Manufacture of silicone-polyolefin hybrid materials

Abstract

The present invention relates to a process for the manufacture of silicone-polyolefin hybrid materials in a conical screw tablet press extruder using a silicone rubber base comprising a high viscosity (i.e. greater than 1,000,000 mPa.s at 25°C) silicone polymer, a filler and a suitable polyolefin material. Such high viscosity silicone polymers are commonly referred to in the industry as silicone polymer gums or silicone gums. The present disclosure also relates to the resulting silicone-polyolefin hybrid materials, their uses and products made therefrom.

Description

[0001] This invention relates to a method for manufacturing silicone-polyolefin hybrid materials using a silicone rubber base comprising a high-viscosity (i.e., greater than 1,000,000 mPa·s at 25°C), fillers, and a suitable polyolefin material. Such high-viscosity silicone polymers are commonly referred to in industry as silicone polymer adhesives or silicone rubber. This disclosure also relates to the resulting silicone-polyolefin hybrid materials, their uses, and products made from them.

[0002] Organosilicones are polymeric materials used in many commercial applications, primarily due to their significant advantages over their carbon-based analogues. More specifically known as polymeric siloxanes or polysiloxanes, organosilicones comprise an inorganic silicon-oxygen backbone (⋯–Si–O–Si–O–Si–O–⋯) with organic side groups attached to silicon atoms. The organic side groups can be used to link two or more of these backbones together. By varying the -Si-O- chain length, side groups, and crosslinking, organosilicones with a wide range of properties and compositions can be synthesized, with the consistency of the organosilicon network ranging from liquid to gel to rubber to rigid plastic. Cured organosilicon materials and siloxane-based materials are used in countless end-use applications and environments, including as components in a variety of industrial, home care, and personal care formulations. Many of these materials offer enhanced performance and benefits due to their properties, enabling unique technologies. Because of their highly reliable properties, they can be used in a variety of applications, including, for example, power supplies (e.g., high-voltage electrical insulation), electronics, automotive applications, and consumer applications.

[0003] Unfortunately, despite widespread success in many technologies, the use of cured silicone-based materials remains limited in certain applications, and carbon-based polymers such as polyolefins are often used as alternatives. In many such applications, there is a growing desire for solutions that can utilize the benefits of both cured silicone materials and carbon-based materials such as polyolefins. In some cases, this has led to the manufacture of molded composite parts comprising silicone elastomers and carbon-based polymers such as polyolefins. However, the preparation of such composites has proven difficult due to the lack of adhesion between the silicone elastomer and the polyolefin, which is chemically inert, hydrophobic, and has low surface energy. Therefore, the desired applications of composites of silicone elastomer materials with thermoplastic substrates such as polyolefins are limited because a sufficiently strong bond cannot be formed between the two.

[0004] An alternative is to prepare organosilicon-polyolefin hybrid compositions; however, conventional siloxanes are incompatible with most carbon-based polymers, usually due to their immiscibility and / or antagonistic properties.

[0005] Such hybrid materials, such as silicone-polyolefin (SiPO) hybrids, are typically prepared through reactive compatibility of different materials during a mixing process. The mixing process produces a dispersed phase and a continuous or bulk phase containing the dispersed phase, and a chemical reaction occurs at the surface of the dispersed phase, which makes the dispersed phase compatible and / or incorporated into the continuous material. The mixing process is typically in the form of reactive extrusion (REX) performed on a continuous high-shear equipment such as a twin-screw extruder (TSE). The high temperature used for REX helps provide the heat of reaction required for compatibility. Generally, the resulting mechanical properties of the hybrid material and the morphology of the dispersed polyolefin domains are not affected by variations in mixing operations (such as mixing speed or temperature) performed using a TSE. In the case of manufacturing polyolefin-silicone hybrids in which PO is dispersed within silicone, TSE is the obvious choice for mixing polyolefin-silicone hybrids because silicone requires higher amounts of heat and shear to reduce viscosity, thereby allowing dispersion and promoting the REX reaction.

[0006] This document provides a method for preparing a silicone-polyolefin hybrid material by mixing a silicone polymer base (A) comprising one or more silicone polymers and / or copolymers with one or more functionalized polyolefins (B) and a reactive compatibilizer (C), wherein the silicone polymers and / or copolymers have a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08. The method includes the following steps:

[0007] (i) The silicone polymer base material (A) comprising one or more silicone polymers and / or copolymers is introduced into the mixing chamber of a mixer and mixed while being heated to a predetermined temperature of 100°C to 200°C, wherein the silicone polymer and / or copolymer has, in each case, a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08;

[0008] (ii) At the same time as step (i) or when the silicone polymer base (A) has reached the predetermined temperature of 100°C to 200°C, one or more functionalized polyolefins (B) are introduced into the mixing chamber of the mixer while mixing continues to form an initial silicone-polyolefin hybrid composition mixture.

[0009] (iii) When carried out together with steps (i) and (ii) simultaneously or after step (ii), a polysiloxane polymer having at least one reactive group or a reactive compatibilizer (C) substantially composed of or consisting of such a polymer is introduced into the mixing chamber of the mixer while mixing continues; wherein at least one reactive group of the reactive compatibilizer (C) is capable of reacting with one or more functionalized polyolefins (B); and mixing is carried out simultaneously.

[0010] This forms the initial organosilicon-polyolefin hybrid composition mixture;

[0011] (iv) Continue mixing the initial organosilicon-polyolefin hybrid composition mixture for a predetermined period of time so that the reactive groups of the reactive compatibilizer (C) can react with the functional groups of the functionalized polyolefin (B) to form an organosilicon-polyolefin hybrid material product.

[0012] (v) Cooling the organosilicon-polyolefin hybrid product of step (iv);

[0013] (vi) Extruding the silicone-polyolefin hybrid product of step (iv) or the cooled silicone-polyolefin hybrid product of step (v) from the mixer at a temperature of 25°C to 75°C.

[0014] The mixer is characterized as follows: it is a conical screw tableting extruder comprising a conical twin-screw mixing chamber containing two counter-rotating conical screws converging toward an extrusion die having an inlet and an outlet, wherein the passage through the extrusion die is controlled by a shut-off device such that the outlet of the extrusion die is adapted to be closed by the shut-off device until the product of step (iv) or (v) is extruded from the conical screw tableting extruder, and is adapted to be opened after step (iv) or (v) if or when the silicone-polyolefin hybrid product will be further processed or stored outside the conical screw tableting extruder, such that during mixing, the contents of the mixer are driven toward the extrusion die by a pair of counter-rotating conical screws, then forced back when the extrusion die is closed by the shut-off device, and then opened after step (iv) or (v) to allow the product of step (iv) or (v) to be extruded through the extrusion die for further processing and / or storage.

[0015] Organosilicon-polyolefin hybrid products that can be obtained by or through the methods described above are also provided.

[0016] Also provided is the use of a conical screw extruder as an apparatus for preparing silicone-polyolefin hybrid composition products, which are prepared by mixing a silicone polymer base (A) comprising one or more silicone polymers and / or copolymers, one or more functionalized polyolefins (B), and a reactive compatibilizer (C), the silicone polymers and / or copolymers having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08, the method comprising the following steps:

[0017] (i) The silicone polymer base material (A) is introduced into the mixing chamber of the mixer and mixed while being heated to a predetermined temperature of 100°C to 200°C;

[0018] (ii) Simultaneously with step (i) or once the silicone polymer base material (A) has reached the predetermined temperature of 100°C to 200°C, one or more functionalized polyolefins (B) are introduced into the mixing chamber of the mixer while mixing continues to form the initial silicone-polyolefin hybrid composition mixture;

[0019] (iii) When carried out together with or after steps (i) and (ii), a silicone polymer containing at least one functional group or a reactive compatibilizer (C) thereof is introduced into the mixing chamber of the mixer while mixing continues; wherein the functional group of the compatibilizer is capable of reacting with the polyolefin of step (ii) having reactive groups grafted thereon; and mixing is carried out simultaneously.

[0020] This forms the initial organosilicon-polyolefin hybrid composition mixture;

[0021] (iv) Continue mixing the initial organosilicon-polyolefin hybrid composition mixture for a predetermined period of time so that the reactive groups of the reactive compatibilizer (C) can react with the functional groups of the functionalized polyolefin (B) to form an organosilicon-polyolefin hybrid material product.

[0022] (v) Cooling the organosilicon-polyolefin hybrid product of step (iv);

[0023] (vi) Extruding the silicone-polyolefin hybrid product of step (iv) or the cooled silicone-polyolefin hybrid product of step (v) from the mixer at a temperature of 25°C to 75°C.

[0024] The mixer is characterized as follows: it is a conical screw tableting extruder comprising a conical twin-screw mixing chamber containing two counter-rotating conical screws converging toward an extrusion die having an inlet and an outlet, wherein the passage through the extrusion die is controlled by a shut-off device such that the outlet of the extrusion die is adapted to be closed by the shut-off device until the product of step (iv) or (v) is extruded from the conical screw tableting extruder, and is adapted to be opened after step (iv) or (v) if or when the silicone-polyolefin hybrid composition will be further processed or stored outside the conical screw tableting extruder, such that during mixing, the contents of the mixer are driven toward the extrusion die by a pair of counter-rotating conical screws, then forced back when the extrusion die is closed by the shut-off device, and then opened after step (iv) or (v) to allow the product of step (iv) or (v) to be extruded through the extrusion die for further processing and / or storage.

[0025] To avoid any doubt, a hybrid material is a combination of two different materials that are compatible to form a stable heterogeneous substance with synergistic properties. Therefore, the object of this disclosure is to provide a suitable method for effectively reactively compatibilizing an organosilicon polymer base comprising one or more organosilicon polymers and / or copolymers having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08 with one or more functionalized polyolefins (B) to an acceptable organosilicon-polyolefin hybrid material using a reactive compatibilizer (C). This method utilizes the reactive compatibilizer (C) to generate a dispersed phase (e.g., functionalized polyolefin (B)) and a continuous or bulk phase (e.g., one or more organosilicon polymers and / or copolymers having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08) (or vice versa), wherein the reactive compatibilizer comprises or is composed of an organosilicon polymer having at least one functional group that reacts with reactive groups of one or more functionalized polyolefins (B) at the surface of the dispersed phase, thereby making the dispersed phase compatible and / or incorporated into the continuous material.

[0026] Surprisingly, it was found that using a conical discharge extruder does indeed seem to affect the mechanical properties of the resulting hybrid material and the morphology of the dispersed polyolefin domains, while also appearing to be more energy-efficient than using a conventional twin-screw extruder.

[0027] (A) Organosilicon polymer base material

[0028] The silicone polymer base (A) described herein comprises one or more silicone polymers and / or copolymers (A)(1) having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08 and one or more fillers (A)(2) selected from reinforcing fillers such as pyrolytic silica and precipitated silica, non-reinforcing fillers, and combinations of reinforcing and non-reinforcing fillers.

[0029] To avoid any doubt, the silicone polymer base does not contain any curing agents and / or crosslinking agents; that is, it is uncatalyzed and therefore cannot be cured into elastomers, etc., until it is converted into a curable compound composition containing curing agents and / or crosslinking agents (if desired) and other additives.

[0030] Fillers, particularly reinforcing fillers, are incorporated into silicone rubber materials to enhance the strength and toughness of the cured elastomer. Reinforcing fillers are highly surface-active and have a large surface area, reinforcing the cured siloxane polymer matrix through hydrogen bonding and other mechanisms. Unreinforcing fillers typically have a lower surface area and are primarily used to reduce the cost of silicone rubber. Reinforcing fillers generally enhance at least one of the following mechanical properties: tensile strength, tear strength and flexural fatigue resistance, wrinkle hardening, improved resistance to compression set, and can provide silicone elastomers with, for example, excellent heat aging resistance.

[0031] (A)(1) One or more having Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08 Organosilicon polymers and / or copolymers

[0032] As understood by those skilled in the art, organosilicon polymers and / or copolymers (A)(1) having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08 are silicon-based compounds comprising a siloxane backbone (i.e., at least a semi-continuous chain consisting of inorganic silicon-oxygen-silicon groups (i.e., -Si-O-Si-)) wherein organosilicon and / or organic side groups are attached to silicon atoms. Such siloxanes are typically characterized by the number, type, and / or proportion of [M], [D], [T], and / or [Q] units / silyloxy groups (each representing a structural unit of the various functional groups present in a polysiloxane, such as organosilicon and organopolysiloxane). Specifically, [M] represents the general formula R''3SiO 1 / 2 The single functional unit; [D] represents the general formula R''2SiO 2 / 2 The bifunctional unit; [T] represents the general formula R''SiO 3 / 2 The three functional units; and [Q] represents the general formula SiO 4 / 2 The four functional units are shown in the following general structural part:

[0033] .

[0034] In these general structural moieties, each R'' is independently a monovalent or polyvalent substituent. As understood in the art, there are no particular limitations on the specific substituents applicable to each R'' (e.g., they can be monoatomic or polyatomic, organic or inorganic, linear or branched, substituted or unsubstituted, aromatic, aliphatic, saturated or unsaturated, etc., and various combinations thereof). In typical examples, each R'' is independently selected from hydrocarbon groups, alkoxy and / or aryloxy groups, and silanoxy groups. Regarding the hydrocarbon groups applicable to R'', examples generally include monovalent hydrocarbon moieties and their derivatives and modifications, which can be independently substituted or unsubstituted, straight-chain, branched, cyclic, or combinations thereof, and saturated or unsaturated. Regarding such hydrocarbon groups, the term "unsubstituted" describes a hydrocarbon moieties consisting of carbon and hydrogen atoms, i.e., free of heteroatom substituents. The term "substituted" describes a hydrocarbon moiety in which at least one hydrogen atom is replaced by an atom or group other than hydrogen (e.g., a halogen atom, an alkoxy group, an amine group, etc.) (i.e., as a side-attached or terminal substituent), a carbon atom within the chain / main chain of the hydrocarbon is replaced by an atom other than carbon (e.g., a heteroatom, such as oxygen, sulfur, nitrogen, etc.) (i.e., as part of the chain / main chain), or both conditions are met simultaneously. Therefore, a suitable hydrocarbon group may comprise or be a hydrocarbon moiety having one or more substituents (i.e., attached to and / or integrated with the carbon chain / main chain) in and / or on its carbon chain / main chain, such that the hydrocarbon moiety may comprise or otherwise be referred to as an ether, ester, etc. Straight-chain and branched hydrocarbon groups may be independently saturated or unsaturated, and when unsaturated, may be conjugated or non-conjugated. Cyclic hydrocarbon groups can be monocyclic or polycyclic independently and encompass cycloalkyl groups, aryl groups, and heterocycles, which can be aromatic, saturated, non-aromatic, and / or non-conjugated. Examples of combinations of straight-chain hydrocarbon groups and cyclic hydrocarbon groups include alkylaryl groups, aralkyl groups, etc. General examples suitable for use in hydrocarbon groups or as hydrocarbon moieties include alkyl groups, aryl groups, etc., and their derivatives, modifications, and combinations. Examples of alkyl groups include methyl, ethyl, propyl (e.g., isopropyl 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, etc. (i.e., other straight-chain or branched saturated hydrocarbon groups, for example, having more than 6 carbon atoms). Examples of aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, dimethylphenyl, etc., as well as their derivatives and modifications, which may overlap with alkylaryl groups (e.g., benzyl) and aralkyl groups (e.g., tolyl, dimethylphenyl, etc.).

[0035] The organosilicon polymer and / or copolymer of component (A)(1) may also contain substituted alkyl groups such as halogenated hydrocarbon groups and reactive groups such as alkenyl, alkynyl, alkoxy, aryloxy, and hydroxyl groups; however, in this case, it is desirable that any such reactive groups present do not react with the Y group of the functionalized polyolefin (B) and the X group of the reactive compatibilizer (C). For the avoidance of doubt, non-reactive or unreactive groups should be considered to include reactive groups that do not react with X or Y at a competing rate under the reaction conditions of X and Y. The terms non-reactive and unreactive as used herein are interchangeable and are intended to have the same meaning.

[0036] General examples of halogenated hydrocarbon groups include halogenated derivatives of the hydrocarbon moiety described above, such as halogenated alkyl groups (e.g., any of the alkyl groups described above, wherein one or more hydrogen atoms are replaced by halogen atoms (such as F or Cl), aryl groups (e.g., any of the aryl groups described above, wherein one or more hydrogen atoms are replaced by halogen atoms (such as F or Cl), and combinations thereof. Examples of 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 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl, etc., as well as their derivatives and modifications. Examples of halogenated aryl groups include chlorobenzyl, pentafluorophenyl, fluorobenzyl groups, etc., as well as their derivatives and modifications.

[0037] Regarding reactive groups, examples of alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, cyclohexenyl groups, and their derivatives and modifications; examples of alkynyl groups may be exemplified by, but are not limited to, ethynyl, propynyl, and butynyl groups. Regarding alkoxy and / or aryloxy groups applicable to R'', examples generally include hydrocarbon groups (e.g., alkyl, aryl, etc.) bonded to silicon atoms via oxygen atoms (i.e., forming silyl ethers). The hydrocarbon groups in these examples may include any of the hydrocarbon groups described above. Regarding silanoxy groups applicable to R'', examples generally include silanoxy groups represented by combinations of the above [M], [D], [T], and / or [Q] units.

[0038] However, the organosilicon polymers and / or copolymers of component (A)(1) are essentially linear, i.e. substantially free of branching attributable to [T] units and / or [Q] units, and are generally referred to as “linear”. However, it should be understood that linear (i.e., MDM type) siloxanes may contain individual molecules having T and / or Q units, and the average unit formula based on the siloxane as a whole is still considered “linear”, and furthermore, they are preferably free of any halogenated hydrocarbon groups.

[0039] Therefore, each of the one or more silicone polymers and / or copolymers having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08 in (A)(1) may, for example, be selected from polydimethylsiloxane, alkylmethylpolysiloxane, alkylarylpolysiloxane or copolymers thereof (wherein the alkyl group referred to means any suitable alkyl group, alternatively having two or more carbons), and thus, for illustrative purposes, may be:

[0040] Trialkyl-terminated polydimethylsiloxanes, trialkyl-terminated dimethylmethylphenylsiloxanes, dialkylalkenyl-terminated polydimethylsiloxanes, such as dimethylvinyl-terminated polydimethylsiloxanes; dialkylalkenyl-terminated dimethylmethylphenylsiloxanes, such as dimethylvinyl-terminated dimethylmethylphenylsiloxanes; trialkyl-terminated dimethylmethylvinyl polysiloxanes; dialkylvinyl-terminated dimethylmethylvinyl polysiloxane copolymers; dialkylvinyl-terminated methylphenyl polysiloxanes, dialkylalkenyl-terminated methylvinylmethylphenylsiloxanes; dialkylalkenyl-terminated methylvinyldiphenylsiloxanes; dialkylalkenyl-terminated methylvinylmethylphenyldimethylsiloxanes; trimethyl-terminated methylvinylmethylphenylsiloxanes; trimethyl-terminated methylvinylmethylphenylsiloxanes; or trimethyl-terminated methylvinylmethylphenyldimethylsiloxanes, provided that the alkenyl group does not react with X or Y. In one embodiment, one or more silicone polymers and / or copolymers (A)(1) having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08 are trialkyl-terminated polydimethylsiloxanes or trialkyl-terminated dimethylmethylphenylsiloxanes.

[0041] Such one or more silicone polymers and / or copolymers having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08 (A)(1) are organopolysiloxane polymer adhesives. Organopolysiloxane polymer adhesives have a viscosity value of at least 1,000,000 mPa·s at 25°C, and typically several million mPa·s at 25°C. Due to the difficulty in measuring these viscosity values, adhesives are often described by their Williams plasticity value according to ASTM D-926-08 rather than by viscosity. Therefore, organopolysiloxane adhesives have Williams plasticity of 75mm / 100 to 500mm / 100 as measured by ASTM D-926-08, alternatively 100mm / 100 to 450mm / 100 as measured by ASTM D-926-08, alternatively 120mm / 100 to 400mm / 100 as measured by ASTM D-926-08, and alternatively 120mm / 100 to 375mm / 100 as measured by ASTM D-926-08.

[0042] Typically, when present, for each organopolysiloxane polymer containing at least two silicon-bonded alkenyl groups per molecule of component (a), the alkenyl and / or alkynyl content (e.g., vinyl content) of the polymer is from 0.01 wt% to 3 wt%, alternatively, the organopolysiloxane or component (a) of each organopolysiloxane containing at least two unsaturated groups per molecule is from 0.01 wt% to 2.5 wt%, alternatively, component (a) is from 0.001 wt% to 2.0 wt%, or 0.01 wt% to 1.5 wt%, wherein the 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 infrared analysis according to ASTM E168.

[0043] (A)(2) Packing

[0044] Component (A)(2) comprises at least one reinforcing filler, a non-reinforcing filler, or a combination thereof. The filler (A)(2) may be at least one reinforcing filler. Preferably, the reinforcing filler is in a finely granulated form. The reinforcing filler of the filler (A)(2) may be exemplified by pyrolytic silica, colloidal silica, and / or precipitated silica.

[0045] Precipitated silica, pyrolytic silica, and / or colloidal silica are particularly preferred due to their relatively high surface area (typically at least 50 m² / g (BET method according to ISO 9277: 2010)); alternatively, a surface area of ​​50 m² / g to 450 m² / g (BET method according to ISO 9277: 2010) is typically used, and alternatively, a surface area of ​​50 m² / g to 300 m² / g (BET method according to ISO 9277: 2010) is used. All these types of silica are commercially available. The reinforcing fillers of filler (A)(2) are naturally hydrophilic and are preferably treated with one or more treatment agents to make them hydrophobic. Such surface-modified reinforcing fillers are finely chopped because they do not agglomerate and can be uniformly incorporated into component (A)(1) to produce the organosilicon polymer matrix (A) described herein.

[0046] Given that silica-reinforced fillers are naturally hydrophilic, they are typically treated in situ with a hydrophobic treatment agent during the manufacturing process of the silicone polymer base material, unless they have been pretreated to give the surface appropriate hydrophobicity. Any suitable treatment agent capable of making the silica surface hydrophobic can be used. For example, they can be selected from suitable organosilanes, polydiorganosiloxanes, or organosilazanes, such as hexaalkyldisilazane, short-chain siloxane diols, and / or short-chain fluorosiloxane diols.

[0047] Specific examples of hydrophobic agents include, but are not limited to, silanol-terminated trifluoropropylmethylsiloxane, silanol-terminated vinylmethyl (ViMe)siloxane, silanol-terminated methylphenyl (MePh)siloxane, liquid hydroxydimethyl-terminated polydiorganosiloxane containing an average of 2 to 20 repeating units of diorganosiloxane per molecule, hydroxydimethyl-terminated phenylmethylsiloxane, hexaorganodisiloxanes such as hexamethyldisiloxane and divinyltetramethyldisiloxane. Alkanes; hexaorganodisilazanes, such as hexamethyldisilazane (HMDZ), divinyltetramethyldisilazane and tetramethylbis(trifluoropropyl)disilazane; hydroxydimethyl-terminated polydimethylmethylvinylsiloxane, octamethylcyclotetrasiloxane and silanes, including but not limited to methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, trichloromethylsilane.

[0048] A small amount of water and a silica treatment agent as a processing aid may be added.

[0049] The filler (A)(2) may also contain or consist of one or more non-reinforcing fillers. When present, suitable non-reinforcing fillers for use in the silicone polymer matrix (A) may include crushed quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide, precipitated calcium carbonate, ground calcium carbonate, zinc oxide and carbon black, talc, hydroxyapatite, and wollastonite. Other fillers that may be used in addition to the above include alumina, calcium sulfate (anhydrite), gypsum, calcium sulfate, magnesium carbonate, clay (such as kaolin), magnesium hydroxide (e.g., brucite), graphite, copper carbonate (e.g., malachite), nickel carbonate (e.g., nickel carbonate), barium carbonate (e.g., barite), and / or strontium carbonate (e.g., strontium strontium).

[0050] Other fillers may include silicates selected from the group consisting of: olivine; garnet; aluminosilicates; cyclosilicates; chain silicates; and platy silicates. Olivine includes silicate minerals such as, but not limited to, forsterite and Mg₂SiO₄. Garnet includes ground silicate minerals such as, but not limited to, pyrope; Mg₃Al₂Si₃O₄. 12 Grossular garnet and Ca2Al2Si3O 12 Aluminosilicates include milled silicate minerals such as, but not limited to, sillimanite; Al₂SiO₅; mullite; 3Al₂O₃·2SiO₂; kyanite; and Al₂SiO₅. Cyclosilicates can be used as non-reinforcing fillers; these include silicate minerals such as, but not limited to, cordierite and Al₃(Mg,Fe)₂[Si₄AlO₂]. 18 Chain silicates include ground silicate minerals, such as, but not limited to, wollastonite and Ca[SiO3]. Flake silicates may alternatively or otherwise be used as non-reinforcing fillers, wherein suitable classes contain silicate minerals, such as, but not limited to, mica; K2Al 14 [Si6Al2O 20 (OH)4; pyrophyllite; Al4[Si8O 20 (OH)4; Talc; Mg6[Si8O 20 (OH)4; serpentine, for example asbestos; kaolinite; Al4[Si4O] 10 (OH)8; and vermiculite. The non-reinforced filler can also be treated with a hydrophobic agent, as discussed above for reinforced fillers. Preferably, component (A)(2) comprises one or more reinforcing fillers and optionally one or more non-reinforced fillers.

[0051] The surface treatment of filler (A)(2) can be performed before or in situ before introduction into the composition (i.e., by blending these components together at a temperature of about 25°C or higher until the filler is fully treated, in the presence of at least a portion of the other components of the composition herein). Typically, untreated filler (A)(2) is treated in situ with a treatment agent in the presence of component (A)(1), which results in the preparation of an uncatalyzed organosilicon polymer base as described above.

[0052] The treatment agent may be present in an amount of 0.1% to 20% by weight of the total base material starting component, alternatively 0.5% to 15% by weight of the total base material starting component, and alternatively 1% to 10% by weight of the total organosilicon base material content (which = 100% by weight).

[0053] Preferably, one or more fillers (A)(2) are present in the silicone polymer base material (A) in an amount of 5% to 55% by weight of the combined weight of (A)(1) + (A)(2), alternatively 5% to 50% by weight of the combined weight of (A)(1) + (A)(2), alternatively 5% to 45% by weight of the combined weight of (A)(1) + (A)(2), alternatively 5% to 40% by weight of the combined weight of (A)(1) + (A)(2).

[0054] When the organosilicon polymer base material (A) forms a continuous phase in the organosilicon-polyolefin hybrid material, the organosilicon polymer base material (A) accounts for at least 50% by weight of the starting components used to prepare the organosilicon-polyolefin hybrid material, wherein:

[0055] Organosilicon polymer base (A) + functionalized polyolefin (B) + reactive compatibilizer (C) = 100% by weight

[0056] Or when an optional non-reactive polyolefin (D) is present as described below.

[0057] Organosilicon polymer base (A) + functionalized polyolefin (B) + reactive compatibilizer (C) + non-reactive polyolefin (D) = 100% by weight

[0058] Preferably, in any of the above cases, the amount of the organosilicon polymer base (A) is at least 55% by weight of the starting component for preparing the organosilicon-polyolefin hybrid material, and alternatively at least 60% by weight of the starting component for preparing the organosilicon-polyolefin hybrid material.

[0059] One or more functionalized polyolefins (B)

[0060] As noted above, the organosilicon-polyolefin composition also comprises a functionalized polyolefin (B). Each molecule of the functionalized polyolefin (B) contains, on average, at least one functional group Y, for example, as a substituent in the polyolefin backbone. In some embodiments, each molecule of the functionalized polyolefin (B) contains, on average, at least two functional groups Y. As described herein, functional group Y is capable of reacting with functional group X of the reactive compatibilizer (C) and forming a bond between them. Therefore, it should be understood that component (B) of the organosilicon-polyolefin composition generally comprises a polyolefin prepared with functional group Y as a substituent, obtained with functional group Y as a substituent, or otherwise functionalized to include functional group Y as a substituent. Thus, the functionalized polyolefin (B) may comprise, and alternatively may be, terminally substituted (i.e., functionally group-terminated) polyolefins, side-chain substituted polyolefins, or combinations thereof.

[0061] Generally, examples of polyolefins suitable for functionalized polyolefins (B) include polymers prepared from olefinic monomers, olefinic macromonomers, and oligomers, as well as combinations thereof. Regardless of the actual synthetic route for preparing functionalized polyolefins (B), those skilled in the art will readily understand the range of polyolefin components of functionalized polyolefins (B) in terms of their constituent parts (or theoretical constituent parts) (i.e., the olefinic base monomers polymerized to prepare the polyolefin). The term "olefin" as used in the context of the base monomers constituting functionalized polyolefins (B) refers to the presence of olefinically unsaturated end groups, meaning it can polymerize with the olefinically unsaturated groups of other olefinic monomers to provide a polyolefin. In this way, "polyethylene" should be understood as a polyolefin derived from or theoretically capable of being derived from the monomer ethylene (which is the smallest olefinically unsaturated compound). Similarly, a polyethylene-methacrylate copolymer is a polyolefin derived from or theoretically capable of being derived from the comonomers ethylene and methacrylate, wherein the latter monomer contains terminal olefinically unsaturated groups, i.e., α-olefins (e.g., ~C=CH2). Therefore, it should be understood that in a typical implementation, the functionalized polyolefin (B) comprises a poly-α-olefin backbone.

[0062] The polyalphaolefin backbone of functionalized polyolefins (B) is not particularly restricted, and generally contains components derived from, or at least theoretically capable of being derived from, those having the general formula R. 2 The monomeric unit of an α-olefin with 2C=CH2, wherein each R 2 It is a hydrogen or hydrocarbon group (i.e., a substituted or unsubstituted hydrocarbon group), such as any of the above. For example, in some embodiments, an R 2 It is methyl and another R 2 It is an ester carbon, such that the α-olefin is a methacrylate (e.g., methyl methacrylate or ethyl methacrylate, where the other R is an ester carbon). 2 (These are methyl ester or ethyl ester, respectively). In some embodiments, at least one R 2It is hydrogen and α-olefins have the general formula R 2 CH=CH2, where R 2 Selected from hydrogen and straight-chain or branched hydrocarbon groups having 1 to 12, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 or 2 carbon atoms. Such hydrocarbon groups may be substituted or unsubstituted, and as per the above with respect to R'' and R... 1 The appropriate description of the hydrocarbon group is illustrated below. However, it should be understood that oligomers of such α-olefins can also be used to prepare polyα-olefin backbones. For example, polyethylene (PE) oligomers can be used to prepare polyethylene polymers, which can also be prepared using ethylene as the sole monomer. Similarly, polyethylene (PE) and polypropylene (PP) oligomers can be copolymerized to prepare polyethylene-polypropylene (PE-PP) copolymers, such as PE-PP block copolymers. Examples of other oligomers that can be used to prepare polyα-olefin backbones of functionalized polyolefins (B) include polypropylene oligomers, polybutene oligomers, polyisobutylene oligomers, polyisoprene oligomers, polybutadiene oligomers, and combinations thereof, such as polyethylene / polypropylene oligomers and copolymers, polyethylene / polybutene oligomers and copolymers, poly(ethylene / butene)-polyisoprene oligomers and copolymers, etc.

[0063] In some embodiments, the functionalized polyolefin (B) comprises a polyalpha-olefin backbone containing monomer units selected from ethylene, propylene, butene, and 2-methyl-propylene (i.e., isobutylene). In these or other embodiments, the polyalpha-olefin backbone comprises monomer units derived from (or theoretically capable of being derived from) alpha-olefins exemplified by: hexene, hepten, octene, styrene, acrylates, or methacrylate compounds (e.g., acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylates, or methacrylates, such as C1-C of acrylic acid or methacrylic acid). 12 Alkyl esters, dienes (such as butadiene), or combinations thereof. Therefore, it should be understood that functionalized polyolefins (B) may comprise, and alternatively may be, homopolymers (i.e., having only one type of monomeric unit, or prepared from oligomers of only one monomer or only one monomer) or interpolymers (i.e., having at least two different monomeric subunits, typically prepared from oligomers of at least two monomers or containing two or more monomeric subunits). It should be understood that the term "interpolymer" encompasses copolymers and terpolymers, i.e., polymers each containing two or three different monomeric units, and polymers prepared from four, five, six, or more monomers.

[0064] In certain embodiments, the functionalized polyolefin (B) comprises functionalized polyethylene, polypropylene, or a polyethylene-α-olefin copolymer. In some such embodiments, the polyethylene-α-olefin copolymer is selected from copolymers and terpolymers comprising polyethylene and at least one of polypropylene and polybutene. Various forms of such polyolefins may also be used. For example, the density (ρ) of the polyethylene may be high-density polyethylene (HDPE, ρ ≥ 0.941 g / cm³). 3 Medium density (MDPE, ρ=0.926g / cm³) 3 Up to 0.940 g / cm 3 Low density (LDPE, ρ=0.910g / cm³) 3 Up to 0.940 g / cm 3 or ultra-low density (ULDPE, ρ≤0.880g / cm³) 3 ) and their variants, such as linear low-density polyethylene (LLDPE, ρ=0.915g / cm³). 3 Up to 0.925 g / cm 3 While such polyethylenes are distinguished from each other by density, those skilled in the art will understand that various other physical properties of such variants also differ and can be selected to impart specific properties to silicone-polyolefin compositions, as well as curable compositions and cured products that can be prepared therefrom.

[0065] As described above, each molecule of functionalized polyolefin (B) contains, on average, at least one, and optionally at least two, functional groups Y. For illustrative purposes, functionalized polyolefin (B) can be represented by the general formula L(-Y). l Let L be the polyolefin backbone, and Y be a functional group as described above, with subscript l ≥ 1. It should be understood that each functional group Y can be independently chosen in each part indicated by subscript l, which is at least one, alternatively at least two, but theoretically much larger, as will be understood given the description of the degree of substitution of the functionalized polyolefin (B). Furthermore, there are no particular restrictions on the position of each functional group Y along the polyolefin backbone L, such that any functional group Y can represent an end group or a side group.

[0066] In some implementations, the functionalized polyolefin (B) includes the following common unit formula:

[0067] R 4 [CH2C(R 3 (Y)] o [CH2CH(R 3 )] p R 4

[0068] Each Y is an independently chosen functional group as described above, and each R... 3Independently selected from H and substituted and unsubstituted hydrocarbon groups, each R 4 is an independently selected end group, and the subscripts o and p are each mole fractions such that o + p = 1, provided that 0 < o < 1 and 0 < p < 1. The functionalized polyolefin (B) contains at least one, alternatively at least two, functional groups Y, and the portions indicated by the subscripts o and p can be in any order in the functionalized polyolefin (B).

[0069] Referring to the general unit formula of the above functionalized polyolefin (B), those skilled in the art will understand that the group R 3 is generally selected or otherwise controlled based on the specific α-olefin monomer used to prepare the functionalized polyolefin (B) or at least its main chain. For example, in the case where the functionalized polyolefin (B) is a functionalized polypropylene, R 3 is a methyl group in each portion indicated by the subscript k. In such cases, the nature of R 3 in the portion indicated by the subscript j will depend on how the functionalized polyolefin (B) is prepared. Specifically, in the case where such a functionalized polyethylene is a copolymer prepared from polypropylene and an α-olefin containing the group Y, R 3 will be H in each portion indicated by the subscript o (different from the methyl group R 3 in the portion indicated by the subscript p). On the other hand, in the case where such a functionalized polypropylene is a polypropylene homopolymer grafted with the functional group Y (e.g., via a radical-mediated graft), R 3 will generally be a methyl group throughout the functionalized polyolefin (B). Therefore, it should be understood that any R 3 can be selected such that any one of the portions indicated by the subscript p can reflect the polymerization product of any α-olefin monomer described herein, or alternatively, graft-functionalized onto a polymer prepared from such an α-olefin.

[0070] In view of the above, it should be understood that each R 3 can be the same as or different from any other R 3 of the functionalized polyolefin (B). In certain embodiments, each R 3 is the same as each other R 3 of the functionalized polyolefin (B). For example, in some such embodiments, each R 3 is a methyl group. In other embodiments, at least one R 3 is different from at least one other R 3 of the functionalized polyolefin (B). For example, in certain embodiments, R 3 is predominantly hydrogen throughout the functionalized polyolefin (B) (i.e., from an ethylene monomer), where a small portion of R 3 is selected from alkyl groups (i.e., from a propylene or higher α-olefin monomer).

[0071] As described above, each R 4 These are independently selected terminal groups. More specifically, each R 4 Generally, R refers to monomers from the terminal reaction of the polymerization of functionalized polyolefins (B), polymerization byproducts (i.e., from radial initiation, propagation, and / or termination steps, etc.), or simply hydrogen atoms. Those skilled in the art will understand that R 4 Therefore, there are no particular restrictions, and the choice will generally depend on the route of preparation of the functionalized polyolefin (B), and it is usually present in a small amount in the functionalized polyolefin (B) without substantially affecting the average unit formula indicated by the subscripts o and p. Therefore, it should be understood that for the compositions and methods provided herein, R 4 This usually indicates a non-reactive group.

[0072] As described above, each molecule of the functionalized polyolefin (B) contains at least one, and optionally at least two, functional groups, which are represented by part Y in the general unit formula of the functionalized polyolefin (B). Generally, the functional group Y is selected based on the functional group X of the reactive compatibilizer (C), such that the functionalized polyolefin (B) reacts with the reactive compatibilizer (C) in a coupling reaction involving functional groups X and Y. More specifically, as described above, the functional group Y of the functionalized polyolefin (B) can react with the functional group X of the reactive compatibilizer (C) and form a bond between them after the reaction. In other words, a functional group Y and a functional group X can react together (i.e., via addition coupling / crosslinking reaction) to covalently bond the functionalized polyolefin (B) and the reactive compatibilizer (C) together.

[0073] Therefore, each functional group Y contains functional groups that can participate in the above-described coupling / crosslinking reactions (such as functional groups via substitution, addition, coupling, or combinations thereof), as well as any specific variants described above regarding functional group X. Specific examples of such reactions include nucleophilic substitution, ring-opening addition, alkoxylation and / or transalkoxylation, hydrosilylation, olefin metathesis, condensation, radical coupling and / or polymerization, and combinations thereof.

[0074] Therefore, functional group Y may include, or alternatively, functional groups or various combinations thereof that are capable of hydroaddition, condensation, substitution, nucleophilicity or other reactions with functional group X (e.g., grafting, linking, etc.). Therefore, functional group Y can include or be hydrosilylated functional groups (e.g., silicon-bonded hydrogen atoms, alkene (i.e., alkene-bonded) unsaturated groups such as alkenyl groups, alkynyl groups, etc.), condensable groups (e.g., hydroxyl groups, carboxyl groups, methanol groups, alkoxysilyl groups, silanol groups, amide groups, acid anhydride groups, etc., or hydrolyzable and subsequently condensable groups), substitutable groups (e.g., "leaving groups" as understood in the art, such as halogen atoms, or other groups that are stable in ionic form once substituted, or functional groups containing such leaving groups, such as esters, acid anhydrides, amides, epoxides, etc.), nucleophilic groups (e.g., heteroatoms with lone pairs of electrons, anions or anionizable groups, such as hydroxyl groups (e.g., the hydroxyl group of methanol), amine groups, thiol groups, silanol groups, carboxylic acid groups, groups, etc.), electrophilic groups (e.g., isocyanates, epoxides, etc.) or various combinations thereof.

[0075] In some embodiments, each functional group Y is a hydrosilylation-capable group. Examples of such hydrosilylation-capable groups include olefinic unsaturated groups (e.g., olefinic unsaturated groups) described above with respect to hydrosilylation-capable groups applicable to functional group X. In specific embodiments, each functional group Y comprises, alternatively, a vinyl-substituted organosilicon group (e.g., including vinylsilyl groups).

[0076] In embodiments where functional group Y comprises one of the above-mentioned olefinic unsaturated groups, it should be understood that functional group Y may further comprise a divalent linking group between the olefinic unsaturated group and a carbon atom of the polyolefin backbone of the functionalized polyolefin (B). In some embodiments, each functional group Y comprises, alternatively, a methacryl group, a methacryloxy group, or a methacrylate group.

[0077] Other examples of groups capable of hydrosilylation suitable for functional group Y include hydride silyl groups. Examples of such hydride silyl groups are generally derived from the formula – [Z 3 ] q –Si(R 5 )2H represents, where Z 3 It is a divalent linker, with the subscript q being 0 or 1, and each R 5Independently, it is an H or hydrocarbon group. Such a portion may be selected based on or otherwise provided based on a specific α-olefin-functionalized organosilicon compound polymerized in the preparation of the functionalized polyolefin (B). For example, in some embodiments, the functionalized polyolefin (B) comprises a copolymer of ethylene and 7-octenyldimethylsilane, such that the aforementioned general formula unit formula and the sub-formula of functional group Y of the functionalized polyolefin (B), each R 3 It is H, each subscript q is 1, and each linking group is Z. 3 It is –(CH2)6–, and each R 5 The methyl group is present. In specific embodiments, the functionalized polyolefin (B) comprises the polymerization product of ethylene, an alkenyl functionalized silane compound, and optionally one or more additional α-olefins (e.g., propylene, butene, etc.). Examples of suitable alkenyl functionalized silane compounds in such embodiments include 7-octenyldimethylsilane (ODMS), 5-hexenyldimethylsilane (HDMS), allyldimethylsilane (ADMS), and combinations thereof. It should be understood that such alkenyl functionalized silane compounds can also be grafted onto polyolefin polymers to prepare functionalized polyolefin (B). There are no particular limitations on the specific methods used to prepare functionalized polyolefin (B), and many examples of such methods are known in the art.

[0078] In addition to the foregoing examples, those skilled in the art will understand that other α-olefin-functionalized organosilicon compounds can also be used to prepare functionalized polyolefins (B) to obtain hydride silyl groups suitable for the functional group Y. More specifically, such organosilicon compounds can be prepared by the formula H₂C=C(H)–[Z 3 ] q –Si(R 5 )2H means that each R 5 Z 3 The subscript q is as defined above. In some cases, the divalent linker Z... 3 It can be a silyl or silanoxy group. In this case, hydrosilylation is not the preferred route because a suitable catalyst is required (as discussed elsewhere), but it is certainly the choice for the reaction between X and Y if needed.

[0079] In some embodiments, each functional group Y is a condensation-capable group, i.e., capable of participating in a condensation reaction. In specific embodiments, each functional group Y comprises a condensation-capable group selected from anhydride groups, amine groups, silanol groups, methanol groups, and alkoxysilyl groups.

[0080] Examples of suitable anhydrides and amines for functional group Y generally include those described above with respect to condensation-capable groups suitable for functional group X. However, given the foregoing examples and descriptions of functionalized polyolefins (B), those skilled in the art will understand that anhydrides available from anhydride functional compounds having olefinic unsaturation will be particularly suitable for some embodiments, such as those in which the anhydride functional compound can be readily copolymerized with or grafted onto α-olefin homopolymers (e.g., via radical grafting, metathesis, etc.).

[0081] Examples of suitable amines for functional group Y generally include primary amino-substituted derivatives of the aforementioned hydrocarbon groups, such as aminoalkyl groups as described above with respect to functional group X.

[0082] In some embodiments, at least one, alternatively at least two, alternatively functional group Y comprises, alternatively is a silanol group. In some embodiments, at least one functional group Y comprises, alternatively is a group of the formula –Z-SiR. 1 3-c (OH) c Part of which each D, R 1 The subscript c is chosen independently and is defined above. In some embodiments, Z is an oxygen atom. In other embodiments, Z is a divalent hydrocarbon group having 2 to 18, alternatively 2 to 16, alternatively 2 to 14, alternatively 2 to 16, alternatively 2 to 12, alternatively 2 to 10, alternatively 2 to 8, alternatively 2 to 6, or alternatively 2 to 4 carbon atoms.

[0083] In some embodiments, at least one, alternatively at least two, alternatively each functional group Y comprises, alternatively is a methanol group. The methanol functional groups may be the same as or different from each other.

[0084] In some embodiments, the methanol functional group independently includes those having the general formula –Z 1 –O d –(C e H 2e O) f –H part, where Z 1 It is a covalently bonded or divalent hydrocarbon linking group having 2 to 18 carbon atoms, the subscript d is 0 or 1, the subscript e is independently selected from 2 to 4 in each part indicated by the subscript f, and the subscript f is 0 to 500, provided that the subscripts d and f are not simultaneously 0. For example, in some embodiments, the subscript f is at least 1, such that at least one of the methanol functional groups has the following general formula:

[0085] –Z 1 –O d –[C2H4O] g [C3H6O]h [C4H8O] i –H;

[0086] Z 1 The subscripts d, g, h, and i are chosen independently and are defined above.

[0087] In another embodiment, the subscript f is 0 and the subscript d is 1, such that at least one of the methanol functional groups includes a portion having the following general formula: –Z 1 -OH, where Z 1 In the above description, in these embodiments, the methanol functional group having the general formula is not a polyether group or part thereof.

[0088] When functional group Y is directly bonded to a carbon atom in the functionalized polyolefin (B), Z 1 It can be a covalent bond.

[0089] In some embodiments, at least one, alternatively at least two, alternatively each functional group Y comprises, alternatively is an alkoxysilyl group.

[0090] In embodiments where at least one functional group Y is alkoxysilyl, each alkoxysilyl group may independently comprise either a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group. In a particular embodiment, the alkoxysilyl group comprises, alternatively, a monoalkoxysilyl group. In other embodiments, the alkoxy group comprises, alternatively, a dialkoxysilyl group. In still other embodiments, the alkoxysilyl group comprises, alternatively, a trialkoxysilyl group.

[0091] In some embodiments, at least one functional group Y comprises, or alternatively is, of the form –Z 2 -SiR 1 3-j (OR 6 ) j Part of which each Z 2 It is a covalent bond, an oxygen atom, or a divalent hydrocarbon group, R 1 Independently selected and defined above, with subscript j being 1, 2, or 3, and each R 6 It is an independently chosen alkyl group having 1 to 12 carbon atoms. Typically, each R... 6 It is an independently selected alkyl group having 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 1 to 3, alternatively 1 or 2, or alternatively 1 carbon atom.

[0092] Typically, each R 6is 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 from 1 to 3, alternatively 1 or 2, alternatively 1 carbon atom.

[0093] Specific examples of suitable alkoxysilyl groups include those containing trimethoxysilyl group, triethoxysilyl group, dimethoxyethoxysilyl group, dimethoxymethyl group, diethoxymethyl group, methoxyethoxymethyl group, dimethylmethoxy group, dimethylethoxy group, etc.

[0094] In some embodiments, at least one, alternatively at least two, alternatively each functional group Y comprises, alternatively is an epoxy group. Examples of suitable epoxy groups include 3-glycidoxypropyl group, 4-glycidoxybutyl group or similar glycidoxyalkyl (i.e., glycidyloxy) groups; 2-(3,4-epoxycyclohexyl)ethyl group, 3-(3,4-epoxycyclohexyl)propyl group or similar epoxycyclohexyl groups; 4-oxetanyl group and 8-oxepanyl group. Such epoxy groups can be directly bonded to the functionalized polyolefin (B). Alternatively, a divalent hydrocarbon group may be present in the functional group Y between the epoxy group and the atom to which the functional group Y is bonded. In some of these embodiments, the divalent hydrocarbon group comprises, alternatively is an alkylene group having the general formula –(CH2) k –, where the subscript k is as defined above. In other embodiments, the divalent hydrocarbon group contains from 2 to 10 carbon atoms and contains at least one ether moiety, i.e., at least one heteroatom oxygen.

[0095] Further referring to the general unit formula of the functionalized polyolefin (B), as introduced above, the subscripts o and p are each mole fractions such that o + p = 1. Generally, 0 < o < 1, and 0 < p < 1, such that the functionalized polyolefin (B) can contain at least one functional group Y and can theoretically contain many such groups, but is not completely substituted for each olefinic subunit present in the functionalized polyolefin (B) (e.g., as indicated by subscript p > 0). In some embodiments, the portion indicated by subscript o accounts for 0.01% to 5%, alternatively 0.01% to 2.5% of the total number of olefinic subunits in the functionalized polyolefin (B) (e.g., o + p). In these or other embodiments, the portion indicated by subscript o can account for 0.05% to 10% by weight of the functionalized polyolefin (B) (e.g., based on the total weight).

[0096] The specific properties and physical characteristics of the functionalized polyolefin (B) can vary. In some embodiments, the functionalized polyolefin (B) comprises a number-average molecular weight of 10 kDa to 100 kDa (such as 10 kDa to 90 kDa, alternatively 15 kDa to 90 kDa, alternatively 15 kDa to 80 kDa, alternatively 20 kDa to 80 kDa, alternatively 20 kDa to 70 kDa, alternatively 20 kDa to 65 kDa). In these or other embodiments, the functionalized polyolefin (B) comprises a molecular weight distribution expressed as a polydispersity index (PDI) of 1 to 12 (such as 1 to 10) (e.g., determined by gel permeation chromatography (GPC)). In some embodiments, the functionalized polyolefin (B) exhibits a PDI of 1 to 5 (such as 1 to 4, alternatively 1.5 to 3.5, 1.75 to 3.25, alternatively 2 to 3). In some implementations, the functionalized polyolefin (B) exhibits a PDI of 3 to 6 (such as 3.5 to 5.5, or alternatively 4 to 5).

[0097] In some embodiments, the functionalized polyolefin (B) is anhydride-functionalized. In these or other embodiments, the functionalized polyolefin (B) contains 0.5% to 2.0% by weight of the functional group Y. The functionalized polyolefin (B) typically has a melt flow index (MFI) of 1 g / 10 min to 49 g / 10 min. The MFI can be measured according to ASTM D1238-86.

[0098] The functionalized polyolefin (B) can be introduced into the mixer in any suitable form, for example, the functionalized polyolefin (B) can be provided and introduced into the mixer in the form of pellets.

[0099] Reactive compatibilizer (C)

[0100] The reactive compatibilizer (C) is a polysiloxane polymer having at least one group X that reacts with group Y of the functionalized polyolefin (B). It can be defined as being structurally similar to component (A) described above.

[0101] Generally, a reactive compatibilizer (C) comprises a polydiorganosiloxane backbone having at least one functional group X per molecule. Typically, the reactive compatibilizer (C) is substantially linear, or alternatively linear. In such cases, those skilled in the art will understand that the reactive compatibilizer (C) typically does not contain [T]siloxy units and / or [Q]siloxy units, as described above.

[0102] In some implementations, the reactive compatibilizer (C) has the following general average unit formula:

[0103] [X m R 1 3-m SiO1 / 2 a [X n R 1 2-n SiO 2 / 2 b ,

[0104] where X is a functional group as defined above, each R 1 is an independently selected hydrocarbyl group, the subscript m is independently 1 or 0 in each moiety indicated by the subscript a, the subscript n is independently 1 or 0 in each moiety indicated by the subscript b, and the subscripts a and b are each mole fractions such that a + b = 1, provided that 0 < a < 1, 0 < b < 1, and the reactive compatibilizer (C) contains at least one functional group X.

[0105] Referring to the general unit formula of the reactive compatibilizer (C) above, the hydrocarbyl groups applicable to R 1 are generally illustrated by those above. Generally, each R 1 is a substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms. For example, in some embodiments, each R 1 is an independently selected hydrocarbyl group having 1 to 12, alternatively 1 to 8, alternatively 1 to 6 carbon atoms. In some such embodiments, each R 1 is further defined as an alkyl group, an aryl group, or a combination thereof. For example, in some embodiments, R 1 represents an independently selected substituted or unsubstituted alkyl group. Specific examples of such alkyl groups include methyl group, ethyl group, propyl groups (e.g., n-propyl group and isopropyl group), butyl groups (e.g., n-butyl group, sec-butyl group, isobutyl group, and tert-butyl group), pentyl group, hexyl group, etc., as well as their derivatives and / or modifications. Examples of derivatives and / or modifications of such alkyl groups include their substituted forms, for example where hydroxyethyl group would be understood as a derivative and / or modification of the above ethyl group.

[0106] Each R 1 can be the same as or different from any other R 1 of the reactive compatibilizer (C). In certain embodiments, each R 1 is the same as each other R 1 of the reactive compatibilizer (C). For example, in some such embodiments, each R 1 is methyl. In other embodiments, at least one R 1 is different from at least one other R 1 of the reactive compatibilizer (C). For example, in certain embodiments, R 1 ​​The reactive compatibilizer (C) is predominantly methyl, with one or more other groups suspended in small amounts on the polydiorganosiloxane backbone (e.g., from the preparation of the reactive compatibilizer (C), environmental reactions, or impurities). In some embodiments, each R... 1 It is a fluoroalkyl group, so the reactive compatibilizer (C) can be further defined or called fluoroorganosilicon or fluoropolysiloxane.

[0107] As described above, each molecule of the reactive compatibilizer (C) contains, on average, at least one functional group, as represented by part X in the general formula of the reactive compatibilizer (C) above. However, in some embodiments, each molecule of the reactive compatibilizer (C) contains, on average, at least two functional groups X.

[0108] As described herein, functional group X of the reactive compatibilizer (C) can react with functional group Y of the functionalized polyolefin (B) to form a bond between them. In other words, a functional group X and a functional group Y can react together (i.e., via coupling, crosslinking, etc.) to covalently bond the reactive compatibilizer (C) and the functionalized polyolefin (B) together. It should be understood that terms such as “coupling,” “capable of coupling,” “capable of reacting,” “crosslinking,” and “capable of crosslinking” as used herein are not intended to suggest any directionality of the reaction, but are to be understood in the conventional sense as referring to coupling promoted by groups X and Y, without inferring a particular reactivity between them or their role in the reaction. As described herein, in some embodiments, the average molecule of components (B) and / or (C) has at least two groups capable of participating in the coupling reaction, such that a single molecule of the reactive compatibilizer (C) can, on average, couple with two or more molecules of the functionalized polyolefin (B) at least once, or similarly, couple with a single molecule of the functionalized polyolefin (B) at least twice.

[0109] Generally, each functional group X contains, or alternatively, a functional group capable of participating in the aforementioned coupling / crosslinking reactions. Examples of such functional groups are typically reactive via substitution, addition, coupling, or combinations thereof. Specific examples of such reactions include nucleophilic substitution, ring-opening addition, alkoxylation and / or trans-alkoxylation, hydrosilylation, olefin metathesis, condensation, radical coupling and / or polymerization, and combinations thereof. Therefore, functional group X may comprise either a hydrosilylation functional group (e.g., a silicon-bonded hydrogen atom, an alkene (i.e., an alkene-bonded) unsaturated group, such as an alkenyl group, an alkynyl group, etc.), a condensable functional group (e.g., a hydroxyl group, a carboxyl group, a methanolic group, an alkoxysilyl group, a silanol group, an amide group, an anhydride group, etc., or a hydrolyzable and subsequently condensable group), a substitutional functional group (e.g., a "leaving group" as understood in the art, such as a halogen atom, or other groups that are ionicly stable once substituted, or functional groups containing such leaving groups, such as esters, anhydrides, amides, epoxides, etc.), a nucleophilic functional group (e.g., a heteroatom with a lone pair of electrons, an anion or anionizable group, such as a hydroxyl group (e.g., the hydroxyl group of methanol), an amine group, a thiol group, a silanol group, a carboxylic acid group, etc.), an electrophilic functional group (e.g., an isocyanate, an epoxide, etc.), or various combinations thereof.

[0110] In some embodiments, at least one, alternatively at least two, alternatively each functional group X is a hydrosilylation-capable group, and is therefore selected from olefinic unsaturated groups (e.g., olefinic unsaturated groups) and H. In some such embodiments, each hydrosilylation-capable group represented by X is H, such that the reactive compatibilizer (C) is silane-functionalized. In other such embodiments, each hydrosilylation-capable group represented by X is an olefinic unsaturated group.

[0111] Examples of alkene-bonded unsaturated groups typically include substituted or unsubstituted hydrocarbon groups having at least one alkene or alkyne functional group. For example, in some embodiments, each functional group X comprises, alternatively, an alkenyl group or an alkynyl group. Examples include H2C=CH–, H2C=CHCH2–, H2C=CHCH2CH2–, H2C=CH(CH2)3–, H2C=CH(CH2)4–, H2C=C(CH3)–, H2C=C(CH3)CH2–, H2C=C(CH3)CH2CH2–, H2C=C(CH3)CH2CH(CH3)–, H2C=C(CH3)CH(CH3)CH2–, H2C=C(CH3)C(CH3)2–, HC≡C–, HC≡CCH2–, HC≡CCH(CH3)–, HC≡CC(CH3)2–, and HC≡CC(CH3)2CH2–. In a specific embodiment, each functional group X comprises, optionally, a vinyl group.

[0112] In embodiments where functional group X comprises one of the above-described olefinic unsaturated groups, it should be understood that functional group X may also comprise a divalent linking group between the olefinic unsaturated group and the silicon atom of the reactive compatibilizer (C). Examples of such divalent linking groups include divalent forms of the above-described hydrocarbon groups, such as alkyl groups. For example, functional group X may have the formula H2C=CH–(CH2)5–, which can be considered to represent an alkenyl group H2C=CHCH2– with a butene linking group, an alkenyl group H2C=CH(CH2)4– with a methylene linking group, etc. In some embodiments, each functional group X comprises, alternatively, a methacryloyloxy group, such as a silicon-bonded methacryloyloxyalkyl group.

[0113] In some embodiments, at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is a condensation-capable group, i.e., capable of participating in a condensation reaction. In a specific embodiment, each functional group X comprises a condensation-capable group selected from anhydride groups, amine groups, silanol groups, methanol groups, and alkoxysilyl groups.

[0114] Examples of suitable anhydrides with functional group X generally include anhydrides of monocarboxylic acids (e.g., acetic acid, lactic acid, propionic acid, valeric acid, methacrylic acid, etc.), which can be homohydric or mixed anhydrides, as well as anhydrides of polycarboxylic acids such as succinates (i.e., succinic anhydride), maleates (i.e., maleic anhydride), phthalates, etc. Those skilled in the art will understand that various substitution modes are possible with respect to attaching such anhydrides to the silicon atoms of the reactive compatibilizer (C). Typically, such anhydrides can be grafted onto siloxane polymers to prepare the reactive compatibilizer (C), and therefore those skilled in the art will understand the applicability of other anhydrides and carboxylic acids / carboxylic esters that may also be used (e.g., via direct grafting to the reactive compatibilizer (C) or alternatively via initial grafting and subsequent reaction to prepare the anhydride). For example, anhydrides containing at least one olefinically unsaturated group (such as alkenyl succinic anhydride, bromomaleic anhydride, chloromaleic anhydride, citrate anhydride, methyl nadic anhydride, nadic anhydride, tetrahydrophthalic anhydride, etc.) can be grafted onto siloxanes (e.g., via hydrosilylation). Radical-based grafting schemes can also be used to generate anhydride-functionalized siloxanes from reagents such as maleic anhydride and vinylsiloxanes.

[0115] Examples of suitable amines for functional group X generally include derivatives with primary amino substitutions of the aforementioned hydrocarbon groups. For example, functional group X may comprise, and alternatively may be, an aminoalkyl group, such as an amino-substituted alkyl group having 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.). In a specific embodiment, the reactive compatibilizer (C) comprises only an amino functional group as functional group X.

[0116] In some embodiments, at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is a silanol group. In some embodiments in which at least one functional group X comprises a silanol group, the silicon atom of the silanol group is a silicon atom of the backbone of the reactive compatibilizer (C). In other embodiments, at least one X comprises, alternatively is a material of the formula –Z-SiR 1 3-c (OH) c The part where each Z is a covalent bond, oxygen atom, or divalent hydrocarbon group, R 1 Independently chosen and defined above, with subscript c being 1, 2, or 3. When subscript c is 3, the silicon atom of the silanol group comprises three silicon-bonded hydroxyl groups; when subscript c is 2, the silicon atom of the silanol group comprises two silicon-bonded hydroxyl groups; when subscript c is 1, the silicon atom of the silanol group comprises two silicon-bonded hydroxyl groups. In some embodiments, Z is an oxygen atom. In other embodiments, Z is a divalent hydrocarbon group having 2 to 18, alternatively 2 to 16, alternatively 2 to 14, alternatively 2 to 16, alternatively 2 to 12, alternatively 2 to 10, alternatively 2 to 8, alternatively 2 to 6, or alternatively 2 to 4 carbon atoms.

[0117] In some embodiments, each functional group X comprises, alternatively, a silicon-bonded hydroxyl group.

[0118] In some embodiments, at least one, alternatively at least two, alternatively each functional group X comprises, alternatively, a methanol group. The methanol functional group bonded to the silicon atom in the organopolysiloxane differs from the silanol group. Specifically, the methanol functional group comprises a carbon-bonded hydroxyl group, and the silanol functional group comprises a silicon-bonded hydroxyl group. In other words, the methanol functional group comprises at least one portion of the formula –COH, while the silanol functional group has the formula –SiOH. These functional groups behave differently; for example, the silanol functional group can readily condense, which generally does not occur on the methanol functional group (at least under the same catalysis of the hydrolysis / condensation of the silanol functional group). The methanol functional groups may be the same as or different from each other.

[0119] In some embodiments, the methanol functional group independently includes those having the general formula –Z 1 –O d –(C e H 2e O) f –H part, where Z 1 It is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, the subscript d is 0 or 1, the subscript e is independently selected from 2 to 4 in each part indicated by the subscript f, and the subscript f is 0 to 500, provided that the subscripts d and f are not both 0.

[0120] In some such embodiments, the subscript f is at least one, such that at least one of the methanol functional groups includes a portion having the following general formula:

[0121] –Z 1 –O d –[C2H4O] g [C3H6O] h [C4H8O] i –H;

[0122] Z 1 In the above definitions, 0 ≤ g ≤ 500, 0 ≤ h ≤ 500, and 0 ≤ i ≤ 500, provided that 1 ≤ g + h + i ≤ 500. In these embodiments, the methanol functional group may alternatively be referred to as a polyether group or portion, but the polyether group or portion is terminated with –COH instead of –COR, where R is a monovalent hydrocarbon group, as is the case with some conventional polyether groups or portions. As understood in the art, the portion indicated by the subscript g is an ethylene oxide (EO) unit, the portion indicated by the subscript h is a propylene oxide (PO) unit, and the portion indicated by the subscript i is a butane oxide (BO) unit. The EO, PO, and BO units (if present) may be in block or random form in the polyether group or portion. The relative amounts of the EO, PO, and BO units (if present) may be selectively controlled based on desired properties (e.g., hydrophilicity and other properties).

[0123] In other embodiments, the subscript f is 0 and the subscript d is 1, such that at least one of the methanol functional groups includes a portion having the following general formula: –Z 1 -OH, where Z 1 In the above description, in these embodiments, the methanol functional group having the general formula is not a polyether group or part thereof.

[0124] In some embodiments, at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is an alkoxysilyl group.

[0125] In embodiments where at least one X is alkoxysilyl, each alkoxysilyl group may independently comprise either a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group. In a particular embodiment, the alkoxysilyl group comprises, alternatively, a monoalkoxysilyl group. In other embodiments, the alkoxy group comprises, alternatively, a dialkoxysilyl group. In still other embodiments, the alkoxysilyl group comprises, alternatively, a trialkoxysilyl group.

[0126] In some embodiments, the silicon atom of the alkoxysilyl group is a silicon atom in the main chain of the reactive compatibilizer (C). In other embodiments, at least one X comprises, alternatively, a silicon atom of the formula –Z. 2 -SiR 1 3-j (OR 6 ) j Part of which each Z 2 It is a covalent bond, an oxygen atom, or a divalent hydrocarbon group, R 1 Independently selected and defined above, with subscript j being 1, 2, or 3, and each R 6 It is an independently chosen alkyl group having 1 to 12 carbon atoms. Typically, each R... 6 It is an independently selected alkyl group having 1 to 10, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 to 4, alternatively 1 to 3, alternatively 1 or 2, or alternatively 1 carbon atom.

[0127] Specific examples of alkoxysilyl groups include those containing trimethoxysilyl groups, triethoxysilyl groups, dimethoxyethoxysilyl groups, dimethoxymethyl groups, diethoxymethyl groups, methoxyethoxymethyl groups, dimethylmethoxy groups, dimethylethoxy groups, etc.

[0128] In some embodiments, at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is an epoxy group. Examples of suitable epoxy groups include 3-glycidyl etheroxypropyl, 4-glycidyl etheroxybutyl, or similar glycidyl etheroxyalkyl (i.e., glycidyloxy) groups; 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, or similar epoxycyclohexyl groups; 4-oxacyclopropylbutyl, and 8-oxacyclopropyloctyl. Such epoxy groups can be directly bonded to the reactive compatibilizer (C). Alternatively, a divalent hydrocarbon group may be present in X between the epoxy group and the silicon atom to which X is bonded. In some of these embodiments, the divalent hydrocarbon group comprises, alternatively is a group having the general formula –(CH2). k – an alkylene group, wherein the subscript k is 2 to 10. In other embodiments, the divalent hydrocarbon group comprises 2 to 10 carbon atoms and includes at least one ether moiety, i.e., at least one oxygen atom. Such divalent hydrocarbon groups are also suitable for use as divalent linking groups as described herein (e.g., Z, Z). 1 Z 2 wait).

[0129] Referring to the general unit formula of the reactive compatibilizer (C) above, the subscript m is independently 1 or 0 in each part indicated by subscript a, and the subscript n is independently 1 or 0 in each part indicated by subscript b. Therefore, subscripts m and n only indicate the presence of 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). When each subscript m is 0 (i.e., subscript m is 0 in each part indicated by subscript a), the reactive compatibilizer (C) contains at least one side-chain functional X (i.e., bonded to the [D] unit). When each subscript n is 0 (i.e., subscript n is 0 in each part indicated by subscript b), the reactive compatibilizer (C) contains at least one terminal functional X (i.e., bonded to the [M] unit). In some embodiments, the reactive compatibilizer (C) is terminally functionalized only with respect to functional group X, such that subscript n is 0 in each part indicated by subscript b. In some such embodiments, the reactive compatibilizer (C) comprises at least two portions indicated by subscript a, and subscript m is 1 in at least two portions indicated by subscript a. In other embodiments, the reactive compatibilizer (C) comprises at least one terminal functional group X. In other embodiments, the reactive compatibilizer (C) comprises only side-chain functionality with respect to functional group X, such that subscript m is 0 in each portion indicated by subscript a, the reactive compatibilizer (C) comprises at least two portions indicated by subscript b, and subscript n is 1 in at least two portions indicated by subscript b.

[0130] Continuing to refer to the general unit formula of the above reactive compatibilizer (C), subscripts a and b are each mole fractions such that a + b = 1, provided that 0 < a < 1 and 0 < b < 1. It should be understood that the portions indicated by subscripts a and b are generally [M] and [D] siloxane units, respectively. Thus, in certain embodiments, the reactive compatibilizer (C) can be defined as an MDM-type polysiloxane. Accordingly, in such embodiments, the reactive compatibilizer (C) can be defined as a linear polysiloxane (or more simply, "linear siloxane"). Nevertheless, it should be understood that the above general formula can be an average unit formula, i.e., an average formula based on all the molecules in the reactive compatibilizer (C). Thus, as generally described above with respect to siloxanes, the reactive compatibilizer (C) can contain a limited amount of branching (e.g., attributable to [T] and / or [Q] units) without departing from the scope of linearity understood by those skilled in the art, even if such units are not included in the above general unit formula. Generally, the reactive compatibilizer (C) is substantially free, alternatively free, of [T] and / or [Q] units.

[0131] In some embodiments, each of the units represented by subscripts a and b is independently selected, and at least two units of the reactive compatibilizer (C) contain the functional group X. In such embodiments, the foregoing general formula of the reactive compatibilizer (C) can be rewritten as the following expanded average unit formula:

[0132] [XR 1 2SiO 1 / 2 a’ [XR 1 SiO 2 / 2 b’ [R 1 2SiO 2 / 2 b’’ [R 1 3SiO 1 / 2 a’’ ,

[0133] where each X and R 1 is defined as above, and subscripts a', a'', b', and b'' each indicate the quantity of the corresponding portion present in the reactive compatibilizer (C). In this way, a' + a'' equals the quantity of [M] siloxane units present in the above general formula at the mole fraction represented by subscript a, and b' + b'' equals the quantity of [D] siloxane units present in the above general formula at the mole fraction represented by subscript b. For example, generally speaking, a' + a'' ≥ 2, a' + b' ≥ 2, and b' + b'' ≥ 1. In the above specific embodiment, in the case where the reactive compatibilizer (C) is only terminally functional, a' = 2, b' = 0, b'' ≥ 1, and a'' = 0.

[0134] ​​​​Generally, the reactive compatibilizer (C) can have a number-average degree of polymerization (DP) of 10 to 10,000. Therefore, referring to the aforementioned extended formula of the reactive compatibilizer (C), a'+a''+b'+b'' is generally 10 to 10,000. In some embodiments, the reactive compatibilizer (C) has a DP of 10 to 1200, alternatively 50 to 1200. Similarly, in these embodiments, a'+a''+b'+b'' is generally 10 to 1200, alternatively 20 to 1200, alternatively 50 to 1200. For example, in some embodiments, the reactive compatibilizer (C) has a DP of 50 to 1100, alternatively 50 to 1000, alternatively 100 to 1000. In specific embodiments, a' and a'' are each 0 to 2, typically a'+a''=2. The subscript b'' can be 0 to 10,000, such as 5 to 5,000, alternatively 50 to 1200, alternatively 50 to 1100, alternatively 50 to 1000, alternatively 100 to 1000. In these and other embodiments, the subscript b' is 0 to 200, such as 0 to 10, alternatively 1 to 10, alternatively 1 to 8.

[0135] In some embodiments, the reactive compatibilizer (C) has a degree of substitution (DS) of 1 to 200. It should be understood that the DS of the reactive compatibilizer (C) can be represented by the sum of the subscripts a' and b' in the above extended formula, i.e., the number of its indicator functional groups X. In some embodiments, the reactive compatibilizer (C) has a DS of 1 to 100, alternatively 1 to 50, alternatively 1 to 20, alternatively 1 to 10, or alternatively 2 to 10.

[0136] In some embodiments, the reactive compatibilizer (C) comprises a molecular weight distribution, expressed as a polydispersity index (PDI) of less than 3, alternatively less than 2.5, alternatively less than 2.25, and simultaneously greater than or equal to 1, i.e., weight-average molecular weight / number-average molecular weight (Mw / Mn). For example, the reactive compatibilizer (C) may comprise a PDI of 1 to 3 (such as 1 to 2.5, alternatively 1.5 to 2.5, alternatively 1.5 to 2.2, alternatively 1.8 to 2.2, alternatively about 2). Methods for determining the PDI of the reactive compatibilizer (C) are known in the art and generally involve gravimetric determination via rheology, solution viscosity, gel permeation chromatography (GPC), etc., the standards and procedures of which are readily understood and available.

[0137] Typically, the reactive compatibilizer (C) used in the silicone-polyolefin composition is flowable, meaning it contains a sufficiently low viscosity to exhibit flowability under ambient conditions (e.g., at 25°C). In some embodiments, the reactive compatibilizer (C) is a liquid at room temperature. In some embodiments, the reactive compatibilizer (C) exhibits a zero-shear viscosity of at least 1000 mPa·s, alternatively at least 3500 mPa·s, and a maximum viscosity of up to about 25,000 mPa·s at 25°C.

[0138] Unless otherwise stated, all viscosity measurements given are zero shear viscosity (η). o The zero-shear viscosity (ZHV) value is obtained by extrapolating (or simply averaging) values ​​obtained at low shear rates from a viscosity-shear rate curve that is independent of the rate. This is a method-independent value provided a suitable, properly operated rheometer is used. For example, the ZHV of a substance at 25°C can be obtained using a commercial rheometer, such as the Anton-Parr MCR-301 rheometer equipped with a cone-plate clamp of appropriate diameter or the TA Instruments AR-2000 rheometer, at a range of low shear rates such as 0.01 s⁻¹. -1 0.1s -1 and 1.0s -1 This generates a sufficient torque signal without exceeding the transducer's torque limit. Alternatively, viscosity measurements can be taken using an ARES-G2 rotational rheometer, commercially available from TA Instruments, on a 25 mm cone plate using a 0.1 s... -1 up to 10s -1 The stable rate scan is used to obtain the data. If a zero-shear plateau region cannot be observed at the shear rate achievable by the rheometer or viscometer, report a plateau at 0.1 s at 25°C. -1 Viscosity measured at the standard shear rate.

[0139] In some embodiments, the reactive compatibilizer (C) is further defined as a functionalized polydimethylsiloxane (PDMS), i.e., each R... 1 It is methyl. In some such embodiments, the reactive compatibilizer (C) is selected from amine-functional PDMS (i.e., each functional group X contains an amine, such as a primary aminoalkyl group) and vinyl-functional PDMS (i.e., each functional group X contains, alternatively, a vinyl group).

[0140] Based on the above description, examples of such amine-functionalized PDMS suitable for use or as a reactive compatibilizer (C) will be understood to include terminal and / or side-chain amine-functionalized PDMS oligomers and polymers. However, it should also be understood that in some embodiments, the reactive compatibilizer (C) may comprise, and alternatively may be, terminal and / or side-chain amine-functionalized random, grafted, or block copolymers or co-oligomers of PDMS and non-reactive siloxanes (e.g., polyphenylmethylsiloxane, tris(trifluoropropyl)methylsiloxane, etc.). In the same manner, examples of vinyl-functionalized polydimethylsiloxane (PDMS) suitable for use or as a reactive compatibilizer (C) include terminal and / or side-chain vinyl-functionalized PDMS oligomers and polymers, as well as random, grafted, or block copolymers or co-oligomers of PDMS. In a specific embodiment, the reactive compatibilizer (C) comprises, and alternatively is aminoalkyl-terminated PDMS, such as α,ω-aminopropyl-terminated PDMS. In some embodiments, the reactive compatibilizer (C) comprises, alternatively, vinyl-terminated PDMS, such as α,ω-vinyl-terminated PDMS. In some embodiments, the reactive compatibilizer (C) comprises, alternatively, methacrylpropyl-terminated PDMS, silanol-terminated PDMS, succinic anhydride-terminated PDMS, SiH-terminated PDMS, vinyl-terminated PDMS, monomethanol-functionalized PDMS, or aminopropyl-terminated PDMS.

[0141] When X or Y is an unsaturated group such as an alkenyl or alkynyl group, and the other of X and Y is a Si-H group, they will undergo a hydrosilylation reaction to make (A) and (B) compatible into an organosilicon-polyolefin hybrid material. In this case, a hydrosilylation catalyst may be required to ensure the reaction is completed. It can be introduced into the mixer as a separate additive before or after the introduction of the reactive compatibilizer (C), or it can be mixed into the reactive compatibilizer (C).

[0142] When present, hydrosilylation catalysts may comprise or consist of platinum group metals or compounds thereof. These catalysts are typically selected from catalysts of platinum group metals (platinum, ruthenium, osmium, rhodium, iridium, and palladium), or compounds of one or more of these metals. Alternatively, platinum and rhodium compounds are preferred due to the high activity levels of these catalysts in hydrosilylation reactions, with platinum compounds being the most preferred.

[0143] The hydrosilylation catalyst can be a platinum group metal, a platinum group metal deposited on a support (such as activated carbon, metal oxides such as silica, silica gel, or charcoal powder), or a compound or complex of a platinum group metal. Preferably, the platinum group metal is platinum.

[0144] Examples of preferred hydrosilylation catalysts are platinum-based catalysts, such as platinum black, platinum oxide (Adams catalyst), platinum on various solid supports, chloroplatinic acid (e.g., hexachloroplatinic acid (Pt oxidation state IV) (Speier catalyst)), chloroplatinic acid in solution of alcohols (e.g., isooctanol or pentanol) (Lamoreaux catalyst), and complexes of chloroplatinic acid with olefinically unsaturated compounds (such as alkenes) and organosiloxanes containing olefinically unsaturated silicon-bonded hydrocarbon groups, such as tetravinyltetramethylcyclotetrasiloxane-platinum complex (Ashby catalyst). Soluble platinum compounds that can be used include, for example, platinum-olefin complexes of the formula (PtCl2.olefin)2 and H (PtCl3.olefin), preferably in this context olefins having 2 to 8 carbon atoms, such as isomers of ethylene, propylene, butene, and octene, or cycloalkanes having 5 to 7 carbon atoms, such as cyclopentene, cyclohexene, and cycloheptene. Other soluble platinum catalysts include, for example, platinum-cyclopropane complexes of formula (PtCl2C3H6)2, reaction products of hexachloroplatinic acid with alcohols, ethers, and aldehydes, or mixtures thereof, or reaction products of hexachloroplatinic acid and / or its conversion products with vinylsiloxanes (such as methylvinylcyclotetrasiloxane) in the presence of an ethanol solution containing sodium bicarbonate. Platinum catalysts with phosphorus, sulfur, and amine ligands, such as (Ph3P)2PtCl2, can also be used; as well as platinum complexes with vinylsiloxanes, such as symmetrical divinyltetramethyldisiloxane (Castel catalyst).

[0145] Therefore, specific examples of suitable platinum-based catalysts for component (d)(ii) include:

[0146] (i) A complex of chloroplatinic acid as described in US 3,419,593 with an organosiloxane containing an olefinic unsaturated hydrocarbon group.

[0147] (ii) Chloroplatinic acid in hexahydrate or anhydrous form;

[0148] (iii) A platinum-containing catalyst, which is obtained by a method comprising the steps of reacting chloroplatinic acid with an aliphatic unsaturated organosilicon compound (such as divinyltetramethyldisiloxane);

[0149] (iv) olefin-platinum-silyl complexes as described in U.S. Patent No. 6,605,734, such as (COD)Pt(SiMeCl2), wherein “COD” is 1,5-cyclooctadiene; and / or

[0150] (v) Karstedt catalyst, which is a platinum-divinyltetramethyldisiloxane complex typically containing about 1% by weight of platinum in a vinylsiloxane polymer. Solvents such as toluene and similar organic solvents have historically been used as alternatives, but the use of vinylsiloxane polymers is currently the preferred choice. These are described in US3,715,334 and US3,814,730. In a preferred embodiment, the catalyst may be selected from a platinum coordination compound. In one embodiment, hexachloroplatinic acid and its conversion product with a vinyl-containing siloxane, the Karstedt catalyst, and the Speier catalyst are preferred. In one embodiment, the catalyst may be encapsulated during storage, especially in the case of a single-component composition, to prevent premature curing.

[0151] The catalytic amount of a hydrosilylation catalyst is typically between 0.01 ppm and 10,000 parts by weight of platinum group metals per million parts (ppm), alternatively between 0.1 ppm and 7,500 ppm; alternatively between 100 ppm and 75,000 ppm; alternatively between 500 ppm and 6,000 ppm. This range may refer only to the metal content within the catalyst or to the entire catalyst (including its ligands) as detailed, but typically these ranges refer only to the metal content within the catalyst. The catalyst can be added as a single substance or as a mixture of two or more different substances. When using a hydrosilylation catalyst, a hydrosilylation curing inhibitor can also be used as an additive.

[0152] However, in a preferred embodiment, the group Y of component (B) is an anhydride functional group, such as maleic anhydride; and the group X of compatibilizer (C) contains a reactive amine group, which will react with the anhydride upon heating, resulting in components (B) and (C) being bonded together.

[0153] (D) Non-reactive polyolefins (optional)

[0154] In the method for preparing organosilicon-polyolefin hybrid materials as described herein, a non-reactive polyolefin (D) may also be included as an optional additional starting component. For the purposes of this disclosure, "non-reactive" means that the non-reactive polyolefin (D) cannot react with component (B) or (C), i.e., the non-reactive polyolefin (D) does not contain functional groups that can react with the reactive group X of the reactive compatibilizer (C) or the functional group Y of the functionalized polyolefin (B).

[0155] In some embodiments, the non-reactive polyolefin (D) may include functional groups, provided that such functional groups are incapable of reacting with the reactive group X of the reactive compatibilizer (C) or the functional group Y of the functionalized polyolefin (B). Such functional groups are readily understood by those skilled in the art based on the choice of functional groups X and Y. However, typically, the non-reactive polyolefin (D) does not contain any functional groups, i.e., groups capable of reacting with other functional groups.

[0156] The non-reactive polyolefin (D) may be selected from any of the above-mentioned functionalized polyolefins (B), the only difference being that the non-reactive polyolefin (D) does not include the functional group Y present in component (B).

[0157] In one embodiment, the non-reactive polyolefin (D) is a post-consumer recycled resin. In another embodiment, the non-reactive polyolefin (D) is a virgin material. The non-reactive polyolefin (D) may also comprise a combination of post-consumer recycled resin and virgin material.

[0158] The term "post-consumer recycled resin" (or "PCR") refers to polymeric materials previously used for consumer or industrial packaging. In other words, PCR is waste plastic. PCR is typically collected from recycling programs and recycling plants. PCR usually requires additional cleaning and treatment before it can be reintroduced into the production line. PCR is a PCR multilayer membrane that has completed its first use; that is, a PCR multilayer membrane after it has fulfilled its first purpose. It should be understood that PCR includes post-industrial recycled (PIR) resin. In an embodiment, the PCR multilayer membrane is a waste barrier membrane used to hold or otherwise store consumer edible oils.

[0159] PCR differs from virgin polymers. Because PCR has undergone initial heating and molding, it is not a "virgin" polymer. "Virgin polymers" are polymers that have not undergone, or otherwise have not been subjected to, heat treatment or molding. PCR resins have different physical, chemical, and flow properties compared to virgin polymers.

[0160] Polypropylene waste (PCR) can be considered waste plastic. PCR may include, for example, HDPE packaging such as bottles (milk jugs, juice containers), LDPE / LLDPE packaging such as films. PCR also includes residues from its original use, such as paper, adhesives, inks, colorants, dyes, nylon, ethylene vinyl alcohol (EVOH), polyethylene terephthalate (PET), and other odor-causing substances. When PCR contains HDPE, it can contain up to 40% polypropylene contaminants.

[0161] Non-limiting examples of commercially available PCRs include those produced by Envision Plastics, North Carolina, USA, under the trade name EcoPrime. ™ PRISMA ™ PCR products are sold by KW Plastics, Inc. (Alabama, USA) under the trade names KWR101-150, KWR101-150-M5-BLK, KWR101-150-M10 BLK, KWR102-8812 BLK, KWR102, KWR102LVW, KWR105, KW620, KWR102-M4, KWR-105M2, KWR105M4, and KWR621. PCR products sold under the names FDA, KWR621-20-FDA, KW308A, KW621, KW621-T10, KW621-T20, KW622-20, KW622-35, KW627C, KW1250G, and KWBK10-NB.

[0162] In one embodiment, when present, the non-reactive polyolefin (D) comprises a PCR blended with an olefin-based polymer that is not a PCR. In other words, in this embodiment, the PCR is mixed with a “native olefin-based polymer” to obtain the non-reactive polyolefin (D).

[0163] Non-reactive polyolefins (D) typically have a melt flow index (MFI) ranging from 0.5 g / 10 min to 35 g / 10 min. MFI can be measured according to ASTM D1238-86.

[0164] When used, component (D) is introduced into the method during step (i) together with the silicone polymer base material, or during step (ii) together with the functionalized polyolefin (B), or during the simultaneous combination steps (i) and (ii).

[0165] The conical screw extruder used as a mixer in the method for preparing organosilicon-polyolefin hybrid materials described herein includes a conical twin-screw mixing chamber containing two counter-rotating conical screws converging toward an extrusion die having an inlet and an outlet. The passage through the extrusion die is controlled by a shut-off device such that the outlet of the extrusion die is adapted to be closed by the shut-off device until the end of step (v), and then opened in step (vi) to extrude the organosilicon-polyolefin hybrid material through the extrusion die for further processing or storage outside the conical screw extruder.

[0166] The closure device is in the form of a plate that can move between an open position and a closed position, such that in the closed position, the closure device is designed to prevent the contents of the conical screw extruder from flowing out during the preparation of the silicone-polyolefin hybrid material, and in the open position, it allows the preparation product of the silicone-polyolefin hybrid material to flow out through the extrusion die.

[0167] Two intermeshing conical screws operate in counter-rotating motions and are driven by a motor forming part of the conical screw tableting extruder. If desired, the intermeshing conical screws may include lip seals on their shafts. The conical screw tableting extruder may include multiple inlets for, for example, silicone polymer base materials (A), functionalized polyolefins (B), reactive compatibilizers (C), and optionally non-reactive polyolefins (D), but more than one component may be introduced via the same inlet if desired or desired. In each case, these components may be stored in any preferred manner prior to introduction into the conical screw tableting extruder. They may also be designed such that predetermined amounts can be periodically metered and added to the mixing chamber of the conical screw tableting extruder for mixing and preparing silicone-polyolefin hybrid material products.

[0168] One or more steps in preparing organosilicon-polyolefin hybrid material products can be carried out in an inert atmosphere, such as under nitrogen or in a vacuum.

[0169] Furthermore, the mixing chamber of the conical screw extruder can be purged with nitrogen before the introduction of the silicone polymer base (A), the functionalized polyolefin (B), the reactive compatibilizer (C), and the optional non-reactive polyolefin (D), and during the preparation of the silicone-polyolefin hybrid material product.

[0170] Furthermore, typical conical screw tableting extruders feature a clamshell-style opening design, which allows for easy cleaning during use as a conical screw tableting extruder if needed. It has also been determined that tipping and scraping are virtually unnecessary or completely eliminated between batches of silicone-polyolefin hybrid products, as the total batch weight loss (tailing) retained in the mixer after extrusion is minimal. This also has the advantage of reducing the labor intensity of the method and further limiting operator exposure to the starting components and byproducts involved in the method described herein.

[0171] Additionally, conical screw tableting extruders can have integrated vacuum system capabilities, allowing for the removal of volatiles using vacuum. Examples of such conical screw tableting extruders are described in US7556419 and US11925911, both of which are incorporated herein by reference, and such conical screw tableting extruders are commercially available from Colmec SpA, Busto Arsizio, Italy.

[0172] In the method described herein, during the mixing of the silicone polymer base, the initial silicone-polyolefin hybrid composition mixture and the final silicone-polyolefin hybrid material product (when present in the mixer) are pushed toward the extrusion die by a pair of counter-rotating conical screws, and then forced back when the extrusion die is closed by a closing device.

[0173] In step (i) of the method, a silicone polymer base material (A) comprising a combination of one or more silicone polymers and / or copolymers (A)(1) having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08 and one or more fillers (A)(2) is introduced into a conical twin-screw mixing chamber through a suitable inlet. This is typically carried out at approximately room temperature, for example at approximately 25°C, followed by mixing of the base material while heating to a predetermined temperature of 100°C to 200°C. If desired, the mixer may be partially preheated before the introduction of the silicone polymer base material (A).

[0174] In one embodiment, the silicone polymer base material (A) may be prepared in a conical screw tableting extruder and then conveyed therefrom to an inlet for introduction into the mixer described herein. In another embodiment, as a preliminary step in the method for preparing the silicone-polyolefin hybrid material described herein, the silicone polymer base material (A) may be prepared in the same conical screw tableting extruder. The silicone polymer base material (A) and / or silicone rubber may be conveyed to and / or introduced into the CTM by any suitable means, such as using one or more conveying devices, extruders, gear pumps, rollers, or combinations thereof.

[0175] When preparing the silicone polymer base material (A) in the same conical screw extruder as a pre-processing step, solid materials (ranging in size from powder to granules, such as silica) can be added simultaneously with the mixing of component (A)(1), for example by a single addition or by a continuous addition method. Solid materials can be introduced into the CTM by weight analysis, for example, directly from the shaft, by vacuum pumping, via a screw conveyor, or other systems. In one embodiment, component (A)(2), i.e., the filler, is added gradually / continuously to the CTM while the CTM screw rotates and continuously mixes component (A)(1) to prevent possible accumulation in dead zones or the formation of bags of unincorporated solid material.

[0176] If desired, any two or more starting components described herein may be premixed in a suitable mixer before entering the conical twin-screw extruder, such as the components mentioned above, for example, functionalized polyolefins (B) and non-reactive polyolefins (D). Furthermore, as part of the preparation method, components (C) and (D) and / or any additives introduced into the mixture may be introduced in the form of a masterbatch or concentrate in, for example, an organosiloxane polymer or organosilicon. This is a suitable way to add flammable, difficult-to-disperse, or difficult-to-handle materials. The masterbatch may be added via a feed conveyor or a side opening on the mixer hopper.

[0177] In use, in step (i), when only the silicone polymer base material is present, the base material present in the mixing chamber of the conical twin-screw extruder is pushed toward the extrusion die by the counter-rotating screws. However, when the shut-off device is closed, it is forced back into the conical twin-screw extruder mixing chamber for further recycling / additional mixing. The two counter-rotating screws are in converging and intersecting conical channels, where the outer circumferential profile of the screw threads extends adjacent to the channel surface. Thus, the material is forced to follow the conical profile of the screws to reach a gradually narrowing volume, and the pressure increases as the composition approaches the closed extrusion die before being mixed with the functionalized polyolefin (B) and optional compatibilizer in step (ii). This can optionally be carried out in an inert atmosphere or under vacuum. The screws can be operated at any suitable speed, e.g., 25 rpm to 100 rpm, or even higher if deemed necessary.

[0178] The material introduced into the conical twin-screw extruder gradually becomes hotter through heating and shear heating via the mixing process, potentially reaching up to 200°C, optionally up to about 190°C, in the 180°C region.

[0179] The silicone polymer base (A), functionalized polyolefin (B), reactive compatibilizer (C), and optional non-reactive polyolefin (D) introduced into the mixing chamber of the conical twin-screw extruder in steps (i), (ii), and / or (iii) may be introduced in any suitable manner, for example, manually or otherwise from any suitable container or using an automatic metering method, such as a screw-type automatic metering method from a hopper, etc.

[0180] In step (ii) of the method for preparing a silicone-polyolefin hybrid material described herein, which is performed simultaneously with or after step (i), once one or more silicone polymer base materials (A) have reached the predetermined temperature of 100°C to 200°C, one or more functionalized polyolefins (B) are introduced into the mixing chamber of a mixer while mixing continues to form an initial silicone-polyolefin hybrid composition mixture. The reaction temperature can be any suitable reaction temperature that facilitates the mixing of components (A) and (B) and component (D), if present. One or more functionalized polyolefins (B) can be introduced into the mixing chamber of the mixer as needed, either in a single addition or gradually.

[0181] Meanwhile, mixing continues until the mixer is completely filled. The predetermined temperature is 100°C to 200°C, alternatively 125°C to 200°C, alternatively 125°C to 190°C, alternatively 130°C to 190°C, alternatively 140°C to 190°C. Step (ii) can be carried out under vacuum or in an inert atmosphere, such as in a nitrogen atmosphere, for example by periodically introducing nitrogen to control the oxygen level in the mixer during mixing.

[0182] In step (ii) of the method, a conical screw extruder is used to add the functionalized polyolefin (B) and mix the silicone polymer base material (A) and the functionalized polyolefin (B).

[0183] Components (A) and (B) are then mixed in the same manner as previously described with respect to step (i), i.e., in the mixing chamber of a conical screw tableting extruder, where they are pushed toward the extrusion die by counter-rotating screws, with the closure device closed, forcing them back into the conical twin-screw mixing chamber for further recycling / additional mixing to enhance the homogeneity of the composition at preparation. The two counter-rotating screws are located in converging and intersecting conical channels, where the outer periphery of the threads extends adjacent to the channel surface. Thus, the material is forced to follow the conical profile of the screws to reach a gradually narrowing volume, with pressure increasing as the components approach the closed extrusion die during mixing. This pressure increase enables the recirculation of the contents of the mixing chamber. The method is significantly enhanced by introducing a compatibilizer simultaneously with or subsequently with components (A) and (B) in step (iii).

[0184] In the absence of a reactive compatibilizer (C), the miscibility of organosilicon polymer base materials and functionalized polyolefins is poor.

[0185] The introduction of a compatibilizer in step (iii) significantly improves the miscibility of components (A) and (B), wherein the reaction occurs between functional group Y from the functionalized polyolefin (B) and reactive group X from the reactive compatibilizer (C). The reaction between components (B) and (C) makes the composition compatible with further mixing in step (iv) to form a silicone-polyolefin hybrid product. Step (iv) can last for any suitable duration from a few minutes to a few hours, but is typically between 5 minutes and 3 hours, alternatively between 5 minutes and 2 hours, and alternatively between 5 minutes and 90 minutes.

[0186] When steps (i) and (ii) are performed simultaneously but prior to step (iii), the polymer base material (A), the functionalized polyolefin (B), and the optional non-reactive polyolefin (D) may be introduced into the mixer at room temperature, or at any preferred temperature between room temperature and a predetermined temperature between 100°C and 200°C, prior to mixing and heating. When steps (i), (ii), and (iii) are performed simultaneously, the polymer base material (A), the functionalized polyolefin (B), the reactive compatibilizer (C), and the optional non-reactive polyolefin (D) may be introduced into the mixer at any desired temperature between room temperature and 100°C and 200°C, or at any preferred temperature between room temperature and a predetermined temperature between 100°C and 200°C, prior to mixing and heating.

[0187] In one embodiment, when step (iii) occurs after step (ii), the reactive compatibilizer (C) can be added to the mixer at any suitable temperature that will allow the reaction between groups X and Y to occur. For example, step (iii) can be carried out at approximately the same temperature as step (ii), or at a higher temperature if desired.

[0188] Polytetrafluoroethylene (PTFE) packing can be used on the shaft of the tapered screw, and in one embodiment, the screw may include a lip seal on the shaft of the screw if desired.

[0189] In step (iii) of the method, when performed after steps (i) and (ii), the temperature of the mixing chamber is optionally maintained within a predetermined range of 100°C to 200°C for a period of up to 6 hours to remove volatiles and thermodynamically promote the reaction between components (B) and (C), thereby promoting the compatibility of the resulting organosilicon-polyolefin hybrid material product.

[0190] Similarly, when performed separately after steps (i) and (ii), step (iii) can be carried out under a vacuum or in an inert atmosphere, such as nitrogen, and heating may be necessary if / when the heat generated during shear mixing in step (ii) is insufficient to ensure that the temperature is maintained in step (iii). Using a vacuum at this stage may be useful, depending on the X and Y groups involved in the reaction that occurs, to enable the removal of volatiles.

[0191] In step (v) of the method, the resulting product is cooled to a selected temperature between 25°C and 120°C, enabling step (vi) to occur, i.e., once the closure device is moved to the open position to allow the product to be extruded through the extrusion die, the cooled silicone-polyolefin hybrid product of step (v) is extruded from the mixer at a temperature of 25°C to 75°C. In one embodiment, the cooling step is carried out at a reduced screw speed compared to the previous step, for example, 5 rpm to 40 rpm, alternatively 5 rpm to 30 rpm, or alternatively 5 rpm to 20 rpm. If desired, for example, when the method is nearing completion or during step (v), the rotation of the two screws in the CTM may also be temporarily reversed to assist the mixing or cooling process. During the cooling phase, the blade mixing speed can be reduced or reversed to reduce the heat generated by shear. The reduction in mixing speed reduces the heat generated by shear mixing, and the continuous mixing of the material helps to remove any trapped internal heat.

[0192] The extrusion die has an inlet and an outlet, wherein the passage through the extrusion die from the inlet to the outlet in the conical screw tablet extruder is controlled by the aforementioned closure device. The temperature to which the product needs to be cooled depends on whether it is intended for further processing or storage, such as packaging for future use or sale.

[0193] Therefore, for example, if the product is to be stored and / or packaged, it needs to be cooled to a sufficiently low temperature to prevent the packaging material from melting. For example, in the case of polyethylene, it must be cooled to a temperature not exceeding 90°C, such as a predetermined temperature of about 30°C to 80°C, alternatively about 30°C to 70°C, or alternatively about 40°C to 70°C.

[0194] The cooling step (v) of the method can be performed, for example, as follows:

[0195] (I) The process is carried out entirely in a conical screw extruder used for preparing silicone-polyolefin hybrid materials, in which the resulting silicone-polyolefin hybrid materials are cold-extruded at a temperature in the range of 30°C to 40°C.

[0196] (II) Partially carried out in a conical screw extruder for preparing silicone-polyolefin hybrid materials, wherein the resulting silicone-polyolefin hybrid material is extruded at a moderate temperature in the range of 50°C to 80°C and then transferred to an alternative device for further cooling, such as a tray or other container; or

[0197] (III) The process is carried out entirely outside the conical screw extruder used to prepare the silicone-polyolefin hybrid material, in which case the resulting silicone-polyolefin hybrid material is “hot” extruded at a temperature of 80°C to 120°C, or alternatively at a temperature of 90°C to 120°C (i.e., after step (iv)), and then transferred to an alternative device for cooling, such as a second “cooling” conical screw extruder, a disc or other container, in which case the conical screw extruder used to prepare the silicone-polyolefin hybrid material can be reused without delay to prepare another batch of silicone-polyolefin hybrid material.

[0198] If the conical screw extruder used for preparing silicone-polyolefin hybrid materials is also used to cool the base material to approximately 25°C, this could increase costs and time and reduce plant output, making options (II) and (III) attractive. However, in alternative (III), the hot product from step (iv) is extruded from the CTM before cooling begins and transferred to an alternative cooling CTM or other cooling device for cooling, and then extruded once cooled.

[0199] As the product of step (iv) is extruded from the CTM, cooled CTM, or other cooling device, the silicone-polyolefin hybrid material can be transferred through a filtration device, such as a screen. For example, the silicone-polyolefin hybrid material can be filtered directly through a screen attached to the CTM, or filtered in an auxiliary device. Filtration can also be combined with a device for degassing the material. Such additional steps can remove any improperly mixed clumps or particles, thereby providing a smooth and consistent material.

[0200] If necessary, after step (vi), the resulting product may be granulated before storage for future use, such as as a major component in a blending process. Any suitable method may be used to granulate the product, and such granulated product is considered a preferred storage method prior to further use (e.g., for blending).

[0201] The product flowing from the conical screw tableting extruder through the extrusion die can be collected for further cooling and / or can be collected and transferred to suitable packaging equipment or transported elsewhere for further processing and application. With further cooling, it can be extruded into bulk drums or other containers, or it can be passed directly through a gear pump and then packaged.

[0202] In one embodiment, the silicone-polyolefin hybrid material flowing from the conical screw tableting extruder is extruded into another device for further processing, such as another conical screw tableting extruder or a conical twin-screw extruder with a gear pump, where it can be filtered and packaged, or alternatively any suitable compounding device, such as a Sigma blade kneader mixer, a bottom discharge kneader mixer, a conical screw tableting extruder, a planetary extruder, a co-kneader extruder, a twin-screw extruder, a single-screw extruder, and / or a twin-roll mill, but in this case, in a preferred embodiment, it may be a second conical screw tableting extruder.

[0203] The organosilicon-polyolefin hybrid products prepared by the method described herein can be mixed with other components to form curable compositions.

[0204] In one embodiment, the method for preparing the silicone-polyolefin hybrid material forms part of a continuous compounding method, for example, using a cascade of conical screw extruders, wherein a first conical screw extruder can be used to prepare a silicone polymer base (A), and a second conical screw extruder can be used to prepare the silicone-polyolefin hybrid material as described above, and a third conical screw extruder can be used at least partially for cooling and subsequently for packaging.

[0205] If desired, any suitable type of compounding machine can be used to blend the silicone-polyolefin hybrid product with other components, such as a Sigma blade kneader mixer, a bottom discharge kneader mixer, a conical twin mixer (e.g., a screw extruder), a planetary extruder, a co-kneader extruder, a twin-screw extruder, a single-screw extruder, and / or a twin-roll mill. Where necessary, depending on the selected mixer (e.g., for a kneader mixer), a pressure plate can be used to assist in the introduction of additives. In a preferred embodiment, a second conical screw extruder can be used to introduce catalysts, crosslinking agents, etc., into the silicone-polyolefin hybrid material.

[0206] The curable composition comprises a silicone-polyolefin hybrid product and a curing agent, but other optional additives may be added to the composition. The curing agent typically comprises, and alternatively, a free radical initiator and / or a photoinitiator.

[0207] Examples of 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'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylbutyronitrile) (AMBN), tert-amyl peroxide, tert-butyl peracetic acid, tert-butyl peroxide, tert-butyl peroxyisopropyl carbonate, cumyl hydroperoxide, and potassium persulfate.

[0208] Any amount of free radical initiator can be used in the curable composition, but typically only a catalytic amount is required. For example, in some embodiments, the curable composition comprises 0.01 wt% to 10 wt% of the total weight of the curable composition, alternatively 0.1 wt% to 9 wt% of the total weight of the curable composition, 0.2 wt% to 7.5 wt% of the total weight of the curable composition, or 0.2 wt% to 6 wt% of the total weight of the curable composition, of the silicone-polyolefin hybrid product and the free radical initiator. Amounts outside these ranges may also be used, but it should be recognized that excessive amounts of free radical initiator may not significantly increase the time or efficiency of the curing process. The curing process typically takes 1 to 30 minutes, depending on the method used, alternatively 1 to 20 minutes, or 1 to 15 minutes.

[0209] Examples of suitable photoinitiators include onium salts, nitrobenzyl sulfonates, diaryliodoonium salts of sulfonic acids, triarylsulfonium salts of sulfonic acids, diaryliodoonium salts of boric acids, triarylsulfonium salts of boric acids, bis-diaryliodoonium salts (such as bis(dodecylphenyl)iodoonium hexafluoroarsenate and bis(dodecylphenyl)iodoonium hexafluoroantimonate), dialkylphenyliodoonium hexafluoroantimonate, diaryliodoonium salts of sulfonic acids, triarylsulfonium salts of sulfonic acids, diaryliodoonium salts of boric acids, and triarylsulfonium salts of boric acids.

[0210] Examples of suitable diaryliodoium salts of sulfonic acids include diaryliodoium salts of perfluoroalkyl sulfonic acids and diaryliodoium salts of aryl sulfonic acids. Examples of suitable diaryliodoium salts of perfluoroalkyl sulfonic acids include diaryliodoium salts of perfluorobutane sulfonic acid, perfluoroethane sulfonic acid, perfluorooctane sulfonic acid, and trifluoromethane sulfonic acid. Examples of suitable diaryliodoium salts of aryl sulfonic acids include diaryliodoium salts of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, and 3-nitrobenzenesulfonic acid. Examples of suitable triarylsulfonium salts of sulfonic acids include triarylsulfonium salts of perfluoroalkyl sulfonic acids and triarylsulfonium salts of aryl sulfonic acids. Examples of suitable triaryl sulfonates of perfluoroalkyl sulfonic acids include triaryl sulfonates of perfluorobutane sulfonic acid, perfluoroethane sulfonic acid, perfluorooctane sulfonic acid, and triaryl sulfonates of trifluoromethane sulfonic acid. Examples of suitable triaryl sulfonates of aryl sulfonic acids include triaryl sulfonates of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, and 3-nitrobenzenesulfonic acid. Examples of suitable diaryliodomonium salts of boric acids include diaryliodomonium salts of perhaloarylboronic acids, and preferred triaryl sulfonates of boric acids are perhaloarylboronic acids.

[0211] The amount of photoinitiator is typically in the range of 0.001 wt% to 5 wt% based on the total weight of the curable composition, alternatively 0.1 wt% to 5 wt% based on the total weight of the curable composition, alternatively 0.25 wt% to 5 wt% based on the total weight of the curable composition, alternatively 0.25 wt% to 5 wt% based on the total weight of the curable composition, alternatively 0.5 wt% to 5 wt% based on the total weight of the curable composition.

[0212] Curable compositions are typically prepared by combining a curing agent with a silicone-polyolefin hybrid product. There are no particular limitations on the process used for combination, and any of the mixing equipment described above can be used. Similarly, the curable composition can be prepared sequentially with a silicone-polyolefin blend (e.g., by adding the curing agent to the blend during or shortly thereafter). However, it should be understood that curable compositions can be prepared using separate and / or different mixers or mixing processes. For example, after extrusion from the mixer in the methods described above, the curing agent can be ground into the silicone-polyolefin hybrid product using a roller mill to prepare the curable composition. Those skilled in the art will understand that various mixing processes and equipment (including any of those described herein and combinations thereof) can be used to combine the curing agent and the silicone-polyolefin and prepare curable compositions. Attached Figure Description

[0213] Figure 1The following content is shown

[0214] A. SEM images of hybrid materials prepared from twin-screw extruder products at 10,000x magnification.

[0215] B. Hybrid material prepared by a conical screw extruder after mixing for 10 minutes, magnified at 10,000x.

[0216] C. Material prepared by a conical screw extruder after mixing for 20 minutes, with a magnification of 10,000x.

[0217] In some embodiments, the curable composition further comprises one or more optional additives. For example, in some embodiments, the curable composition may comprise one or more additional additives, such as, for example, binders; thickeners; tackifiers; adhesion promoters; extenders; plasticizers; end-sealing agents; desiccants; colorants (e.g., pigments, dyes, etc.); anti-aging additives; curing inhibitors, such as alkynols and their derivatives, such as 1-ethynyl-1-cyclohexanol (ETCH); biocides; flame retardants; corrosion inhibitors; UV absorbers; antioxidants; light stabilizers; pre-catalysts or catalyst generators; initiators (e.g., thermally activated initiators, electromagnetically activated initiators, etc.); photoacid generators; heat stabilizers; etc., and their derivatives, modifiers, and combinations thereof. It should be understood that such additives may be classified according to different technical terms, and the fact that an additive is classified under a specific term and / or characterized according to a specific function does not mean that it is therefore limited to that function. Furthermore, some additives may be present in specific components of the curable composition, or alternatively may be incorporated during the formation of the curable composition. In theory, curable compositions can contain any number of additional components and additives, depending on the specific type and / or function of the additional components and additives in the curable composition.

[0218] When present, one or more additives may be combined with the curing agent or the silicone-polyolefin hybrid product before, during, or after combining the curing agent and the silicone-polyolefin hybrid product. In other words, one or more additives may be combined with the silicone-polyolefin hybrid product (or curing agent) to form an intermediate composition, which is then combined with the curing agent (or silicone-polyolefin blend) to obtain a curable composition. Alternatively, the silicone-polyolefin hybrid product, the curing agent, and a number of suitable additives may be combined in a synergistic step. Those skilled in the art will readily understand that the specific order of addition and / or combination applicable to a given additive will depend on the nature of the additive and other components of the curable composition, and will therefore be selected independently based on the specific components and parameters employed.

[0219] Similarly, a cured product of a curable composition and a method for preparing the cured product are also provided. Specifically, the curable composition can be cured to obtain a cured product. As those skilled in the art will understand, such curing typically involves activating the curing agent, for example by heating the composition to a temperature sufficient to activate a free radical initiator (e.g., via thermal decomposition), irradiating a photoinitiator, etc. Such activation processes are known in the art and will be selected based on the specific curing agent used.

[0220] The curable composition is cured via free radical curing (i.e., upon activation of the free radical initiator) to form a cured product. It should be understood that the cured curable composition typically comprises crosslinking components such as reactive compatibilizers (C) and one or more silicone polymers and / or copolymers (A)(1) having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08.

[0221] The cured product can be referred to as an organosilicon-polyolefin elastomer or a hybrid elastomer.

[0222] Therefore, methods for preparing cured products generally involve heating the curable composition to an elevated temperature (such as 90°C to 300°C, alternatively 100°C to 300°C, alternatively 100°C to 250°C, alternatively 100°C to 200°C) for a time sufficient to cure the curable composition. In some embodiments, the curable composition is cured at a temperature of 150°C to 220°C for 1 minute to 20 minutes, alternatively 5 minutes to 20 minutes, or alternatively 5 minutes to 15 minutes.

[0223] Unexpected advantages were found when using a conical screw tableting extruder as described herein compared to other standard mixers. Several problems were encountered when attempting to prepare silicone-polyolefin hybrid products using a standard twin-screw extruder compared to a conical screw tableting extruder. It was found that using silicone polymer base materials (A)(1) made from silicone (such as one or more silicone polymers and / or copolymers (A)(1)) having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08) was unusable because twin-screw extruders can only handle pre-formed silicone base materials that can flow into the twin-screw extruder via a pipe, which is not possible when using silicone.

[0224] Another issue is that polyolefin components B and D (when present) also require the polyolefin material to be pumped in liquid form (by melt) or added directly to the twin-screw extruder in pellet form, which limits the source material requirements, especially when non-reactive polyolefins (D) are included, which, for sustainability reasons, requires separate processes to form pellets or melts when, for example, it includes post-consumption recycling (PCR).

[0225] Furthermore, it was determined that conical screw extruders are significantly better at controlling certain mechanical properties of silicone-polyolefin hybrid products by limiting the mixing time of the material. With increasing mixing time, hardness, modulus at 100% elongation, and resilience all decreased, while tensile strength, elongation, and type B tear resistance all increased. In addition, the domain morphology of polyolefins was also affected by the mixing time in conical screw extruders. It was found that this is not the case in twin-screw extruders, where changing the mixing operation by altering the mixing speed or temperature has no effect on the domain morphology of the dispersed polyolefins.

[0226] Unexpectedly, attempts to prepare the aforementioned products were far less successful than expected on mixers that did not fully encapsulate their mixing elements (blades, teeth, etc.) to facilitate constant high-shear mixing. Such mixers, for example, failed to successfully prepare silicone-polyolefin hybrids when using co-kneading mixers such as the Haake mixer and the Sigma blade co-kneading mixer. Furthermore, it was found that the morphology of the dispersed phases (components (B) and (D), when present) of the hybrid materials did not change significantly under varying mixing conditions when using other mixers.

[0227] The formation of polyolefin-silicone hybrids on twin-screw extruders presents additional limitations, such as raw material sourcing. Twin-screw extruders are generally not used to form high-viscosity silicone base materials (which are typically carried out on large inclined mixers), thus limiting the silicone source to pre-formed silicone base materials that must be able to flow through pipes into the twin-screw extruder barrel. Therefore, using a conical screw extruder avoids the need for additional equipment, such as the metering equipment required to produce silicone-polyolefin hybrids, and it has been found that the process can be controlled by heating, mixing speed, and mixing time on a conical screw extruder.

[0228] Based on the above description and the following examples, it should be understood that, due to the low cost of the precursors and the solvent-free nature of the formulations, the methods and compositions provided herein offer a cost-effective way to obtain unique organosilicon-polyolefin hybrid materials.

[0229] The compositions of this invention enable the preparation of products and articles with enhanced performance properties, including those formed via organic compositions, organosilicon compositions, or conventional hybrid organosilicon-organic compositions. For example, injection-molded and compression-molded articles can be made from the compositions of this invention, which have improved toughness (e.g., increased tear strength), chemical resistance (e.g., improved resistance to solvent swelling), excellent elongation and tensile strength, and delayed elastic recovery, compared to typical organosilicon rubber elastomers.

[0230] Such products and articles can be used in a wide range of applications or in the production of a wide range of consumer products and articles. Examples include products and articles in or for consumer wearable electronics; packaging and dispensing of consumer products, such as for food, personal care and beauty care products and / or products; vibration isolation components; electrical protection in wire and cable applications; and coating or co-molding on substrates such as buttons, knobs and user interface controls or components. Example

[0231] The following series of examples are provided to demonstrate the suitability of a method for preparing silicone-polyolefin hybrid materials using a conical screw extruder from a silicone polymer base (A), a functionalized polyolefin (B), a reactive compatibilizer (C), and optionally a non-reactive polyolefin (D) comprising one or more silicone polymers and / or copolymers, wherein the silicone polymers and / or copolymers in each case have a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08. Unless otherwise stated, all viscosity measurements given are zero shear viscosity (η). o The zero-shear viscosity (ZHV) value is obtained by extrapolating (or simply averaging) values ​​obtained at low shear rates from a viscosity-shear rate curve that is independent of the rate. This is a method-independent value provided a suitable, properly operated rheometer is used. For example, the ZHV of a substance at 25°C can be obtained using a commercial rheometer, such as the Anton-Parr MCR-301 rheometer equipped with a cone-plate clamp of appropriate diameter or the TA Instruments AR-2000 rheometer, at a range of low shear rates such as 0.01 s⁻¹. -1 0.1s -1 and 1.0s -1 This generates a sufficient torque signal without exceeding the transducer's torque limit.

[0232] The following embodiments illustrating implementations of this disclosure are intended to be illustrative and not limiting of the invention.

[0233] An overview is provided in Table 1 below, which illustrates information about certain abbreviations, acronyms, and components used in the examples. Viscosities are typically reported as zero-shear viscosity measured at 25°C. Degrees of polymerization (DP) are typically reported as number-average DP (e.g., relative to standards such as polystyrene) from sources such as NMR, IR, and / or GPC.

[0234] Table 1: Materials Used

[0235]

[0236] In the examples, according to the method described herein for preparing organosilicon-polyolefin hybrid materials, Colmec, which is available from ColmecSpA (Busto Arsizio, Italy), was used. ™ The CTM-65 mixer, used as a conical screw extruder, has been used to prepare a series of organosilicon-polyolefin hybrid materials.

[0237] The composition of the starting components used in the method for preparing the embodiments is shown in Table 2 below.

[0238] Table 2: Composition of starting components

[0239]

[0240] In the method used in the first set of embodiments, steps (i) and (ii) are performed simultaneously, wherein the organosilicon-based material 1 and the functionalized polyolefin 1 are introduced together into Colmec ™ In a CTM-65 mixer, set the mixer to heat the contents to 150°C while the screw rotates at approximately 70 rpm. The stopper remains in the closed position. Mixing continues as the mixing chamber is heated by the mixer's own heat source and by shear heat generated within the chamber due to the mixing process, until the mixture within the chamber reaches a temperature of approximately 150 to 180°C after approximately 1 hour of mixing silicone-based material 1 and functionalized polyolefin 1. Mixing is then stopped, and a compatibilizer is added by pouring it onto the silicone-based material 1 / functionalized polyolefin 1 mixture in the mixer. The materials are then mixed for the time specified on the runner (5 to 60 minutes). The temperature is then lowered to ambient temperature, and the Colmec... ™ In the CTM-65 mixer, the screw mixing speed is reduced to 10 rpm to facilitate cooling. The maleic anhydride group X of the functional polyolefin 1 and the amine group Y of the compatibilizer react to enable compatibility and form an organosilicon-polyolefin hybrid product. Once the temperature is observed to be between room temperature (approximately 25°C) and 50°C, the closure device (3) in the conical screw extruder is opened, thereby allowing the resulting cooled organosilicon-polyolefin hybrid to be extruded through the extrusion die and conveyed to a storage location or for further processing, such as processing into a curable composition.

[0241] In this embodiment, the extruded silicone-polyolefin hybrid product is used to prepare a curable composition by directly blending the silicone-polyolefin hybrid product with a curing agent (by weight, 1 part / 100 pph of the silicone portion of the silicone-polyolefin hybrid product) on a twin-roll mill until the resulting material is visually homogeneous. This material is then divided into portions to fill 110% of a die with an internal cavity size of 6”×6”×2mm (15.24cm×15.24cm×2mm). Individual portions of the extruded silicone-polyolefin hybrid product are pre-formed into flat sheets slightly smaller than 6”×6” (15.24cm×15.24cm) placed in the die at room temperature.

[0242] The resulting hybrid blends were compression molded in a heated hydraulic Greenerd press. They were initially placed between two sheets of brown Teflon and a 1 / 4" aluminum backing. The samples were pressed at room temperature for 2 to 3 minutes to fill the mold and expel all air bubbles, then pressed at 175°C and 1500 psi (10.34 MPa) for 10 minutes and removed from the mold immediately after curing. The cured hybrid elastomer sheets were left to stand at room temperature for 24 hours before characterization. In Example 9, the same method as in Examples 1-8 was used, except that functionalized polyolefins and non-reactive polyolefins were introduced simultaneously.

[0243] The physical properties of the cured compound were then analyzed. For tear strength samples, tensile and type B tear samples were prepared using ASTM D412C and a type B tear die. Specific gravity samples were cut from the material fragments left after cutting the tensile and type B tear samples. In the table below, hardness was measured according to a Shore A hardness tester (ASTM D2240), tensile strength and elongation were measured according to ASTM D412, tear strength was measured according to ASTM D624 die B, specific gravity was measured according to ASTM D792 using a Mettler Toledo balance, and springback was measured according to ASTM D2632.

[0244] For the moving mold rheometer (MDR) test, the maximum torque (MH) of the compound product sample with 1 pph curing agent (relative to the silicone portion of the silicone-polyolefin hybrid material) was tested. TS2 and TC90 were measured for 6 minutes at 175°C using the Alpha Tech Premier MDR.

[0245] Scanning electron microscopy imaging was performed using the following methods.

[0246] A slice was cut from each sample, placed in the microtome chuck, and trimmed with a razor blade to form a block. Samples were polished using a Leica UC7:FC7 ultramicrotome at -140°C with a MicroStar cryotome (LH) blade. Samples were imaged using a ThermoFisher Nova NanoSEM 600 in low vacuum mode with a water pressure of 0.6 Torr. Backscattered electron images were collected using a gas detection device (GDD detector). The results are presented in Tables 3a and 3b below.

[0247] Table 3a: Physical property results

[0248]

[0249] Table 3b: Other physical property results

[0250]

[0251] Using Colmec ™ Examples 1 through 9 were conducted using the CTM-65 conical screw extruder (CTM), and it was found that they exhibited mechanical properties that varied with mixing time, which is not possible when using a twin-screw extruder (TSE). Significant differences were found in certain properties between the CTM and TSE methods. For example, resilience, an indicator of the noise reduction capability of the hybrid material, showed higher resilience when using CTM for shorter mixing times. Hardness and modulus also increased when using CTM, thus broadening the material's applicability to customer requirements.

[0252] In another embodiment, prior to step (i) of the method, in Colmec ™ A silicone polymer base material (A) in the form of a high-strength silicone rubber (HCR) base material with a hardness of 30 was prepared in a CTM-65 conical screw extruder. In this case, the base material composition is described in Table 4 below:

[0253] Table 4: Composition of Organosilicon Rubber Base Material (A)

[0254]

[0255] Organosilicon 1 is a dimethyl vinyl-terminated polydimethylsiloxane polymer with a Williams plasticity of approximately 148 mm / 100 according to ASTM D-926-08.

[0256] Organosilicon 2 is a dimethyl vinyl-terminated polydimethylsiloxane polymer with approximately 150 mm / 100 Williams plasticity according to ASTM D-926-08.

[0257] The pyrolytic silica used is CAB-O-SIL, which is commercially available from Cabot Corporation. ™ MS-75 silica.

[0258] Organopolysiloxane 1 is a vinyl dimethyl-terminated methyl vinyl dimethylsiloxane copolymer with a viscosity of about 15,000 mPa·s at 25°C and a vinyl content of 7.7% by weight.

[0259] Organopolysiloxane 2 is a hydroxyl-terminated polydimethylsiloxane polymer with a viscosity of 42 mPa·s according to ASTM D-445.

[0260] The base material was prepared as follows: First, silicone 1 and 2, organosiloxane 1, and water were introduced into a CTM mixer and mixed for 5 minutes, then the mixer was rinsed with nitrogen. Then, pyrolytic silica and a treatment agent were added during further mixing. Once the addition was complete and further mixing was performed, the resulting base material (component (A)) was further mixed under vacuum, and then the CTM was heated to 150°C. When the temperature in the CTM reached 150°C, component (B) in the form of functionalized polyolefin 1 was introduced, and the process was then carried out in the same manner as in the previous embodiment, where the required time for mixing the resulting silicone base material, polyolefin, and compatibilizer was taken, followed by cooling (if necessary). The CTM was cooled to room temperature, but once the temperature dropped below 50°C, it could be extruded from the CTM.

[0261] The organosilicon-polyolefin hybrid materials prepared above have the approximate composition shown in Table 5 below.

[0262] Table 5: Starting Composition of Organosilicon-Polyolefin Hybrid Materials .

[0263]

[0264] Similarly, the resulting extruded silicone-polyolefin hybrid product was used to prepare a curable composition by directly blending the silicone-polyolefin hybrid product with a curing agent (by weight, 1 part / 100 pph of the silicone portion of the silicone-polyolefin hybrid product) on a twin-roll mill until the resulting material was visually uniform. These were then cured according to the curing method used in the foregoing examples.

[0265] Similarly, the resulting cured hybrid elastomer sheet was left to stand at room temperature for 24 hours. For comparison, the curing agent of silicone base material 3 was added to silicone base material 3 in the same manner as the hybrid material and cured. The physical properties of the cured sheets of both the catalytic silicone rubber base material 3 (C.2) and the resulting catalytic hybrid material (Example 10) were evaluated, and the results are shown in Table 6 below.

[0266] Table 6: Physical property results

[0267]

[0268] The testing methods used are the same as those indicated above.

Claims

1. A method for preparing a silicone-polyolefin hybrid material, said silicone-polyolefin hybrid material being prepared by mixing a silicone polymer base (A) comprising one or more silicone polymers and / or copolymers with one or more functionalized polyolefins (B) and a reactive compatibilizer (C), said silicone polymers and / or copolymers having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08, said method comprising the following steps: (i) The silicone polymer base material (A) comprising one or more silicone polymers and / or copolymers is introduced into the mixing chamber of a mixer and mixed while being heated to a predetermined temperature of 100°C to 200°C, wherein the silicone polymers and / or copolymers have a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08 in each case; (ii) Simultaneously with step (i) or once the silicone polymer base material (A) has reached the predetermined temperature of 100°C to 200°C, one or more functionalized polyolefins (B) are introduced into the mixing chamber of the mixer while mixing continues to form an initial silicone-polyolefin hybrid composition mixture; (iii) When carried out together with or after steps (i) and (ii), a polysiloxane polymer having at least one reactive group or a reactive compatibilizer (C) thereof is introduced into the mixing chamber of the mixer while mixing continues; wherein the at least one reactive group of the reactive compatibilizer (C) is capable of reacting with the one or more functionalized polyolefins (B); and mixing is carried out simultaneously. This forms the initial organosilicon-polyolefin hybrid composition mixture; (iv) Continue mixing the initial organosilicon-polyolefin hybrid composition mixture for a predetermined period of time so that the reactive groups of the reactive compatibilizer (C) can react with the functional groups of the functionalized polyolefin (B). To form organosilicon-polyolefin hybrid material products; (v) Cooling the organosilicon-polyolefin hybrid material product of step (iv); (vi) Extruding the silicone-polyolefin hybrid product of step (iv) or the cooled silicone-polyolefin hybrid product of step (v) from the mixer at a temperature of 25°C to 75°C; The mixer is characterized as follows: it is a conical screw tableting extruder comprising a conical twin-screw mixing chamber containing two counter-rotating conical screws converging toward an extrusion die having an inlet and an outlet, wherein the passage through the extrusion die is controlled by a shut-off device such that the outlet of the extrusion die is adapted to be closed by the shut-off device until the product of step (iv) or (v) is extruded from the conical screw tableting extruder, and is adapted to be used in step (i) in the following cases. Open after step (v) or (v): If or when the silicone-polyolefin hybrid product is to be further processed or stored outside the conical screw extruder, such that during mixing, the contents of the mixer are driven toward the extrusion die by the pair of counter-rotating conical screws, and then forced back when the extrusion die is closed by the closure device, and then opened after step (iv) or (v) to allow the product of step (iv) or (v) to be extruded through the extrusion die for further processing and / or storage.

2. The method for preparing organosilicon-polyolefin hybrid materials according to claim 1, wherein: (') Each functional group X contains an aminoalkyl group, a methacryloyloxy group, a silicon-bonded hydroxyl group, an anhydride group, a silicon-bonded hydrogen atom, an olefinic unsaturated group, or a methanol group. (ii') The reactive compatibilizer (C) has a zero-shear viscosity of at least 3,000 mPa·s at 25°C; (iii') Based on the total weight of the starting components, the reactive compatibilizer (C) is present in the organosilicon-polyolefin composition in an amount of 0.5% to 15% by weight; or Any combination of (iv')(') to (iii').

3. The method for preparing organosilicon-polyolefin hybrid materials according to claim 1, wherein at least one or more organosilicon polymers and / or copolymers of the organosilicon polymer base (A) have a Williams plasticity of at least 125 mm / 100 according to ASTM D-926-08.

4. The method for preparing organosilicon-polyolefin hybrid materials according to any one of claims 1 to 3, wherein: The functionalized polyolefin (B) comprises functionalized polyethylene (PE), polypropylene (PP) or polyethylene-α-olefin copolymer; (ii”) Each functional group Y contains an epoxy group, an aminoalkyl group, a trimethoxysilyl group, a hydride silyl group, or an anhydride group; (iii) The functionalized polyolefin (B) has a content of 0.86 g / cm³. 3 Up to 0.96 g / cm 3 The density; (iv”) The functionalized polyolefin (B) is functionalized with 0.05% to 10% by weight of a functional portion containing the functional group Y, based on the total weight of the functionalized polyolefin (B). (v”) Based on the total weight of the organosilicon-polyolefin composition, the functionalized polyolefin (B) is present in the organosilicon-polyolefin composition in an amount of 1% to 40% by weight; or Any combination of (vi”)(”) to (v”).

5. The method for preparing organosilicon-polyolefin hybrid materials according to any one of claims 1 to 4, wherein Y is an anhydride group and X is an amino group.

6. The method for preparing organosilicon-polyolefin hybrid materials according to any one of claims 1 to 5, wherein an organosilicon polymer base material (A) is prepared in the conical screw extruder prior to step (i) of the method.

7. The method for preparing a silicone-polyolefin hybrid material according to any one of claims 1 to 6, wherein the method for preparing the silicone-polyolefin hybrid material forms part of a continuous compounding process, i.e., a series of conical screw extruders, wherein a first conical screw extruder is capable of preparing a silicone polymer base (A), and a second conical screw extruder is capable of preparing the silicone-polyolefin hybrid material according to any one of claims 1 to 6, and optionally a third conical screw extruder is at least partially used for cooling and subsequently for packaging.

8. The method for preparing an organosilicon-polyolefin hybrid material according to any one of claims 1 to 7, wherein after step (vi), the organosilicon-polyolefin hybrid material product is prepared into a curable composition by adding a free radical initiator and / or a photoinitiator.

9. The method for preparing organosilicon-polyolefin hybrid materials according to any one of claims 1 to 8, wherein the starting component further comprises component (D) a non-reactive polyolefin.

10. The method for preparing organosilicon-polyolefin hybrid materials according to claim 9, wherein the non-reactive polyolefin (D) is a post-consumer recycled resin, a virgin material, or a combination of a post-consumer recycled resin and a virgin material.

11. The method for preparing organosilicon-polyolefin hybrid materials according to any one of claims 1 to 8, wherein a non-reactive polyolefin (D) is introduced into the mixer during step (ii), wherein step (ii) is performed simultaneously with step (i), or both are performed simultaneously.

12. An organosilicon-polyolefin hybrid product that can be obtained by or through any of the methods described in any one of claims 1 to 11.

13. Use of a conical screw extruder as an apparatus for preparing a silicone-polyolefin hybrid composition product, said silicone-polyolefin hybrid composition product being prepared by mixing a silicone polymer base (A) comprising one or more silicone polymers and / or copolymers, one or more functionalized polyolefins (B), and a reactive compatibilizer (C), said silicone polymers and / or copolymers having a Williams plasticity of at least 75 mm / 100 according to ASTM D-926-08, said method comprising the following steps: (i) The silicone polymer base material (A) is introduced into the mixing chamber of the mixer and mixed while being heated to a predetermined temperature of 100°C to 200°C; (ii) Simultaneously with step (i) or once the silicone polymer base material (A) has reached the predetermined temperature of 100°C to 200°C, one or more functionalized polyolefins (B) are introduced into the mixing chamber of the mixer while mixing continues to form an initial silicone-polyolefin hybrid composition mixture; (iii) When carried out together with or after steps (i) and (ii), a reactive compatibilizer (C) comprising an organosilicon polymer having at least one functional group is introduced into the mixing chamber of the mixer while mixing continues; wherein the functional group of the compatibilizer is capable of reacting with the polyolefin having reactive groups grafted thereon from step (ii); mixing is carried out simultaneously. This forms the initial organosilicon-polyolefin hybrid composition mixture; (iv) Continue mixing the initial organosilicon-polyolefin hybrid composition mixture for a predetermined period of time so that the reactive groups of the reactive compatibilizer (C) can react with the functional groups of the functionalized polyolefin (B) to form an organosilicon-polyolefin hybrid material product. (v) Cooling the organosilicon-polyolefin hybrid material product of step (iv); (vi) Extruding the silicone-polyolefin hybrid product of step (iv) or the cooled silicone-polyolefin hybrid product of step (v) from the mixer at a temperature of 25°C to 75°C; The mixer is characterized as follows: it is a conical screw tableting extruder comprising a conical twin-screw mixing chamber containing two counter-rotating conical screws converging toward an extrusion die having an inlet and an outlet, wherein the passage through the extrusion die is controlled by a shut-off device such that the outlet of the extrusion die is adapted to be closed by the shut-off device until the product of step (iv) or (v) is extruded from the conical screw tableting extruder, and is adapted to be used in step (iv) in the following cases. Open after step (iv) or (v): If or when the silicone-polyolefin hybrid composition is to be further processed or stored outside the conical screw extruder, such that during mixing, the contents of the mixer are driven toward the extrusion die by the pair of counter-rotating conical screws, and then forced back when the extrusion die is closed by the closure device, and then opened after step (iv) or (v) to allow the product of step (iv) or (v) to be extruded through the extrusion die for further processing and / or storage.

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