Phenylsilicone composition for high-temperature motor oil resistance

Abstract

What is provided is (A) a molecule containing at least two silicon bonds C 2~10 Alkenyl group and at least one silicon bond C 6~20 A linear organopolysiloxane having an aryl group, and B) at least one C in the molecule 2~10 Alkenyl group and at least one C 6~20 An organopolysiloxane resin containing an aryl group, and C) a molecule containing at least one silicon-bonded hydrogen atom and at least one silicon-bonded C 6~20 The silicone composition comprises an organopolysiloxane having an aryl group and E) a hydrosilylation reaction catalyst, and is a fluorine-free hydrocarbon fluid-resistant silicone composition.

Description

[Technical Field]

[0001] This disclosure relates to hydrocarbon fluid-resistant silicone compositions, and more particularly to phenyl silicone compositions having high temperature resistance in motor oil. [Background technology]

[0002] Introduction Electric vehicles (EVs) use electric motors that convert energy stored in batteries into clean, zero-emission electricity, instead of internal combustion engines. xEV vehicles are all-electric, offering clean and efficient transportation and becoming ideal urban companions. EVs have been around for over a century, but large-scale production and marketing of xEVs only began a few years ago. The potential of electric vehicles to create a more sustainable future is driving the industry's proliferation and rapid growth.

[0003] The powertrain system is the core component of an xEV (electric vehicle), responsible for generating the power needed to move the vehicle and delivering it to the wheels. Generally, a powertrain system consists of an electric motor, battery pack, charger, and converter. The electric motor, a key component of the powertrain system, is an electromechanical device that converts electrical energy into mechanical energy and primarily determines the driving performance of the electric vehicle.

[0004] Motor oil is used to lubricate the moving parts of a motor, reduce friction between components, and protect them from unnecessary wear and deterioration or rubbing against each other. By reducing friction between parts, motor oil also helps keep the motor cooler. In order to maintain the effective operation of an electric motor, a large amount of heat is generated during motor operation, so motor sealants need to have excellent motor oil resistance, especially high-temperature oil resistance.

[0005] However, existing encapsulants are still not entirely satisfactory for some applications. While RTV silicone compounds, mixed with dihydroxy-terminated silicone fluids and filler materials, can offer good oil resistance to hydrocarbon fluids, they take longer to achieve deep curing and may not meet customer needs for productivity. Some encapsulants contain halogen-containing resins, particularly fluorosilicone resins, which have the problem of releasing halogens and causing environmental pollution when the resin is disposed of as waste. The raw material cost of fluorosilicone is very high, and the supply of fluorosilicone is very limited.

[0006] From the aforementioned perspective, there is still some acceptance for fluorine-free silicone compositions that exhibit good high-temperature motor oil resistance while maintaining mechanical properties including hardness, elongation, and adhesive strength. [Overview of the project]

[0007] After persistent exploration, we have surprisingly discovered that a phenyl silicone sealant comprising Vi-containing phenyl resin, Vi-containing phenyl polymer, SiH-containing phenyl polymer, and a phenyl epoxy silicone resin-based adhesion promoter exhibits high-temperature (150°C) motor oil resistance while maintaining good hardness, elongation, and adhesive strength.

[0008] In a first aspect of this disclosure, the disclosure relates to a hydrocarbon fluid-resistant silicone composition, A) At least two silicon bonds in the molecule C 2~10 Alkenyl group and at least one silicon bond C 6~20 A linear organopolysiloxane having an aryl group, B) At least one C in the molecule 2~10 Alkenyl group and at least one C 6~20 An organopolysiloxane resin containing an aryl group, C) The molecule contains at least one silicon-bonded hydrogen atom and at least one silicon-bonded C 6~20Organopolysiloxanes having an aryl group, E) A hydrosilylation reaction catalyst, The present invention provides a fluorine-free, hydrocarbon fluid-resistant silicone composition.

[0009] In a second aspect of the present disclosure, the present disclosure provides a encapsulant comprising a cured product formed by curing a hydrocarbon fluid-resistant silicone composition described herein.

[0010] In a third aspect of this disclosure, the disclosure provides the use of the compositions described herein in the preparation of encapsulants.

[0011] Please understand that both the general description above and the detailed description below are illustrative and descriptive, and do not limit the claimed invention. [Modes for carrying out the invention]

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art in which the present invention pertains. Furthermore, all publications, patent applications, patents, and other references referenced herein are incorporated by reference.

[0013] Where disclosed herein, the terms “composition,” “formulation,” or “mixture” refer to a physical blend of different components obtained by simply mixing different components by physical means.

[0014] In this specification, “and / or” means “and, or alternatively.” All scopes include endpoints unless otherwise indicated.

[0015] "Alkyl" means an acyclic, branched, or unbranched saturated monovalent hydrocarbon group. Alkyls are exemplified by, but are not limited to, Me, Et, Pr (e.g., iso-Pr and / or n-Pr), Bu (e.g., iso-Bu, n-Bu, tert-Bu and / or sec-Bu), pentyl (e.g., iso-pentyl, neo-pentyl and / or tert-pentyl), hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, as well as branched saturated monovalent hydrocarbon groups with 6 to 12 carbon atoms. Alkyl groups may have 1 to 30, alternatively 1 to 24, alternatively 1 to 20, alternatively 1 to 12, alternatively 1 to 10, alternatively 1 to 8, and alternatively 1 to 6 carbon atoms.

[0016] "Alkoxy" means -O-alkyl, and alkyl is as described above.

[0017] "Alkenyl" refers to an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Alkenyls are exemplified by, but are not limited to, vinyl, allyl, methallyl, propenyl, and hexenyl. An alkenyl group may have 2 to 30, 2 to 24, 2 to 20, 2 to 12, 2 to 10, or 2 to 6 carbon atoms.

[0018] "Aryl" refers to a completely unsaturated cyclic hydrocarbon group. Examples of aryls include, but are not limited to, cyclopentadienyl, phenyl, anthracenyl, and naphthyl. Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7, or alternatively 5 to 6 carbon atoms. Polycyclic aryl groups may have 10 to 17, or 10 to 14, or 12 to 14 carbon atoms.

[0019] Unless otherwise specified, the term "substituted", when used in reference to another group, for example a hydrocarbyl group, means that one or more hydrogen atoms on the hydrocarbyl group are replaced with another substituent. Examples of such substituents include, but are not limited to: halogen atoms, for example chlorine, fluorine, bromine and iodine; halogen atom-containing groups such as chloromethyl group, perfluorobutyl group, trifluoroethyl group, and nonafluorohexyl group; oxygen atom; oxygen atom-containing groups such as (meth)acryl group and carboxyl group; nitrogen atom; nitrogen atom-containing groups such as amine, amino functional groups, amido functional groups and cyano functional groups; sulfur atom; and sulfur atom-containing groups such as mercapto group.

[0020] M, D, T and Q units generally are R u SiO( 4-u) / 2 [wherein u is 3, 2, 1 and 0 for M, D, T and Q respectively, and R is an independently selected hydrocarbyl group]. M, D, T, Q represent one (Mono), two (Di), three (Tri), or four (Quad) oxygen atoms covalently bonded to a silicon atom that is bonded to the remaining molecular structure.

[0021] The hydrocarbon fluid-resistant silicone composition comprises: A) at least two silicon-bonded C in the molecule 2~10 alkenyl groups and at least one silicon-bonded C 6~20 a linear organopolysiloxane having an aryl group; B) at least one C in the molecule 2~10 alkenyl groups and at least one C 6~20 an organopolysiloxane resin comprising an aryl group; C) at least one silicon-bonded hydrogen atom and at least one silicon-bonded C in the molecule 6~20 an organopolysiloxane having an aryl group; D) optionally, an adhesion promoter; E) a hydrosilylation reaction catalyst, wherein the silicone composition does not contain fluorine.

[0022] Components of the composition A) At least two silicon bonds in the molecule C 2~10 Alkenyl group and at least one silicon bond C 6~20 Linear organopolysiloxanes containing aryl groups The composition contains at least two silicon bonds C in the molecule. 2~10 Alkenyl group and at least one silicon bond C 6~20 Linear organopolysiloxanes having aryl groups are either matrix polymers or become matrix polymers after the composition is cured. An example of an organopolysiloxane is a curable, crosslinkable organopolysiloxane. Linear organopolysiloxanes have at least 0.05% by weight of silicone-linked alkenyl groups, preferably at least 0.2% by weight of silicone-linked alkenyl groups, and more preferably at least 0.4% by weight of silicone-linked alkenyl groups. 2~10 Examples of alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, pentenyl, and hexenyl. 6~20 Examples of aryl groups include, but are not limited to, phenyl, anthracenyl, and naphthyl.

[0023] Examples of linear organopolysiloxanes include, but are not limited to, dimethylvinylsiloxy-terminated phenyldimethylpolysiloxane, methylphenylvinylsiloxy-terminated dimethylpolysiloxane, dimethylvinylsiloxy-terminated dimethylsiloxane-methylphenylsiloxane copolymer, silanol-terminated dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer, and mixtures of two or more thereof. Preferably, the molecule contains at least two silicon bonds C 2~10 Alkenyl group and at least one silicon bond C 6~20 The linear organopolysiloxane component A) having an aryl group is a dimethylvinylsiloxy-terminated phenylpolydimethylsiloxane.

[0024] The amount of organopolysiloxane A) is preferably 20-50% by weight, more preferably 21-45% by weight, and even more preferably 22-42% by weight, based on the weight of the composition.

[0025] B) At least one C in the molecule 2~10 Alkenyl group and at least one C 6~20 Organopolysiloxane resin containing aryl groups Component B) contains at least one C in M ​​units within the molecule 2~10 alkenyl group and at least one C in the T unit 6~20 Contains an aryl group, average unit formula: (R 1 3SiO 1 / 2 ) a (R 2 SiO 3 / 2 ) b It is expressed by, in the formula, R 1 However, in each appearance, independently selected from alkyls having 1 to 10 carbon atoms (such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, preferably alkyls having 1 to 8 carbon atoms, preferably alkyls having 1 to 6 carbon atoms, more preferably alkyls having 1 to 4 carbon atoms) and alkenyls having 2 to 10 carbon atoms (such as vinyl, allyl, butenyl, pentenyl, and hexenyl, preferably alkenyls having 2 to 8 carbon atoms, preferably alkenyls having 2 to 6 carbon atoms, more preferably alkenyls having 2 to 4 carbon atoms), R 1 The condition is that 0.1 to 40 mol% of R is an alkenyl group. 2 However, in each occurrence, independently selected from aryl groups having 6 to 20 carbon atoms (such as phenyl or naphthyl, preferably aryl groups having 6 to 14 carbon atoms), where the subscript "a" is a number in the range of 10 to 40, preferably 15 to 35, more preferably 20 to 30, and the subscript "b" is a number in the range of 60 to 90, preferably 65 to 85, more preferably 70 to 80.

[0026] Component B) has at least 1% by weight of silicone-bonded alkenyl groups, preferably at least 2% by weight of silicone-bonded alkenyl groups, and more preferably at least 4% by weight of silicone-bonded alkenyl groups.

[0027] Preferably, component B) is a (ViMe2SiO) in which a and b are defined as above. 1 / 2 ) a (PhSiO 3 / 2 ) b An example of component B) is (ViMe2SiO 0.5 ) 25 -(PhSiO 1.5 ) 75 (ViMe2SiO 0.5 ) 20 -(PhSiO 1.5 ) 80 These are some examples, but they are not limited to these.

[0028] The amount of component B) is preferably 45-70% by weight, more preferably 45-65% by weight, and even more preferably 45-62% by weight, based on the weight of the composition.

[0029] C) The molecule contains at least one silicon-bonded hydrogen atom and at least one silicon-bonded C 6~20 organopolysiloxanes having an aryl group Component C) contains at least one silicon-bonded hydrogen atom (SiH) and at least one silicon-bonded C such as phenyl. 6~20 It contains an aryl group. SiH phenylpolysiloxane is sometimes referred to as a chain extender or crosslinker in the composition. Preferably, component (C) includes the following components (C-1) and (C-2): (C-1) Organopolysiloxanes represented by the following average empirical formulas: (HR 3 2SiO 1 / 2 )(R 4 2SiO 2 / 2 ) c (HR3 2SiO 1 / 2 ), (C-2) Organopolysiloxanes represented by the following average empirical formulas: (HR 5 2SiO 1 / 2 ) d (R 6 SiO 3 / 2 ) f .

[0030] In the above equation, R 3 and R 5 In each appearance, independently selected from alkyl groups having 1 to 10 carbon atoms (such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, preferably alkyl groups having 1 to 8 carbon atoms, preferably alkyl groups having 1 to 6 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms), R 4 and R 6 In each occurrence, is independently selected from aryl groups (preferably phenyl or naphthyl) having 6 to 20 carbon atoms, H is hydrogen, the subscript "c" is a number in the range of 1 to 100, preferably 1 to 80, the subscript "d" is a number in the range of 50 to 70, preferably 50 to 60, and the subscript "f" is a number in the range of 30 to 50, preferably 40 to 50.

[0031] Component C) has at least 0.1% by weight of silicone-bonded hydrogen atoms, preferably at least 0.4% by weight of silicone-bonded hydrogen atoms, more preferably at least 0.6% by weight of silicone-bonded hydrogen atoms, and 1% or less of silicone-bonded hydrogen atoms. Therefore, the SiH content is 0.1% to 1%, preferably 0.4% to 1%, or 0.6% to 1%, based on the total weight of component C). The ratio of SiH in component C) to the total alkenyl groups in components (A) and (B) is less than 1, preferably less than 0.9.

[0032] Preferably, component C) is a dimethyl hydrogen-terminated diphenyltrisiloxane copolymer or a dimethyl hydrogen-terminated phenylsilsesquioxane.

[0033] Generally, the amount of component C1) used herein is preferably 8 to 15% by weight, more preferably 9 to 14% by weight, and even more preferably 9 to 12% by weight, based on the weight of the composition. The content of component C2) used herein is preferably 0.01 to 2% by weight, more preferably 0.1 to 1.8% by weight, and even more preferably 0.2 to 1.6% by weight, based on the weight of the composition.

[0034] D) Optional adhesion promoter The composition may further include an adhesion promoter D). The adhesion promoter includes at least one of the following components (D-1) and (D-2): (D-1) Organopolysiloxanes represented by the following average empirical formulas: (R 7 3SiO 1 / 2 ) x (R 8 SiO 3 / 2 ) y (R 9 2SiO 2 / 2 ) z In the formula, R 7 However, in each appearance, independently selected from alkyls having 1 to 10 carbon atoms (such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, preferably alkyls having 1 to 8 carbon atoms, preferably alkyls having 1 to 6 carbon atoms, more preferably alkyls having 1 to 4 carbon atoms) and alkenyls having 2 to 10 carbon atoms (such as vinyl, allyl, butenyl, pentenyl, and hexenyl, preferably alkenyls having 2 to 8 carbon atoms, preferably alkenyls having 2 to 6 carbon atoms, more preferably alkenyls having 2 to 4 carbon atoms), R 7 The condition is that 0.1 to 40 mol% of R is an alkenyl group. 8 However, in each appearance, an aryl group having 6 to 20 carbon atoms (such as phenyl or naphthyl, preferably an aryl having 6 to 14 carbon atoms) is independently selected, R9 However, in each occurrence, independently selected from alkyloxys having 1 to 8 carbon atoms (such as methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, or tert-butoxy, preferably alkoxys having 1 to 6 carbon atoms, more preferably alkoxys having 1 to 4 carbon atoms), where the subscript "x" is a number in the range of 10 to 40, preferably 15 to 35, more preferably 20 to 30; "y" is a number in the range of 60 to 90, preferably 65 to 85, more preferably 70 to 80; and "z" is a number in the range of 20 to 60, preferably 30 to 50, more preferably 35 to 40; (D-2) Organopolysiloxanes represented by the following average empirical formulas: (R 10 3SiO 1 / 2 )(R 11 2SiO 2 / 2 ) m (R 12 2SiO 2 / 2 ) n (R 10 3SiO 1 / 2 ) In the formula, R 10 However, in each appearance, an alkyloxy having 1 to 8 carbon atoms is independently selected (such as methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, or tert-butoxy, preferably alkoxy having 1 to 6 carbon atoms, more preferably alkoxy having 1 to 4 carbon atoms), R 11, independently at each occurrence, is selected from alkyl having 1 to 10 carbon atoms (such as methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, or tert-butyl, preferably alkyl having 1 to 8 carbon atoms, preferably alkyl having 1 to 6 carbon atoms, more preferably alkyl having 1 to 4 carbon atoms) and alkenyl having 2 to 10 carbon atoms (such as vinyl, allyl, butenyl, pentenyl, and hexenyl, preferably alkenyl having 2 to 8 carbon atoms, preferably alkenyl having 2 to 6 carbon atoms, more preferably alkenyl having 2 to 4 carbon atoms), R 11 , with the proviso that 0.1 to 40 mol% of R are alkenyl groups, R 12 , independently at each occurrence, is selected from alkyl having 1 to 10 carbon atoms (such as methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, or tert-butyl, preferably alkyl having 1 to 8 carbon atoms, preferably alkyl having 1 to 6 carbon atoms, more preferably alkyl having 1 to 4 carbon atoms), "m" is a number in the range of 10 to 40, and "n" is a number in the range of 10 to 40.

[0035] The amount of the adhesion promoter used herein is, based on the weight of the composition, preferably 0 to 5% by weight, more preferably 0.1 to 3% by weight, even more preferably 0.5 to 2% by weight.

[0036] E) Hydrosilylation reaction catalyst The hydrosilylation reaction catalyst may comprise any substance capable of promoting a hydrosilylation reaction. Suitable hydrosilylation catalysts are known in the art and are commercially available. Component E) may comprise a platinum group metal selected from platinum, rhodium, ruthenium, palladium, osmium, or iridium, or an organometallic compound thereof, or a combination thereof. Preferable are platinum compounds such as chloroplatinic acid, reaction products of chloroplatinic acid and alcohols, platinum-olefin complexes, platinum-vinylsiloxane complexes, platinum-ketone complexes, and platinum-phosphine complexes; rhodium compounds such as rhodium-phosphine complexes and rhodium-sulfide complexes; and palladium compounds such as palladium-phosphine complexes, with platinum compounds being more preferable, and platinum-vinylsiloxane complexes being particularly preferable.

[0037] The hydrosilylation catalyst E) is exemplified by fine platinum metal powder, platinum black, platinum dichloride, platinum tetrachloride; chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid hexahydrate; and complexes of the above compounds, for example, platinum complexes of olefins, platinum complexes of carbonyls, platinum complexes of alkenylsiloxanes such as 1,3-divinyltetramethyldisiloxane, platinum complexes of low molecular weight organopolysiloxanes such as 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane, complexes of chloroplatinic acid and β-diketones, complexes of chloroplatinic acid and olefins, and complexes of chloroplatinic acid and 1,3-divinyltetramethyldisiloxane.

[0038] The hydrosilylation catalyst E) may also be represented by the formula: RhX3[(R a )2S]3;(R b 3P)2Rh(CO)X,(R b 3P)2Rh(CO)H,Rh2X2Y4,H k Rh g (En) h Cl i , or Rh[O(CO)R] 3-j (OH) jIt may be a rhodium compound, such as those represented by (wherein X represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and Y is a methyl group, an ethyl group, or a similar alkyl group, CO, C8H) 14 Or 0.5C8H 12 Represents R a R represents a methyl, ethyl, propyl, or similar alkyl group; cyclopentyl, cyclohexyl, or similar cycloalkyl group; or phenyl, tolyl, xylyl, or similar aryl group. b (wherein "Rh" represents a methyl group, ethyl group, or similar alkyl group; phenyl, tolyl, xylyl, or similar aryl group; methoxy, ethoxy, or similar alkoxy group; "En" represents ethylene, propylene, butene, hexene, or similar olefin; "k" is 0 or 1, "g" is 1 or 2, "h" is an integer from 1 to 4, "i" is 2, 3, or 4, and "j" is 0 or 1). More specifically, rhodium compounds include RhCl(Ph3P)3, RhCl3[S(C4H9)2]3, [Rh(O2CCH3)2]2, Rh(OCCH3)3, and Rh2(C8H 15 These are O2)4, Rh(C5H7O2)3, Rh(C5H7O2)(CO)2, and Rh(CO)[Ph3P](C5H7O2).

[0039] The hydrosilylation catalyst E) may also be an iridium group catalyst represented by the following formulas: Ir(OOCCH3)3, Ir(C5H7O2)3, [Ir(Z)(En)2]2, or [Ir(Z)(Dien)]2 (wherein "Z" represents a chlorine atom, a bromine atom, an iodine atom, or a methoxy group, an ethoxy group, or an similar alkoxy group; "En" represents ethylene, propylene, butene, hexene, or an similar olefin; and "Dien" represents cyclooctadiene)tetrakis(triphenyl). Component (E) may also be a mixture of palladium, palladium black, and triphenylphosphine.

[0040] The hydrosilylation catalyst E) can be a 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complex. In particular, the hydrosilylation catalyst E) is a mixture containing a 1.5% by weight complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane diluted in 6% by weight tetramethyldivinyldisiloxane and platinum, and 92% by weight dimethylvinylsiloxy-terminated dimethylsiloxane.

[0041] The amount used is a catalytic amount and can be appropriately selected according to the desired curing conditions. Generally, the catalyst content used herein is 0.01% or more, at most 1.0% by weight, preferably at most 0.5% by weight, and more preferably at most 0.25% by weight, based on the total weight of the composition.

[0042] F) Other adjuvants The compositions of this disclosure may optionally include F) other adjuvants. Either a single compound F) or a mixture of two or more compounds may be used. These adjuvants F) include, for example, inhibitors, thixotropic agents, fillers, fungicides, fragrances, rheological additives, moisture scavengers, filler treatment agents, antioxidants, light stabilizers, flame retardants, dispersants, solvents, pigments, dyes, plasticizers, and heat stabilizers. They include metal carbonates, metal sulfates, metal salts of carboxylic acids, fibers such as glass fibers and plastic fibers, and plastic powders.

[0043] Suitable inhibitors include polymethylvinylcyclosiloxanes such as methyl(tris(1,1-dimethyl-2-propynyloxy))silane, 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyne-2-ol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-dodecine-3-ol, methylvinylcyclosiloxane, 1,3,5,7-tetravinyltetramethyltetracyclosiloxane, divinyltetramethyldisiloxane, tetravinyldimethyldisiloxane, trialkylcyanurates, alkylmaleates, organic sulfoxides, organic amines, diamines, phosphanes and phosphites, nitriles, diaziridines, and oximes, acetylene compounds, phosphites, maleates, amines, or alcohols, which can be used to adjust the processing life, starting temperature, and crosslinking rate of the compositions of this disclosure to suit the purpose.

[0044] The content of the inhibitor (e.g., methyl(tris(1,1-dimethyl-2-propynyloxy))silane) is 0-1.5% by weight, 0.01%-1.0% by weight, or 0.02%-0.5% by weight, based on the total weight of the composition.

[0045] Examples of fillers include, but are not limited to, fumed silica, Al2O3, Al(OH)3, MgO, ZnO, SiO2, AlN, BN, Mg(OH)2, diamond, graphene, graphite, finely ground quartz, chalk, talc, diatomaceous earth, zeolite, Ag, carbon black, metal oxides, functional nanoparticles, and hollow beads. These fillers can be made hydrophobic by treatment with organosilanes and / or organosiloxanes, stearic acid, or other agents, for example. The fillers used herein may preferably be surface-treated fumed silica. In one example, the filler used herein is hexamethyldisilazane-treated fumed silica.

[0046] The shape of the filler particles is not particularly limited; however, rounded or spherical particles can prevent the viscosity from increasing to an undesirable level when the filler is heavily loaded into the composition. The average particle size of the filler will depend on various factors, such as the type of filler selected for component E), the exact amount added to the curable composition, and the device in which the cured product of the composition will be used. In some specific cases, the filler may have an average particle size in the range of 0.1 micrometers to 80 micrometers, or 0.1 micrometers to 50 micrometers, or 0.1 micrometers to 10 micrometers.

[0047] The amount of filler used herein can be appropriately selected according to the desired application. Generally, the filler content used herein is 0 to 10% by weight, preferably 0 to 5% by weight, based on the total weight of the composition.

[0048] composition The composition is a two-component hydrocarbon fluid-resistant silicone composition. Preferably, A) the molecule contains at least two silicon bonds C 2~10 Alkenyl group and at least one silicon bond C 6~20 A linear organopolysiloxane having an aryl group, B) at least one C in the molecule 2~10 Alkenyl group and at least one C 6~20 A) an organopolysiloxane resin containing an aryl group, D) an adhesion promoter, and optionally F) other adjuvants (such as inhibitors, thixotropic agents, and fillers) are present in part A of the hydrocarbon fluid-resistant silicone composition, and C) the molecule contains at least one silicon-bonded hydrogen atom and at least one silicon-bonded C 6~20 An organopolysiloxane having an aryl group, E) a hydrosilylation reaction catalyst, and optionally F) other adjuvants (inhibitors, thixotropic agents, fillers, etc.) are present in part B of the hydrocarbon fluid-resistant silicone composition.

[0049] Preferably, the SiH / alkenyl ratio in the composition (including vinyl and non-vinyl alkenyl groups) is less than 1, preferably less than 0.9 and 0.5 or more. The SiH / alkenyl ratio in the composition can be 0.5 to 0.8, preferably 0.55 to 0.7.

[0050] Preferably, the composition further comprises one or more or all of the following components: an inhibitor, a thixotropic agent, and a filler.

[0051] Preferably, component A) is present in an amount of 20% to 50% by weight based on the total weight of the composition, component B) is present in an amount of 45% to 70% by weight based on the total weight of the composition, component C1) is present in an amount of 8% to 15% by weight based on the total weight of the composition, component C2) is present in an amount of 0.01% to 2% by weight based on the total weight of the composition, and component D) is present in an amount of 0 to 5% by weight based on the total weight of the composition. The composition does not contain fluorine.

[0052] manufacturing technology A) At least two silicon bonds in the molecule C 2~10 Alkenyl group and at least one silicon bond C 6~20 A linear organopolysiloxane having an aryl group, B) at least one C in the molecule 2~10 Alkenyl group and at least one C 6~20 An organopolysiloxane resin containing an aryl group, D) an adhesion promoter, and optionally F) other adjuvants (such as inhibitors, thixotropic agents, and fillers) are mixed together to form part A of a hydrocarbon fluid-resistant silicone composition.

[0053] C) The molecule contains at least one silicon-bonded hydrogen atom and at least one silicon-bonded C 6~20 An organopolysiloxane having an aryl group, E) a hydrosilylation reaction catalyst, and optionally F) other adjuvants (inhibitors, thixotropic agents, fillers, etc.) are mixed together to form part B of the hydrocarbon fluid-resistant composition.

[0054] The present invention also provides a encapsulant comprising a cured product formed by curing the hydrocarbon fluid-resistant silicone composition of the present disclosure.

[0055] This application also relates to the use of the compositions of this disclosure in the preparation of encapsulants. Preferably, the encapsulants are used in electric vehicles. [Examples]

[0056] Next, some embodiments of the present invention will be described in the following examples. Here, all parts and percentages are given by weight unless otherwise specified.

[0057] The raw materials used in the examples are listed in Table 1 below.

[0058] [Table 1-1]

[0059] [Table 1-2]

[0060] Composition and experimental procedures of CE1-5 samples and IE1-5 Samples CE1 and CE4 are commercially available fluorosilicone materials from Dow. Sample CE2 is Loctite® SI5970, an alkoxysilicone material commercially available from Henkel, which is claimed to have good resistance to automotive engine oil. Sample CE3 is Loctite® 5188, a methacrylate material commercially available from Henkel, which is also claimed to have resistance to motor oil and automatic transmission fluids.

[0061] The compositions of CE1, CE4, IE1-IE5, and CE5 are shown in the table below.

[0062] [Table 2]

[0063] [Table 3]

[0064] The CE1 sample was prepared as follows: All components of CE1 listed in Table 1, excluding the platinum catalyst, were mixed in a Speed ​​mixer. After the components were completely mixed, the platinum catalyst was added and mixed to obtain a fully blended CE1 sample. The CE4 sample was prepared as follows: All components of CE4 listed in Table 2, excluding titanium dioxide, were mixed in a Speed ​​mixer. After the components were completely mixed, titanium dioxide was added and mixed to obtain a fully blended CE4 sample.

[0065] [Table 4]

[0066] Experimental Procedure The sample was prepared by mixing the polymer and filler in a speed mixer. Linear vinyl group-containing organopolysiloxane, vinyl group-containing phenylorganopolysiloxane resin, and adhesion promoter were added to a container, the filler was gradually added at room temperature, and then SiH-containing phenylpolyorganosiloxane and catalyst were added. When the sample paste was prepared, the paste was filled into an alumina dish to form a durometer pack. A dogbone sample was formed by rubbing a 2 mm film of the sample with the paste. The sample paste was sandwiched between two Al plates, each measuring 25.4 mm × 10 mm square and 1 mm thick, and cured at 150°C for 1 hour.

[0067] The hardness of unused durometer packs, the elongation of unused dogbone samples, and the adhesive strength of unused samples on Al / Al were tested. The durometer packs, dogbone samples, and adhesive samples were then immersed in stainless steel containers filled with motor oil, and the containers were placed in an electric oven at the experimental temperature of 150°C. After maintaining this for a specific period, such as 7 or 21 days, the durometer packs, dogbone samples, and adhesive samples were removed, allowed to cool to room temperature, and then tested for their relevant properties.

[0068] [Table 5]

[0069] [Table 6]

[0070] The test results indicate that the dogbone and hardness samples of CE3 require curing of the alkyl material under anaerobic conditions and therefore cannot be cured under air or heat. Accordingly, this specification provides only the lap shear strength results on Al / Al for CE3. CE1 and CE2 exhibit lower lap shear strengths of 0.84 MPa and 1.38 MPa on Al / Al, respectively, and fail to meet the initial performance requirements.

[0071] Unused IE1-5 and CE4 samples exhibit elongation exceeding 80%, tensile strength exceeding 1.5 MPa, hardness exceeding 20 Shore A, and overlapping shear strength exceeding 1.5 MPa on Al / Al. The initial performance of these samples fully meets the required requirements for sealants in automatic transmissions or electric motors. After aging at 150°C for 21 days, the elongation of CE4 is 252%, the tensile strength remains at 2.52 MPa, the overlapping shear strength is 1.34 MPa, and the hardness gradually decreases from 35 Shore A to 28 Shore A. The post-aging performance of CE4 can meet performance standards. However, CE4 is a fluorosilicone material, which can cause environmental problems and is very expensive.

[0072] After 21 days of aging, IE1 showed an elongation of 93% from its initial value of 139%, a slight decrease in tensile strength from 1.65 MPa to 1.43 MPa, a stiffness remaining at 45 Shore A, and a lap shear strength maintaining 2.41 MPa. For IE2, after 21 days of aging, the elongation gradually decreased from 104% to 80%, the tensile strength remained unchanged at 2.51 MPa, the stiffness increased from 62 Shore A to 72 Shore A, and the lap shear strength was 2.02 MPa. For IE3, after 21 days of aging, the elongation was 95%, the tensile strength was 1.24 MPa, the stiffness slightly decreased from 41 Shore A to 37 Shore A, and the lap shear strength decreased from 2.11 MPa to 1.67 MPa. After 21 days of aging in motor oil at 150°C, IE4 exhibits 103% elongation, 2.65 MPa tensile strength, 47 Shore A hardness, and 1.30 MPa overlap shear strength. Unused IE5 shows 81% elongation, 3.8 MPa tensile strength, 57 Shore A hardness, and 2.78 MPa overlap shear strength. After 21 days of aging in motor oil at 150°C, the elongation slightly decreases to 65%, the tensile strength remains at 3.8 MPa, the hardness remains at 55 Shore A, and the overlap shear strength slightly increases to 3.09 MPa. The unused and aged performance of IE1, IE2, IE3, IE4, and IE5 can meet the performance standards.

[0073] Unused CE5 samples exhibited low elongation, tensile strength, and overlapping shear strength on Al / Al, failing to meet performance standards. The low tensile strength and overlapping shear strength of CE5 after 7 days of aging also failed to meet performance standards. The low performance of CE5 both before and after aging is attributed to the low amount of vinyl group-containing phenylorganopolysiloxane resin and the low SiH / Vi ratio in the CE5 samples.

[0074] This disclosure provides a non-fluorinated silicone that can provide high temperature resistance in hydrocarbon fluids such as motor oil, and after immersion in motor oil and aging for 21 days up to a maximum of 150°C, it has an elongation of more than 80%, a tensile strength of more than 1.5 MPa, a hardness of more than 20 Shore A but less than 70 Shore A, and a lap shear strength of more than 1.5 MPa, as well as an elongation retention of more than 60%, a tensile strength of more than 1.2 MPa, a hardness of more than 20 Shore A but less than 70 Shore A, and a lap shear strength of more than 1.2 MPa.

[0075] Determination of hardness The hardness of unused and aged durometer packs was tested using a Shore A durometer (Instron Conveloader EAETS-EQ029) according to the CMT standard method (CTM 0099B).

[0076] Determination of adhesive strength Using an adhesive testing machine (Instron), the adhesive strength of unused and aged samples on an Al / Al substrate was measured according to the CMT standard method (CTM 0293).

[0077] Determination of elongation and tensile strength Using a tensile testing machine (Instron), the elongation and tensile strength of unused and aged dogbone samples were estimated according to the CMT standard method (CTM 0137A).

Claims

1. A hydrocarbon fluid-resistant silicone composition, A) At least two silicon bonds in the molecule C ２～１０ Alkenyl group and at least one silicon bond C ６～２０ A linear organopolysiloxane having an aryl group, B) At least one C in the molecule ２～１０ Alkenyl group and at least one C ６～２０ An organopolysiloxane resin containing an aryl group, C) A molecule containing at least one silicon-bonded hydrogen atom and at least one silicon-bonded C ６～２０ Organopolysiloxanes having an aryl group, E) A hydrosilylation reaction catalyst, The silicone composition is a hydrocarbon fluid-resistant silicone composition that does not contain fluorine.

2. The component B) has the following average unit formula: (R １ ３ SiO １／２ ) ａ (R ２ SiO ３／２ ) ｂ It is expressed by the formula, where each R １ However, C １～１０ Alkyl alkyl group or C ２～１０ It is an alkenyl group, R １ 0.1 to 40 mol% of the group is an alkenyl group, and R ２ However, C ６～２０ The composition according to claim 1, wherein the aryl group is a number in the range of 10 to 40 and the number in the range of 60 to 90.

3. The composition according to claim 1, wherein component C) comprises the following components (C-1) and (C-2): (C-1) Organopolysiloxanes represented by the following average empirical formulas: (HR ３ ２ SiO １／２ )(R ４ ２ SiO ２／２ ) ｃ (HR ３ ２ SiO １／２ ) In the formula, each R ３ However, C １～１０ Each R is an alkyl group. ４ However, C ６～２０ It is an aryl group, and "c" is a number in the range of 1 to 100; (C-2) Organopolysiloxanes represented by the following average empirical formulas: (HR ５ ２ SiO １／２ ) ｄ (R ６ SiO ３／２ ) ｆ In the formula, each R ５ However, C １～１０ It is an alkyl group, R ６ However, C ６～２０ It is an aryl group, where "d" is a number in the range of 50 to 70, and "f" is a number in the range of 30 to 50.

4. The composition according to claim 1, further comprising an adhesion promoter comprising at least one of the following components (D-1) and (D-2): (D-1) Organopolysiloxanes represented by the following average empirical formulas: (R ７ ３ SiO １／２ ) ｘ (R ８ SiO ３／２ ) ｙ (R ９ ２ SiO ２／２ ) ｚ In the formula, each R ７ However, C １～１０ Alkyl alkyl group or C ２～１０ It is an alkenyl group, R ７ 0.1 to 40 mol% of the group is an alkenyl group, and R ８ However, C ６～２０ It is an aryl group, and each R ９ However, it is an alkoxy group having 1 to 6 carbon atoms, where "x" is a number in the range of 10 to 40, "y" is a number in the range of 60 to 90, and "z" is a number in the range of 20 to 60; (D-2) Organopolysiloxanes represented by the following average empirical formulas: (R １０ ３ SiO １／２ )(R １１ ２ SiO ２／２ ) ｍ (R １２ ２ SiO ２／２ ) ｎ (R １０ ３ SiO １／２ ) In the formula, each R １０ However, it is an alkoxy group having 1 to 6 carbon atoms, and each R １１ However, C １～１０ Alkyl alkyl group or C ２～１０ It is an alkenyl group, R １１ 0.1 to 40 mol% of the group is an alkenyl group, and each R １２ However, C １～１０ It is an alkyl group, where "m" is a number in the range of 10 to 40, and "n" is a number in the range of 10 to 40.

5. The molecule contains at least two silicon bonds C ２～１０ Alkenyl group and at least one silicon bond C ６～２０ The composition according to claim 1, wherein the constituent A) linear organopolysiloxane having an aryl group is a dimethylvinylsiloxy-terminated phenylpolydimethylsiloxane.

6. The composition according to claim 1, wherein the component A) is present in an amount of 20% to 50% by weight based on the total amount of the composition.

7. The composition according to claim 1, wherein the component B) is present in an amount of 45% to 70% by weight based on the total amount of the composition.

8. The composition according to claim 3, wherein the component C1) is present in an amount of 8% to 15% by weight based on the total amount of the composition.

9. The composition according to claim 3, wherein the component C2) is present in an amount of 0.01% to 2% by weight based on the total amount of the composition.

10. The composition according to claim 1, wherein the SiH content is 0.1 to 1% based on the total weight of the component C), and the ratio of SiH to total alkenyl groups in the composition is less than 1.

11. The composition according to claim 1, wherein the composition further comprises one or more or all of the following components: an inhibitor, a thixotropic agent, and a filler.

12. A sealing material comprising a cured product formed by curing a hydrocarbon fluid-resistant silicone composition according to any one of claims 1 to 11.

13. Use of the composition according to any one of claims 1 to 11 in the preparation of a sealing material.

14. The use according to claim 13, wherein the sealing material is used in an electric vehicle.

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