Curable silicone-based compositions and applications thereof

Abstract

To provide curable silicone compositions with desired mechanical and chemical properties.SOLUTION: The present technology provides a curable silicone-based composition comprising a hybrid silicone polymer, a catalyst and a filler. The present technology provides a curable silicone composition comprising a polymer A comprising an organic molecule or a siloxane molecule comprising an alkoxy radical, a hydroxyl radical, an isocyanate radical, a primary amine or a carboxylic radical; optionally a polymer B comprising an organic molecule, a siloxane molecule, or a hybrid-siloxane molecule; a catalyst; and a filler.SELECTED DRAWING: None

Description

Technical Field

[0001] This application claims the priority and benefit of Indian Provisional Application No. 201821049328, filed on December 26, 2018, the disclosure of which is incorporated herein by reference in its entirety.

[0002] The present technology relates to curable silicone-based compositions. In particular, the present technology relates to curable silicone-based compositions comprising a hybrid silicone polymer, a catalyst, and a filler. The composition provides a silicone composite material upon curing.

Background Art

[0003] Silicones are known for their inherent properties such as high thermal stability, flexibility, and / or chemical resistance. Based on the above properties, siloxanes are used in electronic or electrical applications. While it may be desirable to use siloxanes in applications where conductivity can be important, the development of conductive silicone materials is difficult.

[0004] Electrical properties can be achieved in silicones by adding a filler to the silicone matrix, and the desired conductivity can be achieved by increasing the loading of the filler in the composition. However, at higher loadings, the filler particles may separate from the composition over a period of time. Therefore, the dispersion of high-loading fillers into the siloxane matrix is a major challenge. Higher loading of fillers in the composition can also adversely affect the cure kinetics and processability of the composition. Other common problems include, but are not limited to, variable contact resistance and volume resistivity.

[0005] In order to solve these technical problems, efforts have been made to develop curable silicone compositions with desired mechanical and chemical properties.

Summary of the Invention

[0006] A curable silicone composition is provided that can provide good electrical conductivity along with desired adhesion and other mechanical and chemical properties. In some embodiments, the present technology provides a curable composition comprising Polymer A, a catalyst, and one or more fillers, where Polymer A comprises siloxane or hybrid siloxane molecules.

[0007] In some embodiments, the curable composition further comprises Polymer B. In one or more embodiments, Polymer B can function as a crosslinking agent. In one or more embodiments, Polymer B can comprise siloxane, hybrid siloxane, silane, or combinations thereof. In these embodiments, the curable composition comprises Polymer A, Polymer B, a catalyst, and one or more fillers, where Polymer A comprises siloxane or hybrid siloxane molecules. In these embodiments, Polymer A comprises alkoxy radicals, hydroxyl radicals, isocyanate radicals, primary amines, or carboxyl radicals.

[0008] In some embodiments, a curable silicone composition is provided. The composition comprises (i) Polymer A of Formula 1; (ii) a filler; (iii) a catalyst; and optionally (iv) Polymer B of Formula 2, where the curable silicone composition is a condensation curing system; and the cured form of the curable composition is an electrically conductive material. Polymer A can be represented by Formula 1, (R) a (W) b (R) a’’ Formula 1 where a, a’’ and b can be zero or greater than zero, provided that the condition is that a + a’’ + b is always greater than 0, R can be linear or branched and can be represented by Formula (1a), (CH2) c (CH2O) d (CHOH) e (S) f (X) g Formula (1a) S can be independently selected from hydroxyl radicals, isocyanate radicals, primary amines, or carboxyl radicals, and X is independently selected from formula (1b),

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical Formula

Chemical formula

[0009] These and other embodiments and aspects are further understood with reference to the following detailed description.

Modes for Carrying Out the Invention

[0010] In the following specification and the following claims, several terms are referred to which must be defined to have the following meanings.

[0011] The singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. “Optional” or “optionally” means that the event or circumstance described thereafter may or may not occur, and that the description includes examples where the event occurs and examples where the event does not occur.

[0012] The approximating language that may be applied throughout the specification and claims in this context is intended to modify any quantitative representation that may vary tolerably without resulting in a change in the basic function to which it is related. Accordingly, a value modified by one or more terms such as “about” is not to be limited to the precise value specified. In some instances, the approximating language may correspond to the precision of the instrument for measuring the value.

[0013] As used herein, the terms "aromatic" and "aromatic radical" are used interchangeably and refer to an array of atoms having at least one valence and including at least one aromatic group. An array of atoms having at least one valence and including at least one aromatic group may contain heteroatoms such as nitrogen, sulfur, selenium, silicon, and oxygen, or may consist of only carbon and hydrogen. As used herein, the term "aromatic" includes, but is not limited to, phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene, and biphenyl radicals. As noted above, an aromatic radical includes at least one aromatic group. An aromatic group is always a cyclic structure having 4n + 2 "delocalized" electrons, where "n" is an integer of 1 or greater, as represented by a phenyl group (n = 1), a thienyl group (n = 1), a furanyl group (n = 1), a naphthyl group (n = 2), an azulenyl group (n = 2), an anthracenyl group (n = 3), etc. An aromatic radical may also contain non-aromatic components. For example, a benzyl group is an aromatic radical containing a phenyl ring (an aromatic group) and a methylene group (a non-aromatic component). Similarly, a tetrahydronaphthyl radical is an aromatic radical containing an aromatic group (C6H3) condensed with a non-aromatic component -(CH2)4-. For convenience, the terms "aromatic radical" or "aromatic" are defined herein to encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, haloaromatic groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (e.g., carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, etc. For example, a 4-methylphenyl radical is a C7 aromatic radical containing a methyl group, and the methyl group is a functional group that is an alkyl group. Similarly, a 2-nitrophenyl group is a C6 aromatic radical containing a nitro group, and the nitro group is a functional group.Aromatic radicals include halogenated aromatic radicals such as 4-trifluoromethylphenyl, hexafluoroisopropylidene bis(4-phen-1-yloxy) (i.e., -OPhC(CF3)2PhO-), 4-chloromethylphen-1-yl, 3-trifluorovinyl-2-thienyl, 3-trichloromethylphen-1-yl (i.e., 3-CCl3Ph-), 4-(3-bromoprop-1-yl)phen-1-yl (i.e., 4-BrCH2CH2CH2Ph-), etc. Further examples of aromatic radicals include 4-allyloxyphen-1-oxy, 4-aminophen-1-yl (i.e., 4-H2NPh-), 3-aminocarbonylphen-1-yl (i.e., NH2COPh-), 4-benzoylphen-1-yl, dicyanomethylidene bis(4-phen-1-yloxy) (i.e., -OPhC(CN)2PhO-), 3-methylphen-1-yl, methylene bis(4-phen-1-yloxy) (i.e., -OPhCH2PhO-), 2-ethylphen-1-yl, phenylethenyl, 3-formyl-2-thienyl, 2-hexyl-5-furanyl, hexamethylene-1,6-bis(4-phen-1-yloxy) (i.e., -OPh(CH2)6PhO-), 4-hydroxymethylphen-1-yl (i.e., 4-HOCH2Ph-), 4-mercaptomethylphen-1-yl (i.e., 4-HSCH2Ph-), 4-methylthiophen-1-yl (i.e., 4-CH3SPh-), 3-methoxyphen-1-yl, 2-methoxycarbonylphen-1-yloxy (e.g., methyl salicylate), 2-nitromethylphen-1-yl (i.e., 2-NO2CH2Ph), 3-trimethylsilylphen-1-yl, 4-t-butyldimethylsilylphen-1-yl, 4-vinylphen-1-yl, vinylidene bis(phenyl), etc. The term "C3-C10 aromatic radical" includes aromatic radicals containing at least 3 but no more than 10 carbon atoms. The aromatic radical 1-imidazolyl (C3H2N2-) represents a C3 aromatic radical. The benzyl radical (C7H7-) represents a C7 aromatic radical. In one or more embodiments, the aromatic group may include a C6-C30 aromatic group, a C10-C30 aromatic group, a C15-C30 aromatic group, a C20-C30 aromatic group.In some specific embodiments, the aromatic group may include a C3-C10 aromatic group, a C5-C10 aromatic group, or a C8-C10 aromatic group.

[0014] As used herein, the terms "alicyclic group" and "alicyclic radical" may be used interchangeably and refer to a radical having at least one valence, and where the radical includes an arrangement of atoms that is cyclic but not aromatic. As defined herein, an "alicyclic radical" does not include an aromatic group. An "alicyclic radical" may include one or more acyclic components. For example, the cyclohexylmethyl group (C6H 11 CH2-) is an alicyclic radical that includes a cyclohexyl ring (an arrangement of atoms that is cyclic but not aromatic) and a methylene group (an acyclic component). An alicyclic radical may include heteroatoms such as nitrogen, sulfur, selenium, silicon, and oxygen, or may be composed of only carbon and hydrogen. For convenience, the term "alicyclic radical" is defined herein to encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (e.g., carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, etc. For example, the 4-methylcyclopent-1-yl radical is a C6 alicyclic radical that includes a methyl group, and the methyl group is a functional group that is an alkyl group. Similarly, the 2-nitrocyclobut-1-yl radical is a C4 alicyclic radical that includes a nitro group, and the nitro group is a functional group. An alicyclic radical may include one or more halogen atoms that may be the same or different. Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine. Alicyclic radicals that include one or more halogen atoms include 2-trifluoromethylcyclohex-1-yl, 4-bromodifluoromethylcyclooct-1-yl, 2-chlorodifluoromethylcyclohex-1-yl, hexafluoroisopropylidene-2,2-bis(cyclohex-4-yl) (i.e., -C6H 10 C(CF3)2C6H 10-), 2-chloromethylcyclohex-1-yl, 3-difluoromethylene cyclohex-1-yl, 4-trichloromethyl cyclohex-1-yloxy, 4-bromodichloromethyl cyclohex-1-ylthio, 2-bromoethyl cyclopent-1-yl, 2-bromopropyl cyclohex-1-yloxy (e.g., CH3CHBrCH2C6H 10 O-), etc. Further examples of alicyclic radicals include 4-allyloxycyclohex-1-yl, 4-aminocyclohex-1-yl (i.e., H2C6H 10 -), 4-aminocarbonyl cyclopent-1-yl (i.e., NH2COC5H8-), 4-acetoxycyclohex-1-yl, 2,2-dicyanoisopropylidene bis(cyclohex-4-yloxy) (i.e., -OC6H 10 C(CN)2C6H 10 O-), 3-methylcyclohex-1-yl, methylene bis(cyclohex-4-yloxy) (i.e., -OC6H 10 CH2C6H 10 O-), 1-ethylcyclobut-1-yl, cyclopropylethenyl, 3-formyl-2-tetrahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl, hexamethylene-1,6-bis(cyclohex-4-yloxy) (i.e., -OC6H 10 (CH2)6C6H 10 O-), 4-hydroxymethylcyclohex-1-yl (i.e., 4-HOCH2C6H 10 -), 4-mercaptomethylcyclohex-1-yl (i.e., 4-HSCH2C6H 10 -), 4-methylthiocyclohex-1-yl (i.e., 4-CH3SC6H 10 -), 4-methoxycyclohex-1-yl, 2-methoxycarbonyl cyclohex-1-yloxy (2-CH3OCOC6H 10 O-), 4-nitromethylcyclohex-1-yl (i.e., NO2CH2C6H 10-), 3-trimethylsilylcyclohex-1-yl, 2-t-butyldimethylsilylcyclopent-1-yl, 4-trimethoxysilylethylcyclohex-1-yl (e.g., (CH3O)3SiCH2CH2C6H 10 -), 4-vinylcyclohexen-1-yl, vinylidenebis(cyclohexyl), and the like. The term "C3-C10 alicyclic radical" includes alicyclic radicals containing at least 3 but no more than 10 carbon atoms. The alicyclic radical 2-tetrahydrofuranyl (C4H7O-) represents a C4 alicyclic radical. The cyclohexylmethyl radical (C6H 11 CH2-) represents a C7 alicyclic radical. In some embodiments, the alicyclic group may include a C3-C20 cyclic group, a C5-C15 cyclic group, a C6-C10 cyclic group, or a C8-C10 cyclic group.

[0015] As used herein, the terms "aliphatic group" and "aliphatic radical" are used interchangeably and refer to an organic radical having at least one valence consisting of a straight-chain or branched arrangement of non-cyclic atoms. An aliphatic radical is defined to contain at least one carbon atom. The arrangement of atoms containing an aliphatic radical may contain heteroatoms such as nitrogen, sulfur, silicon, selenium, and oxygen, or may consist of only carbon and hydrogen. For convenience, the term "aliphatic radical" is defined herein to include a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (e.g., carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, etc., as part of a "linear or branched arrangement of non-cyclic atoms". For example, the 4-methylpent-1-yl radical is a C6 aliphatic radical containing a methyl group, and the methyl group is a functional group that is an alkyl group. Similarly, the 4-nitrobut-1-yl group is a C4 aliphatic radical containing a nitro group, and the nitro group is a functional group. An aliphatic radical can be a haloalkyl group containing one or more halogen atoms that may be the same or different. Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine. Aliphatic radicals containing one or more halogen atoms include, for example, halogenated alkyls such as trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl, hexafluoroisopropylidene, chloromethyl, difluorovinylidene, trichloromethyl, bromodichloromethyl, bromoethyl, 2-bromotrimethylene (e.g., -CH2CHBrCH2-), etc.Further examples of aliphatic radicals include allyl, aminocarbonyl (i.e., -CONH2), carbonyl, 2,2-dicyanoisopropylidene (i.e., -CH2C(CN)2CH2-), methyl (i.e., -CH3), methylene (i.e., -CH2-), ethyl, ethylene, formyl (i.e., -CHO), hexyl, hexamethylene, hydroxymethyl (i.e., -CH2OH), mercaptomethyl (i.e., -CH2SH), methylthio (i.e., -SCH3), methylthiomethyl (i.e., -CH2SCH3), methoxy, methoxycarbonyl (i.e., CH3OCO-), nitromethyl (i.e., -CH2NO2), thiocarbonyl, trimethylsilyl (i.e., (CH3)3Si-), t-butyldimethylsilyl, 3-trimethoxysilylpropyl (i.e., (CH3O)3SiCH2CH2CH2-), vinyl, vinylidene, and the like. As a further example, a C1-C10 aliphatic radical contains at least 1 but no more than 10 carbon atoms. A methyl group (i.e., CH3-) is an example of a C1 aliphatic radical. A decyl group (i.e., CH3(CH2)9-) is an example of a C10 aliphatic radical. In one or more embodiments, the aliphatic group or aliphatic radical can include, but is not limited to, a straight-chain or branched-chain hydrocarbon having 1-20 carbon atoms, 2-15 carbon atoms, 3-10 carbon atoms, or 4-8 carbon atoms.

[0016] The present technology provides curable silicone-based compositions and the use of such compositions in various applications. The curable silicone compositions provide desired adhesion and other mechanical and chemical properties along with good electrical conductivity. As described herein, the selection of Polymer A, and one or more fillers, and optional Polymer B in the composition provides a hybrid composite material having multifaceted properties. Further, the present compositions enable the use of a relatively high loading of fillers in the silicone matrix without affecting the curing and processing conditions of the composition. The presence of non-silicone organic units can be used to provide further advantages to the overall properties of the hybrid silicone composite materials.

[0017] In some embodiments, the present technology provides a curable composition comprising polymer A, a catalyst, and one or more fillers, where polymer A comprises hybrid siloxane molecules. The composition can be cured by condensation curing. This curing does not require a separate crosslinking agent. In some embodiments, the curable composition further comprises polymer B.

[0018] One or more embodiments of the present technology provide a curable composition comprising polymer A, one or more fillers, and optional polymer B. Polymer A comprises organic molecules or siloxane molecules containing alkoxy radicals, hydroxyl radicals, isocyanate radicals, primary amines, or carboxyl radicals. Polymer B comprises organic molecules, siloxane molecules, or hybrid siloxane molecules. In some of those embodiments, polymer B can function as an organic crosslinking agent, a siloxane crosslinking agent, or a hybrid crosslinking agent. Hybrid crosslinking agents have both organic units and siloxane units. The curable compositions of these embodiments can form hybrid silicone composite materials upon curing.

[0019] In some embodiments, polymer A can be represented by Formula 1, (R) a (W) b (R) a’’ Formula 1 where a and a’’ can be zero or greater, and b cannot be zero, provided that a + a’’ + b is always greater than zero, R can be represented by Formula (1a), (CH2) c (CH2O) d (CHOH) e (S) f (X) g Formula (1a) R shown in Formula (1a) can represent a linear or branched structure, S can be independently selected from hydroxyl radicals, isocyanate radicals, primary amines, or carboxyl radicals, X is independently selected from formula (1b),

Chemical formula

Chemical formula

Chemical formula

[0020] In an embodiment, each of a, a’’ and b of R is 1, and c, d, e of R can be independently 0, 1 - 10, 10 - 20, 5 - 20, 10 - 30. f, g are independently 1. Further, h and i of W are independently 1. x’’, y’’, m, n of Y are independently 0 - 10. j, k, l of Y are independently 0 - 100. D * o, p of D are independently 0 - 10. q, r of Z are independently 1. t, s of J are independently 0, 1 - 10, 10 - 20, and M is carbon / or nitrogen. u, v, w, x of J are independently 0, 1 - 10, or 10 - 20, and y is 1 - 10.

[0021] In one or more embodiments, polymer A can be represented by the following structure. [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula]

[0022] In some embodiments, polymer B can be represented by formula (2a), [Chemical formula] where M’ can be independently selected from a carbon atom or a heteroatom, G’ is a heteroatom selected from oxygen, s’ can be 0 or greater, t’ > 0, L1’ can be independently selected from isocyanates or primary amines or from R’ represented by formula (2b) or (2n), where formula (2b) is a compound of the following formula: (M3) y’’ (D7) c’ (D8) d’ (D ** ) e’ (T2) f’ (Q2) g’ (M4) z’ Formula (2b) where M3 is represented by formula (2c): R 25 R 26 R 27 SiI’ 1 / 2 Formula (2c) D7 is represented by formula (2d): R 28 R 29 SiI’ 2 / 2 Formula (2d) D8 is represented by formula (2e): R 30 R 31 SiI’ 2 / 2 Formula (2e) D ** is represented by formula (2f):

Chemical formula

[0023] In some embodiments, polymer B can be represented by formula (2a’), [E’]q’ [J’] r’ Formula (2a’) Here, E’ is independently selected from R’, isocyanate, amine, hydrogen, monovalent cyclic or acyclic, aliphatic or aromatic, substituted or unsubstituted hydrocarbon, or fluorinated hydrocarbon having C1-C 20 those having carbon atoms, or combinations thereof, Here, q’ and r’ can be zero or greater than that, provided that the condition is q’ + r’ > 0, J’ can be independently selected from Formula (2b’), [Chemical formula] Here, L2’, L3’, L4’ can be independently selected from phthalimide radical, fluorinated hydrocarbon, substituted or unsubstituted hydrocarbon, substituted or unsubstituted aliphatic or aromatic hydrocarbon, urea bond, alkoxy or urethane bond, u’, v’, w’, x’ can be 0 or greater than that, provided that the condition is (u’ + v’ + w’ + x’) > 0, K can be independently selected from carbon, silicon, heteroatom, hydrocarbon radical, or carbonyl radical, provided that the condition is y’ > 0.

[0024] In an embodiment, M’ can be independently carbon or nitrogen. s’ is 1, and t’ is independently 1-5, 5-10, or 10-20. c’, d’, e’ of R’ are independently 0-100, and f’, g’, y’’, z’ of R’ are independently 0, or 1-10. D ** In D, h’ and i’ can be independently 0 or 1-10. Further, a’ and a’’ are 1 at L1’, and b’ is 1-15. When r’ is zero, q’ is 1. u’, v’, w’, x’ of J’ are independently 0, 1-10, or 10-20, and y’ is 1.

[0025] In one or more embodiments, polymer B can be represented by the following structure.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0026] Various weight ratios of Polymer A, Polymer B, or both Polymer A and Polymer B are added to the composition to achieve the desired properties in the hybrid composite material. In one or more embodiments, the curable composition comprises from about 5% to 60% of Polymer A. In some embodiments, the curable composition comprises from about 10% to 50% of Polymer A. In some embodiments, the curable composition comprises from about 20% to 50% of Polymer A. In some embodiments, the curable composition comprises from about 30% to 50% of Polymer A. In some embodiments, the curable composition comprises from about 30% to 40% of Polymer A. In some embodiments, the curable composition comprises from about 25% to 40% of Polymer A. In some embodiments, the curable composition comprises 30% of Polymer A. In some of these embodiments, the composition comprises only 30% of Polymer A.

[0027] In one or more embodiments, the curable composition further comprises polymer B, where polymer B ranges from about 1% to 80%. In some embodiments, the curable composition comprises polymer B in the range of about 2% to 75%. In some embodiments, the curable composition comprises polymer B in the range of about 10% to 75%. In some embodiments, the curable composition comprises polymer B in the range of about 15% to 80%. In some embodiments, the curable composition comprises polymer B in the range of about 20% to 75%. In some embodiments, the curable composition comprises polymer B in the range of about 30% to 80%. In some embodiments, the curable composition comprises polymer B in the range of about 10% to 30%.

[0028] As described above, the composition includes one or more fillers, where the fillers include, but are not limited to, alumina, silicon, magnesia, ceria, hafnia, lanthanum oxide, neodymium oxide, samaria, praseodymium oxide, thoria, urania, yttria, zinc oxide, zirconia, silicon aluminum oxynitride, borosilicate glass, barium titanate, silicon carbide, silica, boron carbide, titanium carbide, zirconium carbide, boron nitride, silicon nitride, aluminum nitride, titanium nitride, zirconium nitride, zirconium boride, titanium diboride, aluminum dodecaboride, barite, barium sulfate, asbestos, baryte, diatomite, feldspar, gypsum, hormite, kaolin, mica, nepheline amphibole, perlite, phillipsite, smectite, talc, vermiculite, zeolite, calcite, calcium carbonate, wollastonite, calcium metasilicate, clay, aluminum silicate, talc, magnesium aluminum silicate, hydrated alumina, hydrated aluminum oxide, silica, silicon dioxide, titanium dioxide, glass fiber, glass flake, clay, exfoliated clay, or other high aspect ratio fibers, rods, or flakes, calcium carbonate, zinc oxide, magnesia, titania, calcium carbonate, talc, mica, wollastonite, alumina, aluminum nitride, graphite, graphene, metal-coated graphite, metal-coated graphene, aluminum powder, copper powder, bronze powder, brass powder, carbon fibers or whiskers, graphite, silicon carbide, silicon nitride, alumina, aluminum nitride, silver, zinc oxide, carbon nanotube, boron nitride nanosheet, zinc oxide nanotube, black phosphorus, silver-coated aluminum, silver-coated glass, silver-plated aluminum, nickel-plated silver, nickel-plated aluminum, carbon black of different structures, Monel mesh and wire, or combinations of two or more thereof.

[0029] In one or more embodiments, the filler includes graphite, nickel-coated graphite, silver, copper, or a combination thereof. In one or more embodiments, the filler includes graphite, nickel-coated graphite, or a combination thereof. In one embodiment, the filler is nickel-coated graphite.

[0030] In some embodiments, the composition further includes a secondary filler. The secondary filler can be a non-metal-based filler. In one or more embodiments, polypyrrole is used as the secondary filler. In some embodiments, the composition includes from 0.1% to 50% of the secondary filler. In some embodiments, the composition includes from 0.1% to 30% of the secondary filler. In one embodiment, the composition includes 20% of the secondary filler.

[0031] To achieve the desired properties of the hybrid composite material, fillers in various weight ratios are added to the composition. In one or more embodiments, the curable composition includes from about 5% to 80% of the filler. In some embodiments, the curable composition includes from about 20% to 80% of the filler. In some embodiments, the curable composition includes from about 20% to 60% of the filler. In some embodiments, the curable composition includes from about 30% to 80% of the filler. In some embodiments, the curable composition includes from about 30% to 60% of the filler. In some embodiments, the curable composition includes from about 50% to 80% of the filler. In some embodiments, the curable composition includes from about 60% to 80% of the filler.

[0032] As described above, the curable composition includes a catalyst, where at least one catalyst is a condensation and / or crosslinking catalyst. In some embodiments, the composition can include a catalyst selected from the group consisting of a metal condensation catalyst and a non-metal condensation catalyst. The metal condensation catalyst can be at least one selected from the group consisting of tin, titanium, zirconium, lead, iron, cobalt, antimony, manganese, bismuth, and zinc compounds. In one or more embodiments, the composition includes a tin catalyst.

[0033] In some embodiments, the composition comprises only polymer A, a catalyst, and a filler. In such embodiments, the catalyst is selected from Sn catalysts. In the presence of an Sn catalyst, polymer A cures to a cured composition without using a crosslinking agent. In such embodiments, polymer A can be a silylated organic polymer, or a silylated polyurethane organic polymer (silylated polyurethane resin or SPUR).

[0034] The catalyst will typically be used in the preparation of isocyanate-terminated PU prepolymers. Advantageously, condensation catalysts are used because they also catalyze the curing (hydrolysis and subsequent crosslinking) of the SPU-resin component of the curable composition of the present invention. Suitable condensation catalysts include dialkyltin dicarboxylates such as dibutyltin dilaurate and dibutyltin diacetate, tertiary amines, stannous salts of carboxylic acids such as stannous octoate and stannous acetate, and the like. In one embodiment of the present invention, a dibutyltin dilaurate catalyst is used in the production of the PUR prepolymer. Other useful catalysts include zirconium-containing and bismuth-containing complexes such as KAT XC6212, K-KAT XC-A209, and K-KAT348 supplied by King Industries, Inc., aluminum chelates such as the TYZER® type available from the DuPont company, and the KR type available from Kenrich Petrochemical, Inc., and other organometallic catalysts such as those containing metals such as Zn, Co, Ni, Fe, and the like.

[0035] In some embodiments, the composition comprises from 0.0001 wt% to 0.1 wt% of a catalyst. In some other embodiments, the composition comprises from 0.0005 to 0.001 wt% of a catalyst. In some other embodiments, the composition comprises from 0.001 wt% to 0.1 wt% of a catalyst. In some other embodiments, the composition comprises from 0.005 wt% to 0.1 wt% of a catalyst.

[0036] In some embodiments, the curable composition further comprises an adhesion promoter selected from trialkoxyepoxysilane, trialkoxy primary aminosilane, a combination of primary and secondary amine-containing trialkoxysilane, tris-(trialkoxy) isocyanurate-based silane, and alkylthiocarboxylated trialkoxysilane.

[0037] In some embodiments, the curable composition further comprises a reactive diluent. The reactive diluent may include, but is not limited to, substituted glycidyl ethers. The reactive diluent may include one or more solvents. Suitable solvents may include, but are not limited to, liquid hydrocarbons or silicone fluids. The hydrocarbon solvent may include hexane or heptane, and the silicone fluid may include polydiorganosiloxane.

[0038] In some embodiments, the curable composition further comprises a rheology modifier or a flow additive. The rheology modifier may include, but is not limited to, tetrahydrolinalool, a thermoplastic resin, and polyvinyl acetal. The flow additive may include, but is not limited to, a silicone fluid or an acrylate copolymer.

[0039] In one or more embodiments, the formulation is prepared by homogenizing a hybrid siloxane (Polymer A) and a filler in the presence of a catalyst. The hybrid siloxane polymer (Polymer A), a transition metal catalyst, and optionally a crosslinking agent (Polymer B) are mixed with the particulate filler in a high-speed mixer at 2000 rpm for 30 - 60 seconds. The mixture cures at room temperature. A series of examples (shown in the following examples) are prepared using the cured composition. In one or more embodiments, the curing of the curable composition is condensation curing.

[0040] In some embodiments, the uses of the cured material and its end uses are coatings, adhesives, sealants, electrodes, inks, thermally conductive materials, electrically conductive materials, sensors, actuators, heating pads, antibacterial packaging materials, electrically conductive plastics, and electromagnetic shielding materials.

[0041] The description according to this disclosure uses examples to disclose the invention, including the best mode, and to enable those skilled in the art to practice the invention, including making and using any device or system and performing any incorporation method. The patentable scope of the invention is defined by the claims and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims or if they include equivalent structural elements that do not differ substantially from the literal language of the claims.

Example

[0042] Example 1 of Polymer A: Synthesis of Urethane-Functional Alkoxysiloxane (Structure I) 50 g of A-link35 * (Momentive Performance Materials) was placed in a three-necked round-bottom flask under a nitrogen atmosphere. To it, an Sn catalyst (0.01 - 0.05%) was added to the reaction mixture. 6.27 g of ethylene glycol was added dropwise at room temperature. The reaction mixture was gently heated from room temperature to 80 °C for 12 hours. After monitoring the FTIR spectrum to complete the reaction, the reaction mixture was treated with activated carbon to inactivate the catalyst Sn. The reaction mixture was filtered off using a celite bed. The product was further purified by vacuum distillation to obtain a product with a purity of about 70%. The product (Structure I) was isolated and stored at room temperature.

Chemical formula

[0043] Example 2 of Polymer A: Synthesis of Alkoxy-Functional Cyclic Siloxane (Structure II) Under a nitrogen atmosphere, 8.6 g of vinyltrimethoxysilane was placed in a three-necked round-bottom flask. The reactants were heated to 75 °C, and subsequently, Karstedt catalyst (5 - 10 ppm) was added to the reaction mixture. 15 g of heptamethylcyclotetrasiloxane was added dropwise to the reaction mixture, and the exotherm in the reaction mixture was observed until it reached 90 °C. The reaction mixture was stirred at 75 °C for 2 hours. After monitoring the 1H NMR spectrum to complete the reaction, the reaction mixture was treated with activated carbon to deactivate the catalyst Pt. The reaction mixture was filtered off using a celite bed. The product was further purified by vacuum distillation to obtain a product with a purity of approximately 80%. The product (Structure II) was isolated and stored at room temperature. [Chemical formula]

[0044] Example 1 of Polymer B: Synthesis of urethane-functional alkoxysilane (Structure III) having a fluorine-substituted phenyl ring 76 g of A-link35 * (Momentive Performance Materials) was placed in a three-necked round-bottom flask under a nitrogen atmosphere. To this, an Sn catalyst (0.01 - 0.05%) was added to the reaction mixture. 67 g of 4-(trifluoromethyl)benzyl alcohol was added dropwise at room temperature. The reaction mixture was gently heated from room temperature to 70 °C over 12 hours. After monitoring the FTIR spectrum to complete the reaction, the reaction mixture was treated with activated carbon to deactivate the catalyst Sn. The reaction mixture was filtered off using a celite bed. The product was further purified by vacuum distillation to obtain a product with a purity of approximately 65%. The product (Structure III) was isolated and stored at room temperature. [Chemical formula]

[0045] Example 2 of Polymer B: Synthesis of fluoroether-functional alkoxysiloxane (Structure IV) 20 g of Fluorolink-E10H and 20 ml of 1,3-bis(trifluoromethyl)benzene as a solvent were placed in a three-necked round-bottom flask under a nitrogen purge. To this, an Sn catalyst (0.01 - 0.05%) was added to the reaction mixture. Next, 5.1 g of A-link35 * (Momentive Performance Materials) was added to the reaction mixture. The reaction mixture was heated at 70 °C for 10 hours. After monitoring the FTIR spectrum to complete the reaction, the reaction mixture was treated with activated carbon to inactivate the catalyst Sn. The reaction mixture was filtered off using a celite bed. The product was further purified by vacuum distillation to obtain a product with a purity of about 70%. The product (Structure IV) was isolated and stored at room temperature.

Chemical formula

[0046] Summary of materials used SPUR+ * 1050, MTMS, trimethoxyepoxysilane A187, trimethoxyaminosilane A1110 were purchased from Momentive Performance Materials. Bishydroxyl-terminated silanol (D400) was purchased from Gelest, Inc. The hybrid silane was synthesized as described in Examples 1 and 2. Table 1 shows the descriptions and suppliers of the various materials used in the formulations.

Table 1

[0047] Preparation of various formulations Using Polymer A and optionally Polymer B, a hybrid silicone composite material was prepared in the presence of one or more fillers. Fillers in various weight ratios were added to the mixture of Polymer A and optionally Polymer B. After mixing Polymer A, the filler, and optionally Polymer B, the mixture was cured at room temperature. Details of the various formulations are shown in Table 2 below. For the various formulations, various types of curable silicones with various functionalities and various types of fillers were selected. The various formulations are shown in Table 2. Metal catalysts (Sn and Ti based catalysts) were used in the production of the formulations.

Table 2

[0048] Test Methodology for Physical and Mechanical Properties EMI Shield Measurement: The EMI shield measurement of samples in different forms was carried out according to the IEEE299 standard, while the Electrical Conductivity Measurement: The electrical resistivity measurement of samples in various forms was carried out according to the ASTM D257 standard using a four-probe device. The obtained electrical resistance values were converted to electrical conductivity. Thermal Conductivity: The thermal conductivity measurement of the samples was carried out according to the ASTM E1530 standard. The lap shear of the developed formulations was measured using the ASTM D3163 standard. An Instron device was used as well. Hardness Measurement: The hardness of the developed composite material was measured according to the ASTM D2240 standard.

[0049]

Table 3

[0050] The EMI shield ability of the developed formulations was also confirmed in the range of 6 GHz to 12 GHz. The thickness of the samples was between 0.5 mm and 1.5 mm. The EMI shield effect of the selected samples is shown in Table 4. The values of the thermal conductivity of the selected samples are shown in Table 5.

[0051]

Table 4

[0052] [Table 5]

[0053] Comparative Example 1 To show the comparison between a hybrid silicone-based formulation and a pure silicone-based formulation, a control sample (compared to formulation F7) was prepared and tested. [Table 6]

[0054] Embodiments of the present technology have been described above, and upon reading and understanding this specification, modifications and changes may occur to others. The following claims are intended to cover all modifications and changes as long as they are within the scope of the claims or their equivalents.

Claims

1. A curable silicone composition comprising: (i) 25% to 40% by weight of polymer A of formula 1; (ii) 50% to 80% by weight of a conductive filler; (iii) a catalyst, and optionally (iv) polymer B of formula 2; wherein the curable silicone composition is a condensation curing system; and the cured form of the curable composition is an electrically conductive material, (R) ａ (W) ｂ (R) ａ’’ Formula 1 where a and a'' are zero or greater, provided that a + a'' > 0, and b cannot be zero, where R is represented by formula (1a), (CH ２ ) ｃ (CH ２ O) ｄ (CHOH) ｅ (S) ｆ (X) ｇ Formula (1a) S is independently selected from hydroxyl radical, isocyanate radical, primary amine, or carboxyl radical, and X is independently selected from formula (1b), 【Chemical 1】 Here, R １ , R １ ’, and R １ ’’ are independently selected from an alkyl radical and an alkoxy radical, c, d, e, f, g are each integers of 0 or greater, provided that f + g > 0, and d, e, f are 0, W of formula 1 is represented by formula (1c), (Y) ｈ (Z) ｉ Formula (1c) where h, i are zero or greater, provided that h + i > 0, Y of formula (1c) is represented by formula (1d), (M １ ) ｘ’’ (D １ ) ｊ (D ２ ) ｋ (D ＊ ) ｌ (T １ ) ｍ (Q １ ) ｎ (M ２ ) ｙ’’ Formula (1d) where j, k, l, m, n, x'', and y'' are zero or greater, provided that (j + k + l + m + n + x'' + y'') > 0, Here, M １ is represented by formula (1e), R ２ R ３ R ４ SiI １／２ Formula (1e) D １ is represented by formula (1f), R ５ R ６ SiI ２／２ Formula (1f) D ２ is represented by formula (1g), R ７ R ８ SiI ２／２ Formula (1g) D ＊ is represented by formula (1h), [Chemical 2] D ３ is represented by the formula (1i), R ９ R １０ SiI ２／２ Formula (1i) D ４ is represented by formula (1j), R １１ R １２ SiI ２／２ Formula (1j) D ５ is represented by formula (1k), R １３ R １４ SiI ２／２ Formula (1k) D ６ is represented by formula (1l), R １５ R １６ SiI ２／２ Formula (1l) T １ is represented by Formula (1m), R １７ SiI ３／２ Formula (1m) Q １ is represented by formula (1n), SiI ４／２ Formula (1n) M ２ is represented by formula (1o), R １８ R １９ R ２０ SiI １／２ Formula (1o) R ２ -R ２０ is independently selected from R, or a monovalent acyclic, aliphatic or aromatic, unsubstituted hydrocarbon, or a fluorinated hydrocarbon having 1 to 20 carbon atoms, where o, p are zero or greater, provided that o + p > 0, I is O, Z of formula (1c) is represented by formula (1p), [E] ｑ [J] ｒ Formula (1p) where E is independently selected from urethane, urea, anhydride, amide, imide, hydrogen radical, aliphatic, unsubstituted hydrocarbon, or fluorinated hydrocarbon having 1 - 20 carbon atoms, q can be 0 or greater, r > 0, J is independently selected from (1q'), [Chemical Formula 4] where M is independently selected from carbon atom or heteroatom, G is a heteroatom selected from oxygen, where t, s are zero or greater, provided that t + s > 0, L １ is independently selected from urethane, urea, anhydride, or amide, L ２ 、 L ３ 、 L ４ is independently selected from alkoxy, fluorinated hydrocarbon, and unsubstituted hydrocarbon, and u, v, w, and x can be 0 or greater than 0, K is independently selected from carbon, silicon, heteroatom, hydrocarbon, or carbonyl radical, provided that y > 0, Polymer B is of formula (2a) or (2a'), [Chemical Formula 5] where M' is independently selected from carbon atom or nitrogen atom, G' is a heteroatom selected from oxygen, s' can be 0 or greater, t' > 0, L １ ' is independently selected from isocyanate, primary amine, or R' represented by formula (2b), (M ３ ) ｙ’’ (D ７ ) ｃ’ (D ８ ) ｄ’ (D ＊＊ ) ｅ’ (T ２ ) ｆ’ (Q ２ ) ｇ’ (M ４ ) ｚ’ Formula (2b) Here, M ３ is represented by formula (2c), R ２５ R ２６ R ２７ SiI’ １／２ Formula (2c) D ７ is represented by formula (2d), R ２８ R ２９ SiI’ ２／２ Formula (2d) D ８ is represented by formula (2e), R ３０ R ３１ SiI’ ２／２ Formula (2e) D ＊＊ is represented by formula (2f), 【Chemical Formula 6】 D ９ is represented by formula (2g), R ３２ R ３３ SiI’ ２／２ Formula (2g) D １０ is represented by formula (2h), R ３４ R ３５ SiI’ ２／２ Formula (2h) D １１ is represented by formula (2i), R ３６ R ３７ SiI’ ２／２ Formula (2i) D １２ is represented by formula (2j), R ３８ R ３９ SiI’ ２／２ Formula (2j) T ２ is represented by formula (2k), R ４０ SiI’ ３／２ Formula (2k) Q ２ is represented by formula (2l), SiI’ ４／２ Formula (2k) M ４ is represented by formula (2m), R ４１ R ４２ R ４３ SiI’ １／２ Formula (2m) Here, R ２５ -R ４３ is independently selected from alkoxy radicals, I' is CH ２ group, and c', d, e', f', g', y''' are 0, and z' is zero or greater, L of formula (2a) １ ' is represented by formula (2n), (R') ａ’ (W') ｂ’ (R') ａ’’’’ formula (2n) Here, R' is represented by the above formula (2b), W' is independently selected from functional groups such as substituted or unsubstituted hydrocarbon radicals having 1 to 20 carbon atoms, fluorinated hydrocarbons, or perfluoroethers, a', a''' are 0 or greater than 0, provided that the condition a' + a''' > 0 is satisfied, and b' can be 0 or greater than 0, Formula (2a') is as follows, [E'] ｑ’ [J'] ｒ’ Formula (2a') where E' is independently selected from R', isocyanate, amine, hydrogen, monovalent cyclic or acyclic, aliphatic or aromatic, substituted or unsubstituted hydrocarbons, or fluorinated hydrocarbons having C1 - C20 carbon atoms, or combinations thereof, where q', r' are zero or greater than 0, provided that the condition q' + r' > 0 is satisfied, J' is independently selected from formula (2b'), 【Chemical Formula 7】 Here, L ２ ’, L ３ ’ and L ４ ’ are independently selected from a phthalimide radical, a fluorinated hydrocarbon, a substituted or unsubstituted hydrocarbon, a substituted or unsubstituted aliphatic or aromatic hydrocarbon, a urea bond, an alkoxy, or a urethane bond, u', v', w', x' are 0 or greater than 0, provided that the condition u' + v' + w' + x' > 0 is satisfied, K is independently selected from carbon, silicon, heteroatoms, hydrocarbon radicals, or carbonyl radicals, provided that the condition y' > 0 is satisfied, The cured material formed from the curable silicone composition has an electromagnetic interference (EMI) shielding effect between 50 and 170 dB, Curable silicone composition.

2. The curable silicone composition according to claim 1, wherein polymer A comprises silanol, hybrid silanol, silylated organic polymer, or hybrid siloxane.

3. The curable silicone composition according to claim 1, wherein formula (1a) is selected from a linear, branched, or cyclic structure.

4. The curable silicone composition according to claim 1, wherein polymer B represented by formula 2a or 2a' is used as a crosslinking agent or chain extender.

5. The curable silicone composition according to claim 1, wherein polymer B represented by formula 2a or 2a' is selected from a linear polymer, branched polymer, or cyclic polymer.

6. The curable silicone composition according to claim 1, wherein polymer B represented by formula 2a is a cyclic polymer.

7. The curable silicone composition according to claim 6, wherein M' is selected from heteroatoms.

8. The curable silicone composition according to claim 6, wherein W' of formula 2n is selected from substituted or unsubstituted hydrocarbon radicals having 1 - 20 carbon atoms, fluorinated hydrocarbons, or perfluoroethers.

9. The curable silicone composition according to any one of claims 1 to 8, wherein polymer B is present in the range of about 1% to 80%.

10. The curable silicone composition according to any one of claims 1 to 9, wherein the filler is selected from the group consisting of graphite, graphene, metal-coated graphite, metal-coated graphene, aluminum powder, copper powder, bronze powder, brass powder, carbon fibers or whiskers, graphite, silicon carbide, silicon nitride, alumina, aluminum nitride, silver, zinc oxide, carbon nanotubes, boron nitride nanosheets, zinc oxide nanotubes, black phosphorus, silver-coated aluminum, silver-coated glass, silver-plated aluminum, nickel-plated silver, nickel-plated aluminum, carbon black of different structures, Monel mesh and wire, or a combination of two or more thereof.

11. The curable silicone composition according to any one of claims 1 to 10, further comprising a catalyst selected from tin, titanium, zirconium, lead, iron, cobalt, antimony, manganese, bismuth, and zinc compounds.

12. The curable silicone composition according to claim 11, wherein the catalyst is present in the range of about 0.0001% by weight to about 0.1% by weight.

13. The curable silicone composition according to any one of claims 1 to 12, further comprising an adhesion promoter selected from the group consisting of trialkoxy epoxy silane, trialkoxy primary amino silane, a combination of primary and secondary amine-containing trialkoxy silanes, tris-(trialkoxy) isocyanurate-based silane, alkylthiocarboxylated trialkoxy silane, and a combination of two or more thereof.

14. The curable silicone composition according to any one of claims 1 to 13, further comprising a reactive diluent selected from the group consisting of substituted glycidyl ethers, liquid hydrocarbons, silicone fluids, and combinations thereof.

15. A curable silicone composition according to any one of claims 1 to 14, further comprising a rheology modifier selected from the group consisting of alkanes, silanes, silicones, acrylic copolymers, glycols, polyols, ethers, esters, polyesters, alcohols, amides, polyamides, amines, polyamines, imines, polyimines, urethanes, polyurethanes, ketones, polyketones, saccharides, polysaccharides, cellulose, fluorinated compounds, thermoplastic or thermosetting resins, polyvinyls, synthetic or natural oils, natural additives, guar, xanthan, alginates, lactates, lactides, anhydrides, gums, silicates, borates, oxides, sulfides, sulfates and combinations thereof.

16. A cured material of the curable composition according to any one of claims 1 to 15.

17. The cured material according to claim 16, wherein the cured material is thermally conductive, electrically conductive, or a combination thereof.

18. The cured material according to claim 17, wherein the cured material has an electromagnetic interference (EMI) shielding effect between 50 and 170 dB.

19. The cured material according to claim 17, wherein the cured material is used in coatings, adhesives, sealants, electrodes, inks, thermally conductive materials, electrically conductive materials, sensors, actuators, heating pads, antibacterial packaging materials, conductive plastics, or EMI shielding materials.

20. (i) Mixing together a polymer A containing one or more alkoxy functional groups, one or more fillers, a catalyst, and a polymer B containing one or more alkoxy functional groups to form a mixture, wherein the catalyst is added with respect to the total weight of polymer A, polymer B, and the filler, (ii) Next, homogenizing the mixture to form a mixture, and (iii) Next, the homogenized mixture is cured by condensation curing, wherein polymer A and polymer B are silicone polymers, A method for producing the silicone composition according to claim 1.

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