Silicone-polyolefin hybrid elastomer

Abstract

A silicone-polyolefin composition is disclosed. The silicone-polyolefin composition comprises a curable silicone comprising (A) a polysiloxane, (B) a functionalized polyolefin, (C) a polyolefin not capable of reacting with components (A) or (B), and (D) at least one of an elastomeric component or a liquid rubber. The polysiloxane (A) comprises, on average, at least one functional group X per molecule, and the functionalized polyolefin (B) comprises, on average, at least one functional group Y per molecule, where the functional groups X and Y are capable of reacting to form a bond therebetween. Also disclosed are silicone-polyolefin blends, curable compositions comprising the silicone-polyolefin blends, cured products of the curable compositions, and methods of preparing the silicone-polyolefin blends, the curable compositions, and the cured products.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and all benefits of U.S. Provisional Patent Application No. 63 / 249,755, filed September 29, 2021, the contents of which are incorporated herein by reference.

[0002] The present disclosure relates generally to silicone compositions, and more particularly to hybrid silicone-polyolefin compositions, related curable compositions, and silicone-polyolefin hybrid elastomers formed therefrom. [Background technology]

[0003] Silicones are polymeric materials used in many commercial applications, primarily because of the distinct advantages they offer over their carbon-based analogues. Silicones, more precisely called polymerized siloxanes or polysiloxanes, contain inorganic silicon-oxygen backbone chains (...-Si-O-Si-O-Si-O-...) with organic side groups attached to the silicon atoms. 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 crosslinks, silicones with a wide variety of properties and compositions can be synthesized, with silicone networks varying in consistency from liquid to gel, rubber, and hard plastic. Silicone and siloxane-based materials are utilized in a myriad of end uses and environments, including as components in a wide variety of industrial, home care, and personal care formulations.

[0004] The most common silicone materials are based on linear organopolysiloxane polydimethylsiloxane (PDMS), silicone oils, followed by silicone resins formed with branched and cage-shaped oligosiloxanes. Many of these materials enable unique technologies by offering improved performance and benefits due to the inherent attributes of organopolysiloxanes, including low loss and stable optical transmission, high thermal and oxidative stability, and biocompatibility.

[0005] Unfortunately, despite widespread success in many technologies, the use of silicone materials in certain applications remains limited, even if viable, due to the undesirable attributes of many traditional siloxanes, such as their weak mechanical properties, which can manifest in materials with insufficient or inappropriate characteristics, such as low tensile strength, low tear strength, etc. Thus, carbon-based polymers, such as those based on polyolefins, polyacrylates, and polyurethane resins, are frequently used in applications that can benefit from certain inherent attributes of silicones. To further complicate matters, traditional siloxanes are incompatible with most carbon-based polymers, typically exhibiting immiscible and / or antagonistic properties. Summary of the Invention

[0006] A silicone-polyolefin composition ("Composition") is provided. The Composition comprises: (A) a polysiloxane containing, on average, at least one functional group X per molecule; (B) a functionalized polyolefin containing, on average, at least one functional group Y per molecule; (C) a polyolefin not capable of reacting with components (A) or (B); and (D) a curable silicone comprising at least one of an elastomeric component or a liquid rubber. The functional group X of the polysiloxane (A) and the functional group Y of the functionalized polyolefin (B) are capable of reacting to form a bond therebetween.

[0007] Also provided is a method for preparing a silicone-polyolefin blend ("Preparation Method") that includes combining a polysiloxane (A), a functionalized polyolefin (B), a polyolefin (C), and a curable silicone (D) to prepare a silicone-polyolefin composition, and reacting the polysiloxane (A) with the anhydride-functional polyolefin (B) in the presence of the polyolefin (C) and the curable silicone (D), thereby preparing the silicone-polyolefin blend.

[0008] Silicone-polyolefin blends prepared according to this preparation method are also provided.

[0009] A curable composition is also provided, the curable composition comprising a silicone-polyolefin blend and a curing agent.

[0010] Cured products of the curable compositions and methods for preparing the cured products are also provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Provided herein is a silicone-polyolefin composition ("composition"). As will be understood from the description herein, the composition provides a hybrid composition containing both a silicone component and a polyolefin component, and can be prepared and used without the use of a solvent. Since the silicone and polyolefin components are generally understood to be immiscible or otherwise incompatible with each other, the specific compounds and conditions utilized provide unique hybrid materials that exhibit desirable characteristics and properties that may not be obtainable with conventional methods and materials. Similarly, the composition may be utilized as a platform for the efficient and economical preparation of many functional compositions and their components, including some applications that are poorly suited, if at all practical, for use with conventional materials. Indeed, also provided herein are compatibilized silicone-polyolefin blends, curable compositions prepared therewith, and cured products prepared therefrom, as well as methods for making each of them, as exemplified in the following examples.

[0012] In view of this disclosure, one skilled in the art will readily appreciate that the unique structural and physical characteristics of the compositions of the present invention are compatible with useful manufacturing techniques such as melt blending and reactive extrusion, without the particular drawbacks inherent in using such techniques with conventional materials. Additionally, as described and exemplified herein, the compositions of the present invention allow for the preparation of products with improved performance characteristics, including injection moldable articles with improved toughness (e.g., increased tear strength) and chemical resistance (e.g., increased solvent swell resistance), satisfactory elongation and tensile strength, and desirable tactile sensation. Such articles may be particularly used in consumer articles where certain performance characteristics provided by conventional materials are often mutually exclusive, and improving any one property may diminish the user's positive tactile experience.

[0013] An "ethylene-based polymer" is a polymer that contains greater than 50 weight percent (wt%) polymerized ethylene monomer (based on the total amount of polymerizable monomers) and may optionally contain at least one comonomer. Ethylene-based polymers include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene-based polymer" and "polyethylene" may be used interchangeably. Non-limiting examples of ethylene-based polymers (polyethylenes) include low density polyethylene (LDPE) and linear polyethylene. Non-limiting examples of linear polyethylene include linear low density polyethylene (LLDPE), ultra low density polyethylene (ULDPE), very low density polyethylene (VLDPE), multi-component ethylene-based copolymer (EPE), ethylene / α-olefin multi-block copolymers (also called olefin block copolymers (OBC)), substantially linear or linear plastomers / elastomers, and high density polyethylene (HDPE).

[0014] High density polyethylene (or "HDPE") is an ethylene homopolymer or ethylene / α-olefin copolymer having at least one C4-C10 α-olefin comonomer or C4-C8 α-olefin comonomer and having a viscosity of at least 0.940 g / cm 3 , or at least 0.945 g / cm 3 , or at least 0.950 g / cm 3 , e.g., 0.953 g / cm 3 ~0.955g / cm 3 , or at least 0.960 g / cm 3 , or at least 0.965 g / cm3 , or at least 0.970 g / cm 3 , or at least 0.975 g / cm 3 , or at least 0.980 g / cm 3 is the density of the polymer. HDPE may be a unimodal or multimodal copolymer. A "unimodal ethylene copolymer" is an ethylene / C4-C10 α-olefin copolymer having one distinct peak in gel permeation chromatography (GPC) which shows the molecular weight distribution. A "multimodal ethylene copolymer" is an ethylene / C4-C10 α-olefin copolymer having at least two distinct peaks in GPC which shows the molecular weight distribution. Multimodal includes copolymers having two peaks (bimodal) as well as copolymers having three or more peaks.

[0015] "Low-density polyethylene" (or "LDPE") is an ethylene homopolymer or a polyethylene glycol having a molecular weight of 0.915 g / cm 3 ~0.940g / cm 3 and comprises an ethylene / α-olefin copolymer containing at least one C3-C10 α-olefin containing long chain branching having a wide range of MWD.

[0016] "Linear low density polyethylene" (or "LLDPE") is a linear ethylene / α-olefin copolymer containing a heterogeneous distribution of short chain branches including units derived from ethylene and at least one C3-C10 α-olefin comonomer. LLDPE is characterized by the presence of little, if any, long chain branching, in contrast to conventional LDPE. LLDPE has a viscosity of 0.910 g / cm 3 ~0.940g / cm 3 has a density of less than .

[0017] An "olefin-based polymer" or "polyolefin" is a polymer that contains a majority or greater than 50 weight percent polymerized olefin monomer, such as, for example, ethylene or propylene (based on the weight of the polymer), and may optionally contain at least one comonomer. Non-limiting examples of olefin-based polymers are ethylene-based polymers and propylene-based polymers.

[0018] A "propylene-based polymer" is a polymer that contains more than 50% by weight polymerized propylene monomer (based on the total amount of polymerizable monomers) and may optionally contain at least one comonomer. The terms "propylene-based polymer" and "polypropylene" may be used interchangeably.

[0019] "Very low density polyethylene" (or "ULDPE") and "very low density polyethylene" (or "VLDPE") are each linear ethylene / α-olefin copolymers containing a heterogeneous distribution of short chain branches comprising units derived from ethylene and at least one C3-C10 α-olefin comonomer. ULDPE and VLDPE each have a density of 0.885 g / cm 3 ~0.915g / cm 3 has a density of

[0020] The silicone-polyolefin composition generally comprises a curable silicone comprising at least one of (A) a polysiloxane, (B) a functionalized polyolefin, (C) a polyolefin not capable of reacting with components (A) or (B), and (D) an elastomeric component or a liquid rubber. The polysiloxane (A) comprises, on average, at least one functional group X per molecule, and the functionalized polyolefin (B) comprises, on average, at least one functional group Y per molecule. In some embodiments, the polysiloxane (A) comprises, on average, at least two functional groups X per molecule. In these or other embodiments, the functionalized polyolefin (B) comprises, on average, at least two functional groups Y per molecule. As will be understood in light of the description and examples herein, the functional group X of the polysiloxane (A) and the functional group Y of the functionalized polyolefin (B) can react (e.g., via an addition functionality reaction) to form a bond therebetween, i.e., to couple the polysiloxane (A) and the functionalized polyolefin (B).

[0021] The polysiloxane (A), the functionalized polyolefin (B), the polyolefin (C), and the curable silicone (D) are described sequentially below, along with additional compounds that may be present in the silicone-polyolefin composition, which may be referred to collectively herein as the "components" of the silicone-polyolefin composition (i.e., "component (A)," "component (B)," "component (C)," "component (D)," etc., respectively) or similarly as "compounds" and / or "reagents" (A), (B), (C), and / or (D), etc.

[0022] As introduced above, the silicone-polyolefin composition comprises a polysiloxane (A). As will be understood by those skilled in the art, a polysiloxane is a silicon-based compound that comprises a siloxane backbone, i.e., at least a semi-continuous chain composed of inorganic silicon-oxygen-silicon groups (i.e., -Si-O-Si-), with organosilicon and / or organic side groups bonded to the silicon atoms. Such siloxanes are typically characterized in terms of the number, type, and / or proportion of [M], [D], [T], and / or [Q] units / siloxy groups, each of which represents the structural units of the individual functional groups present in polysiloxanes, such as organosiloxanes and organopolysiloxanes. Specifically, [M] is a siloxane having the general formula R″3SiO 1 / 2 [D] represents a monofunctional unit of the general formula R″2SiO 2 / 2 [T] represents a difunctional unit of the general formula R″SiO 3 / 2 and [Q] represents a trifunctional unit of the general formula SiO 4 / 2 and is represented by the following general structural moiety:

[0023] [ka]

[0024] In these general structural moieties, each R" is independently a monovalent or polyvalent substituent. As understood in the art, the specific substituents suitable for each R" are not particularly limited (e.g., monoatomic or polyatomic, organic or inorganic, linear or branched, substituted or unsubstituted, aromatic, aliphatic, saturated or unsaturated, etc., and various combinations thereof). In a typical example, each R" is independently selected from hydrocarbyl groups, alkoxy and / or aryloxy groups, and siloxy groups. With respect to the hydrocarbyl groups suitable for R", examples generally include monovalent hydrocarbon moieties, and derivatives and modifications thereof, which may be independently substituted or unsubstituted, linear, branched, cyclic, or combinations thereof, and saturated or unsaturated. With respect to such hydrocarbyl groups, the term "unsubstituted" refers to a hydrocarbon moiety composed of carbon and hydrogen atoms, i.e., without heteroatom substituents. The term "substituted" refers to a hydrocarbon moiety in which at least one hydrogen atom is replaced with an atom or group other than hydrogen (e.g., a halogen atom, an alkoxy group, an amine group, etc.) (i.e., as a pendant or terminal substituent), a carbon atom in the hydrocarbon chain / backbone is replaced with an atom other than carbon (e.g., a heteroatom such as oxygen, sulfur, nitrogen, etc.) (i.e., as part of the chain / backbone), or both. As such, suitable hydrocarbyl groups include or can be a hydrocarbon moiety having one or more substituents in and / or on (i.e., attached and / or integral with) its carbon chain / backbone, such that the hydrocarbon moiety can include ethers, esters, etc., or can otherwise be referred to as ethers, esters, etc. Linear and branched hydrocarbyl groups can be independently saturated or unsaturated, and if unsaturated, can be conjugated or non-conjugated. Cyclic hydrocarbyl groups can be independently monocyclic or polycyclic, and include cycloalkyl groups, aryl groups, and heterocycles, which can be aromatic, saturated and non-aromatic and / or non-conjugated, etc. Examples of combinations of linear and cyclic hydrocarbyl groups include alkaryl groups, aralkyl groups, and the like.General examples of hydrocarbon moieties suitable for use in or as hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, alkynyl groups, halocarbon groups, and the like, as well as derivatives, modifications, and combinations thereof. 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, and the like (i.e., other linear or branched saturated hydrocarbon groups, e.g., having more than 6 carbon atoms). Examples of aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, dimethylphenyl, and the like, as well as derivatives and modifications thereof, which may overlap with alkaryl groups (e.g., benzyl) and aralkyl groups (e.g., tolyl, dimethylphenyl, and the like). Examples of alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, cyclohexenyl groups, and the like, as well as derivatives and modifications thereof. Common examples of halocarbon groups include halogenated derivatives of the above hydrocarbon moieties, such as halogenated alkyl groups (e.g., any of the alkyl groups listed above in which one or more hydrogen atoms have been replaced with a halogen atom, such as F or Cl), aryl groups (e.g., any of the aryl groups listed above in which one or more hydrogen atoms have been replaced with a halogen atom, 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, 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl, and the like, and derivatives and modifications thereof. Examples of halogenated aryl groups include chlorobenzyl, pentafluorophenyl, fluorobenzyl, and the like, and derivatives and modifications thereof. With respect to suitable alkoxy and / or aryloxy groups for R'', examples generally include hydrocarbyl (e.g., alkyl, aryl, etc.) groups bonded to a silicon atom via an oxygen atom (i.e., forming a silyl ether). The hydrocarbyl groups in these examples may include any of the hydrocarbyl groups described above. With respect to suitable siloxy groups for R'', examples generally include siloxy groups represented by any one or combination of the [M], [D], [T], and / or [Q] units described above.

[0025] Those skilled in the art will understand how [M], [D], [T] and [Q] units and their relative proportions (i.e., mole fractions) affect and control the structure of a siloxane, and polysiloxanes can generally be monomeric, polymeric, oligomeric, linear, branched, cyclic, and / or resinous, depending on the selection of [M], [D], [T] and / or [Q] units therein. For example, [T] units and / or [Q] units are typically present in a siloxane resin, but a siloxane polymer (e.g., silicone) typically does not contain such [T] units and / or [Q] units. [D] units are typically present in both the siloxane resin and the polymer. Those skilled in the art will also understand that siloxanes can be named based on the type and proportion of such siloxy units. For example, the siloxane resins mentioned above can be characterized as DT resins, MQ resins, MDQ resins, etc. Similarly, siloxanes that are substantially free of branching due to [T] and / or [Q] units are typically referred to as "linear." However, it will be understood that a linear (i.e., MDM-type) siloxane may contain individual molecules having T and / or Q units and still be considered "linear" based on the average unit formula of the siloxane as a whole.

[0026] Generally, polysiloxane (A) comprises a polydiorganosiloxane-containing backbone having at least one functional group X per molecule. Typically, polysiloxane (A) is substantially linear, or alternatively linear. In such cases, a person skilled in the art will understand that polysiloxane (A) typically does not comprise [T]siloxy units and / or [Q]siloxy units as described above.

[0027] In some embodiments, the polysiloxane (A) has the following general average unit formula: [X m R 1 3-m SiO 1 / 2 ] a [X n R 1 2-n SiO 2 / 2 ]b、 In the formula, X is a functional group defined above, and each R 1 is an independently selected hydrocarbyl group, the subscript m is independently 1 or 0 in each part represented by the subscript a, the subscript n is independently 1 or 0 in each part represented by the subscript b, and the subscripts a and b are molar fractions such that a + b = 1, provided that 0 < a < 1, 0 < b < 1, and the polysiloxane (A) contains at least one functional group X.

[0028] Regarding the general unit formula of the above polysiloxane (A), R 1 Preferred hydrocarbyl groups for are generally exemplified by those described above. Typically, 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 alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and iso-propyl groups), butyl (e.g., n-butyl, sec-butyl, iso-butyl, and tert-butyl groups), pentyl, hexyl, etc., as well as their derivatives and / or modified forms. Examples of such derivatives and / or modified forms of alkyl groups include their substituted types. For example, a hydroxyethyl group is understood to be a derivative and / or modified form of the above ethyl group.

[0029] Each R 1 may be the same as or different from the other R 1 of the polysiloxane (A). In a particular embodiment, each R 1 is each other R of the polysiloxane (A) 1For example, in some embodiments, each R 1 is methyl. In other embodiments, at least one R 1 is at least one other R of the polysiloxane (A). 1 For example, in certain embodiments, R 1 are predominantly methyl throughout the polysiloxane (A), with one or more other groups pendant in small amounts from the polydiorganosiloxane backbone (e.g., from the preparation of polysiloxane (A), environmental reactions, or impurities, etc.). In some embodiments, each R 1 is a fluoroalkyl group, i.e., so that polysiloxane (A) may be further defined or referred to as a fluorosilicone or fluoropolysiloxane.

[0030] As introduced above, polysiloxane (A) contains, on average, at least one functional group per molecule, as represented by the moiety X in the general formula of polysiloxane (A) above. However, in some embodiments, polysiloxane (A) contains, on average, at least two functional groups X per molecule.

[0031] As described herein, the functional group X of the polysiloxane (A) is capable of reacting with the functional group Y of the functionalized polyolefin (B) to form a bond therebetween. In other words, one functional group X and one functional group Y can react together (i.e., via a coupling reaction, a crosslinking reaction, etc.) to covalently bond the polysiloxane (A) and the functionalized polyolefin (B) together. It should be understood that terms such as "coupling," "couplable," "reactable," "crosslinking," and "crosslinkable," as used herein, are not intended to imply any directionality to the reaction, but instead are understood in their conventional sense to refer to the coupling facilitated by the groups X and Y, without inference regarding their particular reactivity or role in the reaction between them. As described herein, in some embodiments, the average molecule of components (A) and / or (B) has at least two groups capable of participating in a coupling reaction such that a single molecule of polysiloxane (A) can, on average, couple at least once to two or more molecules of functionalized polyolefin (B), or equivalently, at least twice to a single molecule of functionalized polyolefin (B).

[0032] Generally, each functional group X comprises, or is, a functional group that can participate in the above-mentioned coupling / crosslinking reactions. Examples of such functional groups are typically reactive via substitution reactions, addition reactions, coupling reactions, or combinations thereof. Specific examples of such reactions include nucleophilic substitution, ring-opening addition, alkoxylation and / or transalkoxylation, hydrosilylation, olefin metathesis, condensation, radical coupling and / or polymerization, etc., and combinations thereof. Thus, the functional group X may include or be a hydrosilylatable functional group (e.g., a silicon-bonded hydrogen atom, an olefinically (i.e., ethylenically) unsaturated group such as an alkenyl group, an alkynyl group, and the like), a condensable functional group (e.g., a hydroxyl group, a carboxyl group, a carbinol group, an alkoxysilyl group, a silanol group, an amide group, an anhydride group, and the like, or a group that is hydrolyzable and then condensable), a displaceable functional group (e.g., a "leaving group" as understood in the art, such as a halogen atom, or other group that is stable in ionic form once displaced, or a functional group that includes such a leaving group, such as an ester, anhydride, amide, epoxide, and the like), a nucleophilic functional group (e.g., a heteroatom having a lone pair of electrons, anionic or anionizable groups, and the like, such as a hydroxyl group (e.g., a carbinol), an amine group, a thiol group, a silanol group, a carboxylic acid group, and the like), an electrophilic functional group (e.g., an isocyanate, epoxide, and the like), or various combinations thereof.

[0033] In some embodiments, at least one, alternatively at least two, alternatively each functional group X is a hydrosilylatable group and is thus selected from olefinically unsaturated groups (e.g., ethylenically unsaturated groups) and H. In some such embodiments, each hydrosilylatable group represented by X is H, such that polysiloxane (A) is silicon hydride functional. In other such embodiments, each hydrosilylatable group represented by X is an ethylenically unsaturated group.

[0034] Examples of ethylenically unsaturated groups generally include substituted or unsubstituted hydrocarbon groups having at least one alkene or alkyne functional group. For example, in certain embodiments, each functional group X includes, or is, an alkenyl or alkynyl group. Specific 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, or is, a vinyl group.

[0035] In embodiments in which the functional group X comprises one of the above ethylenically unsaturated groups, it will be understood that the functional group X may comprise a divalent linking group between the ethylenically unsaturated group and the silicon atom of the polysiloxane (A). Examples of such divalent linking groups include divalent versions of the above hydrocarbyl groups, such as alkyl groups. For example, the functional group X may have the formula H2C=CH-(CH2)5-, which may be considered to represent an alkenyl group H2C=CHCH2- with a butylene linking group, an alkenyl group H2C=CH(CH2)4- with a methylene linking group, and the like. In certain embodiments, each functional group X comprises a methacryloxy group, such as a silicon-bonded methacryloxyalkyl group, or alternatively is the methacryloxy group.

[0036] In some embodiments, at least one, alternatively at least two, and alternatively each functional group X comprises, or alternatively is, a condensable group, i.e., a group that can participate in a condensation reaction. In specific embodiments, each functional group X comprises a condensable group selected from an anhydride group, an amine group, a silanol group, a carbinol group, and an alkoxysilyl group.

[0037] Examples of anhydrides suitable for the functional group X generally include anhydrides (which may be homoanydrides or mixed anhydrides) of monocarboxylic acids (e.g., acetic acid, lactic acid, propanoic acid, pentanoic acid, methacrylic acid, etc.), as well as 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 patterns are possible with such anhydrides with respect to the attachment of the anhydride to the silicon atom of polysiloxane (A). Typically, such anhydrides may be grafted onto a siloxane polymer to prepare polysiloxane (A), and therefore those skilled in the art will understand the applicability of other anhydrides and carboxylic acids / carboxylates that may also be utilized, for example, via direct grafting to polysiloxane (A) or alternatively, via first grafting and subsequent reaction to prepare the anhydride. For example, anhydrides containing at least one olefinically unsaturated group, such as alkenylsuccinic anhydride, bromomaleic anhydride, chloromaleic anhydride, citraconic anhydride, methylnadic anhydride, nadic anhydride, tetrahydrophthalic anhydride, etc., can be grafted onto the siloxane (e.g., via hydrosilylation). Free radical-based grafting schemes can also be used to generate anhydride-functional siloxanes from reagents such as maleic anhydride and vinyl siloxanes.

[0038] Examples of suitable amines for the functional group X generally include primary amino-substituted derivatives of the hydrocarbyl groups described above. For example, the functional group X may comprise or alternatively 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 polysiloxane (A) comprises only amino functional groups as the functional group X.

[0039] In some embodiments, at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is, a silanol group. In certain 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 polysiloxane (A). In other embodiments, at least one X is a group of the formula -D-SiR 1 3-c (OH) c wherein each D is a covalent bond, an oxygen atom, or a divalent hydrocarbon group; 1 are independently selected and defined above, and subscript c is 1, 2, or 3. When subscript c is 3, the silicon atom of the silanol group contains three silicon-bonded hydroxyl groups, when subscript c is 2, the silicon atom of the silanol group contains two silicon-bonded hydroxyl groups, and when subscript c is 1, the silicon atom of the silanol group contains two silicon-bonded hydroxyl groups. In certain embodiments, D is an oxygen atom. In other embodiments, D 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.

[0040] In some embodiments, each functional group X comprises, or alternatively is, a silicon-bonded hydroxyl group.

[0041] In some embodiments, at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is, a carbinol group. The carbinol functional group bonded to the silicon atom in the organopolysiloxane is distinct from a silanol group. Specifically, the carbinol functional group comprises a carbon-bonded hydroxyl group, and the silanol functional group comprises a silicon-bonded hydroxyl group. In other words, the carbinol functional group comprises at least one moiety of the formula -COH, while the silanol functional group is a moiety of the formula -SiOH. These functional groups function differently, for example, the silanol functional group can easily condense, whereas the carbinol functional group generally does not (at least under the same catalysis as the hydrolysis / condensation of the silanol functional group). The carbinol functional groups can be the same as each other or different.

[0042] In certain embodiments, the carbinol functional groups are independently represented by the general formula -D 1 -O d -(C e H 2e O) f -H, wherein D 1 is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript d is 0 or 1, subscript e is independently selected from 2 to 4 at each moiety designated by subscript f, and subscript f is 0 to 500, with the proviso that subscripts d and f are not simultaneously 0.

[0043] In some such embodiments, subscript f is at least 1, such that at least one of the carbinol functional groups includes a moiety having the general formula: -D 1 -O d -[C2H4O] g [C3H6O] h [C4H8O] i -H, In the formula, D 1 and subscript d are defined above, with 0≦g≦500, 0≦h≦500, and 0≦i≦500, with the proviso that 1≦g+h+i≦500. In these embodiments, the carbinol functional group may alternatively be referred to as a polyether group or moiety, but the polyether group or moiety terminates with -COH rather than -COR, and R is a monovalent hydrocarbon group, which is the case for certain conventional polyether groups or moieties. As understood in the art, the moieties denoted by subscript g are ethylene oxide (EO) units, the moieties denoted by subscript h are propylene oxide (PO) units, and the moieties denoted by subscript i are butylene oxide (BO) units. The EO, PO, and BO units, if present, may be in block or randomized form in the polyether group or moiety. The relative amounts of EO, PO, and BO units, if present, may be selectively controlled based on the desired properties, such as hydrophilicity and other properties.

[0044] In other embodiments, subscript f is 0 and subscript d is 1, such that at least one of the carbinol functional groups has the general formula: -D 1 D 1 is described above. In these embodiments, the carbinol functionality having this general formula is not a polyether group or moiety.

[0045] In some embodiments, at least one, alternatively at least two, alternatively each functional group X comprises, alternatively is, an alkoxysilyl group.

[0046] In embodiments where at least one X is an alkoxysilyl group, each alkoxysilyl group can independently comprise or be a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group, respectively. In certain embodiments, the alkoxysilyl group comprises, or is alternatively a monoalkoxysilyl group. In other embodiments, the alkoxy group comprises, or is alternatively a dialkoxysilyl group. In yet other embodiments, the alkoxysilyl group comprises, or is alternatively a trialkoxysilyl group,.

[0047] In certain embodiments, the silicon atom of the alkoxysilyl group is a silicon atom of the backbone of the polysiloxane (A). In other embodiments, at least one X is a silicon atom of the formula -D 2 -SiR 1 3-j (OR 6 ) j wherein each D 2 is a covalent bond, an oxygen atom, or a divalent hydrocarbon group; R 1 are independently selected and defined above, subscript j is 1, 2, or 3, and each R 6 is an independently selected alkyl group having 1 to 12 carbon atoms. Typically, each R 6 is independently an independently selected alkyl group having 1-10, alternatively 1-8, alternatively 1-6, alternatively 1-4, alternatively 1-3, alternatively 1 or 2, alternatively 1 carbon atom.

[0048] Specific examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, a dimethoxyethoxysilyl group, a dimethoxymethyl group, a diethoxymethyl group, a methoxyethoxymethyl group, a dimethylmethoxy group, and a dimethylethoxy group.

[0049] In some embodiments, at least one, alternatively at least two, alternatively each functional group X comprises an epoxy group, alternatively is an epoxy group. Examples of suitable epoxy groups include 3-glycidoxypropyl, 4-glycidoxybutyl, or similar glycidoxyalkyl (i.e., glycidyloxyalkyl) groups, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, or similar epoxycyclohexylalkyl groups, 4-oxiranylbutyl, and 8-oxiranyloctyl groups. Such epoxy groups can be directly bonded to the polysiloxane (A). Alternatively, a divalent hydrocarbon group can be present in X between the epoxide group and the silicon atom to which X is bonded. In some of these embodiments, the divalent hydrocarbon group has the general formula -(CH2) k -, or alternatively an alkylene group, where the subscript k is 2 to 10. In other embodiments, the divalent hydrocarbon group contains 2 to 10 carbon atoms and at least one ether moiety, i.e., at least one oxygen heteroatom. Such divalent hydrocarbon groups can be linked to any of the divalent linking groups described herein, such as D, D 1 , D 2 etc.).

[0050] With respect to the general unit formula of polysiloxane (A) above, subscript m is independently 1 or 0 in each portion indicated by subscript a, and subscript n is independently 1 or 0 in each portion indicated by subscript b. Thus, subscripts m and n simply indicate the presence of functional group X in any particular [M] unit (i.e., indicated by subscript a) or [D] unit (i.e., indicated by subscript b). When each subscript m is 0 (i.e., subscript m is 0 in each portion indicated by subscript a), polysiloxane (A) includes at least one pendant functional group X (i.e., attached to a [D] unit). When each subscript n is 0 (i.e., subscript n is 0 in each portion indicated by subscript b), polysiloxane (A) includes at least one terminal functional group X (i.e., attached to a [M] unit). In some embodiments, polysiloxane (A) is only terminally functional with respect to functional group X, and subscript n is 0 in each moiety denoted by subscript b. In some such embodiments, polysiloxane (A) comprises at least two moieties denoted by subscript a, and subscript m is 1 in at least two moieties denoted by subscript a. In other embodiments, polysiloxane (A) comprises at least one terminal functional group X. In yet other embodiments, polysiloxane (A) comprises only pendant functional groups with respect to functional group X, subscript m is 0 in each moiety denoted by subscript a, polysiloxane (A) comprises at least two moieties denoted by subscript b, and subscript n is 1 in at least two moieties denoted by subscript b.

[0051] Continuing to refer to the general unit formula of the above polysiloxane (A), the subscripts a and b are each mole fractions such that a + b = 1, provided that 0 < a < 1 and 0 < b < 1. It will be understood that the portions represented by the subscripts a and b are generally [M] and [D] siloxy units, respectively. Thus, in certain embodiments, polysiloxane (A) can be defined as an MDM type polysiloxane. Thus, in such embodiments, polysiloxane (A) can be defined as a linear polysiloxane (or, more simply, a "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 polysiloxane (A). Thus, as generally described above with respect to siloxanes, polysiloxane (A) can contain a limited amount of branching (e.g., due to [T] and / or [Q] units) without departing from the range of linearity understood by those skilled in the art, although such units are not included in the above general unit formula. Typically, polysiloxane (A) substantially does not contain, or alternatively does not contain, [T] and / or [Q] units.

[0052] In some embodiments, each of the units represented by the subscripts a and b is independently selected, and at least two units of polysiloxane (A) contain the functional group X. In such embodiments, the above general formula of polysiloxane (A) can be rewritten as the following extended average unit formula: [XR 1 2SiO 1 / 2 a’ [XR 1 SiO 2 / 2 b’ [R 1 2SiO 2 / 2 b’’ [R 1 3SiO 1 / 2 a’’ , wherein each X and R 1 ​​​​are as defined above, with the subscripts a', a'', b', and b'' each indicating the number of the corresponding moieties present in polysiloxane (A). Thus, a'+a'' is equal to the number of [M] siloxy units present in the mole fraction represented by subscript a in the general formula above, and b'+b'' is equal to the number of [D] siloxy units present in the mole fraction represented by subscript b in the general formula above. For example, generally, a'+a''≧2, a'+b''≧2, and b'+b''≧1. In the specific embodiment above where polysiloxane (A) is only end-functional, a'=2, b'=0, b''≧1, and a''=0.

[0053] In general, polysiloxane (A) may have a number average degree of polymerization (DP) of 10 to 10,000. Thus, with respect to the above expanded formula of polysiloxane (A), a'+a''+b'+b'' is generally 10 to 10,000. In some embodiments, polysiloxane (A) 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, polysiloxane (A) 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. Subscript b'' can be from 0 to 10,000, such as from 5 to 5,000, alternatively from 50 to 1200, alternatively from 50 to 1100, alternatively from 50 to 1000, alternatively from 100 to 1000. In these or other embodiments, subscript b' is from 0 to 200, such as from 0 to 10, alternatively from 1 to 10, alternatively from 1 to 8.

[0054] In certain embodiments, polysiloxane (A) has a degree of substitution (DS) from 1 to 200. It will be understood that the DS of polysiloxane (A) can be represented by the sum of subscripts a' and b' in the expanded formula above, i.e., this indicates the number of functional groups X. In some embodiments, polysiloxane (A) has a DS from 1 to 100, alternatively from 1 to 50, alternatively from 1 to 20, alternatively from 1 to 10, alternatively from 2 to 10.

[0055] In some embodiments, polysiloxane (A) has a molecular weight distribution, as represented by a polydispersity index (PDI) (i.e., weight average molecular weight / number average molecular weight (Mw / Mn)), of less than 3, alternatively less than 2.5, alternatively less than 2.25, and at the same time greater than or equal to 1. For example, polysiloxane (A) may comprise a PDI of 1 to 3, e.g., 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 polysiloxane (A) are known in the art and generally include gravimetric determination by rheology, solution viscosity, gel permeation chromatography (GPC), and the like, with standards and procedures readily understood and available.

[0056] Typically, the polysiloxane (A) utilized in the silicone-polyolefin composition is flowable, i.e., comprises a viscosity low enough to flow under ambient conditions (e.g., 25°C). In some embodiments, the polysiloxane (A) is liquid at room temperature. In certain embodiments, the polysiloxane (A) exhibits a viscosity of at least 1000 cP, alternatively at least 3500 cP at 25°C (e.g., as determined via a viscometer such as a Brookfield LV DV-E viscometer equipped with an appropriate spindle).

[0057] In certain embodiments, the polysiloxane (A) is a functionalized polydimethylsiloxane (PDMS), i.e., each R 1is further defined as being methyl. In some such embodiments, polysiloxane (A) is selected from amine-functional PDMSs (i.e., where each functional group X comprises an amine, such as a primary aminoalkyl group) and vinyl-functional PDMSs (i.e., where each functional group X comprises, or alternatively is, a vinyl group).

[0058] In view of the above description, examples of such amine-functionalized PDMS suitable for use in or as polysiloxane (A) will be understood to include terminal and / or pendant amine-functional PDMS oligomers and polymers. However, it will also be understood that in certain embodiments, polysiloxane (A) may include, or alternatively may be, terminal and / or pendant amine-functional random, graft, or block copolymers or co-oligomers of PDMS and non-reactive siloxanes (e.g., polyphenylmethylsiloxane, tris(trifluoropropyl)methylsiloxane, etc.). Similarly, examples of vinyl-functionalized PDMS suitable for use in or as polysiloxane (A) include terminal and / or pendant vinyl-functional PDMS oligomers and polymers, and PDMS and non-reactive random, graft, or block copolymers or co-oligomers. In specific embodiments, polysiloxane (A) comprises, or is, an aminoalkyl-terminated PDMS, such as α,ω-aminopropyl-terminated PDMS. In certain embodiments, polysiloxane (A) comprises, or is, a vinyl-terminated PDMS, such as α,ω-vinyl-terminated PDMS. In some embodiments, polysiloxane (A) comprises, or is, a methacryloylpropyl-terminated PDMS, a silanol-terminated PDMS, a succinic anhydride-terminated PDMS, a SiH-terminated PDMS, a vinyl-terminated PDMS, a monocarbinol-functional PDMS, or an aminopropyl-terminated PDMS.

[0059] As introduced above, the silicone-polyolefin composition also includes a functionalized polyolefin (B). The functionalized polyolefin (B) includes, on average, at least one functional group Y per molecule, for example as a substituent of the polyolefin backbone. In some embodiments, the functionalized polyolefin (B) includes, on average, at least two functional groups Y per molecule. As described herein, the functional group Y is capable of reacting with the functional group X of the polysiloxane (A) to form a bond therebetween. Thus, it will be understood that the silicone-polyolefin composition component (B) generally includes a polyolefin that is prepared with, obtained with, or otherwise functionalized with a functional group Y to include the functional group Y as a substituent. Thus, the functionalized polyolefin (B) may include, or alternatively may be, a terminally substituted (i.e., functional group terminated) polyolefin, a pendantly substituted polyolefin, or a combination thereof.

[0060] In general, suitable polyolefins for the functionalized polyolefin (B) are exemplified by polymers prepared from olefin monomers, olefin macromonomers and oligomers, and combinations thereof. Regardless of the actual synthetic route by which the functionalized polyolefin (B) is prepared, those skilled in the art will readily understand the scope of the polyolefin components of the functionalized polyolefin (B) in terms of its constituent parts (or theoretical parts), i.e., the olefinic base monomers polymerized to prepare the polyolefin. The term "olefinic" used in the context of the base monomers that comprise the functionalized polyolefin (B) refers to the presence of ethylenically unsaturated end groups, i.e., the ability to polymerize with the ethylenically unsaturated groups of other olefinic monomers to provide polyolefins. Thus, it will be understood that "polyethylene" is a polyolefin derived or theoretically derivable from the monomer ethene (ethylene), which is the smallest ethylenically unsaturated compound. Similarly, a polyethylene-methacrylate copolymer is a polyolefin derived or theoretically derivable from the comonomers ethylene and methacrylate, the latter monomer containing a terminal ethylenically unsaturated group, i.e., an alpha-olefin (e.g., -C=CH2).It will thus be understood that in a typical embodiment, the functionalized polyolefin (B) comprises a poly-alpha-olefin backbone.

[0061] The poly-alpha-olefin backbone of the functionalized polyolefin (B) is not particularly limited and generally has the general formula R 2 and comprising monomer units derived, or at least theoretically derivable, from an alpha olefin having 2C=CH2, wherein each R 2 is hydrogen or a hydrocarbyl group (i.e., a substituted or unsubstituted hydrocarbyl group), such as any of those described above. For example, in certain embodiments, the alpha olefin may be a methacrylate (e.g., other R 2 is a methyl ester or an ethyl ester, respectively), so that one R 2 is methyl, and the other R2 is an ester carbon. Some embodiments include at least one R 2 is hydrogen, and alpha olefins have the general formula R 2 CH=CH2, where R 2 are selected from hydrogen and linear or branched hydrocarbyl groups having 1 to 12, alternatively 1 to 8, alternatively 1 to 6, alternatively 1 or 2 carbon atoms. Such hydrocarbyl groups may be substituted or unsubstituted and R″ and R 1 Examples of suitable hydrocarbyl groups for are given above. However, it will be understood that oligomers of such alpha-olefins can also be used to prepare the poly-alpha-olefin backbone. For example, polyethylene (PE) oligomers can be used to prepare polyethylene polymers, which can also be prepared using ethene as the only 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 the poly-alpha-olefin backbone of the functionalized polyolefin (B) include polypropylene oligomers, polybutylene oligomers, polyisobutylene oligomers, polyisoprene oligomers, polybutadiene oligomers, and combinations thereof, such as polyethylene / polypropylene oligomers and copolymers, polyethylene / polybutylene oligomers and copolymers, poly(ethylene / butylene)-polyisoprene oligomers and copolymers, and the like.

[0062] In certain embodiments, the functionalized polyolefin (B) comprises a poly-alpha-olefin backbone comprising monomer units selected from ethylene, propylene, butylene, and 2-methyl-propylene (i.e., isobutylene). In these or other embodiments, the poly-alpha-olefin backbone comprises hexene, heptene, octene, styrene, acrylate or methacrylate compounds (e.g., acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylic or methacrylic acid esters, e.g., C1-C acrylic acid or methacrylic acid). 12 The functionalized polyolefin (B) may comprise monomer units derived (or theoretically derivable) from alpha-olefins exemplified by alkyl esters, dienes such as butadiene, or combinations thereof. It will thus be understood that the functionalized polyolefin (B) may comprise, or alternatively may be, a homopolymer (i.e., having only one type of monomer unit or prepared from one monomer or oligomer of only one monomer) or an interpolymer (i.e., having at least two different monomer subunits, typically prepared from at least two monomers or oligomers containing two or more monomer subunits). It will be understood that the term "interpolymer" encompasses copolymers and terpolymers, i.e., polymers containing two or three different monomer units, respectively, as well as polymers prepared from four, five, six, or more monomers.

[0063] In certain embodiments, the functionalized polyolefin (B) comprises a functionalized polyethylene, polypropylene, or polyethylene-alphaolefin copolymer. In some such embodiments, the polyethylene-alphaolefin copolymer is selected from copolymers and terpolymers comprising polyethylene and at least one of polypropylene and polybutylene. Various forms of such polyolefins can also be utilized. For example, polyethylene can be used in high density (HDPE, ρ≧0.941 g / cm 3 ), medium density (MDPE, ρ=0.926~0.940g / cm 3), low density (LDPE, ρ=0.910~0.940g / cm 3 ) or ultra-low density (ULDPE, ρ≦0.880g / cm 3 ), and variations thereof, such as linear low density polyethylene (LLDPE, ρ = 0.915 to 0.925 g / cm 3 While such polyethylenes are distinguished from one another by their density, those skilled in the art will appreciate that various other physical characteristics of such variations differ as well and can be selected to impart particular properties to the silicone-polyolefin composition, as well as to the curable compositions and cured products that may be prepared therefrom.

[0064] As introduced above, the functionalized polyolefin (B) contains an average of at least one, alternatively at least two, functional groups Y per molecule. For purposes of illustration, the functionalized polyolefin (B) may be represented by the general formula L(-Y): l where L is a polyolefin backbone and each Y is a functional group as introduced above, with subscript 1≧1. It will be understood that each functional group Y can be independently selected at each moiety, indicated by subscript I, to be at least one, alternatively at least two, but may theoretically be much greater, as will be understood in view of the discussion of the degree of substitution of the functionalized polyolefin (B). Furthermore, the position of each functional group Y along the polyolefin backbone L is not particularly limited, such that any functional group Y may represent a terminal or pendant group.

[0065] In some embodiments, the functionalized polyolefin (B) comprises the general unit formula: R 4 [CH2C(R 3 )(Y)] o [CH2CH(R 3 )] p R 4 where each Y is an independently selected functional group as provided above, and each R 3 is independently selected from H and substituted and unsubstituted hydrocarbyl groups; each R 4are independently selected end groups, where the subscripts o and p are each mole fractions such that o + p = 1, provided that 0 < o < 1 and 0 < p < 1, and 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 may be in any order in the functionalized polyolefin (B).

[0066] Regarding 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 based on the functionalized polyolefin (B), or at least the specific alpha-olefin monomer used to prepare its backbone, or is controlled in other ways. For example, when the functionalized polyolefin (B) is functionalized polypropylene, R 3 is methyl in each portion indicated by the subscript k. In such a case, the nature of R 3 in the portion indicated by the subscript j depends on how the functionalized polyolefin (B) is prepared. Specifically, when such functionalized polyethylene is a copolymer prepared from polypropylene and an alpha-olefin containing the group Y, R 3 is H in each portion indicated by the subscript o (in contrast to the methyl group R 3 in the portion indicated by the subscript p). On the other hand, when such functionalized polypropylene is a polypropylene homopolymer grafted with the functional group Y (e.g., by radical-mediated grafting), R 3 is typically a methyl group throughout the functionalized polyolefin (B). Thus, it will be understood that any R 3 can be selected such that any one portion indicated by the subscript p reflects the polymerization product of any of the alpha-olefin monomers described herein, or alternatively, the graft functionalization onto a polymer prepared from such alpha-olefins.

[0067] Taking the above into account, each R 3is any other R of the functionalized polyolefin (B). 3 It will be understood that each R may be the same as or different from the R. 3 R represents each of the other R of the functionalized polyolefin (B). 3 For example, in some embodiments, each R 3 is methyl. In other embodiments, at least one R 3 is at least one other R of the functionalized polyolefin (B). 3 For example, in certain embodiments, R 3 is primarily hydrogen throughout the functionalized polyolefin (B) (i.e., from the ethene monomers), and R 3 A minor proportion of is selected from alkyl groups (ie, from propene or higher alpha-olefin monomers).

[0068] As mentioned above, each R 4 are independently selected terminal groups. More specifically, each R 4 Generally, R represents a terminal reacted monomer from the polymerization of the functionalized polyolefin (B), a by-product of the polymerization (i.e., from radical initiation, propagation, and / or termination steps, etc.), or simply a hydrogen atom. Thus, one of ordinary skill in the art will recognize that R 4 It will be understood that R is not particularly limited and is generally selected by the route of the functionalized polyolefin (B) and is typically present in the functionalized polyolefin (B) in such small amounts that it does not substantially affect the average unit formula indicated by the subscripts o and p. 4 It should be understood that generally represents a non-reactive group with respect to the compositions and methods provided herein.

[0069] As introduced above, the functionalized polyolefin (B) contains at least one, alternatively at least two functional groups per molecule, and the functional group is represented by the moiety Y in the general unit formula of the functionalized polyolefin (B) above. In general, the functional group Y is selected based on the functional group X of the polysiloxane (A) so that the functionalized polyolefin (B) is reactive with the polysiloxane (A) in a coupling reaction involving the functional group X and the functional group Y. More specifically, as introduced above, the functional group Y of the functionalized polyolefin (B) can react with the functional group X of the polysiloxane (A) to form a bond therebetween. In other words, one functional group Y and one functional group X can react together (i.e., via an addition coupling / crosslinking reaction) to covalently bond the functionalized polyolefin (B) and the polysiloxane (A) together.

[0070] Thus, each functional group Y includes functional groups that can participate in the above coupling / crosslinking reactions, e.g., functional groups that are reactive via substitution reactions, addition reactions, coupling reactions, or combinations thereof, as well as any of the specific variations described above with respect to 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 the like, and combinations thereof.

[0071] Thus, functional group Y can include or be a hydrosilylatable, condensable, substitutable, nucleophilic, or otherwise reactive (e.g., graftable, linkable, etc.) functional group with functional group X, or various combinations thereof. Thus, the functional group Y can include or be a hydrosilylatable functional group (e.g., a silicon-bonded hydrogen atom, an ethylenically unsaturated group such as an alkenyl group, an alkynyl group, and the like), a condensable functional group (e.g., a hydroxyl group, a carboxyl group, an alkoxysilyl group, a silanol group, a carbinol group, an amide group, and the like, or a group that is hydrolyzable and then condensable), a displaceable functional group (e.g., a "leaving group" as understood in the art, such as a halogen atom, or other group that is stable in ionic form once displaced, or a functional group that contains such a leaving group, such as an ester, anhydride, amide, epoxide, and the like), a nucleophilic functional group (e.g., a heteroatom having a lone pair of electrons, anionic or anionizable groups, and the like, such as a hydroxyl group, an amine group, a thiol group, a silanol group, a carboxylic acid group, a group, and the like), an electrophilic functional group (e.g., an isocyanate, epoxide, and the like), or various combinations thereof.

[0072] In some embodiments, each functional group Y is a hydrosilylatable group. Examples of such hydrosilylatable groups include the olefinically unsaturated groups (e.g., ethylenically unsaturated groups) described above with respect to suitable hydrosilylatable groups for functional group X. In a specific embodiment, each functional group Y comprises a vinyl-substituted organosilicon group (e.g., includes a vinylsilyl group), or alternatively is a vinyl-substituted organosilicon group.

[0073] In embodiments in which the functional group Y comprises one of the above ethylenically unsaturated groups, it will be understood that the functional group Y may also comprise a divalent linking group between the ethylenically unsaturated group and a carbon atom of the polyolefin backbone of the functionalized polyolefin (B). In certain embodiments, each functional group Y comprises, or is alternatively, a methacryloyl group, a methacryloxy group, or a methacrylate group.

[0074] Other examples of suitable hydrosilylatable groups for the functional group Y include hydridosilyl groups. Examples of such hydridosilyl groups can generally be represented by the subformula -[D 3 ] q -Si(R 5 )2H, wherein D 3 is a divalent linking group, the subscript q is 0 or 1, and each R 5 are independently H or a hydrocarbyl group. Such moieties may be selected or otherwise provided based on the particular alpha-olefin functional 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, and with respect to the above general unit formula of the functionalized polyolefin (B) and the subformula of the functional group Y, each R 3 is H, each subscript q is 1, and each linking group D 3 is -(CH2)6-, and each R 5 is methyl. In a specific embodiment, the functionalized polyolefin (B) comprises a polymerization reaction product of ethylene, an alkenyl-functional silane compound, and optionally one or more additional alpha-olefins (e.g., propene, butene, etc.). In such an embodiment, examples of suitable alkenyl-functional silane compounds include 7-octenyldimethylsilane (ODMS), 5-hexenyldimethylsilane (HDMS), allyldimethylsilane (ADMS), and the like, as well as combinations thereof. It will be understood that such alkenyl-functional silane compounds can also be grafted onto a polyolefin polymer to prepare the functionalized polyolefin (B). The particular method used to prepare the functionalized polyolefin (B) is not particularly limited, and numerous examples of such methods are known in the art.

[0075] In addition to the above examples, one skilled in the art will appreciate that other alpha-olefin functional organosilicon compounds can be similarly used to prepare the functionalized polyolefin (B) and provide suitable hydridosilyl groups for the functional group Y. More specifically, such organosilicon compounds have the formula H2C=C(H)-[D 3 ] q -Si(R 5 )H, where each R 5 , D 3 and the subscript q are as defined above. 3 can be a silyl group or a siloxy group.

[0076] In some embodiments, each functional group Y is a condensable group, i.e., a group that can participate in a condensation reaction. In specific embodiments, each functional group Y comprises a condensable group selected from an anhydride group, an amine group, a silanol group, a carbinol group, and an alkoxysilyl group.

[0077] Examples of suitable anhydrides and amines for functional group Y generally include those discussed above with respect to suitable condensable groups for functional group X. However, in light of the preceding examples and descriptions of functionalized polyolefins (B), one of ordinary skill in the art will appreciate that anhydrides available from anhydride-functional compounds having olefinic unsaturation are particularly suitable in some embodiments for use, for example, in cases where the anhydride-functional compound can be readily copolymerized with an alpha-olefin monomer (e.g., ethene) or grafted (e.g., via radical grafting, metathesis, etc.) onto an alpha-olefin homopolymer.

[0078] Examples of suitable amines for functional group Y generally include primary amino-substituted derivatives of the hydrocarbyl groups described above as aminoalkyl groups described above for functional group X.

[0079] In some embodiments, at least one, alternatively at least two, alternatively the functional group Y comprises, alternatively is, a silanol group. In certain embodiments, at least one functional group Y has the formula -D-SiR 1 3-c (OH) c wherein each D, R 1 and the subscript c are independently selected and defined above. In certain embodiments, D is an oxygen atom. In other embodiments, D 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.

[0080] In some embodiments, at least one, alternatively at least two, alternatively each functional group Y comprises, alternatively is, a carbinol group. The carbinol functional groups can be the same as one another or can be different.

[0081] In certain embodiments, the carbinol functional groups are independently represented by the general formula -D 1 -O d -(C e H 2e O) f -H, wherein D 1 and subscripts d, e, and f are independently selected and defined above. For example, in some embodiments, subscript f is at least 1, such that at least one of the carbinol functional groups includes a moiety having the general formula: -D 1 -O d -[C2H4O] g [C3H6O] h [C4H8O] i -H, In the formula, D 1 and the subscripts d, g, h, and i are independently selected and defined above.

[0082] In another embodiment, the subscript f is 0 and the subscript d is 1, such that at least one of the carbinol functional groups has the general formula: -D 1 D 1 is described above. In these embodiments, the carbinol functionality having this general formula is not a polyether group or moiety.

[0083] When the functional group Y is directly bonded to a carbon atom in the functionalized polyolefin (B), D 1 can be a covalent bond.

[0084] In some embodiments, at least one, alternatively at least two, alternatively each functional group Y comprises, alternatively is, an alkoxysilyl group.

[0085] In embodiments where at least one functional group Y is an alkoxysilyl group, each alkoxysilyl group can independently comprise or be a monoalkoxysilyl group, a dialkoxysilyl group, or a trialkoxysilyl group, respectively. In certain embodiments, the alkoxysilyl group comprises, or is alternatively a monoalkoxysilyl group. In other embodiments, the alkoxy group comprises, or is alternatively a dialkoxysilyl group. In yet other embodiments, the alkoxysilyl group comprises, or is alternatively a trialkoxysilyl group, a trialkoxysilyl group.

[0086] In certain embodiments, at least one functional group Y is represented by the formula -D 2 -SiR 1 3-j (OR 6 ) j wherein each D 2 , R 1 , R 6 , and the subscript q are independently selected and defined above. Typically, each R 6is independently an independently selected alkyl group having 1-10, alternatively 1-8, alternatively 1-6, alternatively 1-4, alternatively 1-3, alternatively 1 or 2, alternatively 1 carbon atom.

[0087] Specific examples of suitable alkoxysilyl groups include those including trimethoxysilyl, triethoxysilyl, dimethoxyethoxysilyl, dimethoxymethyl, diethoxymethyl, methoxyethoxymethyl, dimethylmethoxy, dimethylethoxy, and the like.

[0088] In some embodiments, at least one, alternatively at least two, alternatively each functional group Y comprises an epoxy group, alternatively is an epoxy group. Examples of suitable epoxy groups include 3-glycidoxypropyl, 4-glycidoxybutyl, or similar glycidoxyalkyl (i.e., glycidyloxyalkyl) groups, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, or similar epoxycyclohexylalkyl groups, 4-oxiranylbutyl, and 8-oxiranyloctyl groups. Such epoxy groups may be directly bonded to the functionalized polyolefin (B). Alternatively, a divalent hydrocarbon group may be present in the functional group Y between the epoxide group and the atom to which the functional group Y is bonded. In some of these embodiments, the divalent hydrocarbon group may be of the general formula -(CH2) k -, or alternatively an alkylene group, where the subscript k is as defined above. In other embodiments, the divalent hydrocarbon group contains 2 to 10 carbon atoms and contains at least one ether moiety, i.e., at least one oxygen heteroatom.

[0089] Referring further to the general unit formula of the functionalized polyolefin (B), as introduced above, the subscripts o and p are each molar fractions such that o + p = 1. Generally, 0 < o < 1 and 0 < p < 1, and thus the functionalized polyolefin (B) can contain at least one functional group Y, and theoretically many such groups, but is not completely substituted with respect to each olefin subunit present in the functionalized polyolefin (B) (e.g., as indicated by subscript p > 0). In some embodiments, the portion indicated by subscript o comprises 0.01 to 5%, alternatively 0.01 to 2.5%, of the total number of olefin subunits in the functionalized polyolefin (B) (e.g., o + p). In these of other embodiments, the portion indicated by subscript o can comprise 0.05 to 10% by weight of the functionalized polyolefin (B) (e.g., based on the total weight).

[0090] The specific properties and physical characteristics of the functionalized polyolefin (B) can vary. In some embodiments, the functionalized polyolefin (B) has a number average molecular weight of 10 to 100 kDa, such as 10 to 90, alternatively 15 to 90, alternatively 15 to 80, alternatively 20 to 80, alternatively 20 to 70, alternatively 20 to 65 kDa. In these or other embodiments, the functionalized polyolefin (B) has a molecular weight distribution represented by a polydispersity index (PDI) (e.g., determined by gel permeation chromatography (GPC)) of 1 to 12, such as 1 to 10. 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 embodiments, the functionalized polyolefin (B) exhibits a PDI of 3 to 6, such as 3.5 to 5.5, alternatively 4 to 5.

[0091] In certain embodiments, the functionalized polyolefin (B) is anhydride-functional. In these or other embodiments, the functionalized polyolefin (B) contains the functional group Y in an amount of 0.5 to 2.0% by weight.

[0092] The functionalized polyolefin (B) typically has a melt flow index (MFI) of 1 to 49 g / 10 min. MFI can be measured according to ASTM D1238-86.

[0093] As introduced above, the silicone-polyolefin composition also includes a polyolefin (C). The polyolefin (C) is not capable of reacting with component (A) or (B). In other words, the polyolefin (C) does not include a functional group that can react with the functional group X of component (A) or the functional group Y of component (B). In certain embodiments, the polyolefin (C) can include a functional group, as long as the functional group is not capable of reacting with the functional group X of component (A) or the functional group Y of component (B). Those skilled in the art will easily understand such functional groups based on the selection of the functional groups X and Y. However, typically, the polyolefin (C) does not include any functional group, i.e., a group that can react with other functional groups.

[0094] The polyolefin (C) can be selected from any of those described above for the functionalized polyolefin (B), the only difference being that the polyolefin (C) does not contain the functional group Y present in component (B).

[0095] In one embodiment, polyolefin (C) is a post-consumer recycled resin. In another embodiment, polyolefin (C) is a virgin material. Polyolefin (C) may also include a combination of post-consumer recycled resin and virgin material.

[0096] The term "post-consumer recycled resin" or "post-consumer recycled resin (PCR)" is a polymeric material that has previously been used as consumer or industrial packaging. In other words, PCR is waste plastic. PCR is typically collected from recycling programs and recycling plants. PCR typically requires additional cleaning and processing before it can be reintroduced into the manufacturing line. PCR is PCR multilayer film after it has completed its first use, i.e., it has already served its initial purpose. It is understood that PCR includes postindustrial recycled (PIR) resin. In one embodiment, the PCR multilayer film is a waste barrier film that was used to hold or otherwise store consumer edible oil.

[0097] PCR is different from virgin polymeric materials. Because PCR has undergone an initial heating and molding process, PCR is not a "virgin" polymeric material. A "virgin polymeric material" is a polymeric material that has not been subjected to or has not been subjected to a heating or molding process. PCR resins have different physical, chemical, and flow properties compared to virgin polymeric resins.

[0098] PCR can be considered waste plastic. PCR may contain, for example, HDPE packaging such as bottles (milk pots, juice containers), LDPE / LLDPE packaging such as films. PCR may also contain residues from its original use, such as paper, adhesives, inks, colorants, dyes, nylon, ethylene vinyl alcohol (EVOH), polyethylene terephthalate (PET), other odor-causing agents, etc. If PCR contains HDPE, it may contain up to 40% polypropylene contamination.

[0099] Non-limiting examples of commercially available PCR resins include those sold under the trade names EcoPrime™, PRISMA™, Natural HDPE PCR Resins, and Mixed Color and Black HDPE PCR Resins by Envision Plastics, North Carolina, USA, and those sold 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, KWR621 by KW Plastics, Alabama, USA. Examples include PCRs sold by FDA, KWR621-20-FDA, KW308A, KW621, KW621-T10, KW621-T20, KW622-20, KW622-35, KW627C, KW1250G, and KWBK10-NB.

[0100] In one embodiment, polyolefin (C) comprises a PCR blended with an olefin-based polymer that is not a PCR. In other words, in this embodiment, the PCR is blended with a "virgin olefin-based polymer" to obtain polyolefin (C).

[0101] The polyolefin (C) typically has a melt flow index (MFI) of 0.5 to 35 g / 10 min. The MFI can be measured according to ASTM D1238-86.

[0102] As introduced above, the silicone-polyolefin composition also includes a curable silicone (D). The curable silicone (D) includes at least one of an elastomer component and a liquid rubber. In one embodiment, the curable silicone (D) includes an elastomer component, or alternatively is an elastomer component. In another embodiment, the curable silicone (D) includes a liquid rubber, or alternatively is a liquid rubber. In yet another embodiment, the curable silicone (D) includes a combination of an elastomer component and a liquid rubber. The elastomer component and the liquid rubber are described below.

[0103] As will be understood by those of skill in the art in light of the description and examples herein, the curable silicone (D) typically represents the major component of the silicone-polyolefin composition and is adapted to facilitate the formation of the curable and cured compositions therefrom.

[0104] In general, the elastomer component of the curable silicone (D) comprises a functional or curable organosiloxane, i.e., a reactive curable silicone, optionally with additional components (such as, for example, fillers as described below). Thus, it will be understood by those skilled in the art that component (D) in these embodiments may be referred to or otherwise described as a "silicone elastomer base", a "curable silicone base", a "curable silicone elastomer base", and / or other such terms known in the art. Thus, it will be understood that component (D) can generally be cured to prepare a silicone elastomer, and typically does not comprise an elastomer itself until such curing.

[0105] The functional organosiloxane suitable for use in or as the elastomeric component of the curable silicone (D) can be described in terms of the [M], [D], [T], and / or [Q] units / siloxy groups of the polymer therein. More specifically, as described above, the elastomeric component of the curable silicone (D) typically comprises a functional organosiloxane, which can comprise any number and / or combination of M, D, T, and / or Q siloxy units, which are combined in various ways to form cyclic, linear, branched, and / or resinous structures as described above. Typically, however, the functional organosiloxane of component (D) is substantially free of resinous segments, or alternatively free of resinous segments. In these or other embodiments, the organosiloxane of component (D) is substantially free of [T] and / or [Q] units, or alternatively free of [T] and / or [Q] units.

[0106] Particular compounds and compositions suitable for use in or as the elastomer component of the curable silicone (D) are commercially available and can be selected based on their particular properties.For example, in some embodiments, the elastomer component of the curable silicone (D) comprises or alternatively is a silicone high-consistency rubber (HCR) base.In a specific embodiment, component (D) can be characterized as a 40 durometer silicone rubber base.

[0107] In specific embodiments, the functional organosiloxane of the elastomeric component of the curable silicone (D) comprises, or is alternatively, a polydiorganosiloxane gum, i.e., an organopolysiloxane that comprises primarily D siloxy units and has a molecular weight high enough that it is not considered a fluid or liquid at room temperature. In some embodiments, the polydiorganosiloxane gum can exhibit a Williams plasticity number (e.g., as determined by American Society for Testing and Materials (ASTM) Test Method 926) of at least 40, such as a plasticity number of 40 to 200, although other or narrower ranges (e.g., 50 to 150) may be selected based on the particular desired application of the silicone-polyolefin composition. In these or other embodiments, the polydiorganosiloxane gum has a viscosity of at least 1,000,000 mPa·s at 25° C. In some embodiments, the polydiorganosiloxane gum comprises a number average molecular weight of at least 600,000 Daltons, such as a molecular weight of 1,000,000 Daltons or greater, alternatively 2,000,000 Daltons or greater.

[0108] The functional organosiloxane of the elastomeric component of the curable silicone (D) is typically reactively curable. In such embodiments, the organosiloxane typically contains, on average, at least two functional groups per molecule, which functional groups are reactive with one or more other components during the curing process, as described in more detail below. Typically, the specific functional groups of such functional organosiloxanes are selected based on the other components of the silicone-polyolefin composition and / or the composition prepared therewith. For example, in some embodiments, the functional organosiloxane contains a functional group that is complementary to and reactive with the functional group X of the polysiloxane (A), for example, to form a bond between them (i.e., via an addition crosslinking reaction). In a specific embodiment, component (D) includes a functional organosiloxane that contains a hydrosilylatable or condensable functional group. In some such embodiments, component (D) comprises olefinic unsaturation, for example in the form of ethylenically unsaturated groups that can be utilized in hydrosilylation reactions. In other embodiments, the functional organosiloxane of component (D) comprises crosslinkable functional groups that are different from those of the functional groups X and Y of components (A) and (B), respectively. For example, in some embodiments, the functional groups X and Y are capable of addition reactions and component (D) comprises a radically curable organosiloxane.

[0109] In some embodiments, the elastomeric component of the curable silicone (D) comprises a functional organosiloxane that comprises one or more functional groups reactive with a filler, for example, directly or in its surface treatment / modification. For example, in some embodiments, component (D) further comprises silica (e.g., treated fumed silica), which can be mutually selected with the functional organosiloxane to affect the reactive curing properties of the silicone-polyolefin composition and / or the curable composition formed thereby. The elastomeric component of the curable silicone (D) can comprise other components in addition to or in relation to certain components such as silica, instead of those mentioned above. For example, the elastomeric component of the curable silicone (D) can comprise one or more fillers or additives, such as those described herein.

[0110] In some embodiments, the elastomeric component of the curable silicone (D) may be further defined as fluorosilicone-based. For example, in a specific embodiment, the functional organosiloxane of component (D) may include a fluoroalkyl silicone, such as trifluoromethyl silicone.

[0111] In these or other embodiments, component (D) comprises a liquid rubber. Liquid rubbers are known in the art and are typically liquid or flowable at 25°C. Generally, liquid rubbers are liquid or flowable at 25°C in the absence of any solvent (e.g., organic solvent) or carrier vehicle. By "flowable" it is meant that the liquid rubber is flowable at 25°C and / or has a viscosity that is measurable at 25°C. Liquid rubbers are commercially available from a variety of suppliers. Liquid rubbers are curable silicone compositions that upon curing provide a silicone rubber as a cured product. Liquid rubbers can be one-part, two-part, or multi-part compositions depending on their selection and curing mechanism.

[0112] In certain embodiments, the liquid rubber is selected from (a) hydrosilylation curable silicone compositions, (b) condensation curable silicone compositions, (c) thiol-ene reaction curable silicone compositions, (d) free radical curable silicone compositions, and (e) ring-opening reaction-curable silicone compositions. The liquid rubber is not limited to hydrosilylation or addition curable liquid rubbers. As understood in the art, these liquid rubbers can be cured through different curing conditions, such as exposure to moisture, exposure to heat, exposure to radiation, but all five silicone rubbers can be cured. Furthermore, these liquid rubbers can be curable upon exposure to different types of curing conditions, such as both heat and radiation, which can be used together or only one. In addition, certain effect conditions, such as heat, can be used to cure or initiate curing of condensation curable silicone compositions, hydrosilylation curable silicone compositions, and free radical curable silicone compositions.

[0113] In certain embodiments, the liquid rubber comprises a hydrosilylation curable silicone composition.In these embodiments, the hydrosilylation curable silicone composition typically comprises an organopolysiloxane having an average of at least two silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms per molecule, an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms or silicon-bonded alkenyl groups per molecule, which can react with the silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms in the organopolysiloxane, and a hydrosilylation catalyst.When the organopolysiloxane comprises a silicon-bonded alkenyl group, the organosilicon compound comprises at least two silicon-bonded hydrogen atoms per molecule, and when the organopolysiloxane comprises a silicon-bonded hydrogen atom, the organosilicon compound comprises at least two silicon-bonded alkenyl groups per molecule.The organosilicon compound may also be referred to as a crosslinker or crosslinking agent.

[0114] The organopolysiloxane and the organosilicon compound can be independently linear, branched, cyclic, or resinous, but typically are independently linear or partially branched.For example, the organopolysiloxane and / or the organosilicon compound can be an organopolysiloxane that includes repeating D units.Such organopolysiloxanes are substantially linear, but may include some branching due to T and / or Q units.Alternatively, such organopolysiloxanes are linear.

[0115] The silicon-bonded alkenyl groups and silicon-bonded hydrogen atoms of the organopolysiloxane and organosilicon compound may each independently be present at the pendant, terminal, or both positions. Suitable alkenyl groups are described above with respect to polysiloxane (A).

[0116] The hydrosilylation catalyst may be any of the known hydrosilylation catalysts including platinum group metals (i.e., platinum, rhodium, ruthenium, palladium, osmium, and iridium) or compounds containing platinum group metals. Typically, the platinum group metal is platinum based on its high activity in hydrosilylation reactions. Examples of hydrosilylation catalysts are:

[0117] The hydrosilylation catalyst may also or alternatively be a photoactivatable hydrosilylation catalyst that can initiate curing upon irradiation and / or heating. The photoactivatable hydrosilylation catalyst may be any hydrosilylation catalyst that is capable of catalyzing a hydrosilylation reaction, particularly upon exposure to radiation having a wavelength of 150 to 800 nanometers (nm).

[0118] The concentration of the hydrosilylation catalyst is sufficient to catalyze the addition reaction between the organopolysiloxane and the organosilicon compound.In certain embodiments, the concentration of the hydrosilylation catalyst is sufficient to provide typically 0.1 to 1000 ppm of platinum group metal, alternatively 0.5 to 100 ppm of platinum group metal, alternatively 1 to 25 ppm of platinum group metal, based on the combined weight of the organopolysiloxane and the organosilicon compound.

[0119] The hydrosilylation curable silicone composition may be a two-part composition, and the organopolysiloxane and the organosilicon compound are in separate parts.In these embodiments, the hydrosilylation catalyst may be present with either or both of the organopolysiloxane and the organosilicon compound.Alternatively, the hydrosilylation catalyst may be separate from the organopolysiloxane and the organosilicon compound and be in a third part, so that the hydrosilylation curable silicone composition is a three-part composition.

[0120] Hydrosilylation curable silicone compositions can generally be solidified or cured upon exposure to radiation and / or heat, depending on the hydrosilylation catalyst utilized.Those skilled in the art understand how the selection of hydrosilylation catalyst affects the technique for solidification and curing.Specifically, photoactivatable hydrosilylation catalysts are typically utilized when radiation curing is desired.

[0121] In certain embodiments, liquid rubber comprises condensation curable silicone composition.In these embodiments, condensation curable silicone composition typically comprises organopolysiloxane having at least 2 silicon-bonded hydroxyl groups or hydrolyzable groups per molecule on average, optionally an organosilicon compound having at least 2 silicon-bonded hydrogen atoms, hydroxyl groups, or hydrolyzable groups per molecule on average, and a condensation catalyst.While any parameter or condition can be selectively controlled during the method of the present invention or any individual step thereof, the relative humidity and water content of ambient conditions can be selectively controlled to further affect the cure speed of condensation curable silicone composition.

[0122] The organopolysiloxane and the organosilicon compound can be independently linear, branched, cyclic, or resinous, but typically are independently linear or partially branched.For example, the organopolysiloxane and / or the organosilicon compound can be an organopolysiloxane that includes repeating D units.Such organopolysiloxanes are substantially linear, but may include some branching due to T and / or Q units.Alternatively, such organopolysiloxanes are linear.

[0123] The silicon-bonded hydroxyl groups and silicon-bonded hydrogen atoms, hydroxyl groups, or hydrolyzable groups of the organopolysiloxanes and organosilicon compounds can each independently be in the pendant, terminal, or both positions.

[0124] As is known in the art, silicon-bonded hydroxyl groups are obtained from hydrolyzing silicon-bonded hydrolyzable groups that can condense to form siloxane bonds with water as a by-product.

[0125] Examples of hydrolyzable groups include the following silicon-bonded groups: H, a halide group, an alkoxy group, an alkylamino group, a carboxy group, an alkyliminooxy group, an alkenyloxy group, or an N-alkylamido group. The alkylamino group may be a cyclic amino group.

[0126] As noted above, the condensation-curable silicone composition further comprises an organosilicon compound. Specific examples of organosilicon compounds include alkoxysilanes [MeSi(OCH3)3, CH3Si(OCH2CH3)3, CH3Si(OCH2CH2CH3)3, CH3Si[O(CH2)3CH3]3, CH3CH2Si(OCH2CH3)3, C6H5Si(OCH3)3, C6H5CH2Si(OCH3)3, C6H5Si(OCH2CH3)3, CH2=CHSi(OCH3)3, CH2=CHCH2Si(OCH3)3, CF3CH2CH2Si(OCH3)3, CH3Si(OCH2CH2OCH3)3, CF3CH2CH2Si(OCH2CH2OCH3)3, CH2=CHSi(OCH2CH2OCH3)3, CH2=CHCH2Si(OCH2CH2OCH3)3, CH6H 5Si(OCH2CH2OCH3)3, Si(OCH3)4, Si(OC2H5)4, and Si(OC3H7)4, etc.], organoacetoxysilanes [CH3Si(OCOCH3)3, CH3CH2Si(OCOCH3)3, and CH2=CHSi(OCOCH3)3, etc.], organoiminooxysilanes [CH3Si[ON=C(CH3)CH2CH3]3, Si[ON=C(CH3)CH2CH3]4, and CH2=CHSi[ON=C(CH3)CH2CH3]3, etc.], organoacetamidosilanes [CH3Si[NHC(=O)CH3]3, and C6H5Si[NHC(=O)CH3]3, etc.], aminosilanes [CH3Si[NH(s-C4H9)]3, and CH3Si(NHC6H 11 ) 3, etc.], as well as organoaminooxysilanes.

[0127] The organosilicon compound can be a single silane or a mixture of two or more different silanes, each as described above, and methods for preparing trifunctional and tetrafunctional silanes are well known in the art, and many of these silanes are commercially available.

[0128] When present, the concentration of organosilicon compound in condensation curable silicone composition is sufficient to cure (crosslink) organopolysiloxane.The specific amount of organosilicon compound utilized varies according to the degree of cure desired, and generally increases as the ratio of the moles of silicon-bonded hydrolyzable groups in organosilicon compound to the moles of silicon-bonded hydroxyl groups in organopolysiloxane increases.The optimal amount of organosilicon compound can be easily determined by routine experimentation.

[0129] The condensation catalyst may be any condensation catalyst typically used to promote the condensation of silicon-bonded hydroxy (silanol) groups to form Si-O-Si bonds. Examples of condensation catalysts include, but are not limited to, amines, and complexes of lead, tin, zinc, and iron with carboxylic acids. Specifically, condensation catalysts (C 1 ) may be selected from tin(II) and tin(IV) compounds (such as tin dilaurate, tin dioctoate, and tetrabutyltin) and titanium compounds (such as titanium tetrabutoxide).

[0130] When present, the concentration of the condensation catalyst is typically from 0.1 to 10 wt%, alternatively from 0.5 to 5 wt%, alternatively from 1 to 3 wt%, based on the total weight of the organopolysiloxane in the condensation-curable silicone composition.

[0131] When condensation curable silicone composition comprises condensation catalyst, condensation curable silicone composition is typically a two-part composition, and organopolysiloxane and condensation catalyst are in separate parts.In this embodiment, organosilicon compound is typically present together with condensation catalyst.Alternatively, condensation curable silicone composition can also be a three-part composition, and organopolysiloxane, organosilicon compound and condensation catalyst are in separate parts.

[0132] In certain embodiments, the liquid rubber comprises a free radically curable silicone composition. In these embodiments, the free radically curable silicone composition may comprise an organopolysiloxane having an average of at least two silicon-bonded unsaturated groups, and an organic peroxide.

[0133] Organopolysiloxanes may be linear, branched, cyclic, or resinous, but are typically linear or partially branched. For example, organopolysiloxanes may contain repeating D units. Such organopolysiloxanes may be substantially linear, but may contain some branching due to T and / or Q units. Alternatively, such organopolysiloxanes are linear.

[0134] The silicon-bonded unsaturated groups of the organopolysiloxane can be in the pendant, terminal, or both positions. The silicon-bonded unsaturated groups can contain ethylenic unsaturation in the form of double and / or triple bonds. Illustrative examples of silicon-bonded unsaturated groups include silicon-bonded alkenyl groups and silicon-bonded alkynyl groups, examples of which are disclosed above with respect to polysiloxane (A).

[0135] The free radical curable silicone composition may further comprise an unsaturated compound selected from (i) at least one organosilicon compound having at least one silicon-bonded alkenyl group per molecule, (ii) at least one organic compound having at least one aliphatic carbon-carbon double bond per molecule, (iii) at least one organosilicon compound having at least one silicon-bonded acryloyl group per molecule; (iv) at least one organic compound having at least one acryloyl group per molecule; and (v) a mixture comprising (i), (ii), (iii) and (iv). The unsaturated compound may have a linear, branched or cyclic structure.

[0136] The organosilicon compound (i) can be an organosilane or an organosiloxane. The organosilane can be a monosilane, disilane, trisilane, or polysilane. Similarly, the organosiloxane can be a disiloxane, trisiloxane, or polysiloxane. Cyclosilanes and cyclosiloxanes typically have 3 to 12 silicon atoms, alternatively 3 to 10 silicon atoms, alternatively 3 to 4 silicon atoms. In acyclic polysilanes and polysiloxanes, the silicon-bonded alkenyl groups can be located at terminal, pendant, or both terminal and pendant positions.

[0137] Specific examples of organosilanes include, but are not limited to, silanes having the following formulas: ViSi, PhSiVi3, MeSiVi3, PhMeSiVi2, Ph2SiVi2, and PhSi(CH2CH=CH2)3, where Me is methyl, Ph is phenyl, and Vi is vinyl.

[0138] Specific examples of organosiloxanes include, but are not limited to, siloxanes having the following formulas: PhSi(OSiMe2Vi)3, Si(OSiMe2Vi)4, MeSi(OSiMe2Vi)3, and Ph2Si(OSiMe2Vi)2, where Me is methyl and Ph is phenyl.

[0139] The organic compound may be any organic compound that contains at least one aliphatic carbon-carbon double bond per molecule, provided that the compound does not prevent the organopolysiloxane from curing to form a silicone resin film. The organic compound may be an alkene, diene, triene, or polyene. Furthermore, in acyclic organic compounds, the carbon-carbon double bond may be located at terminal, pendant, or both terminal and pendant positions.

[0140] The organic compound may contain one or more functional groups other than aliphatic carbon-carbon double bonds.Suitable examples of functional groups include, but are not limited to, -O-, >C=O, -CHO, -CO2-, -C≡N, -NO2, >C=C<, -C≡-, -F, -Cl, -Br, and -I.The suitability of a particular unsaturated organic compound for use in the free radical curable silicone composition of the present invention can be easily determined by routine experimentation.

[0141] Examples of organic compounds containing aliphatic carbon-carbon double bonds include, but are not limited to, 1,4-divinylbenzene, 1,3-hexadienylbenzene, and 1,2-diethenylcyclobutane.

[0142] The unsaturated compound may be a single unsaturated compound or a mixture containing two or more different unsaturated compounds, each as described above. For example, the unsaturated compound may be a single organosilane, a mixture of two different organosilanes, a single organosiloxane, a mixture of two different organosiloxanes, a mixture of organosilane and organosiloxane, a single organic compound, a mixture of two different organic compounds, a mixture of organosilane and organic compound, or a mixture of organosiloxane and organic compound.

[0143] Organic peroxides are used as free radical initiators to initiate the polymerization of organopolysiloxanes.Examples of organic peroxides include diaroyl peroxides (such as dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, and bis-2,4-dichlorobenzoyl peroxide), dialkyl peroxides (such as di-t-butyl peroxide and 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane), diaralkyl peroxides (such as dicumyl peroxide), alkylaralkyl peroxides (such as t-butylcumyl peroxide and 1,4-bis(t-butylperoxyisopropyl)benzene), and alkylaryl peroxides (such as t-butylperbenzoate, t-butylperacetate, and t-butylperoctoate).

[0144] The organic peroxide may be a single peroxide or a mixture containing two or more different organic peroxides. The concentration of the organic peroxide is typically 0.1 to 5% by weight, alternatively 0.2 to 2% by weight, based on the weight of the organopolysiloxane.

[0145] The free radically curable silicone composition may be a two-part composition, where the organopolysiloxane and the organic peroxide are in separate parts.

[0146] In certain embodiments, the liquid rubber comprises a ring-opening reaction curable silicone composition. In these embodiments, the ring-opening reaction curable silicone composition can comprise an organopolysiloxane having an average of at least two epoxy substituents per molecule, and a curing agent. However, the ring-opening reaction curable silicone composition is not particularly limited to epoxy-functional organopolysiloxanes. Other examples of ring-opening reaction curable silicone compositions include those that comprise silacyclobutane and / or benzocyclobutene.

[0147] The organopolysiloxanes may be linear, branched, cyclic, or resinous, but are typically linear or partially branched.

[0148] The epoxy substituent of the organopolysiloxane can be in the pendant, terminal, or both positions. An "epoxy-substituted group" is generally a monovalent organic group in which an oxygen atom is directly bonded to two adjacent carbon atoms of a carbon chain or ring system, i.e., an epoxy substituent. Examples of epoxy-substituted organic groups include, but are not limited to, 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 2-glycidoxyethyl, 3-glycidoxypropyl, 4-glycidoxybutyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3,4-epoxycyclohexyl)propyl, 2-(3,4-epoxy-3-methylcyclohexyl)-2-methylethyl, 2-(2,3-epoxycyclopentyl)ethyl, and 3-(2,3-epoxycyclopentyl)propyl groups.

[0149] The curing agent can be any curing agent suitable for curing organopolysiloxane. Examples of curing agents suitable for this purpose include phenolic compounds, carboxylic acid compounds, acid anhydrides, amine compounds, alkoxy group-containing compounds, hydroxyl group-containing compounds, or mixtures thereof or partial reaction products thereof. More specifically, examples of curing agents include tertiary amine compounds such as imidazole, quaternary amine compounds, phosphorus compounds (such as phosphines), aluminum compounds (such as organoaluminum compounds), and zirconium compounds (such as organozirconium compounds). Furthermore, either the curing agent or the curing catalyst, or a combination of the curing agent and the curing catalyst, can be used as the curing agent. The curing agent can also be a photoacid or a photoacid-generating compound.

[0150] The ratio of the curing agent to the organopolysiloxane is not limited. In a particular embodiment, the ratio is 0.1 to 500 parts by weight of the curing agent per 100 parts by weight of the organopolysiloxane.

[0151] In certain embodiments, the liquid rubber comprises a thiol-ene curable silicone composition. In these embodiments, the thiol-ene curable silicone composition typically comprises an organopolysiloxane having an average of at least two silicon-bonded alkenyl groups or silicon-bonded mercaptoalkyl groups per molecule, an organosilicon compound having an average of at least two silicon-bonded mercapto-alkyl groups or silicon-bonded alkenyl groups per molecule that can react with the silicon-bonded alkenyl groups or silicon-bonded mercapto-alkyl groups in the organopolysiloxane, a catalyst, and an organic compound that optionally contains two or more mercapto groups. When the organopolysiloxane contains silicon-bonded alkenyl groups, the organosilicon compound and / or the organic compound contain at least two mercapto groups per molecule bonded to silicon and / or in the organic compound, and when the organopolysiloxane contains silicon-bonded mercapto groups, the organosilicon compound contains at least two silicon-bonded alkenyl groups per molecule. The organosilicon compound and / or the organic compound may be referred to as a crosslinker or crosslinking agent.

[0152] The catalyst can be any catalyst suitable for catalyzing the reaction between organopolysiloxane and organosilicon compound and / or organic compound.Typically, the catalyst is selected from i) free radical catalyst, ii) nucleophile, and iii) combination of i) and ii).Free radical catalyst suitable for use as catalyst includes photoactive free radical catalyst, thermally active free radical catalyst, room temperature free radical catalyst, such as redox catalyst and alkylborane catalyst, and combinations thereof.Nucleophile suitable for use as catalyst includes amine, phosphine, and combinations thereof.

[0153] Any of the liquid rubbers may optionally and independently further comprise additional components or ingredients, particularly if these components or ingredients do not interfere with the curing of any particular component of the composition. Examples of additional ingredients include, but are not limited to, fillers, inhibitors, adhesion promoters, dyes, pigments, antioxidants, carrier vehicles, heat stabilizers, flame retardants, thixotropic agents, flow control agents, fillers including extending and reinforcing fillers, and crosslinkers. In various embodiments, the composition further comprises a ceramic powder. The amount of ceramic powder can vary and may depend on the 3D printing process utilized.

[0154] One or more of the additives can be present in any suitable weight percent of a particular composition, such as from about 0.1% to about 15%, from about 0.5% to about 5%, or about 0.1% or less, about 1%, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or about 15% or more by weight of the composition.

[0155] Any of the above compositions may be single-part or multi-part compositions as described above for certain compositions. Because certain compositions are highly reactive, multi-part compositions prevent premature mixing and curing of the components. Multi-part compositions may be, for example, two-part systems, three-part systems, etc., depending on the composition and the selection of its components. Any component of the composition may be separate and individually controlled with respect to the remaining components.

[0156] The liquid rubber can be of various viscosities. In certain embodiments, the liquid rubber has a viscosity of less than 500 centistokes, less than 250 centistokes, or less than 100 centistokes at 25° C., alternatively from 1 to 1,000,000 centistokes at 25° C., alternatively from 1 to 100,000 centistokes at 25° C., alternatively from 1 to 10,000 centistokes at 25° C. As would be readily understood in the art, kinematic viscosity can be measured according to ASTM D-445(2011), entitled "Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)".

[0157] The amounts of components (A), (B), (C), and (D) in the silicone-polyolefin composition can vary, as best understood in light of the additional description below.

[0158] Typically, the polysiloxane (A) is present in the silicone-polyolefin composition in an amount of 0.5 to 15 wt%, for example 1 to 12, alternatively 1.5 to 10, alternatively 2 to 7 wt%, based on the total weight of the silicone-polyolefin composition. The functionalized polyolefin (B) is typically present in the silicone-polyolefin composition in an amount of 1 to 40 wt%, alternatively 1 to 30 wt%, based on the total weight of the silicone-polyolefin composition. The polyolefin (C) is typically present in the silicone-polyolefin composition in an amount of 1 to 40, alternatively 1 to 35, alternatively 2 to 30, alternatively 3 to 25, alternatively 4 to 20, alternatively 5 to 25 wt%, based on the total weight of the silicone-polyolefin composition. Component (D) is typically present in the silicone-polyolefin composition in an amount of 55 to 99, alternatively 60 to 99, alternatively 70 to 98 wt%, based on the total weight of the silicone-polyolefin composition.

[0159] In some embodiments, the amounts of components (A), (B), (C), and / or (D) correspond to the ranges set forth above, with the weight percentages being determined based on the combined weight of components (A), (B), (C), and (D) (i.e., should any additional components be present, rather than the silicone-polyolefin composition as a whole).

[0160] With respect to the foregoing embodiments and amounts of components, it should be understood that the remainder of the silicone-polyolefin composition, if present, may include one or more additional components of the silicone-polyolefin composition. For example, as better understood in light of the additional descriptions and methods described herein, the silicone-polyolefin composition may include a catalyst, a solvent or carrier vehicle, or a reaction promoter. However, in some embodiments, the silicone-polyolefin composition does not include, or is alternatively substantially free of, a reaction catalyst or promoter. In these or other embodiments, the silicone-polyolefin composition includes less than 1 wt. % of a solvent, based on the total weight of the silicone-polyolefin composition. In other embodiments, the silicone-polyolefin composition is substantially free, or alternatively is free of, a solvent or carrier vehicle.

[0161] It will be understood that amounts outside the above ranges and ratios can also be utilized, however, as will be better understood in light of the additional descriptions and methods described herein, decreasing the loading of polysiloxane (A) and / or increasing the loading of functionalized polyolefin (B) can result in macrophase separation due to insufficient compatibilization.

[0162] In some embodiments, the silicone-polyolefin composition comprises (E) a catalyst adapted to promote a coupling reaction between functional groups X of the polysiloxane (A) and functional groups Y of the functionalized polyolefin (B).

[0163] The use of catalyst (E) as well as the particular type or compound selected for use in or as catalyst (E) will be selected by one of ordinary skill in the art based on the particular polysiloxane (A) and functionalized polyolefin (B) selected. More specifically, catalyst (E) is selected, without being limited thereto, to catalyze the coupling of components (A) and (B) instead, and thus may include or be any compound suitable for promoting the reaction of polysiloxane (A) with functionalized polyolefin (B) (e.g., via / including the reaction of functional groups X and Y), as will be understood by one of ordinary skill in the art in light of the description herein. For example, in certain embodiments, catalyst (E) is selected from those that promote reactions including hydrosilylation, condensation, substitution, ring opening, nucleophilic substitution, and the like, and combinations of such reactions. It is understood that catalyst (E) itself may include more than one catalyst and / or the reaction may utilize more than one catalyst (E), for example, two, three, or more different catalysts (E).

[0164] In specific embodiments, catalyst (E) comprises, or is, a hydrosilylation catalyst. In such embodiments, functional group X and functional group Y are complementary, couplable, hydrosilylatable groups.

[0165] The hydrosilylation catalyst suitable for use in the silicone-polyolefin composition is not particularly limited and may be any known catalyst for catalyzing hydrosilylation reactions. A combination of different hydrosilylation catalysts may also be utilized.

[0166] In certain embodiments, the hydrosilylation catalyst comprises a Group VIII-XI transition metal, with reference to the latest IUPAC nomenclature, where the Group VIII transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs), the Group IX transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir), the Group X transition metals are nickel (Ni), palladium (Pd), and platinum (Pt), and the Group XI transition metals are copper (Cu), silver (Ag), and gold (Au). Further examples of catalysts suitable for the hydrosilylation catalyst include rhenium (Re), molybdenum (Mo), Group IV transition metals (i.e., titanium (Ti), zirconium (Zr), and / or hafnium (Hf)), lanthanides, actinides, and Group I and II metal complexes (e.g., those containing calcium (Ca), potassium (K), strontium (Sr), etc.). Combinations, complexes (e.g., organometallic complexes), and other forms of such metals may also be utilized as hydrosilylation catalysts.

[0167] The hydrosilylation catalyst may be in any suitable form. For example, the hydrosilylation catalyst may be solid or alternatively disposed in or on a solid support. Examples of solid catalysts typically include platinum-based catalysts, palladium-based catalysts, and similar precious metal-based catalysts, as well as nickel-based catalysts. Specific examples include elemental nickel, palladium, platinum, rhodium, cobalt, and similar metals, as well as elemental mixtures / combinations such as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum, and Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-Al, Cu-Zn-Ti, and similar copper-containing catalysts. Examples of supports include activated carbon, silica, silica-alumina, alumina, zeolites, and other inorganic powders / particles (e.g., sodium sulfate), and the like. The hydrosilylation catalyst may also be deposited, for example, in a solvent that solubilizes the hydrosilylation catalyst, or alternatively in a vehicle that simply supports but does not solubilize the hydrosilylation catalyst. Such vehicles are known in the art.

[0168] In specific embodiments, the hydrosilylation catalyst comprises platinum. In these embodiments, the hydrosilylation catalyst is exemplified by platinum black, chloroplatinic acid (e.g., chloroplatinic acid hexahydrate, reaction product of chloroplatinic acid with monohydric alcohol, or aliphatically unsaturated organosilicon compounds, such as divinyltetramethyldisiloxane), platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum chloride, complexes of any of these compounds with olefins or organopolysiloxanes, and microencapsulated platinum compounds (e.g., matrix or core-shell type). For example, suitable complexes of platinum with organopolysiloxanes, such as 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes of platinum, may be used directly or alternatively in microencapsulated form (e.g., in resin matrix).

[0169] The hydrosilylation catalyst may be a photoactivatable hydrosilylation catalyst, which may initiate curing via irradiation (eg, upon exposure to radiation having a wavelength of 150-800 nm) and / or heat.

[0170] Specific examples of photoactivatable hydrosilylation reaction catalysts suitable for catalyst (E) include platinum(II) β-diketonate complexes, such as platinum(II) bis(2,4-pentanedioate), platinum(II) bis(2,4-hexanedioate), platinum(II) bis(2,4-heptanedioate), platinum(II) bis(1-phenyl-1,3-butanedioate), platinum(II) bis(1,3-diphenyl-1,3-propanedioate), platinum(II) bis(1,1,1,5,5 ,5-hexafluoro-2,4-pentanedioate), (η-cyclopentadienyl)trialkylplatinum complexes such as (Cp)trimethylplatinum, (Cp)ethyldimethylplatinum, (Cp)triethylplatinum, (chloro-Cp)trimethylplatinum, and (trimethylsilyl-Cp)trimethylplatinum, where Cp represents cyclopentadienyl; triazene oxide-transition metal complexes such as [Pt[CHNNNOCH], Pt[p-CN-CHNNNOCH11 ]4, Pt[p-H3COC6H4NNNOC6H 11 ]4, Pt[p-CH3(CH2) x -C6H4NNNOCH3]4, 1,5-cyclooctadienePt[p-CN-C6H4NNNOC6H 11 ]2, 1,5-cyclooctadiene Pt[p-CH3O-C6H4NNNOCH3]2, [(C6H5)3P]3Rh[p-CN-C6H4NNNOC6H 11 ], and Pd[p-CH3(CH2) x -C6H4NNNOCH3]2, where x is 1, 3, 5, 11, or 17; (σ-diolefin)(-aryl)platinum complexes, such as (η 4 -1,5-cyclooctadienyl)diphenylplatinum, (η 4 -1,3,5,7-cyclooctatetraenyl)diphenylplatinum, (η 4 -2,5-norborazienyl)diphenylplatinum, (η 4 -1,5-cyclooctadienyl)bis-(4-dimethylaminophenyl)platinum, (η 4 -1,5-cyclooctadienyl)bis-(4-acetylphenyl)platinum, and (η 4 and (η-diolefin)(-aryl)platinum complexes, such as (η-diolefin)(-aryl)platinum ...

[0171] It will be appreciated that the compounds described above with respect to catalyst (E) above, i.e., if they comprise or are hydrosilylation catalysts, can generally promote rapid reaction (i.e., coupling, crosslinking, etc.) of the components (A) and (B) of the silicone-polyolefin composition, even at room temperature (i.e., if they are capable of reacting via hydrosilylation as described above). Thus, in certain embodiments, the silicone-polyolefin composition further comprises a reaction inhibitor, which may be further defined as a crosslinking reaction inhibitor, a hydrosilylation reaction inhibitor, or a stabilizer. Suitable inhibitors are known in the art and generally include compounds that stop the catalytic action but are volatile or easily decomposed by heat or light (e.g., UV). Examples of such inhibitors include relatively low boiling alkyne- and alkene-based compounds with electron-withdrawing groups that typically form complexes with the catalyst metal, thereby blocking its activity until heat is applied. Common examples of inhibitors include acetylenic alcohols having boiling points below 250° C. (e.g., 2-methyl-3-butyn-2-ol, 1-ethynylcyclohexanol (ETCH)), as well as various fumarates, maleates (e.g., diallyl maleate), small vinyl functional siloxanes (e.g., tetravinyl-tetramethyltetrasiloxane), ethynyl alkenes (e.g., 3-methyl-3-penten-1-yne, 3-methyl-3-hexen-1-yne, 3,5-dimethyl-3-hexen-1-yne, 3-ethyl-3-buten-1-yne, 3-phenyl-3-buten-1-yne, etc.), dialkyl esters of acetylenedicarboxylate (e.g., dimethyl acetylenedicarboxylate (DMAD)), and the like, as well as various derivatives thereof. One of ordinary skill in the art would have selected such an inhibitor for use in or as a reaction inhibitor taking into consideration the particular other components utilized for the silicone-polyolefin composition and its intended application, including the uses and processes disclosed herein.For example, it is well understood that certain hydrosilylation reaction inhibitors / stabilizers exhibit different compatibility and operating windows (e.g., in terms of photosensitivity and / or thermal sensitivity, required loadings, etc.), such that one of ordinary skill in the art will readily select an appropriate inhibitor for use as a reaction inhibitor, as desired, based on the description of the compositions and methods provided herein.

[0172] In specific embodiments, catalyst (E) comprises, or is, a condensation catalyst. In such embodiments, functional group X and functional group Y are complementary condensable groups (e.g., amine (X) + anhydride (Y)).

[0173] Condensation catalysts suitable for use in the silicone-polyolefin compositions can be any known compound (or combination) that is compatible with components (A) and (B) and capable of catalyzing or otherwise promoting the condensation reaction of functional groups X and Y. Combinations of different hydrosilylation catalysts may also be utilized.

[0174] Examples of condensation catalysts are generally inorganic and organic bases and acids (i.e., acid-type or base-type catalysts), which may contain metal atoms, or alternatively may be substantially free of metal atoms, or alternatively may be free of metal atoms. Examples of such catalysts generally include mineral acids and bases (e.g., H2SO4, LiOH, NaOH, KOH, CsOH, etc.), organic bases and amines (e.g., tetramethylammonium hydroxide ((CH3)4NOH), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)), organic and inorganic acids (e.g., carboxylic acids, sulfamic acid, etc.), and certain metal complexes such as titanium alkoxides (e.g., Ti(OiPr)2(acac)2), and the like, as well as derivatives, modifications, and combinations thereof. Such condensation catalysts are well known in the art and are commercially available.

[0175] If utilized, a particular condensation catalyst will be selected by those skilled in the art in consideration of the particular components and conditions utilized in the silicone-polyolefin composition and the process involving them. Certain limitations will be understood in consideration of the following description. For example, in some embodiments, residual amounts of catalyst may be carried over from the silicone-polyolefin composition to other compositions and / or processes that may not be compatible with certain types of condensation catalysts. Thus, in certain embodiments, the catalyst (E), optionally the silicone-polyolefin composition as a whole, is substantially free, or alternatively free, of one or more metal-based condensation catalysts, strong acids and strong bases, oxidizing compounds, and the like.

[0176] It should be understood that other catalysts can also be utilized, whether or not they fall within one of the general descriptions herein. For example, it will be understood that certain coupling reactions described herein can be promoted by various Lewis acid catalysts, such as those based on boron, aluminum, iron, tin, and titanium, such as trivalent or tetravalent halides and their alkoxides. Similarly, in certain embodiments, catalyst (E) includes or is a Piers-Rubinsztajn type catalyst (e.g., tris(pentafluorophenyl)borane), which can be utilized to promote the coupling between one of the hydridosilyl groups (e.g., functional group X) described herein and an alkoxysilyl group or a hydroxysilyl group (e.g., functional group Y).

[0177] Catalyst (E) may be utilized in any amount selected by one of skill in the art depending, for example, on the particular catalyst (E) selected (e.g., the concentration / amount of its active components, the type of catalyst being utilized, the type of coupling reaction being performed, etc.), the scale at which it is utilized (e.g., the total amount of components (A) and (B), the relative amounts of functional groups X and Y, etc.). As best understood in view of the following description, the molar ratio of catalyst (E) to components (A) and / or (B) utilized in the reaction can affect the rate and / or amount of coupling / crosslinking, if desired. Thus, the amount of catalyst (E) relative to components (A) and / or (B), as well as the molar ratio therebetween, can vary. Typically, these relative amounts and molar ratios are selected to maximize the reaction of components (A) and (B) (e.g., via functional groups XY) while minimizing the amount of catalyst (E) added (e.g., to improve the economic efficiency of the reaction, to improve the ease of purification of the reaction product formed, etc.).

[0178] It will be understood that, for example, reducing the catalyst loading beyond the minimum threshold may result in poor reactivity and thus may not achieve the properties and benefits demonstrated and described herein. With respect to this embodiment, such minimum threshold is generally applicable to the hydrosilylation-mediated coupling reaction of components (A) and (B) described herein. Thus, in a typical embodiment in which functional group X and functional group Y are complementary coupleable hydrosilylatable groups, the silicone-polyolefin composition includes a hydrosilylation catalyst of catalyst (E) in an amount of 1 to 100 ppm, alternatively 5 to 100 ppm. However, it will also be understood that loadings outside these ranges may be utilized to achieve the benefits described herein, and that one of ordinary skill in the art will be able to determine the appropriate catalyst loading (e.g., based on reaction rate, compatibilization of components (A) and (B), etc.) in light of the description and examples herein. For example, such minimum threshold amount of catalyst (E) may not be required in other embodiments, such as when an epoxy-amine coupling reaction of components (A) and (B) is utilized.

[0179] Similarly, in yet other embodiments, the silicone-polyolefin composition is substantially free, or alternatively free, of reaction catalysts or accelerators, including those described above with respect to catalyst (E). As will be understood in light of the additional description herein, certain features of the silicone-polyolefin composition and related methods and compositions may be realized and / or achieved without the use of catalysts or accelerators. For example, in specific embodiments, functional groups X and Y are complementary condensable groups (e.g., amine (X) + anhydride (Y)), and the silicone-polyolefin composition is substantially free, or alternatively free, of condensation catalysts or accelerators. Other crosslinking chemistries such as amine-methacrylate, silanol-alkoxysilane, and carbinol-anhydride coupling provided herein can also be used without modest catalyst loading.

[0180] In certain embodiments, catalyst (E) is utilized in the silicone-polyolefin composition in an amount (i.e., weight / weight) of 0.000001-5% by weight based on the total amount of component (A) utilized. For example, catalyst (E) may be used in an amount of 0.00001-5% by weight, such as 0.00001-4% by weight, alternatively 0.00001-3% by weight, alternatively 0.00001-2% by weight, alternatively 0.0001-2% by weight, alternatively 0.0001-1% by weight, alternatively 0.0001-0.5% by weight, alternatively 0.001-0.5% by weight, alternatively 0.005-0.5% by weight based on the total amount of component (A) utilized. Similarly or alternatively, catalyst (E) may be utilized in the silicone-polyolefin composition in an amount (i.e., weight / weight) of 0.000001 to 5% by weight based on the total amount of component (B) utilized. For example, catalyst (E) may be used in an amount of 0.00001 to 5% by weight, such as 0.00001 to 4% by weight, alternatively 0.00001 to 3% by weight, alternatively 0.00001 to 2% by weight, alternatively 0.0001 to 2% by weight, alternatively 0.0001 to 1% by weight, alternatively 0.0001 to 0.5% by weight, alternatively 0.001 to 0.5% by weight, alternatively 0.005 to 0.5% by weight based on the total amount of component (B) utilized.

[0181] In some embodiments (e.g., where the type of reaction dictates the stoichiometric loading), the amount of catalyst (E) utilized may be selected and / or determined as a molar ratio based on one or more components of the silicone-polyolefin composition, as would be understood by one of skill in the art. In such embodiments, catalyst (E) may be utilized in the silicone-polyolefin composition in an amount of 0.0001 to 5 mole percent, based on the total amount of component (A) and / or component (B) utilized. For example, catalyst (E) may be used in an amount of 0.0005 to 5 mole percent, alternatively 0.0005 to 3 mole percent, alternatively 0.0005 to 1 mole percent, alternatively 0.001 to 1 mole percent, based on the total amount of component (A) utilized.

[0182] The functionalized polyolefin (B) and polyolefin (C) are typically immiscible or substantially immiscible with the curable silicone elastomer component (D). Thus, as introduced above, a method for preparing a hybrid silicone-polyolefin blend from a silicone-polyolefin composition ("preparation method") is also provided, which generally comprises compatibilizing the functionalized polyolefin (B) and polyolefin (C) with the polysiloxane (A) in the silicone-polyolefin composition.

[0183] More specifically, the preparation method allows for the preparation of a homogeneous dispersion of functionalized polyolefin (B) and polyolefin (C) in component (D) (i.e., as a polyolefin-in-silicone dispersion), where these components are based on otherwise incompatible chemistries (i.e., polysiloxane and polyolefin).Furthermore, the preparation method provides the silicone-polyolefin blend as a homogeneous composition having small domains (e.g., polyolefin domains) and useful features that support the application of the silicone-polyolefin blend in a curable composition.

[0184] Polysiloxane (A) can, for example, compatibilize functionalized polyolefin (B) via the addition coupling / crosslinking reaction between functional group X and functional group Y, respectively. Thus, the preparation method includes reacting polysiloxane (A) with functionalized polyolefin (B). Typically, components (A) and (B) react in the presence of components (C) and (D). Thus, it will be understood that the preparation method may be performed on a silicone-polyolefin composition in a pre-made form, or may include preparing a silicone-polyolefin composition (e.g., by combining polysiloxane (A), functionalized polyolefin (B), polyolefin (C), and component (D) with any of the additional and / or optional components described herein, such as catalyst (E)). As such, the silicone-polyolefin composition may be referred to or characterized as a reactive premix or compatibilized mixture comprising at least components (A), (B), (C), and (D), or the silicone-polyolefin composition.

[0185] With respect to the process components, the polysiloxane (A), the functionalized polyolefin (B), the polyolefin (C), and the curable silicone (D) can each be prepared (i.e., as part of a preparation process) or can otherwise be obtained, for example, as prepared reagents / feedstocks. Methods for preparing each of these components (e.g., reactive / crosslinkable polydiorganosiloxanes, functionalized poly-alphaolefin-alkenyl copolymers, reactive curable polydiorganosiloxane gums, etc.) are known in the art, and suitable precursors and starting materials are commercially available from a variety of suppliers.

[0186] Components (A), (B), (C), and (D) can be utilized in any amount, taking into consideration the upper limits / ratios of functionalized polyolefin (B) for compatibilization with polysiloxane (A) discussed above. Thus, suitable amounts selected by one of ordinary skill in the art will depend, for example, on the particular components selected, the reaction parameters used for compatibilization, the extent of compatibilization (e.g., the total amounts of components (A), (B), (C), and (D) in the silicone-polyolefin composition utilized, etc.

[0187] In general, components (A), (B), (C), and (D) may be utilized independently in any form, such as solvent-free (i.e., in the absence of a solvent, carrier vehicle, diluent, etc.) or disposed in a carrier vehicle, such as a solvent or dispersant, as described in more detail below. However, in certain embodiments, each of (A), (B), (C), and (D) is utilized in a solvent-free or otherwise substantially free of carrier vehicle, alternatively free of carrier vehicle. When substantially free of carrier vehicle, components ((A), (B), (C), and (D) will typically be free (or substantially free) of carrier vehicle / volatiles, or post-compatibilization reactants, reactive with water and any of the components involved in the compatibilization, as described below. Thus, in some embodiments, the compatibilization, or the preparation method as a whole, does not involve the use of carrier vehicle / volatiles that are reactive with the polysiloxane (A) (i.e., at the polysiloxane backbone or functional group X), the functionalized polyolefin (B) (e.g., at functional group Y), or any one or more other components (e.g., catalyst (E), if present) utilized to prepare the silicone-polyolefin composition. The process is carried out in the absence of any substances. For example, in certain embodiments, the preparation method may include stripping a mixture containing one or more of components (A), (B), (C), and (D), and optionally (E) such as a volatile material, solvent, etc. (i.e., a "compatibilizing component"), before combining with any one or other components utilized in the preparation method. Such siloxane, polyolefin, and reaction catalyst stripping techniques are generally known in the art and may include heating, drying, application of reduced pressure / vacuum, azeotroping with a solvent, utilizing a drying agent such as molecular sieves, and combinations thereof, taking care not to initiate premature reactions with functional groups X or Y.

[0188] In some embodiments, one or more of the compatibilizing components may be combined with a carrier vehicle, for example, before and / or during compatibilization of component (B). The above-mentioned stripping process may be performed prior to compatibilization, for example, as part of the preparation of such components or when otherwise combined to facilitate providing and / or metering the components to the compatibilized mixture. It will be understood that if a carrier vehicle is present during compatibilization, the appropriate selection is limited based on compatibility with the components and conditions of the compatibilization process.

[0189] With respect to the carrier vehicle, generally, examples typically include oils (e.g., organic oils and / or silicone oils), fluids, solvents, and the like, and combinations thereof. For example, in some embodiments, one or more of the compatibilizing components are disposed in a carrier fluid before being combined with the other compatibilizing components. In some embodiments, the carrier fluid comprises, or alternatively consists essentially of, a silicone fluid. The silicone fluid is typically a low viscosity and / or volatile siloxane. In some embodiments, the silicone fluid is a low viscosity organopolysiloxane, a volatile methyl siloxane, a volatile ethyl siloxane, a volatile methylethyl siloxane, and the like, or a combination thereof. Typically, the silicone fluid has a viscosity in the range of 1 to 1,000 mPa·s at 25°C. Specific examples of suitable silicone fluids include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy)}trisiloxane, hexamethyl-3,3, siloxane, pentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, hexamethyldisiloxane, heptamethyloctyltrisiloxane, hexyltrimethicone, and the like, as well as derivatives, modifications, and combinations thereof. Additional examples of suitable silicone fluids include 5×10 -7 ~1.5×10 -6 m 2 Polyorganosiloxanes of suitable vapor pressure, such as 1000 vol / sec, include DOWSIL™ 200 Fluids and DOWSIL™ OS FLUIDS, which are commercially available from Dow Silicones Corporation (Midland, Mich., USA).

[0190] In other such embodiments, the carrier fluid comprises, or alternatively consists essentially of, an organic fluid, typically comprising an organic oil, including volatile and / or semi-volatile hydrocarbons, esters, and / or ethers. Common examples of such organic fluids include C6-C 16 Alkanes, C8-C 16 Isoalkanes (e.g., isodecane, isododecane, isohexadecane, etc.), C8 to C 16 Volatile hydrocarbon oils such as branched esters (e.g., isohexyl neopentanoate, isodecyl neopentanoate, etc.), as well as derivatives, modifications, and combinations thereof. Further examples of suitable organic fluids include aromatic and aliphatic hydrocarbons. Hydrocarbons include isododecane, isohexadecane, Isopar L (C 11 ~C 13 ), Isopar H(C 11 ~C 12 ), hydrogenated polydecene. Ethers and esters include isodecyl neopentanoate, neopentyl glycol heptanoate, glycol distearate, dicaprylyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3 ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methylether acetate (PGMEA), propylene glycol methylether (PGME), octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, octyl ether, octyl palmitate, and combinations thereof.

[0191] In yet another such embodiment, the carrier fluid comprises an organic solvent, or alternatively consists essentially of an organic solvent.Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as heptane, hexane, and octane; glycol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, and ethylene glycol n-butyl ether; halogenated hydrocarbons such as dichloromethane, 1,1,1-trichloroethane, and methylene chloride; chloroform; dimethyl sulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran, white spirit; mineral spirit, naphtha, n-methylpyrrolidone, and the like, and derivatives, modifications, and combinations thereof.

[0192] As introduced above, and notwithstanding the preceding paragraph, the compatibilization reaction (i.e., the reaction of components (A) and (B) in the presence of components (C) and (D)) can be carried out under conditions that are substantially free of carrier vehicles or solvents. Indeed, as will be understood from the examples and additional description herein, certain features of the preparation method allow for the solventless preparation of a compatibilized blend of silicone components (e.g., components (A) and (D)) and functionalized polyolefin (B) and polyolefin (C).

[0193] Also, as introduced above, the compatibilizing mixture may include components other than components (A) and (B). For example, in certain embodiments, the reaction (i.e., compatibilizing) is further defined as a hydrosilylation reaction, and the functional groups (X) and (Y) are selected from complementary hydrosilylatable groups (e.g., each X is a silicon-bonded olefinic ethylenically unsaturated group and each Y includes a hydridosilyl group). In such embodiments, the compatibilizing mixture typically includes a hydrosilylation catalyst (E). However, in other embodiments, the compatibilizing is further defined as a condensation reaction, and the functional groups (X) and (Y) are selected from complementary condensable groups (e.g., each X is an aminoalkyl group and each Y includes an anhydride group). In some such embodiments, the compatibilizing does not include a catalyst (e.g., a condensation catalyst (E)).

[0194] The components of the silicone-polyolefin composition are typically mixed in a vessel or reactor to effect compatibilization and disperse components (B) and (C) in component (D), thereby preparing the silicone-polyolefin blend. The compatibilizing components may be fed together or separately into a vessel, or may be placed in the vessel in any order of addition and in any combination, to prepare the compatibilized mixture (i.e., the silicone-polyolefin composition). Similarly, the compatibilized mixture may be prepared in a batch, semi-batch, semi-continuous, or continuous process, unless otherwise noted herein.

[0195] Typically, the silicone-polyolefin blend is prepared via dynamic reaction / crosslinking of the silicone-polyolefin blend, i.e., via mixing together components (A), (B), (D), and optionally (E), as coupling / crosslinking occurs. In this context, the term "dynamic" indicates that the silicone-polyolefin composition is subjected to shear forces during the crosslinking / compatibilization process, as opposed to "static crosslinking," in which the polymer is relatively immobilized during such crosslinking.

[0196] Compatibilization is typically carried out at elevated temperatures with mixing (e.g., under shear). Thus, the vessel or reactor is typically heated, e.g., via a jacket, mantle, exchanger, bath, coil, etc., and equipped with mixing means for blending and / or shearing the compatibilized mixture. In general, the elevated temperature for compatibilization is 100-200°C. In specific embodiments, the elevated temperature is typically 100-180, alternatively 100-170, alternatively 100-160, alternatively 100-150, alternatively 110-150, alternatively 110-140°C.

[0197] Regarding mixing / shearing, the silicone-polyolefin composition is typically homogenized by melt blending or extruding the silicone-polyolefin composition at elevated temperature to prepare the silicone-polyolefin blend. Thus, in certain embodiments, the reactor / vessel is an extruder or melt blender, although other reactors and mixing / blending techniques (e.g., using twin rotor mixers, ribbon blenders, solution blenders, co-kneaders, screw extruders, static mixers, Banbury mixers, etc.) may be utilized. However, those skilled in the art will understand that other mixers can also be utilized. The mixing process is also a function of the selection of component (D). For example, when component (D) is a liquid rubber, mixing can include any method typically utilized with liquid or viscous materials.

[0198] As compatibilization proceeds and the components are mixed and reacted, the functionalized polyolefin (B) and polyolefin (C) are incorporated into and uniformly dispersed throughout component (D), thereby preparing the silicone-polyolefin blend as a polyolefin-in-silicone dispersion.

[0199] As introduced above, the silicone-polyolefin blend comprises a functionalized polyolefin (B) and a polyolefin (C) dispersed in a combination of a polysiloxane (A) and a curable silicone elastomer component (D). The silicone-polyolefin blend exists as a viscous but coatable mixture comprising a discontinuous phase comprising the functionalized polyolefin (B) and the polyolefin (C) uniformly dispersed in a continuous phase comprising the component (D) and the polysiloxane (A). In other words, the silicone-polyolefin blend comprises domains (i.e., "polyolefin domains") of the functionalized polyolefin (B) and the polyolefin (C) dispersed in a silicone matrix presented by the component (D). In certain embodiments, the polyolefin domains are uniformly dispersed throughout the continuous phase comprising the component (D).

[0200] Also provided herein is a curable composition.In the same nature as the silicone-polyolefin composition and blend described above, the curable composition does not require a carrier vehicle or solvent under typical circumstances.Therefore, the curable composition may be solvent-free (i.e., does not include, or alternatively is substantially free of, a carrier vehicle or solvent).

[0201] The curable composition includes a silicone-polyolefin blend and a curing agent, although other components may also be utilized. The curing agent typically includes, or is alternatively, a free radical initiator and / or a photoinitiator.

[0202] 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'-azobisisobutyronitril (AIBN), 2,2'-azodi(2-methylbutyronitrile) (AMBN), tert-amyl peroxybenzoate, tert-butyl peracetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, cumene hydroperoxide, and potassium persulfate. Any amount of free radical initiator may be used in the curable composition, but typically only a catalytic amount is required. For example, in certain embodiments, the curable composition includes a free radical initiator in an amount of 0.01 to 10 wt%, based on the total weight of the curable composition. In some embodiments, the free radical initiator is used in an amount of at least 0.15, alternatively at least 0.2 wt.%, and at the same time no more than 10, alternatively 7, alternatively 5, alternatively 3 wt.%, preferably no more than 5 wt.%, and may be no more than 3 wt.%, based on the total weight of the hardenable composition, recognizing that amounts outside these ranges can also be utilized, with the understanding that excess free radical initiator may not significantly increase the time or efficiency of the curing process, which is typically completed in less than 30 minutes, alternatively less than 20 minutes, alternatively less than 15 minutes, and at the same time, typically more than 1 minute, alternatively more than 5 minutes.

[0203] Examples of suitable photoinitiators include onium salts, nitrobenzyl sulfonate esters, diaryliodonium salts of sulfonic acids, triarylsulfonium salts of sulfonic acids, diaryliodonium salts of boronic acids, triarylsulfonium salts of boronic acids, bis-diaryliodonium salts (such as bis(dodecylphenyl)iodonium hexafluoroarsenate and bis(dodecylphenyl)iodonium hexafluoroantimonate), dialkylphenyliodonium hexafluoroantimonates, diaryliodonium salts of sulfonic acids, triarylsulfonium salts of sulfonic acids, diaryliodonium salts of boronic acids, and triarylsulfonium salts of boronic acids.

[0204] Examples of suitable diaryliodonium salts of sulfonic acids include diaryliodonium salts of perfluoroalkylsulfonic acids and diaryliodonium salts of arylsulfonic acids. Examples of suitable diaryliodonium salts of perfluoroalkylsulfonic acids include diaryliodonium salts of perfluorobutanesulfonic acids, diaryliodonium salts of perfluoroethanesulfonic acids, diaryliodonium salts of perfluorooctanesulfonic acids, and diaryliodonium salts of trifluoromethanesulfonic acids. Examples of suitable diaryliodonium salts of arylsulfonic acids include diaryliodonium salts of paratoluenesulfonic acids, diaryliodonium salts of dodecylbenzenesulfonic acids, diaryliodonium salts of benzenesulfonic acids, and diaryliodonium salts of 3-nitrobenzenesulfonic acids. Examples of suitable triarylsulfonium salts of sulfonic acids include triarylsulfonium salts of perfluoroalkylsulfonic acids and triarylsulfonium salts of arylsulfonic acids. Examples of suitable triarylsulfonium salts of perfluoroalkylsulfonic acids include triarylsulfonium salts of perfluorobutanesulfonic acid, triarylsulfonium salts of perfluoroethanesulfonic acid, triarylsulfonium salts of perfluorooctane sulfonic acid, and triarylsulfonium salts of trifluoromethanesulfonic acid. Examples of suitable triarylsulfonium salts of arylsulfonic acids include triarylsulfonium salts of paratoluenesulfonic acid, triarylsulfonium salts of dodecylbenzenesulfonic acid, triarylsulfonium salts of benzenesulfonic acid, and triarylsulfonium salts of 3-nitrobenzenesulfonic acid. Examples of suitable diaryliodonium salts of boronic acids include diaryliodonium salts of perhaloarylboronic acids, and preferred triarylsulfonium salts of boronic acids are triarylsulfonium salts of perhaloarylboronic acids.

[0205] The photoinitiator is typically used in the range of 0.001 to 5 wt%, based on the total weight of the curable composition. For example, the photoinitiator may be used in an amount of 0.01 wt% or more, for example, 0.1 wt% or more, alternatively 0.15 wt% or more, alternatively 0.2 wt% or more, alternatively 0.4 wt% or more, alternatively 0.6 wt% or more, alternatively 0.8 wt% or more, alternatively even 1.0 wt% or more, based on the total weight of the curable composition, while typically 5 wt% or less, alternatively 4 wt% or less.

[0206] The curable composition is typically prepared by combining the curing agent with the silicone-polyolefin blend. The process for combining is not particularly limited and can be carried out using any of the mixing devices described above. Similarly, the curable composition may be prepared in succession with the silicone-polyolefin blend (e.g., by adding the curing agent to the silicone-polyolefin blend at or immediately after the formation of the silicone-polyolefin blend). However, it will be understood that a separate and / or different mixer or mixing process can be used to prepare the curable composition. For example, in some embodiments, the silicone-polyolefin blend is prepared as described above by dynamic crosslinking of the silicone-polyolefin composition via hot melt extrusion, and then the curing agent is ground into the extruded silicone-polyolefin blend using a roller mill, thereby preparing the curable composition. Those skilled in the art will understand that a variety of mixing processes and devices, including any of those described herein and combinations thereof, can be utilized to combine the curing agent with the silicone-polyolefin to prepare the curable composition.

[0207] Thus, in certain embodiments, the curable composition further comprises one or more additional components, such as one or more additives. For example, in certain embodiments, the curable composition may comprise one or more additives including, alternatively consisting essentially of, or alternatively consisting of, fillers, binders, thickeners, tackifiers, adhesion promoters, compatibilizers, extenders, plasticizers, endblockers, driers, colorants (e.g., pigments, dyes, etc.), anti-aging additives, biocides, flame retardants, corrosion inhibitors, UV absorbers, antioxidants, light stabilizers, catalysts (e.g., other than catalyst (D)), pre-catalysts or catalyst generators, initiators (e.g., thermally activated initiators, electromagnetically activated initiators, etc.), photoacid generators, thermal stabilizers, as well as derivatives, modifications, and combinations thereof. Such additives may be classified under different technical terms, and it should be understood that just because additives are classified under a particular term and / or characterized according to a particular function does not mean that they are so limited to that function. Additionally, some additives may be present in a particular component of the curable composition or may alternatively be incorporated when forming the curable composition. In theory, the curable composition may include any number of additional components and additives depending, for example, on the particular type and / or function in the curable composition.

[0208] If present, one or more additives may be combined with the curing agent or silicone-polyolefin blend before, during, or after the curing agent is combined with the silicone-polyolefin blend. In other words, one or more of the additives may be combined with the silicone-polyolefin blend (or the curing agent) to form an intermediate composition, which may then be combined with the curing agent (or the silicone-polyolefin blend) to obtain a curable composition. Alternatively, the silicone-polyolefin blend, the curing agent, and many of the suitable additives may be combined together in a simultaneous step. Those skilled in the art will readily understand that the particular order of addition and / or combination suitable for a given additive will depend on the nature of the additive and other components of the curable composition, and thus will be independently selected based on the particular components and parameters used. Similarly, it will be understood that certain additives (e.g., those that do not react with components (A), (B), (C), and (D) during the preparation of the curable composition) may be introduced into the silicone-polyolefin blend during or before compatibilization of components (B) and (C).

[0209] Cured products of the curable compositions and methods for preparing the cured products are also provided. In particular, the curable formulations can be cured to obtain the cured products. As will be appreciated by those skilled in the art, such curing typically involves activating the curing agent, for example, via heating the composition to a temperature sufficient to activate a 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 particular curing agent utilized.

[0210] The cured product is formed via radical curing of the curable composition, i.e., upon activation of a radical initiator. It will be understood that curing of the curable composition generally involves crosslinking components thereof, such as the functional organosiloxane of component (D). The cured product may be referred to as a silicone-polyolefin elastomer or hybrid elastomer.

[0211] Thus, methods of preparing the cured product generally include heating the curable composition to an elevated temperature, for example, a temperature of 90-300, alternatively 100-300, alternatively 100-250, alternatively 100-200° C., for a time sufficient to cure the curable composition. In some embodiments, the curable composition is cured at a temperature of 150-220° C. for 1-20 minutes, alternatively 5-20 minutes, alternatively 5-15 minutes.

[0212] In view of the above description and the following examples, it will be appreciated that the methods and compositions provided herein provide a cost-effective route to obtain unique silicone-polyolefin hybrid materials due to the inexpensive precursors and solvent-free preparation. Furthermore, the reactive compatibilization of the functionalized polyolefin (B) generates in situ compatibilized graft copolymers, which localize the compatibilizer at the interface, resulting in increased solvent swell resistance and tear strength. Furthermore, the cured product maintains satisfactory elongation and tensile strength, exhibits improved handling and appearance characteristics, and presents desirable tactile sensation. These and other characteristics of the cured product will be appreciated in view of the following examples.

[0213] The compositions of the present invention allow for the preparation of products and articles with improved performance characteristics compared to products and articles formed via organic compositions, silicone compositions, or conventional hybrid silicone-organic compositions. For example, injection moldable and compression moldable articles can be made from the compositions of the present invention with improved toughness (e.g., increased tear strength), chemical resistance (e.g., increased solvent swell resistance), superior elongation and tensile strength, and delayed elastic recovery when compared to typical silicone rubber elastomers. Articles made with the compositions of the present invention also have a higher modulus at comparable hardness values ​​and desirable tactile properties when compared to typical silicone rubber elastomers. For example, the tactile properties of an article can be improved by forming a layer on the surface of the article with the compositions of the present invention.

[0214] Such products and articles can be used in or for a wide range of applications and in the production of a wide range of consumer products and articles, including products and articles in or for consumer wearable electronics, consumer packaging and distribution materials for food, personal care, and beauty care articles and / or products, vibration isolation components, electrical protection in wire and cable applications, and coatings or co-molding onto substrates such as buttons, knobs, and user interface controls or components.

[0215] The following examples, which represent embodiments of the present disclosure, are intended to illustrate, but not limit, the present invention. Unless otherwise noted, all reactions were carried out under air, and all solvents, substrates, and reagents were purchased or otherwise obtained from various commercial suppliers (e.g., Gelest, Acros Organics, Sigma-Aldrich, etc.) and used as received.

[0216] Instrumentation and characterization parameters The following instruments and characterization procedures / parameters are used to evaluate various physical properties of the compounds and compositions prepared in the examples below.

[0217] Cure Properties: Cure kinetic parameters (S'max, TC90, TS2) were measured using a Moving Die Rheometer at 115°C for 10 minutes using the method specified in ASTM D5289.

[0218] Plasticity: The plasticity of the uncured compositions was measured according to ASTM D926 after grinding and leaving to stand for 3 hours.

[0219] Hardness: The durometer hardness of the cured product was measured according to ASTM D2240.

[0220] Viscosity: Viscosity was measured according to ASTM E3116 using a Brookfield LV DV-E viscometer equipped with the appropriate spindle.

[0221] Elastomeric properties: Tensile strength, elongation and modulus were measured using the methods described in ASTM D412 and toughness values ​​were calculated from the same stress-strain curves thus generated. Tear strength was measured according to ASTM D624, Die B.

[0222] Solvent Resistance: Solvent-immersed specimens were generated by completely immersing die-cut tensile bars (as described in ASTM D412) in the specified solvent for 72 hours at room temperature. Volume change was calculated from specific gravity measurements as described in ASTM D792 before and after solvent immersion. Hardness, tensile strength, and elongation of the specimens after solvent immersion were measured using the same ASTM methods described above.

[0223] Melt Flow Index (MFI): MFI was measured according to ASTM D1238-86, with values ​​typically reported as g / 10 min at 190° C. and 21.6 kg.

[0224] material Table 1 below provides a brief summary and provides information regarding certain abbreviations, shorthand notations, and components used in the examples. Viscosity is typically reported as zero shear viscosity measured at 25° C. Degree of polymerization (DP) is typically reported as number average DP, for example, from NMR, IR, and / or GPC (e.g., against a standard such as polystyrene).

[0225] [Table 1]

[0226] General procedure for preparing hybrid elastomer base Apparatus: The hybrid elastomer base (or silicone-polyolefin composition) was prepared in a 50 cc Haake Rheomix OS system (Haake bowl) with a roller rotor driven and controlled by a PolyoLab OS system.

[0227] Synthesis: The bowl was heated to 180°C and the rotor was set at 75 rpm. Silicone base (D) was added to the bowl in small portions under a stream of N2, followed by polyolefin (B) and polyolefin (C). After approximately 1 minute of blending, a smooth white mixture was obtained. Polysiloxane (A) was added and blending continued for 5 minutes, then the product was dumped onto a steel tray and allowed to cool.

[0228] Cured elastomer: A polished stainless steel mold with internal cavity dimensions of 6" x 6" x 2mm was conditioned by coating the interior surface with a Teflon release coating spray. A curable composition was prepared by blending the hybrid elastomer base with the curative (part per one hundred, pph) directly on a two-roll mill until the resulting mass was visually homogenous, which was then divided to fill 110% of a mold with internal cavity dimensions of 6" x 6" x 2mm. Individual portions of the compounded compound were preformed into flat sheets slightly smaller than 6" x 6" and placed in the mold at room temperature. The compound was compression molded in a heated hydraulic press at 115°C and 1500 psi for 10 minutes and removed from the mold immediately after curing. The cured hybrid elastomer sheets were allowed to rest at room temperature for 24 hours before characterization.

[0229] Examples 1 to 6 and Comparative Examples 1 to 4 Preparation of Examples 1-6 and Comparative Example 1: The synthesis of the hybrid elastomer base was carried out according to the general procedure described above. This procedure was repeated to produce sufficient material for a given test. Each hybrid elastomer base was then cured according to the procedure described above and the physical properties were measured. The specific components, parameters, and properties of the materials obtained for Examples 1-6 and Comparative Examples 1-4 are shown in Tables 2-3 below, respectively.

[0230] [Table 2]

[0231] [Table 3]

[0232] Examples 7 to 15 and Comparative Examples 5 to 8 Preparation of Examples 7-15 and Comparative Examples 5-8: The synthesis of the hybrid elastomer base was carried out according to the general procedure described above. In addition, the curing of each hybrid elastomer base was carried out according to the general procedure described above.

[0233] The specific constituents, parameters, and properties of the materials obtained for Examples 7-15 and Comparative Examples 5-8 are shown in Tables 4 and 5 below, respectively.

[0234] [Table 4]

[0235] [Table 5]

[0236] Examples 16 to 19 and Comparative Examples 9 to 23 Preparation of Examples 16-19 and Comparative Examples 9-23: The synthesis of the hybrid elastomer base was carried out according to the general procedure described above. In addition, the curing of each hybrid elastomer base was carried out according to the general procedure described above.

[0237] The specific constituents, parameters, and properties of the materials obtained for Examples 16-19 and Comparative Examples 9-23 are shown below in Tables 6-8, respectively.

[0238] [Table 6]

[0239] [Table 7]

[0240] [Table 8]

[0241] Example 20 Preparation of Example 20 In Example 20, the masterbatch was prepared in a 50cc Haake Rheomix OS system (Haake bowl) with a roller rotor driven and controlled by a PolyoLab OS system. The bowl was heated to 180°C and the rotor was set at 100 rpm. In Example 20, a liquid rubber was utilized, and the organopolysiloxane of the liquid rubber was added in small portions to the bowl under a flow of N2, followed by the addition of polyolefin (B) and polyolefin (C). After approximately 5 minutes of blending, a smooth white mixture was obtained. Polysiloxane (A) was added and blending continued for 10 minutes, then the product was dumped onto a steel tray and cooled.

[0242] The specific components utilized in the hybrid masterbatch of Example 20 are set forth in Table 9 below.

[0243] [Table 9]

[0244] The hybrid master batch was then utilized in a silicone-polyolefin composition in the form of a two-part formulation. The components and their amounts for each part of the two-part formulation are in Table 10 below. Each part of the two-part formulation is prepared by mixing the components.

[0245] [Table 10]

[0246] Part A was prepared by combining and mixing the components of Part A in a speed mixer (1800 rpm, 3 times for 20 seconds, scraping between mixing). Part B was prepared by incorporating the inhibitor into the silicone base (D)-10 to obtain a premix, combining the premix with the other components of Part B, and mixing in a speed mixer (1800 rpm, 3 times for 20 seconds, scraping between mixing).

[0247] Parts A and B were mixed in a 1:1.1 weight ratio using a speed mixer (1800 rpm for 3 times 20 seconds with scraping between mixing) to obtain a visually homogenous mixture. The visually homogenous mixture was poured into a 10" x 10" x 2mm mold and press cured at 1500 psi and 115°C for 10 minutes. The mold was cooled in a room temperature hydraulic press until it reached room temperature after which the cured rubber plaques were removed for property testing. The results are in Table 11 below.

[0248] [Table 11]

[0249] In Example 20, the curable silicone (D) is a liquid rubber. In contrast, in Examples 1-19, the curable silicone (D) is an elastomeric component.

[0250] Certain silicone-polyolefin hybrid elastomers are subjected to the solvent resistance test as described above. The results of the solvent resistance test for these certain elastomers are shown in Table 12 below. In Table 12, h / RT indicates time at room temperature.

[0251] [Table 12]

[0252] The invention has been described in an illustrative manner, with it being understood that the terminology used is intended to be in the nature of words of description rather than of limitation. Obviously, many modifications and variations of the invention are possible in light of the above teachings. The invention may be practiced otherwise than as specifically described.

Claims

1. 1. A silicone-polyolefin composition comprising: (A) a polysiloxane containing, on average, at least one functional group X per molecule; (B) a functionalized polyolefin containing, on average, at least one functional group Y per molecule, said functional group Y being capable of reacting with said functional group X of said polysiloxane (A) to form a bond therebetween; and (C) a polyolefin not capable of reacting with component (A) or (B); (D) a curable silicone comprising at least one of an elastomeric component or a liquid rubber.

2. The polysiloxane (A) has the following average unit formula: [X ｍ R １ ３－ｍ SiO １／２ ] ａ [X ｎ R １ ２－ｎ SiO ２／２ ] ｂ、 where X is a functional group as defined above, and each R １ are independently selected hydrocarbyl groups; subscript m is independently 1 or 0 in each portion denoted by subscript a; subscript n is independently 1 or 0 in each portion denoted by subscript b; subscripts a and b are each mole fractions such that a+b=1, with the proviso that 0<a<1 and 0<b<1; and said polysiloxane (A) comprises at least one functional group X, or (i) each functional group X is selected from the group consisting of an aminoalkyl group, a methacryloxy group, a silicon-bonded hydroxyl group, an anhydride group, a silicon-bonded hydrogen atom, and a hydroxyl group. , olefinically unsaturated groups, or carbinol groups; (ii) the polysiloxane (A) has a viscosity of at least 3,000 cP at 25° C.; (iv) the polysiloxane (A) has a degree of polymerization (DP) of from 20 to 1,200; (iv) the polysiloxane (A) is present in the silicone-polyolefin composition in an amount of from 0.5 to 15 wt %, based on the total weight of the silicone-polyolefin composition; or (v) any combination of (i)-(iv).

3. (i) the functionalized polyolefin (B) comprises a functionalized polyethylene (PE), polypropylene (PP), or polyethylene-alphaolefin copolymer; (ii) each functional group Y comprises an epoxide group, an aminoalkyl group, a trimethoxysilyl group, a hydridosilyl group, or an anhydride group; or (iii) the functionalized polyolefin (B) has a molecular weight of 0.86 to 0.96 g / cm ３ (iv) the functionalized polyolefin (B) is functionalized with 0.05 to 10 weight percent of a functional moiety comprising the functional group Y, based on the total weight of the functionalized polyolefin (B); (v) the functionalized polyolefin (B) is present in the silicone-polyolefin composition in an amount of 1 to 40 weight percent, based on the total weight of the silicone-polyolefin composition; or (vi) any combination of (i) to (v).

4. 1. A method for preparing a silicone-polyolefin blend, said method comprising: combining the polysiloxane (A), the functionalized polyolefin (B), the polyolefin (C), and the curable silicone (D) to prepare the silicone-polyolefin composition of claim 1; reacting said polysiloxane (A) with said functionalized polyolefin (B) in the presence of said polyolefin (C) and said curable silicone (D), thereby preparing said silicone-polyolefin blend.

5. A silicone-polyolefin blend prepared according to the method of claim 4.

6. A curable composition comprising the silicone-polyolefin blend of claim 5 and a curing agent.

7. 10. A method of preparing a cured product, the method comprising curing the curable composition of claim 6, thereby preparing the cured product.

8. A cured product of the curable composition of claim 6 or prepared according to the method of claim 7.

9. 10. A method for improving the tactile properties of an article having a surface, said method comprising forming a layer on said surface of said article with the silicone-polyolefin composition of claim 1.

10. 10. An article comprising the cured product of claim 8, wherein the article is further defined as a consumer wearable electronic device, a consumer packaging or distribution article and / or product, a vibration isolation component, a wire or cable, or a consumer interface component.