR-2000 rheometer equipped with cone-and- plate fixtures of suitable diameter to generate adequate torque signal at a series of low shear rates, such as 0.01 s -1 , 0.1 s -1 and 1.0 s -1 while not exceeding the torque limits of the transducer.
  • the viscosity measurements may be obtained using an ARES-G2 rotational rheometer, commercially available from TA Instruments using a steady rate sweep from 0.1 to 10 s -1 on a 25 mm cone and plate.
  • the reactive compatibiliser (C) is further defined as a functionalized polydimethylsiloxane (PDMS), i.e., where each R 1 is methyl.
  • the reactive compatibiliser (C) is selected from amine-functional PDMS (i.e., where each functional group X comprises an amine, such as a primary aminoalkyl group) and vinyl-functional PDMS (i.e., where each functional group X comprises, alternatively is, a vinyl group).
  • the reactive compatibiliser (C) may comprise, alternatively may be, a terminal and/or pendant amine-functional random, graft, or block copolymer or co-oligomer of PDMS and a non- reactive siloxane (e.g., a polyphenylmethylsiloxane, a tris(trifluoropropyl)methylsiloxane, etc.).
  • a non- reactive siloxane e.g., a polyphenylmethylsiloxane, a tris(trifluoropropyl)methylsiloxane, etc.
  • examples of vinyl-functionalized polydimethylsiloxane (PDMS) suitable for use in, or as, the reactive compatibiliser (C) include terminal and/or pendant vinyl-functional PDMS oligomers and polymers, as well as random, graft, or block copolymer or co-oligomer of PDMS.
  • the reactive compatibiliser (C) comprises, alternatively is, an aminoalkyl- terminated PDMS, such as an ⁇ , ⁇ -aminopropyl-terminated PDMS.
  • the reactive compatibiliser (C) comprises, alternatively is, a vinyl-terminated PDMS, such as an ⁇ , ⁇ - vinyl-terminated PDMS.
  • the reactive compatibiliser (C) comprises, alternatively is, is a methacryloylpropyl- terminal PDMS, a silanol-terminal PDMS, a succinic anhydride-terminal PDMS, a SiH-terminal PDMS, a vinyl-terminated PDMS, a mono carbinol- functional PDMS, or an aminopropyl-terminated PDMS.
  • X or Y is an unsaturated group such as an alkenyl group or alkynyl group and the other of X and Y is an Si-H group they will undergo a hydrosilylation reaction in order to compatibilise (A) and (B) into a silicone-polyolefin hybrid material.
  • the hydrosilylation catalyst may comprise or consist of a platinum group metal or a compound thereof. These are usually selected from catalysts of the platinum group of metals (platinum, ruthenium, osmium, rhodium, iridium and palladium), or a compound of one or more of such metals. Alternatively, platinum and rhodium compounds are preferred due to the high activity level of these catalysts in hydrosilylation reactions, with platinum compounds most preferred.
  • the hydrosilylation catalyst of can be a platinum group metal, a platinum group metal deposited on a carrier, such as activated carbon, metal oxides, such as silicon dioxide, silica gel or powdered charcoal, or a compound or complex of a platinum group metal.
  • a carrier such as activated carbon
  • metal oxides such as silicon dioxide, silica gel or powdered charcoal
  • a compound or complex of a platinum group metal preferably the platinum group metal is platinum.
  • platinum based catalysts for example, platinum black, platinum oxide (Adams catalyst), platinum on various solid supports, chloroplatinic acids, e.g., hexachloroplatinic acid (Pt oxidation state IV) (Speier catalyst), chloroplatinic acid in solutions of alcohols e.g., isooctanol or amyl alcohol (Lamoreaux catalyst), and complexes of chloroplatinic acid with ethylenically unsaturated compounds such as olefins and organosiloxanes containing ethylenically unsaturated silicon-bonded hydrocarbon groups, e.g., tetra-vinyl-tetramethylcyclotetrasiloxane- platinum complex (Ashby catalyst).
  • platinum based catalysts for example, platinum black, platinum oxide (Adams catalyst), platinum on various solid supports, chloroplatinic acids, e.g., hexachloroplatinic acid (Pt oxidation state IV)
  • Soluble platinum compounds that can be used include, for example, the platinum-olefin complexes of the formulae (PtCl 2 .(olefin) 2 and H(PtCl 3 .olefin), preference being given in this context to the use of alkenes having 2 to 8 carbon atoms, such as ethylene, propylene, isomers of butene and of octene, or cycloalkanes having 5 to 7 carbon atoms, such as cyclopentene, cyclohexene, and cycloheptene.
  • PtCl 2 .(olefin) 2 and H(PtCl 3 .olefin) preference being given in this context to the use of alkenes having 2 to 8 carbon atoms, such as ethylene, propylene, isomers of butene and of octene, or cycloalkanes having 5 to 7 carbon atoms, such as cyclopentene, cyclohe
  • soluble platinum catalysts are, for the sake of example a platinum-cyclopropane complex of the formula (PtCl2C3H6)2, the reaction products of hexachloroplatinic acid with alcohols, ethers, and aldehydes or mixtures thereof, or the reaction product of hexachloroplatinic acid and/or its conversion products with vinyl-containing siloxanes such as methylvinylcyclotetrasiloxane in the presence of sodium bicarbonate in ethanolic solution.
  • platinum-cyclopropane complex of the formula (PtCl2C3H6)2
  • the reaction products of hexachloroplatinic acid with alcohols, ethers, and aldehydes or mixtures thereof or the reaction product of hexachloroplatinic acid and/or its conversion products with vinyl-containing siloxanes such as methylvinylcyclotetrasiloxane in the presence of sodium bicarbonate in ethanolic solution.
  • Platinum catalysts with phosphorus, sulfur, and amine ligands can be used as well, e.g., (Ph 3 P) 2 PtCl 2 ; and complexes of platinum with vinylsiloxanes, such as sym- divinyltetramethyldisiloxane (Karstedt’s catalyst).
  • suitable platinum-based catalysts of component (d)(ii) include: (i) complexes of chloroplatinic acid with organosiloxanes containing ethylenically unsaturated hydrocarbon groups are described in US 3,419,593; (ii) chloroplatinic acid, either in hexahydrate form or anhydrous form; (iii) a platinum-containing catalyst which is obtained by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound, such as divinyltetramethyldisiloxane; (iv) alkene-platinum-silyl complexes as described in US Pat.
  • No.6,605,734 such as (COD)Pt(SiMeCl2) where “COD” is 1,5-cyclooctadiene; and/or (v) Karstedt's catalyst, a platinum divinyl tetramethyl disiloxane complex typically containing about 1 wt. % of platinum typically in a vinyl siloxane polymer.
  • Solvents such as toluene and the like organic solvents have been used historically as alternatives but the use of vinyl siloxane polymers by far the preferred choice. These are described in US3,715,334 and US3,814,730.
  • the catalyst may be selected from co-ordination compounds of platinum.
  • hexachloroplatinic acid and its conversion products with vinyl-containing siloxanes, Karstedt's catalysts and Speier catalysts are preferred.
  • the catalyst may be encapsulated during storage, especially in the case of one-part compositions to prevent premature cure.
  • the catalytic amount of the hydrosilylation catalyst is generally between 0.01 ppm, and 10,000 parts by weight of platinum-group metal, per million parts (ppm), based on the weight of the composition into which it is being added, alternatively, between 0.1 and 7500ppm; alternatively, between 100 and 75000 ppm, and alternatively between 500 and 6,000 ppm.
  • the ranges may relate solely to the metal content within the catalyst or to the catalyst altogether (including its ligands) as specified, but typically these ranges relate solely to the metal content within the catalyst.
  • the catalyst may be added as a single species or as a mixture of two or more different species.
  • a hydrosilylation cure inhibitor may also be utilised as an additive.
  • group Y of component (B) is an anhydride functional groups e.g., maleic anhydride; and group X of the compatibiliser (C) comprises a reactive amine group which upon heating will react with the anhydride resulting in components (B) and (C) being bonded together.
  • Unreactive polyolefin Optional
  • An unreactive polyolefin (D) may also be included as an optional additional starting ingredient in the process for the preparation of the silicone-polyolefin hybrid material as described herein.
  • unreactive it is meant that the unreactive polyolefin (D) is not reactable with components (B) or (C), i.e., unreactive polyolefin (D) does not include a functional group that is reactable with reactive group X of reactive compatibiliser (C) or functional group Y of functionalized polyolefin (B).
  • the unreactive polyolefin (D) can include a functional group so long as the functional group is not reactable with reactive group X of reactive compatibiliser (C) or functional group Y of functionalized polyolefin (B).
  • a functional group so long as the functional group is not reactable with reactive group X of reactive compatibiliser (C) or functional group Y of functionalized polyolefin (B).
  • C reactive compatibiliser
  • B functional group Y of functionalized polyolefin
  • the unreactive polyolefin (D) is free from any functional groups, i.e., groups that are reactable with other functional groups.
  • the unreactive polyolefin (D) may be selected from any of those described above for the functionalized polyolefin (B), with the only difference being that the unreactive polyolefin (D) does not include the functional group Y present in component (B).
  • the unreactive polyolefin (D) is a post-consumer recycle resin. In another embodiment, the unreactive polyolefin (D) is virgin material. The unreactive polyolefin (D) can also comprise a combination of post-consumer recycle resin and virgin material.
  • post-consumer recycle resin or "PCR" is a polymeric material that has been previously used as consumer packaging or industrial packaging. In other words, PCR is waste plastic. PCR is typically collected from recycling programs and recycling plants. PCR typically requires additional cleaning and processing before it can be re-introduced into a manufacturing line.
  • the PCR is the PCR multilayer film after the PCR multilayer film has completed a first use; i.e., having already served its first purpose. It is understood PCR includes postindustrial recycle (PIR) resin.
  • the PCR multilayer film is waste barrier film that was used to hold, or otherwise to store, consumer-edible oil.
  • PCR is distinct from virgin polymeric material. Since PCR has gone through an initial heat and molding process; PCR is not "virgin" polymeric material.
  • a "virgin polymeric material” is a polymeric material that has not undergone, or otherwise has not been subject to, a heat process or a molding process.
  • the physical, chemical and flow properties PCR resin differ when compared to virgin polymeric resin. PCR can be considered waste plastic.
  • PCR can include, for example, HDPE packaging such as bottles (milk jugs, juice containers), LDPE/LLDPE packaging such as films. PCR can also include residue from its original use, residue such as paper, adhesive, ink, colorants, dyes, nylon, ethylene vinyl alcohol (EVOH), polyethylene terephthalate (PET), and other odor causing agents.
  • HDPE packaging such as bottles (milk jugs, juice containers)
  • LDPE/LLDPE packaging such as films.
  • PCR can also include residue from its original use, residue such as paper, adhesive, ink, colorants, dyes, nylon, ethylene vinyl alcohol (EVOH), polyethylene terephthalate (PET), and other odor causing agents.
  • the PCR comprises HDPE
  • the PCR can comprise up to 40% polypropylene contamination.
  • Non-limiting examples commercially available PCR include PCR sold by Envision Plastics, North Carolina, USA, under the tradenames EcoPrimeTM, PRISMATM, Natural HDPE PCR Resins, Mixed Color and Black HDPE PCR Resins; PCR sold by KW Plastics, Alabama, USA under the following tradenames KWR101-150, KWR101-150-M5-BLK, KWR101-150-M10 BLK, KWR102- 8812 BLK, KWR102, KWR102LVW, KWR105, KW620, KWR102-M4, KWR-105M2, KWR105M4, KWR621 FDA, KWR621-20-FDA, KW308A, KW621, KW621-T10, KW621-T20, KW622-20, KW622-35, KW627C, KW1250G, and KWBK10-NB.
  • unreactive polyolefin (D) when present unreactive polyolefin (D) comprises PCR blended with an olefin- based polymer that is not a PCR.
  • PCR is blended with a "virgin olefin-based polymer" to give the unreactive polyolefin (D).
  • the unreactive polyolefin (D) typically has a melt flow index (MFI) of from 0.5 to 35 g/10 min. MFI can be measured in accordance with ASTM D1238–86.
  • the conical screw dump extruder utilised herein as the mixer in the process for the preparation of a silicone-polyolefin hybrid material comprises a conical twin screw mixing chamber housing two counter-rotating conical screws converging towards an extrusion die having an entrance and an exit wherein passage through said extrusion die is controlled by an occlusion means such that the exit of said extrusion die is adapted to be closed by the occlusion means up to the end of step (v) and then is opened for step (vi) for the extrusion of the silicone-polyolefin hybrid material through the extrusion die for further processing or storage outside said conical screw dump extruder.
  • the occlusion means is in the form of a plate which can be moved between an open and a closed position such that in the closed position occlusion means is designed to prevent egress of the content of the conical screw dump extruder during said preparation of a silicone-polyolefin hybrid material and then when in the open position allowing said preparation of a silicone-polyolefin hybrid material product to egress through extrusion die.
  • the two intermeshing conical screws operate in a counter-rotative manner and are driven by a motor which forms part of the conical screw dump extruder.
  • the intermeshing conical screws may, if desired, comprise lip seals on the shafts.
  • the conical screw dump extruder may comprise multiple entry ports for e.g., silicone polymer base (A), functionalized polyolefin (B), reactive compatibiliser (C) and optional unreactive polyolefin (D), although more than one component can be introduced via the same entry port if required or desired.
  • these ingredients may be stored in any preferred manner prior to introduction into the conical screw dump extruder. They may also be designed so that predetermined amounts thereof may be dosed into the conical screw dump extruder mixing chamber periodically for mixing and preparation of the silicone-polyolefin hybrid material product.
  • One or more steps of the preparation of the silicone-polyolefin hybrid material product may be carried out in an inert atmosphere, e.g., under nitrogen, or under vacuum.
  • the mixing chamber of the conical screw dump extruder may be purged with nitrogen prior to the introduction of the silicone polymer base (A), functionalized polyolefin (B), reactive compatibiliser (C) and optional unreactive polyolefin (D), and during preparation of the silicone- polyolefin hybrid material product.
  • typically conical screw dump extruders have a clamshell style opening design which enables easy cleanout, during use as a conical screw dump extruder if required. It has also been determined that very little or no dumping and scraping is required between preparations batches of silicone-polyolefin hybrid material product due to the small loss of the overall batch weight remaining in the mixer following extrusion (heel).
  • the conical screw dump extruders may have an integrated vacuum system capability allowing for vacuum to be used for the removal of volatiles.
  • An example of such a conical screw dump extruder is described in US7556419 and US11925911 both of which are incorporated herein by reference and such conical screw dump extruders are commercially available from Colmec SpA of Busto Arsizio, Italy.
  • step (i) of the process the silicone polymer base (A) comprising one or more silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D- 926-08 (A)(1) in combination with one or more fillers (A)(2) is introduced into the conical twin screw mixing chamber through a suitable inlet.
  • silicone polymer base (A) may be prepared in a conical screw dump extruder and then transported therefrom to the entry port for introduction into the mixer herein.
  • silicone polymer base (A) may be prepared in the same conical screw dump extruder as a pre-step to the process for the preparation of a silicone-polyolefin hybrid material described herein.
  • the silicone polymer base (A) and/or silicone gum may be transported to and/or introduced into the CTM by any suitable means, for example using one or more conveyors, extruders, gear pumps, drums, or a combination thereof.
  • the introduction of solid materials can be added for example, either through a single addition or by way of a continuous addition process while component (A)(1) is being mixed.
  • the solid material may, for example, be introduced into the CTM gravimetrically directly from a shaft, vacuum pumping the material, via screw augers, or other systems.
  • component (A)(2) the filler
  • component (A)(1) is added gradually/continuously into the CTM, while the CTM screws are rotating and continuously mixing component (A)(1) in order to prevent potential buildup in dead zones or creating pockets of unincorporated solid material.
  • any two or more of the starting ingredients herein may be pre-mixed in a suitable mixer before entry into the conical twin screw extruder if desired, such that said components e.g., functionalised polyolefin (B) and unreactive polyolefin (D).
  • components (C) and (D) and/or any additives introduced into the mixture may be done so in the form of masterbatches or concentrates in e.g. an organosiloxane polymer or silicone gum.
  • the masterbatch can be added via an infeed conveyor or the side hatch on the mixer hopper.
  • step (i) when only silicone polymer base is present, the base present in the conical twin screw extruder mixing chamber is driven towards the extrusion die by the counter-rotating screws.
  • the occlusion means is shut, it is forced to move back up the conical twin screw extruder mixing chamber for further recirculation/additional mixing.
  • the two counter-rotating screws are in converging and intersecting conical channels, wherein the peripheral profile of the screw threads runs adjacent to the channel surface.
  • the material is thus forced to follow the conical profile of the screw to a progressively narrower volume, increasing the pressure as composition approaches the closed extrusion die before mixing with the functionalised polyolefin (B) and optionally compatibiliser in step (ii). This may optionally be undertaken in an inert atmosphere or under vacuum.
  • the screws may be operated at any suitable speed e.g., from 25 to 100 rpm or even higher if considered necessary.
  • the materials introduced into the conical twin screw extruder gradually get hotter, potentially up to in the region of 200 o C, alternatively up to about 190 o C, in the region of 180 o C, through heating and shear heating through the mixing process.
  • the silicone polymer base (A), functionalized polyolefin (B), reactive compatibiliser (C) and optional unreactive polyolefin (D), introduced into the conical twin screw extruder mixing chamber in step (i), (ii) and/or (iii) may be introduced in any suitable manner, such as, for the sake of example, from manually or otherwise from any suitable containers or using an automatic-dosing process e.g., an augered, automatic-dosing process from gum hoppers or the like.
  • step (ii) of the process for the preparation of a silicone-polyolefin hybrid material described herein which is simultaneous with or subsequent to step (i) once the one or more silicone polymer base (A) has reached said predetermined temperature of from 100 o C and 200 o C
  • the one or more functionalised polyolefins (B) are introduced into the mixing chamber of the mixer, whilst continuing mixing to form an initial silicone-polyolefin hybrid composition mixture.
  • the reaction temperature may be any suitable reaction temperature which assists in the mixing of components (A) and (B) as well as component (D) if present.
  • the one or more functionalised polyolefins (B) may be introduced into the mixing chamber of the mixer in a single addition or gradually, as desired.
  • Step (ii) may be undertaken under vacuum or in an inert atmosphere e.g., undertaken in a nitrogen atmosphere, e.g., by use of periodic introductions of nitrogen in order to control oxygen levels in the mixer during mixing.
  • step (ii) of the process the conical screw dump extruder is utilised for the addition of functionalised polyolefin (B) and to intermix silicone polymer base (A) and the functionalised polyolefin (B).
  • Components (A) and (B) are then mixed in the same manner as described previously with respect to step (i), i.e., in the conical screw dump extruder mixing chamber they are driven towards the extrusion die by the counter-rotating screws with the occlusion means shut so that they are forced to move back up the conical twin screw mixing chamber for further recirculation/additional mixing to enhance the homogeneity of the composition as it is prepared.
  • the two counter-rotating screws are in converging and intersecting conical channels, wherein the peripheral profile of the screw threads run adjacent to the channel surface. The material is thus forced to follow the conical profile of the screw to a progressively narrower volume, increasing the pressure as the ingredients approach the closed extrusion die during mixing.
  • step (iii) This increase in pressure enables the recirculation of the contents of the mixing chamber.
  • step (iii) The silicone polymer base and functionalized polyolefin are not very miscible in the absence of the reactive compatibiliser (C).
  • Introduction of the compatibiliser in step (iii) greatly enhances miscibility of components (A) and (B) with reactions taking place between functional group Y from functionalized polyolefin (B) and reactive group X from reactive compatibiliser (C).
  • the reactions between components (B) and (C) render the composition compatible with the further mixing in step (iv) to form a silicone-polyolefin hybrid material product.
  • Step (iv) can be for any suitable duration from a few minutes to several hours but is typically between 5 minutes and 3 hours, alternatively 5 minutes and 2 hours, alternatively between 5 and 90 minutes.
  • the polymer base (A), functionalized polyolefin (B), and optional unreactive polyolefin (D) may be introduced into the mixer at room temperature, before mixing and heating or any preferred temperature between room temperature and the predetermined temperature between 100 o C and 200 o C.
  • the polymer base (A), functionalized polyolefin (B), reactive compatibiliser (C) and optional unreactive polyolefin (D) may be introduced into the mixer at any temperature desired between room temperature, before mixing and heating or any preferred temperature between room temperature and the predetermined temperature between 100 o C and 200 o C.
  • reactive compatibiliser (C) may be added into the mixer when step (iii) follows step (ii) at any suitable temperature which will enable the reaction between groups X and Y to take place.
  • step (iii) may be carried out at approximately the same temperature as the temperature of step (ii) or at a higher temperature if desired.
  • PTFE packing may be utilised on the shafts of the conical screws and in one embodiment if desired said screws may comprise lip seals on the shafts of said screws.
  • the temperature of the mixing chamber is optionally maintained within a pre-determined range of from 100 and 200 o C for a period of up to 6 hours to remove volatiles and to thermodynamically encourage reaction between components (B) and (C) to facilitate compatibilization of the resulting silicone-polyolefin hybrid material product.
  • step (iii) when utilised separately after steps (i) and (ii) step (iii) may be carried out under vacuum or in an inert atmosphere e.g., under nitrogen and heating may be required if/when heat generated during shear mixing in step (ii) does not generate sufficient heat to ensure the temperature is maintained in step (iii).
  • the use of vacuum at this stage may be useful depending on the X and Y groups involved in the reaction taking place to enable the removal of volatiles.
  • step (v) of the process the resulting product is cooled to a chosen temperature between 25 o C and 120 o C enabling step (vi) to take place i.e., extruding the cooled silicone-polyolefin hybrid material product of step (v) from the mixer at a temperature of from 25 o C to 75 o C once the occlusion means is moved to the open position to allow the product to be extruded through the extrusion die.
  • the cooling step is undertaken at a reduced screw speed compared to previous steps e.g., from 5 to 40 rpm, alternatively from 5 to 30 rpm, alternatively from 5 to 20 rpm.
  • the rotation of the two screws in the CTM may be also temporarily reversed to assist the mixing or cooling processes.
  • the blade mixing speed can be reduced or reversed to decrease heat generated by shearing.
  • the reduction in mixing speed reduces the amount of heat generated through shear mixing and the continuous mixing of material helps remove any trapped internal heat.
  • the extrusion die has an entrance and an exit wherein passage through the extrusion die from the entrance in the conical screw dump extruder to the exit is controlled by the aforementioned occlusion means.
  • the temperature to which the product needs to be cooled depends on whether it is to be used for further processing or is to be stored e.g., packaged for future use or sale.
  • the product is to be stored and/or packaged cooling needs to be down to a temperature low enough to prevent melting of the packaging material e.g., in the case of polyethylene it has to be cooled to a temperature of no more than 90 o C, for example it may be cooled to a pre-defined temperature of from about 30 o C and 80 o C, alternatively from about 30 o C and 70 o C alternatively from about 40 o C and 70 o C.
  • Cooling step (v) of the process may for example, take place: (I) completely in the conical screw dump extruder used to make the silicone-polyolefin hybrid material in which case the resulting silicone-polyolefin hybrid material is extruded cold at a temperature in the region of 30 to 40 o C; (II) partially in the conical screw dump extruder used to make the silicone- polyolefin hybrid material in which case the resulting silicone-polyolefin hybrid material is extruded at a moderate temperature in the region of 50 to 80 o C and is then transferred to an alternative means for cooling further e.g., a pan or other container; or (III) completely outside of the conical screw dump extruder used to make the silicone-polyolefin hybrid material in which case the resulting silicone-polyolefin hybrid material is extruded “hot” (i.e., after step (iv)) at a temperature of from 80 o C to 120 o C, alternatively at a
  • step (III) the hot product of step (iv) is extruded out of the CTM before cooling commences and is transferred to an alternative cooling CTM or other cooling means for cooling from which it is extruder once cooled.
  • the cooling CTM or other cooling means the silicone-polyolefin hybrid material may be transferred through a straining means e.g., a mesh.
  • the silicone-polyolefin hybrid material may be strained directly through a mesh screen attached to the CTM or strained in a secondary asset. Straining may also be combined with a means for de-airing the material. Such an additional step may remove any agglomerates or granules of material that did not properly mix thereby providing a smooth consistent material.
  • the resulting product may be pelletised prior to storage to ease future use, e.g., as the main ingredient in a compounding process. Any suitable process may be used to pelletise said product and this resulting pelletised product may be considered a preferred means of storage before being used further, e.g., in compounding.
  • the product issuing out of the conical screw dump extruder through the extrusion die may be collected for further cooling and/or may be collected and transferred to a suitable packaging means or is transported elsewhere for further processing and applications. In the case of further cooling, it could be extruded into a bulk tub or other container, or it could be run straight through a gear pump and then packaged. In one embodiment the silicone-polyolefin hybrid material issuing from the conical screw dump extruder is extruded into another apparatus for further processing e.g.
  • a further conical screw dump extruder with a gear pump or a tapered twin screw extruder where it can be strained and packaged or alternatively using any suitable compounding means such as a sigma blade kneader mixer, a bottom discharge kneader mixer, a conical screw dump extruder, a planetary extruder, a co- kneader extruder, a twin-screw extruder, a single screw extruder and/or a two-roll mill but may in this instance in one preferred embodiment be a second conical screw dump extruder.
  • the silicone-polyolefin hybrid material product produced by the method herein may be mixed with other ingredients to form a curable composition.
  • the process for the preparation of silicone-polyolefin hybrid material forms part of a continuous compounding process, for example there may be a cascade of conical screw dump extruders used in that a first conical screw dump extruder may be used for the preparation of silicone polymer base (A) and a second conical screw dump extruder may be utilised for making the silicone-polyolefin hybrid material as described above, a third conical screw dump extruder may be utilised at least partially for cooling and subsequently for packaging.
  • the silicone-polyolefin hybrid material product may be compounded together with other ingredients using any suitable compounder type mixer for example a sigma blade kneader mixer, a bottom discharge kneader mixer, a conical twin mixer e.g., screw dump extruder, a planetary extruder, a co-kneader extruder, a twin-screw extruder, a single screw extruder and/or a two-roll mill.
  • a press plate may be utilised to assist in the introduction of the additives.
  • a second conical screw dump extruder may be utilised for introducing catalysts, cross-linkers and the like into said silicone-polyolefin hybrid material.
  • the curable composition comprises the silicone-polyolefin hybrid material product and a curing agent, although other optional additives may be added into the composition.
  • the curing agent typically comprises, alternatively is, a free radical initiator and/or a photoinitiator.
  • Suitable free radical initiators typically include benzoyl peroxide, tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, peracetic acid, cyclohexanone peroxide, cumene hydroperoxide, tert-butyl peroxide, tert-butyl hydroperoxide, 2,2’-azobisisobutyronitril (AIBN), 2,2’-azodi(2- methylbutyronitrile) (AMBN), tert-amyl peroxybenzoate, tert-butyl peracetate, tert-butyl peroxybenzoate, tert-butylperoxy isopropyl carbonate, cumene hydroperoxide, and potassium persulfate.
  • AIBN 2,2’-azobisisobutyronitril
  • AMBN 2,2’-azodi(2- methylbutyronitrile)
  • tert-amyl peroxybenzoate tert-
  • the curable composition comprises the silicone-polyolefin hybrid material product and the free radical initiator in an amount of from 0.01 to 10 wt.%, based on the total weight of the curable composition, alternatively in an amount of from 0.1 to 9 wt.%, based on the total weight of the curable composition. in an amount of from 0.2 to 7.5 wt.%, based on the total weight of the curable composition in an amount of from 0.2 to 6 wt.%, based on the total weight of the curable composition.
  • Amounts outside of these ranges may also be utilized, recognizing that excess free radical initiator may not significantly increase the time or efficiency of the curing process.
  • the cure process generally takes between 1 and 30 minutes, depending on the means utilised, alternatively between 1 and 20 minutes, between 1 and 15 minutes.
  • photoinitiators include onium salts, nitrobenzyl sulfonate esters, diaryliodonium salts of sulfonic acids, triarylsulfonium salts of sulfonic acids, diaryliodonium salts of boronic acids, triarylsulfonium salts of boronic acids, bis-diaryl iodonium salts (such as bis(dodecyl phenyl) iodonium hexafluoroarsenate and bis(dodecylphenyl) iodonium hexafluoroantimonate), dialkylphenyl iodonium hexafluoroantimonate, diaryliodonium salts of sulfonic acids, triarylsulfonium salts of sulfonic acids, diaryliodonium salts of boronic acids, and triarylsulfonium salts of boronic acids.
  • diaryioadonium salts of sulfonic acid examples include diaryliodonium salts of perfluoroalkylsulfonic acids and diaryliodonium salts of aryl sulfonic acids.
  • suitable diaryliodonium salts of perfluoroalkylsulfonic acids include diaryliodonium salts of perfluorobutanesulfonic acid, diaryliodonium salts of perfluoroethanesulfonic acid, diaryliodonium salts of perfluoro-octanesulfonic acid, and diaryliodonium salts of trifluoromethane sulfonic acid.
  • diaryliodonium salts of aryl sulfonic acids include diaryliodonium salts of para-toluene sulfonic acid, diaryliodonium salts of dodecylbenzene sulfonic acid, diaryliodonium salts of benzene sulfonic acid, and diaryliodonium salts of 3-nitrobenzene sulfonic acid.
  • suitable triarylsulfonium salts of sulfonic acid include triarylsulfonium salts of perfluoroalkylsulfonic acids and triarylsulfonium salts of aryl sulfonic acids.
  • triarylsulfonium salts of perfluoroalkylsulfonic acids include triarylsulfonium salts of perfluorobutanesulfonic acid, triarylsulfonium salts of perfluoroethanesulfonic acid, triarylsulfonium salts of perfluoro-octanesulfonic acid, and triarylsulfonium salts of trifluoromethane sulfonic acid.
  • triarylsulfonium salts of aryl sulfonic acids include triarylsulfonium salts of para-toluene sulfonic acid, triarylsulfonium salts of dodecylbenzene sulfonic acid, triarylsulfonium salts of benzene sulfonic acid, and triarylsulfonium salts of 3-nitrobenzene sulfonic acid.
  • diaryliodonium salts of boronic acids include diaryliodonium salts of perhaloarylboronic acids and preferred triarylsulfonium salts of boronic acids are triarylsulfonium salts of perhaloarylboronic acid.
  • the photoinitiator is typically used in the range of from 0.001 to 5 wt.%, based on the total weight of the curable composition, alternatively from 0.1 to 5 wt.%, based on the total weight of the curable composition, alternatively from 0.25 to 5 wt.%, based on the total weight of the curable composition, alternatively from 0.25 to 5 wt.%, based on the total weight of the curable composition, alternatively from 0.5 to 5 wt.%, based on the total weight of the curable composition.
  • the curable composition is typically prepared by combining the curing agent and the silicone- polyolefin hybrid material product. The process for combining is not particularly limited and may be performed using any of the mixing devices described above.
  • the curable composition may be prepared in sequence with the silicone-polyolefin blend (e.g., by adding the curing agent to the silicone-polyolefin blend upon, or soon after, formation thereof).
  • a separate and/or different mixer, or mixing process may be used to prepare the curable composition.
  • the curing agent may be milled into the silicone-polyolefin hybrid material product, after extrusion from the mixer in the above process, using a roller mill, thereby preparing the curable composition.
  • various mixing processes and equipment including any of those described herein, and combinations thereof, may be utilized to combine the curing agent and the silicone-polyolefin and prepare the curable composition.
  • the curable composition further comprises one or more optional additives.
  • the curable composition may comprise one or more further additives such as, for the sake of example a binder; a thickener; a tackifying agent; an adhesion promotor; an extender; a plasticizer; an end-blocker; a drying agent; a colorant (e.g., a pigment, dye, etc.); an anti-aging additive; a cure inhibitor such as acetylenic alcohols and their derivatives for example 1-ethynyl-1-cyclohexanol (ETCH), a biocide; a flame retardant; a corrosion inhibitor; a UV absorber; an anti-oxidant; a light-stabilizer; a procatalyst, or catalyst generator; an initiator (e.g., a heat activated initiator, an electromagnetically activated initiator, etc.); a photoacid generator; a heat stabilizer; and the like, as well as derivatives, modifications, and combinations thereof.
  • a binder e.g., a thickener
  • additives may be classified under different terms of art and, just because an additive is classified under a specific term and/or characterized according to a particular function does not mean that it is thusly limited to that function.
  • some additives may be present in a particular component of the curable composition, or instead may be incorporated when forming the curable.
  • the curable composition may comprise any number of additional components and additives, e.g., depending on the particular type and/or function of the same in the curable composition.
  • the one or more additives may be combined with the curing agent or the silicone- polyolefin hybrid material product before, during, or after combining the curing agent and the silicone-polyolefin hybrid material product.
  • one or more of the additives may be combined with the silicone-polyolefin hybrid material product (or the curing agent) to form an intermediate composition, which is then combined with the curing agent (or the silicone-polyolefin blend) to give the curable composition.
  • silicone-polyolefin hybrid material product, the curing agent, and many of the suitable additives may be combined together in a concerted step.
  • One of skill in the art will readily appreciate that the particular order of addition and/or combination suitable for a given additive will depend on the nature of the additive and the other components of the curable composition, and thus will be independently selected based on the particular components and parameters being employed.
  • a cured product of the curable composition and a method of preparing the cured product, are also provided.
  • the curable composition may be cured to give the cured product.
  • curing typically comprises activating the curing agent, e.g., via heating the composition to a temperature sufficient to activate the radical initiator (e.g., via thermal decomposition), irradiating the photoinitiator, etc.
  • activation processes are known in the art and will be selected based on the particular curing agent utilized.
  • the cured product is formed via radical cure of the curable composition, i.e., upon activation of the radical initiator.
  • curing the curable composition generally comprises crosslinking components thereof, such as the reactive compatibiliser (C) and the one or more silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08 (A)(1).
  • the cured product can be referred to as a silicone-polyolefin elastomer, or a hybrid elastomer.
  • the method of preparing the cured product generally comprises heating the curable composition to an elevated temperature, such as a temperature of from 90 to 300, alternatively from 100 to 300, alternatively from 100 to 250, alternatively from 100 to 200 °C, for a time sufficient to cure the curable composition.
  • the curable composition is cured at a temperature of from 150 to 220 °C for a time of from 1 to 20, alternatively from 5 to 20, alternatively from 5 to 15 minutes.
  • silicone polymer base (A) made from silicone gums such as the one or more silicone polymers, and/or copolymers having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08 (A)(1) were found to be unusable as the twin screw extruder could only cater for preformed silicone base materials capable of flow through a pipe into a twin screw extruder and this is not possible in the case of silicone gums.
  • polyolefin components B and D when present would also require the polyolefin material to either be pumped as a liquid (through melting) or added as a pellet directly into the twin screw extruder thereby limiting the source material requirements especially on grounds of sustainability aspect when including unreactive polyolefin (D) when e.g., it comprises post- consumer recycled (PCR) that requires a separate process to be formed into pellets or melted.
  • PCR post- consumer recycled
  • the conical screw dump extruder was far better at controlling certain mechanical properties of the silicone-polyolefin hybrid material product through limiting the mixing time of the material.
  • the domain morphology of the polyolefin was also influenced by the mixing time in the conical screw dump extruder. This was found not to be the case in respect to dispersed polyolefin domain morphology are not influenced by change in mixing operations by varying mixing speed or temperature in twin screw extruders. It was unexpectedly found that attempts to make the aforementioned product herein were far less successful than expected on mixers that do not fully encapsulate their mixing elements (blades, teeth, etc.) to facilitate constant high shear mixing.
  • Such mixers were found not to be successful in making silicone-polyolefin hybrid materials, using for example co-kneader mixers such as Haake mixers, and sigma blade co-kneader mixers. Furthermore, it was found that the morphology of the dispersed phase (components (B) and (D) when present) of the hybrid material did not significantly change under varied mixing conditions when using the other mixers. There are additional limitations to forming polyolefin-in-silicone hybrid materials on the Twin screw extruders, such as source in raw material.
  • Twin screw extruders are not typically used for forming high viscosity silicone base material (typically performed on large tilt mixers), so the silicone source is limited to preformed silicone base material that must be capable of flow through a pipe into a Twin screw extruder barrel.
  • use of a conical screw dump extruder avoids the need for additional equipment e.g., dosing equipment that would be needed to generate silicone- polyolefin hybrid materials, and processes were found to be controllable through heating, mixing speed and mixing time on the conical screw dump extruder.
  • inventive compositions provide a cost-effective route to obtaining unique silicone-polyolefin hybrid materials due to inexpensive precursors and the solvent-less preparations.
  • inventive compositions enable the preparation of products and articles with enhanced performance characteristics, including as compared to products and articles formed via organic compositions, silicone compositions, or conventional hybrid silicone-organic compositions.
  • injection moldable articles and compression moldable articles may be made from the inventive compositions having improved toughness (e.g., increased tear strength), chemical resistance (e.g., increased solvent swell resistance), excellent elongation and tensile strength, and delayed elastic recovery when compared to typical silicone rubber elastomers.
  • Such products and articles may be employed in or for a wide range of applications and in the production of a wide range of consumer products and articles.
  • Examples include products and articles in or for consumer wearable electronics; consumer packaging and dispensing, such as for food, personal care, and beauty care articles and/or products; vibration isolation components; electrical protection in wire & cable applications and coating or co-molding on substrates such as buttons, knobs and user interface controls or components.
  • silicone-polyolefin hybrid material from silicone polymer base (A) comprising one or more silicone polymers and/or copolymers, in each instance having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08, functionalized polyolefin (B), reactive compatibiliser (C) and optionally unreactive polyolefin (D) as described herein using a conical screw dump extruder.
  • A silicone polymer base
  • A comprising one or more silicone polymers and/or copolymers, in each instance having a Williams plasticity of at least 75mm/100 in accordance with ASTM D-926-08, functionalized polyolefin (B), reactive compatibiliser (C) and optionally unreactive polyolefin (D) as described herein using a conical screw dump extruder.
  • viscosity measurement given are zero-shear viscosity ( ⁇ o) values, obtained by extrapolating to zero the value taken at low shear rates (or simply taking an average of values) in the limit where the viscosity-shear rate curve is rate-independent, which is a test-method independent value provided a suitable, properly operating rheometer is used.
  • the zero- shear viscosity of a substance at 25 °C may be obtained by using commercial rheometers such as an Anton-Parr MCR-301 rheometer or a TA Instruments AR-2000 rheometer equipped with cone-and- plate fixtures of suitable diameter to generate adequate torque signal at a series of low shear rates, such as 0.01 s -1 , 0.1 s -1 and 1.0 s -1 while not exceeding the torque limits of the transducer.
  • a series of low shear rates such as 0.01 s -1 , 0.1 s -1 and 1.0 s -1 while not exceeding the torque limits of the transducer.
  • Viscosity is typically reported as zero-shear viscosities measured at 25 °C.
  • Degree of polymerization is typically reported as number average DP, e.g., from NMR, IR, and/or GPC (e.g., relative to standards, such as polystyrene).
  • Table 1 Materials Utilized Component Description Silicone Base 1 30 durometer high strength silicone rubber (HCR) base comprising a 2 of g n e xampes a seres o s cone-poyoe n yr maeras were prepare n accor ance w h the process for the preparation of a silicone-polyolefin hybrid material herein using a Colmec TM CTM-65 mixer, available from Colmec SpA of Busto Arsizio, Italy as the conical screw dump extruder. The composition of the starting ingredients used in the process for making the examples is depicted in Table 2 below.
  • HCR high strength silicone rubber
  • Table 2 composition of starting ingredients Chemical Ex.1- 8 (wt.%) Ex.9 (wt. %) Silicone Base 1 76
  • the mixer was set to heat up the contents to a temperature of 150 o C whilst the screws rotated at about 70rpm.
  • the occlusion means was maintained in the closed position. Mixing continued as mixing chamber of the mixer was heated by means of the mixers own heat source and due to shear heat generated within the chamber due to the mixing process until the mixture in the chamber reached a temperature of from about 150 to 180 o C after about an hour of mixing Silicone Base 1 and functionalised polyolefin 1.
  • the maleic anhydride group X of the functional polyolefin 1 and the amine group(s) Y of the compatibiliser underwent their reaction to enable compatiblisation and formation of the silicone-polyolefin hybrid material product and once the temperature was noted as being between room temperature (about 25 o C) and 50 o C the occlusion means (3) in the conical screw dump extruder was opened allowing the resulting cooled silicone-polyolefin hybrid material to be extruded through extrusion die and be transported to storage or for further processing e.g., into a curable composition.
  • the extruded silicone-polyolefin hybrid material product was utilised to prepare a curable composition by blending the silicone-polyolefin hybrid material product with the Cure Agent (1 part per one hundred (pph) parts of the silicone portion of the silicone-polyolefin hybrid material product, by weight) directly on the two-roll mill until the resulting mass was visually homogeneous, which was then divided up into portions to fill 110% of a mold with internal cavity dimension of 6” by 6” by 2 mm (15.24 cm x 15.24cm x 2mm).
  • the individual portion of extruded silicone-polyolefin hybrid material product was preformed into a flat sheet that is slightly smaller than 6” by 6”, (15.24 cm x 15.24cm) placed in the mold at room temperature.
  • the resulting hybrid compounds were compression molded in a heated hydraulic Greenerd press. They were initially placed between two sheets of brown Teflon and 1/4" aluminum back sheets. The sample was pressed at room temperature for 2-3 minutes to fill out the chase and press out any air pockets after which they were pressed at 175 °C and 1500 psi (10.34 MPa) for 10 minutes and removed from the mold immediately after cure.
  • the cured hybrid elastomer sheets were rested at room temperature for 24 hours before characterization.
  • Ex.9 the same process was followed as undertaken with Ex.1-8 except that the functionalized polyolefin and the unreactive polyolefin were introduced at the same time.
  • the cured compounds were then analysed for their physical properties.
  • tear strength samples the plaque was cut using the ASTM D412C and Tear B die punches to make the tensile and Tear B samples. Specific gravity samples were cut from the scraps of material left over from cutting about the tensile and Tear B samples.
  • Durometer was measured in accordance with Shore A durometer (ASTM D2240), tensile strength and elongation were measured according to ASTM D412, Tear strength was measured in accordance with ASTM D624, Die B, specific gravity was measured using a Mettler Toledo balance in accordance with ASTM D792 and Resilience by Vertical rebound was measured in accordance with ASTM D2632.
  • MDR Moving Die Rheometer
  • Table 3a Physical Property results Ex. Time Durometer Tensile Elongation Modulus at Tear B Resilience (Shore A) Strength at break 100% Ext n Resistance (%)
  • Table 3b Further physical property results Step (iv) Max Temp. MDR - MH MDR - MDR - TS2 Specific Ti ( i ) ( o C) (k ) T90 ( ) ( ) G ity
  • Examples 1 to 9 were a carried out using the Colmec TM CTM-65 conical screw dump extruder (CTM) and it was found that they showed changes in mechanical properties with a change in mixing time which was not possible when using a twin-screw extruder (TSE). Certain properties were found to be significantly different between CTM and TSE methods.
  • the Resilience is an indicator of the sound dampening ability the hybrid materials possess and is shown to be higher when using a CTM for shorter mixing periods. There is also an increase in hardness and modulus when using the CTM broadening the material’s applicability to customer requirements.
  • a silicone polymer base (A) in the form of 30 durometer high strength silicone rubber (HCR) base was prepared in the Colmec TM CTM-65 conical screw dump extruder prior to step (i) of the process.
  • silicone rubber base composition (A) Wt.% Silicone gum 1 was a dimethylvinyl terminated polydimethylsiloxane polymer having a Williams plasticity of about 148mm/100 in accordance with ASTM D-926-08. Silicone gum 2 was a dimethylvinyl terminated polydimethylsiloxane polymer having a Williams plasticity of about 150mm/100 in accordance with ASTM D-926-08. The fumed silica used was CAB-O-SIL TM MS-75 Silica commercially available from Cabot Corporation.
  • Organopolysiloxane 1 is a vinyldimethyl terminated methylvinyl dimethylsiloxane copolymer having a viscosity of approximately 15,000 mPa.s at 25 o C having a vinyl content of 7.7 wt. %.
  • Organopolysiloxane 2 is hydroxy-terminated polydimethylsiloxane polymer having a viscosity of 42 mPa.s in accordance with ASTM D-445.
  • the base was prepared by first introducing Silicone gums 1 and 2, organosiloxane 1 and water into the CTM mixer and mixing same for 5 minutes before flushing the mixer with nitrogen. The fumed silica and treating agents were then added during further mixing.
  • component (A) was further mixed under vacuum and then the CTM was heated to 150 o C.
  • component (B) in the form of Functionalised Polyolefin 1 was introduced after which the process proceeded in the same manner as the earlier examples with the generated silicone base, polyolefin, and compatibilizer are mixed for a desired amount of time before cooling, if desired.
  • the CTM was cooled to room temperature but could be extruded out of the CTM once the temperature had dropped to below 50 o C.
  • the silicone-polyolefin hybrid material was prepared above had an approximate composition as shown in Table 5 below. Table 5: silicone-polyolefin hybrid material starting ingredients. Wt.
  • % CTM Prepared Base (Silicone Base 3) 75.66%
  • the resulting extruded silicone-polyolefin hybrid material product was utilised to prepare a curable composition by blending the silicone-polyolefin hybrid material product with the Cure Agent (1 part per one hundred (pph) parts of the silicone portion of the silicone-polyolefin hybrid material product, by weight) directly on the two-roll mill until the resulting mass was visually homogeneous. They were cured following the cure process utilised in the previous examples. Again, the resulting cured hybrid elastomer sheets were rested at room temperature for 24 hours before characterization.
  • silicone base 3 cure agent was added into silicone base 3 as described in the same manner as for the hybrid material and was cured.
  • the resulting cured sheets for both the catalysed silicone rubber base 3 (C.2) and the resulting catalysed hybrid material (Ex.10) were evaluated with respect to their physical properties and the results are depicted in Table 6 below.
  • Table 6 Physical Property results Ex. Durometer Tensile Strength Elongation Modulus at 100% Specific The test methods used were the same as those indicated above.

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Abstract

L'invention concerne un procédé de fabrication d'un matériau hybride de silicone-polyoléfine à l'aide de bases de caoutchouc de silicone comprenant des polymères de silicone à viscosité élevée (c'est-à-dire supérieure à 1 million de mPa.s à 25 °C), des charges et des matériaux polyoléfiniques appropriés dans une extrudeuse à décharge à vis conique. De tels polymères de silicone à viscosité élevée sont souvent désignés dans l'industrie en tant que gommes polymères de silicone ou gommes de silicone. La divulgation concerne également les matériaux hybrides de silicone-polyoléfine obtenus, leurs utilisations et des produits fabriqués à partir de ceux-ci.
PCT/US2024/048266 2023-11-15 2024-09-25 Fabrication de matériaux hybrides de silicone-polyoléfine Pending WO2025106160A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419593A (en) 1965-05-17 1968-12-31 Dow Corning Catalysts for the reaction of = sih with organic compounds containing aliphatic unsaturation
US3715334A (en) 1970-11-27 1973-02-06 Gen Electric Platinum-vinylsiloxanes
US3814730A (en) 1970-08-06 1974-06-04 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
US6605734B2 (en) 2001-12-07 2003-08-12 Dow Corning Corporation Alkene-platinum-silyl complexes
US7556419B2 (en) 2003-10-28 2009-07-07 Colmec S.P.A. Machine for mixing and extruding rubber-based and silicone-based plastic materials and method therefor
WO2022173908A1 (fr) * 2021-02-10 2022-08-18 Dow Silicones Corporation Élastomères hybrides de silicone et de polyoléfine
WO2023055872A1 (fr) * 2021-09-29 2023-04-06 Dow Global Technologies Llc Élastomères hybrides de silicone et de polyoléfine
US11925911B2 (en) 2018-02-20 2024-03-12 Colmec S.P.A. Twin-screw mixer-extruder, including a presser body for defining a controlled volume of a compounding chamber

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3419593A (en) 1965-05-17 1968-12-31 Dow Corning Catalysts for the reaction of = sih with organic compounds containing aliphatic unsaturation
US3814730A (en) 1970-08-06 1974-06-04 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
US3715334A (en) 1970-11-27 1973-02-06 Gen Electric Platinum-vinylsiloxanes
US6605734B2 (en) 2001-12-07 2003-08-12 Dow Corning Corporation Alkene-platinum-silyl complexes
US7556419B2 (en) 2003-10-28 2009-07-07 Colmec S.P.A. Machine for mixing and extruding rubber-based and silicone-based plastic materials and method therefor
US11925911B2 (en) 2018-02-20 2024-03-12 Colmec S.P.A. Twin-screw mixer-extruder, including a presser body for defining a controlled volume of a compounding chamber
WO2022173908A1 (fr) * 2021-02-10 2022-08-18 Dow Silicones Corporation Élastomères hybrides de silicone et de polyoléfine
WO2023055872A1 (fr) * 2021-09-29 2023-04-06 Dow Global Technologies Llc Élastomères hybrides de silicone et de polyoléfine

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