Addition-curable composition containing siloxane-imide copolymer

Abstract

Presented and described herein is a curable silicone adhesive composition comprising a thermally stable siloxane-imide copolymer, an alkenyl silicone, a silicone hydride crosslinker, a hydrosilylation catalyst, and additives, which is curable at relatively low temperatures and exhibits good thermal stability.

Description

[Technical Field]

[0001] The present invention relates to addition-curable compositions. In particular, the present invention relates to addition-curable compositions comprising an olefin-terminated siloxane-imide copolymer, a Si-H crosslinking agent, a catalyst, and other additives to optionally provide a thermally stable material that is stable at high temperatures (e.g., above 350°C). This curable material can be used in a variety of applications, including applications where exposure to high temperatures or extreme temperature changes are expected. [Background technology]

[0002] High-temperature stable materials, such as those stable at around 350°C or higher, are desirable for a wide range of applications. In addition, many applications require not only high-temperature stability but also that the material maintain, or substantially maintains, its mechanical properties and flexibility over a wide temperature range, from extremely low temperatures (e.g., below 0°C to -100°C) to high temperatures (e.g., around 350°C or higher). Many current curable silicone-based materials are generally only stable up to 275°C. Organic polymers such as polyimides and polybenzimidazoles can be stable above 400°C, however, these materials have their own processability and flexibility challenges, making their use difficult for some applications. Considering their individual characteristic constraints (thermal stability and flexibility), pure silicones or pure organic polymers like polyimides alone cannot be used for these wide-temperature applications.

[0003] Siloxane-modified polyimide materials are known in the art. These materials are flexible, self-supporting film-type materials with high thermal stability and high thermal conductivity. However, these materials have several processability challenges, which limits their applicability in large-scale applications.

[0004] Recent attempts to improve thermal stability include the use of mold-making compositions containing siloxane-modified polyimide copolymers or siloxane-polyetherimide block copolymers (see, for example, U.S. Patent No. 8,071,693, U.S. Patent Publication 2003 / 0004268, and U.S. Patent No. 6,451,381). Other attempts are described, for example, in Japanese Patent Nos. 3279635 and 4803371 relating to non-curable siloxaneimide copolymers, and in Korean Patent Publication 10-2014-007363 relating to composite sheets containing siloxaneimide copolymers with reinforcing materials. However, the solutions proposed in these do not target materials with high thermal stability above 350°C. [Overview of the project]

[0005] The following is an overview of the disclosure to provide a basic understanding of several embodiments. This overview is not intended to identify essential or important elements or to impose any limitations on the embodiments or claims. Furthermore, this overview may provide a simplified outline of several embodiments that may be described in more detail in other parts of the disclosure.

[0006] One embodiment provides an addition-curable silicone-imide copolymer composition. This addition-curable silicone-imide copolymer composition has been found to cure at low temperatures in the absence of any solvent.

[0007] In another embodiment, a cured material formed from an addition-curable composition is provided, exhibiting superior thermal stability compared to pure siloxane. This cured material can be provided in various forms for use, for example, as an adhesive, a sealing adhesive or gap filler, as a coating, or for forming a molding material. This cured material has been found to maintain good mechanical and other properties and practically retain flexibility when exposed to extremely low or extremely high temperatures.

[0008] One embodiment provides an addition-curing silicone composition: (A) Alkenyl-functionalized siloxane-imide copolymer; (B) 0 to approximately 80 parts by mass of alkenyl-functional organosiloxane; (C) Polyorganohydrogensiloxane having at least two hydrogen atoms bonded to a silicon atom; (D) Catalyst; (E) Additives; and (F) Contains 0 to about 3000 parts by mass of filler based on the total weight of the curable silicone composition.

[0009] In one embodiment, the siloxane-imide copolymer (A) is selected from the compounds of formula (I): [ka] R in the formula 1 R is independently selected from C5-C20 aryl groups, polycyclic aryl groups containing 2 or more C5-C20 aryl groups, where R 1 It is either unsubstituted or substituted with C1-C6 alkyl groups, halogen groups, haloalkyl groups, hydroxyl groups, and / or C1-C5 alkoxy groups; R 2 This is independently selected from divalent C1-C20 hydrocarbon groups, divalent C4-C20 branched-chain hydrocarbon groups, or C4-C30 cyclic hydrocarbon groups; R 3 , R 4 , R 5 , and R 6 Each of these is independently selected from C1-C10 alkyl groups and C6-C20 aryl groups; m is an integer from 1 to approximately 200; and n is an integer from 1 to approximately 30.

[0010] In one embodiment, R 1is independently selected from benzene, naphthalene, benzophenone, biphenyl, biphenylalkane, biphenyl ether, isopropylidene phenylphenoxy, biphenyl sulfone, biphenyl sulfide, norbornyl, or hexafluoromethyl biphenyl. In one embodiment, each R 1 is benzene.

[0011] In one embodiment, the siloxane - imide copolymer (A) is present in an amount of about 10 parts by weight to about 100 parts by weight, more preferably about 20 parts by weight to about 98 parts by weight, and most preferably about 30 parts by weight to about 95 parts by weight, based on the total weight of the curable silicone - imide composition.

[0012] In one embodiment, the polyorganosiloxane (B) is a compound selected from the formula M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q g wherein: M 1 =R 7 R 8 R 9 SiO 1 / 2 M 2 =R 10 R 11 R 12 SiO 1 / 2 D 1 =R 13 R 14 SiO 2 / 2 D 2 =R 15 R 16 SiO 2 / 2 T 1 =R 17 SiO 3 / 2 T 2 =R 18SiO 3 / 2 Q=SiO 4 / 2 And here R 7 , R 8 , R 9 , R 11 , R 12、 R 13 , R 14 , R 16 , and R 17 This is independently selected from C1-C30 hydrocarbon groups or C6-C30 aromatic groups; R 10 , R 15 , and R 18 R is independently selected from C1-C30 hydrocarbon groups, C6-C30 aromatic groups, C1-C30 alkoxy groups, or C2-C30 alkenyl groups, however R 10 , R 15 , and / or R 18 One or more of these are selected from C2-C30 alkenyl groups; and The subscripts a, b, c, d, e, f, g have the following constraints: 2 <a+b+c+d+e+f+g<2000、b+d+f> It is zero or a positive number below the value of 0.

[0013] In one embodiment, R 7 , R 8 , R 9 , R 11 , R 12、 R 13 , R 14 , R 16 , and R 17 R is independently selected from C1-C30 hydrocarbon groups or C6-C30 aromatic groups, where R 7 , R 8 , R 9 , R 11 , R 12、 R 13 , R 14 , R 16 , and R 17 At least one of these is selected from C6-C30 aromatic groups.

[0014] In one embodiment, R 13 and / or R14 At least one of them is a C6-C30 aromatic group.

[0015] In one embodiment, R 13 and / or R 14 is a phenyl group.

[0016] In one embodiment, component (B) is present in an amount of from about 0 parts by weight to about 80 parts by weight, more preferably from about 0 parts by weight to about 60 parts by weight, and most preferably from about 0 parts by weight to about 50 parts by weight, based on the total weight of the curable silicone composition. In one embodiment, the alkenyl-functional organosiloxane (B) is present in an amount of from about 10 parts by weight to about 50 parts by weight based on the total weight of the curable silicone composition.

[0017] In one embodiment, the alkenyl-functional siloxane-imide copolymer (A) is present in an amount of from about 20 to about 50 parts by weight based on the total weight of the curable silicone composition, and the alkenyl-functional organosiloxane (B) is present in an amount of from about 20 parts by weight to about 50 parts by weight based on the total weight of the curable silicone-imide composition.

[0018] In one embodiment, the alkenyl-functional siloxane-imide copolymer (A) is present in an amount of from about 30 parts by weight to about 40 parts by weight based on the total weight of the curable silicone-imide composition, and the alkenyl-functional organosiloxane (B) is present in an amount of from about 30 parts by weight to about 40 parts by weight based on the total weight of the curable silicone-imide composition.

[0019] In one embodiment, the polyorganohydrogensiloxane component (C) is a compound selected from the formula: M 3 h M 4 i D 3 j D 4 k T 3 m T 4 n Q o wherein: M 3 =R 19 R 20 R 21 SiO 1 / 2 M 4 =R 22 R 23 R 24 SiO 1 / 2 D 3 =R 25 R 26 SiO 2 / 2 D 4 =R 27 R 28 SiO 2 / 2 T 3 =R 29 SiO 3 / 2 T 4 =R 30 SiO 3 / 2 Q=SiO 4 / 2 And here R 19 , R 20 , R 21 , R 25 , R 26 , and R 29 The group is independently selected from C1-C30 hydrocarbon groups, C6-C30 aromatic groups, or C1-C30 alkoxy groups; R 22 , R 23 , R 24 , R 27 , R 28 , and R 30 R is independently selected from hydrogen, C1-C30 hydrocarbon groups, C6-C30 aromatic groups, C1-C30 alkoxy groups, or C2-C30 alkenyl groups, however R 22 , R 23 , R 24 , R 27 , R 28 , and / or R 30 One or more of them are hydrogen; and The subscripts h, i, j, k, m, n, and o have the following constraints: 1 <h+i+j+k+m+n+o<100、i+k+n> It is zero or a positive number below the value of 0.

[0020] In one embodiment, the polyorganohydrogensiloxane component (C) is present in an amount of about 0.05 parts by mass to about 10 parts by mass, more preferably about 0.08 parts by mass to about 6 parts by mass, and most preferably about 1 part by mass to about 4 parts by mass, based on the total weight of the curable composition.

[0021] In one embodiment, catalyst (D) is selected from noble metal catalysts, which include ruthenium, rhodium, palladium, osmium, iridium, and platinum, as well as complexes containing these metals.

[0022] In one embodiment, catalyst (D) is present in an amount of about 1 to about 10 parts by mass, more preferably about 2 to about 8 parts by mass, and most preferably about 3 to about 6 parts by mass, based on the total weight of the curable silicone composition.

[0023] In one embodiment, additive (E) is selected from at least one of pigments, lubricants, viscosity modifiers, heat stabilizers, light stabilizers, flame retardants, inhibitors, adhesion promoters, or two or more combinations thereof.

[0024] In one embodiment, additive (E) is present in an amount of about 0.05 parts by mass to about 3000 parts by mass, more preferably about 15 parts by mass to about 1000 parts by mass, and most preferably about 0.05 parts by mass to about 1 part by mass, based on the total weight of the curable silicone composition.

[0025] In one embodiment, additive (E) is an inhibitor.

[0026] In one embodiment, the inhibitor is present in an amount of about 1 to about 10 parts by mass, more preferably about 0.1 to about 2 parts by mass, and most preferably about 0.05 to about 1 part by mass, based on the total weight of the curable silicone-imide composition. In one embodiment, the inhibitor is present in an amount of about 0.05 to about 10 parts by mass, based on the total weight of the curable silicone-imide composition. In one embodiment, the inhibitor is present in an amount of about 0.05 to about 2 parts by mass, based on the total weight of the curable silicone-imide composition.

[0027] In one embodiment, the inhibitor is selected from ethylenically unsaturated amides, aromatic unsaturated amides, acetylene compounds, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon monoesters of unsaturated acids, conjugated or unconjugated enynes, hydroperoxides, ketones, sulfoxides, amines, phosphines, phosphates, nitrites, diaziridines, or two or more combinations thereof.

[0028] In one embodiment, the inhibitor is selected from alkynyl alcohols, maleates, or a combination thereof.

[0029] In one embodiment, the inhibitor is selected from diallyl maleate, hydroquinone, p-methoxyphenol, t-butylcatechol, phenothiazine, or two or more combinations thereof.

[0030] In one embodiment, filler (F) is selected from silica, fumed silica, TiO2, MgO, ZnO, CaCO3, CeO2, Fe2O3, SiC, clay material, graphene oxide, boron oxide, boron nitride BN, carbon nanotubes, zirconium oxide, fly ash, Zr(OEt)4, Ti(OEt)4, any polyimide in powder form, polybenzimidazole, polyamideimide, polyBPA sulfone, siloxane-polyimide, siloxane-benzimidazole, siloxane-polysulfone, or any other thermally stable filler.

[0031] In one embodiment, the filler (F) is present in an amount of about 0 to about 3000 parts by mass, more preferably about 15 to about 2000 parts by mass, and most preferably about 25 to about 30 parts by mass, based on the total weight of the curable silicone composition.

[0032] In one embodiment, the filler (F) is present in an amount of about 20 to about 30 parts by mass based on the total weight of the curable silicone composition.

[0033] In one embodiment, the filler is Fe2O3.

[0034] In one embodiment, the silicone-imide composition is coated or bonded to a substrate.

[0035] In one embodiment, the substrate is selected from materials that are plastic materials, ceramics, glass, rubber materials, filled metals, metal alloys, metallized plastics, coated or painted metals, or two or more combinations thereof.

[0036] In one embodiment, the substrate material is selected from acrylic polymers, polyesters, polyamides, polyimides, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene polymers, polyvinyl chlorides, polyethylenes, polycarbonates, copolycarbonates, or two or more combinations thereof.

[0037] Further embodiments provide a process for preparing a cured silicone-imide material, which includes contacting the composition of any of the embodiments described above with curing conditions. In one embodiment, the curing conditions are a curing catalyst.

[0038] Another embodiment provides a cured silicone-imide material formed from any of the embodiments and compositions described above.

[0039] In one embodiment, the cured silicone imide material has thermal degradation from 300°C to 600°C as measured by thermogravimetric analysis.

[0040] In one embodiment, the cured silicone-imide material is used in or as part of articles such as aerospace equipment, electronic equipment, electronic components, automobiles, insulators, paints, and solvent-resistant films.

[0041] The following description and drawings disclose various exemplary embodiments. Some improvements and novel embodiments may be explicitly identified, while others may be evident from the description and drawings. [Modes for carrying out the invention]

[0042] The following descriptions refer to exemplary embodiments, examples of which are shown in the accompanying drawings. As will be understood, other embodiments may be used, and structural and functional modifications may be made. Furthermore, features of various embodiments may be combined or modified. Therefore, the following description is presented only as an example and does not limit in any way to the various changes and modifications that may be made to the embodiments described. Many specific details in this disclosure will lead to a full understanding of the subject matter of this disclosure. It should be understood that embodiments of this disclosure may be implemented in other embodiments without necessarily including all embodiments described herein.

[0043] As used in this application, the terms “example” or “exemplary” mean a case or example. The terms “example” or “exemplary” do not indicate that they are important or preferred embodiments or forms. The term “or” is intended to be inclusive, not exclusive, unless the context specifically suggests otherwise. For example, the phrase “A uses B or C” includes all inclusive substitutions (e.g., A uses B; A uses C; or A uses both B and C). Separately, the articles “a” and “one” are generally intended to mean “one or more” unless the context specifically suggests otherwise.

[0044] This disclosure may specify several different ranges for one or more components in a composition. As can be understood, it is possible to combine the numerical values ​​of each range to form new, unspecified ranges.

[0045] The term "alkyl" includes linear, branched, and cyclic monovalent hydrocarbon groups, which may be substituted with heteroatoms or heteroatom-containing groups. In embodiments, the term alkyl may include C1-C30 alkyl groups. Suitable alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and others.

[0046] The term "alkylene" includes linear, branched, and cyclic divalent hydrocarbon groups, which may be substituted with heteroatoms or heteroatom-containing groups. In embodiments, the term alkylene may include C1-C30 alkylene groups. Examples of alkylene groups, but are not limited to, include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene, desilene, and others.

[0047] The term "aryl" includes any monovalent aromatic hydrocarbon group, which may be substituted with a heteroatom or a heteroatom-containing group. The term also includes fusion systems containing aromatic groups and groups comprising multiple aryl groups linked by bonding or linking groups. In embodiments, the term aryl includes C5-C20 aryl groups, fusion aryl groups containing two or more C5-C20 aryl groups, and multiple aryl group structures containing two or more C5-C20 aryl groups linked by linking groups.

[0048] The term "arylene" includes any divalent aromatic hydrocarbon group, which may be substituted with a heteroatom or a heteroatom-containing group. The term also includes fusion systems containing aromatic groups. In embodiments, the term arylene includes C5-C20 arylene groups, fusion arylene groups containing two or more C5-C20 aryl groups, and multiple arylene group structures containing two or more C5-C20 aryl groups linked by linking groups.

[0049] The term "aralkyl" includes linear, branched, and cyclic monovalent hydrocarbon groups substituted with aryl substituents.

[0050] The term “cyclic” or “cyclic” alkyl includes monovalent cyclic hydrocarbons, including single cyclic groups, dicyclic groups, tricyclic groups, and higher-order cyclic structures, as well as crosslinked cyclic groups, fusion cyclic groups, and fusion cyclic groups containing at least one crosslinked cyclic group. In embodiments, cyclic alkyl groups include C3-C20 cyclic alkyl groups. Suitable examples of cyclic groups include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, bicyclo[2.2.2]nonane, adamantyl, or tetrahydronaphthyl (tetraline).

[0051] The term "cyclic" or "cyclic" alkylene includes divalent cyclic hydrocarbons, including single cyclic groups, dicyclic groups, tricyclic groups, and higher-order cyclic structures, as well as bridged cyclic groups, fusion cyclic groups, and fusion cyclic groups containing at least one bridged cyclic group. In embodiments, cyclic alkylene groups include C3-C20 cyclic alkylene groups.

[0052] The term "alkynyl" is defined as a C2-C10 branched or straight unsaturated aliphatic hydrocarbon group having one or more triple bonds between two or more carbon atoms. Examples of alkynes include ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octinyl, and noninyl.

[0053] The term "substitution" means that one or more hydrogens on a molecule, on a part of a molecule, or on an atom are replaced by a substituent, provided that the valency does not exceed the normal valency. Substituents can be heteroatoms. The term "hetero" is used to refer to atoms such as oxygen, nitrogen, sulfur, silicon, phosphorus, and boron, or in relation to another group that contains such atoms or atoms. Suitable examples of substituents include, but are not limited to, -OR, -NR'R, -C(O)R, -SR, -halogens, -CN, -NO2, -SO2, phosphoryl, imino, thioester, carbocyclic groups, aryl, heteroaryl, alkyl, alkenyl, bicyclic, and tricyclic groups. When a substituent is a keto group (i.e., =O), two hydrogens on the atom are replaced. Keto substituents are not present in aromatic moieties. The terms R and R' refer to alkyl groups, which may be the same or different.

[0054] Provided is an addition-curable silicone-imide copolymer composition. This composition may be used to form an adhesive when cured. This composition has been found to cure at low temperatures (e.g., room temperature, e.g., from about 20-25°C to 150°C) without the presence of any solvent. Also provided is a cured material comprising or formed from this composition. The cured material formed from this composition exhibits excellent properties, such as thermal stability at relatively high temperatures (e.g., about 350°C or higher), and temperature stability when exposed to extreme temperature changes from very low to very high temperatures. In embodiments, the cured material formed from this composition exhibits a superior degradation peak (T) compared to that of pure siloxane. d ) indicates.

[0055] In one embodiment, an addition-curable silicone composition: (A) Alkenyl functional siloxane-imides; (B) 0 to 80 parts by mass of alkenyl-functional organosiloxane; (C) A polyorganohydrogensiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule; this polyorganohydrogensiloxane can be provided in an amount such that the amount of hydrogen atoms bonded to a silicon atom is 0.9 to 10 moles per mole of the total amount of alkenyl groups contained in component (A); (D) A catalytic amount of hydrosilylation catalyst; (E) Additives; and (F) Contains filler.

[0056] In one embodiment, the siloxane-imide copolymer (A) is selected from the compounds of formula (I): [ka] During the ceremony: R 1 R is selected from C5-C20 aryl groups, polycyclic aryl groups containing 2 or more C5-C20 aryl groups, where R 1It can be unsubstituted or substituted with C1-C6 alkyl groups, halogen groups, haloalkyl groups, hydroxyl groups, and / or C1-C5 alkoxy groups; R 2 This is independently selected from divalent C1-C20 hydrocarbon groups, divalent C4-C20 branched-chain hydrocarbon groups, or C4-C30 cyclic hydrocarbon groups; R 3 , R 4 , R 5 , and R 6 Each of these is independently selected from C1-C10 alkyl groups and C6-C20 aryl groups; m is an integer from 1 to approximately 200; and n is an integer from 1 to approximately 30.

[0057] R 1 R is independently selected from C5-C20 aryl groups, polycyclic aryl groups containing two or more C5-C20 aryl groups. The polycyclic aryl group can be a fused ring or an unfused system linked by a linking group. 1 Suitable examples of aryl and / or polycyclic aryl groups include, but are not limited to, benzene, naphthalene, benzophenone, biphenyl, biphenylalkane (e.g., biphenylmethane, biphenylethane, biphenylpropane, biphenylisopropane, biphenylbutane, biphenylisobutene, biphenylter-butane, biphenylhexane, biphenyloctane, etc., biphenyl groups having alkyl linking groups selected from C1-C20 alkyls), biphenyl ethers, isopropylidene diphenylphenoxy, biphenyl sulfone, biphenyl sulfide, norbornyl, and hexafluoromethylbiphenyl, among others. In one embodiment, R 1 It is benzene.

[0058] R 2 R is selected from a divalent C1-C20 hydrocarbon group, a divalent C4-C20 branched-chain hydrocarbon group, or a C4-C30 cyclic hydrocarbon group. In embodiments, R 2R is selected from divalent C1-C20 hydrocarbon groups, C2-C15 hydrocarbon groups, C3-C10 divalent hydrocarbon groups, or C4-C6 divalent hydrocarbon groups. In one embodiment, R 2 This is a C1 divalent hydrocarbon group (i.e., a methylene group).

[0059] R 3 , R 4 , R 5 , and R 6 Each is independently selected from C1-C10 alkyl groups and C6-C20 aryl groups. In one embodiment, R 3 , R 4 , R 5 , and R 6 R is selected from C1-C10 alkyl, C2-C8 alkyl, or C4-C6 alkyl. In one embodiment, R 3 , R 4 , R 5 , and R 6 These are each methyl groups.

[0060] In one embodiment, m is an integer between 1 and about 200, about 5 and about 175, about 10 and about 150, about 25 and about 135, about 50 and about 110, or about 75 and about 100.

[0061] In one embodiment, n is an integer between approximately 1 and approximately 30, approximately 2 and approximately 25, approximately 5 and approximately 20, or approximately 10 and approximately 15.

[0062] Siloxane-imide copolymers can be prepared by methods known to those skilled in the art. In one embodiment, a siloxane-imide copolymer can be prepared by the reaction of allylimide of formula (ia) with organohydrogensiloxane (ib): [ka] [ka] R in the formula 1, R 2 , R 3 , R 4 , R 5 , and R 6 This is as stated above.

[0063] The siloxane-imide copolymer (A) may be present in an amount of 10 to about 100 parts by mass, about 20 to about 98 parts by mass, or about 30 to about 95 parts by mass, based on the total weight of the curable silicone-imide composition. In one embodiment, the siloxane-imide copolymer (A) may be present in an amount of about 20 to about 50 parts by mass, about 25 to about 45 parts by mass, or about 30 to about 40 parts by mass, based on the total weight of the curable silicone-imide composition.

[0064] In one embodiment, polyorganosiloxane (B) is of formula M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q g Selected from the compounds, in the formula: M 1 =R 7 R 8 R 9 SiO 1 / 2 M 2 =R 10 R 11 R 12 SiO 1 / 2 D 1 =R 13 R 14 SiO 2 / 2 D 2 =R 15 R 16 SiO 2 / 2 T 1=R 17 SiO 3 / 2 T 2 =R 18 SiO 3 / 2 Q=SiO 4 / 2 And here R 7 , R 8 , R 9 , R 11 , R 12、 R 13 , R 14 , R 16 , and R 17 This is independently selected from C1-C30 hydrocarbon groups or C6-C30 aromatic groups; R 10 , R 15 , and R 18 R is independently selected from C1-C30 hydrocarbon groups, C6-C30 aromatic groups, C1-C30 alkoxy groups, or C2-C30 alkenyl groups, however R 10 , R 15 , and / or R 18 One or more of these are selected from C2-C30 alkenyl groups; and The subscripts a, b, c, d, e, f, g have the following constraints: 2 <a+b+c+d+e+f+g<2000、およびb+d+f> It is zero or a positive number below the value of 0.

[0065] In one embodiment, polyorganosiloxane (B) contains two or more alkenyl groups. In one embodiment, the alkenyl groups are vinyl groups. The polyorganosiloxane can be an alkenyl-terminated siloxane.

[0066] Polyorganosiloxane (B) R 7 , R 8 , R 9 , R 11 , R 12、 R 13 , R 14 , R 16 , and R 17 R is independently selected from C1-C30 hydrocarbon groups or C6-C30 aromatic groups. In one embodiment, R7 , R 8 , R 9 , R 11 , R 12、 R 13 , R 14 , R 16 , and R 17 R is independently selected from C1-C30 alkyl, C2-C20 alkyl, C3-C15 alkyl, C4-C10 alkyl, or C6-C8 alkyl. In one embodiment, R 7 , R 8 , R 9 , R 11 , R 12、 R 13 , R 14 , R 16 , and R 17 R is independently selected from C1-C6 alkyl groups. In one embodiment, R 7 , R 8 , R 9 , R 11 , R 12、 R 13 , R 14 , R 16 , and R 17 Each is selected from the methyl group.

[0067] In one embodiment of polyorganosiloxane (B), R 7 , R 8 , R 9 , R 11 , R 12、 R 13 , R 14 , R 16 , and R 17 R is independently selected from C1-C30 hydrocarbon groups or C6-C30 aromatic groups, where R 7 , R 8 , R 9 , R 11 , R 12 , R 13 , R 14 , R 16 , and R 17 At least one of is selected from C6-C30 aromatic groups. In one embodiment, R 13 and / or R 14At least one of these groups is a C6-C30 aromatic group. An exemplary aromatic group is the phenyl group.

[0068] In one embodiment, polyorganosiloxane (B) is an MDM-type polymer having terminal alkenyl groups. In one embodiment, the MDM-type polymer is a polydimethylsiloxane having two or more terminal alkenyl groups. In one embodiment, the MDM-type polymer is MD H D Ph It is a type M, and has two or more terminal alkenyl groups.

[0069] In the embodiment, 2 <a+b+c+d+e+f+g<2000;5<a+b+c+d+e+f+g<1750;10<a+b+c+d+e+f+g<1500;20<a+b+c+d+e+f+g<1250;25<a+b+c+d+e+f+g<1000;50<a+b+c+d+e+f+g<750;75<a+b+c+d+e+f+g<500;100<a+b+c+d+e+f+g<400;または200<a+b+c+d+e+f+g<300である。

[0070] Polyorganosiloxane (B) may be present in an amount of about 0 to about 80 parts by mass, about 0 to about 60 parts by mass, or about 0 to about 50 parts by mass, based on the total weight of the curable silicone composition. In one embodiment, polyorganosiloxane (B) may be present in an amount of about 10 to about 50 parts by mass, about 20 to about 45 parts by mass, or about 30 to about 40 parts by mass, based on the total weight of the curable silicone composition. In one embodiment, polyorganosiloxane (B) may be present in an amount of about 20 to about 50 parts by mass, about 25 to about 45 parts by mass, or about 30 to about 40 parts by mass, based on the total weight of the curable silicone-imide composition.

[0071] In one embodiment, the polyorganohydrogensiloxane component (C) is of formula M3 h M 4 i D 3 j D 4 k T 3 m T 4 n Q o Selected from the compounds, in the formula: M 3 =R 19 R 20 R 21 SiO 1 / 2 M 4 =R 22 R 23 R 24 SiO 1 / 2 D 3 =R 25 R 26 SiO 2 / 2 D 4 =R 27 R 28 SiO 2 / 2 T 3 =R 29 SiO 3 / 2 T 4 =R 30 SiO 3 / 2 Q=SiO 4 / 2 And here R 19 , R 20 , R 21 , R 25 , R 26 , and R 29 The group is independently selected from C1-C30 hydrocarbon groups, C6-C30 aromatic groups, or C1-C30 alkoxy groups; R 22 , R 23 , R 24 , R 27 , R 28 , and R 30 R is independently selected from hydrogen, C1-C30 hydrocarbon groups, C6-C30 aromatic groups, C1-C30 alkoxy groups, or C2-C30 alkenyl groups, however R 22 , R23 , R 24 , R 27 , R 28 , and / or R 30 One or more of them are hydrogen; and The subscripts h, i, j, k, m, n, and o have the following constraints: 1 <h+i+j+k+m+n+o<100、i+k+n> It is zero or a positive number below the value of 0.

[0072] In one embodiment, R 19 , R 20 , R 21 , R 25 , R 26 , and R 29 , and R in the case of non-hydrogen 22 , R 23 , R 24 , R 27 , R 28 , and R 30 One of these is independently selected from C1-C30 alkyl, C2-C20 alkyl, C3-C15 alkyl, C4-C10 alkyl, or C6-C8 alkyl. In one embodiment, R 19 , R 20 , R 21 , R 25 , R 26 , and R 29 , and R in the case of non-hydrogen 22 , R 23 , R 24 , R 27 , R 28 , and R 30 Each of these is a methyl group.

[0073] In one embodiment, polyorganohydrogensiloxane (C) is M H Q4 or MD H This is the DM model number.

[0074] In one embodiment, polyorganohydrogensiloxane (C) is present in an amount of about 0.05 to about 10 parts by mass, about 0.08 to about 6 parts by mass, or about 1 to about 4 parts by mass, based on the total weight of the curable composition. In embodiments, polyorganohydrogensiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule is used in an amount such that the amount of hydrogen atoms bonded to silicon atoms is 0.9 to 10 moles, 1.5 to 8 moles, 2.5 to 6 moles, or 3 to 5 moles per mole of the total amount of alkenyl groups contained in component (A).

[0075] In one embodiment, the hydrosilylation catalyst (D) may be used to facilitate the reaction of an alkenyl-containing compound with a polyorganohydrogensiloxane. The hydrosilylation catalyst may include, but is not limited to, noble metal catalysts such as ruthenium, rhodium, palladium, osmium, iridium, and platinum, as well as complexes containing these metals. Examples of hydrosilylation catalysts suitable for use in the present invention include, but is not limited to, Ashby catalysts; Lamoreax catalysts; Karstedt catalysts; Modic catalysts; Jeram catalysts; or two or more combinations thereof.

[0076] Catalyst (D) can be used in any amount suitable for promoting the reaction of the alkenyl-containing compound (e.g., component (A) and / or component (B)) with the polyorganohydrogensiloxane (C). In embodiments, catalyst (D) may be present in an amount of about 1 to about 10 parts by mass, about 2 to about 8 parts by mass, or about 3 to about 6 parts by mass, based on the total weight of the curable composition.

[0077] Additive (E) can be selected from a number of additives and may be selected as desired for a specific purpose or intended use. Additives may be selected to impart predetermined properties to the cured material formed from the composition, to assist in the processing of the composition, and for other purposes. In one embodiment, additive (E) is selected from pigments, lubricants, viscosity modifiers, heat stabilizers, light stabilizers, flame retardants, inhibitors, adhesion promoters, or two or more combinations thereof.

[0078] In one embodiment, additive (E) is present in an amount of about 0.05 parts by mass to about 3000 parts by mass, about 0.5 parts by mass to about 1000 parts by mass, or about 0.05 parts by mass to about 1 part by mass, based on the total weight of the curable silicone composition.

[0079] In one embodiment, the additive is selected from inhibitors. In one embodiment, the inhibitor is selected from ethylenically unsaturated amides, aromatic unsaturated amides, acetylene compounds, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon monoesters of unsaturated acids, conjugated or unconjugated enynes, hydroperoxides, ketones, sulfoxides, amines, phosphines, phosphates, nitrites, diaziridines, and others. Inhibitors particularly suitable for the composition are alkynyl alcohols and maleates. Examples of suitable polymerization inhibitors include, but are not limited to, diallyl maleate, hydroquinone, p-methoxyphenol, t-butylcatechol, and phenothiazine.

[0080] In one embodiment, the inhibitor is present in an amount of about 1 to about 10 parts by mass, more preferably about 0.1 to about 2 parts by mass, and most preferably about 0.05 to about 1 part by mass, based on the total weight of the curable silicone-imide composition.

[0081] In one embodiment, additive (E) is selected from polymerization inhibitors. Polymerization inhibitors are not particularly limited and may be selected as desired for a particular purpose or intended use. Examples of suitable inhibitors include, but are not limited to, ethylenically unsaturated amides, aromatic unsaturated amides, acetylene compounds, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon monoesters of unsaturated acids, conjugated or unconjugated enynes, hydroperoxides, ketones, sulfoxides, amines, phosphines, phosphates, nitrites, diaziridines, and others. Inhibitors particularly suitable for this composition are alkynyl alcohols and maleates. Examples of suitable polymerization inhibitors include, but are not limited to, diallyl maleate, hydroquinone, p-methoxyphenol, t-butylcatechol, phenothiazine, and others.

[0082] The amount of inhibitor used in this composition can be any amount that delays the above reaction at room temperature without hindering the reaction at appropriately raised temperatures. In embodiments, the polymerization inhibitor may be present in an amount of about 0.05 parts by mass to about 10 parts by mass, about 0.1 parts by mass to about 5 parts by mass, or about 1 part by mass to about 2 parts by mass.

[0083] The curable composition may also contain antioxidant compounds. Suitable examples of antioxidant compounds include, but are not limited to, hindered amine compounds and / or hindered phenol compounds.

[0084] Examples of hindered amine antioxidant compounds include, but are not limited to, hindered amine antioxidants such as (N,N',N'',N'''-tetrakis-(4,6-bis(butyl-(N-methyl)-2,2,6,6-tetramethylpiperidine-4-yl)amino)-triazine-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine-N-(2,2 Polycondensation product of ,6,6-tetramethyl-4-piperidyl)butylamine, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, [bis(2,2,6,6-tetramethyl-1(octyl)decandioate] [Oxy)-4-piperidyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane] (70%) - polypropylene (30%), bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl- This includes 4-piperidyl)sebacate, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-([3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, and others.

[0085] In one embodiment, the antioxidant compound is a hindered phenol compound. The hindered phenol may be selected as desired for a particular purpose or intended use. Suitable examples of hindered phenols include, but are not limited to, monophenols such as 2,6-di-t-butyl-p-cresol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, and 2,6-t-butyl-4-ethylphenol; bisphenols such as 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), and 4,4'-butylidene-bis(3-methyl-6-t-butylphenol);Furthermore, polycyclic phenols such as 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis(4'-hydroxy-3)-t-butylphenyl) glycol butyrate, and tocopherol (vitamin E), pentaerythritol-tetrakis[3-(3,5-di-t [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropioamide)], 3,5-bis(1,1-dimethylethyl)-4-hydroxyC7-C9 side-chain alkyl ester of benzenepropanoate, 2,4-dimethyl-6-(1- Methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, calcium diethylbis[[[3,5-bis-(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate], 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl] This includes [4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, reaction products of N-phenylbenzeneamine and 2,4,4-trimethylpentene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, and others.

[0086] IRGANOX1330 is a sterically hindrance phenol antioxidant commercially available from BASF ("3,3',3',5,5',5'-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol"). Irganox1010 is a sterically hindrance phenol antioxidant commercially available from BASF ("pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)" or 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene is ETHANOX TM It is commercially available as 330 (Albemarle), pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (Irganox 1010), tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (Irganox 3114), and tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate is commercially available as Irganox 3114.

[0087] The antioxidant may be included in the composition in an amount of about 0 to about 10 parts by mass, about 0 to about 5 parts by mass, or about 0 to about 3 parts by mass.

[0088] The curable composition may optionally contain a light stabilizer. The light stabilizer is not particularly limited and may be selected as desired for a specific purpose or intended use. Examples of suitable materials for the light stabilizer include, but are not limited to, 2,4-di-tert-butyl-6-(5-chlorobenzotriazole-2-yl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, and methyl 3-(3-(21-1-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionene. This includes reaction products of 300 / polyethylene glycol, 2-(2H-benzotriazol-2-yl)-6-(linear and branched dodecyl)-4-methylphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]phenol, octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, Tinuvin 622LD, Tinuvin 144, CHIMASSORB119FL, MARK LA-57, LA-62, LA-67, LA-63, SANDOL LS-765, LS-292, LS-2626, LS-1114, LS-744, and others.

[0089] The light stabilizer may be included in the composition in an amount of about 0 to about 10 parts by mass, about 0 to about 5 parts by mass, or about 0 to about 3 parts by mass.

[0090] The composition optionally contains a filler (F). In one embodiment, additive (F) is selected from the fillers. Suitable filler examples include, but are not limited to, silica, fumed silica, SiO2, TiO2, MgO, ZnO, CaCO3, CeO2, Fe2O3, SiC, clay materials, graphene oxide, boron oxide, boron nitride, carbon nanotubes, zirconium oxide, fly ash, Zr(OEt)4, Ti(OEt)4, any polyimide in powder form, polybenzimidazole, polyamideimide, polyBPA sulfone, siloxane-polyimide, siloxane-benzimidazole, siloxane-polysulfone, or any other thermally stable filler.

[0091] In one embodiment, the filler is present in an amount of about 0 to about 3000 parts by mass, more preferably about 15 to about 2000 parts by mass, and most preferably about 25 to about 30 parts by mass, based on the total weight of the curable silicone composition.

[0092] In one embodiment, the filler is present in an amount of about 20 to about 30 parts by mass based on the total weight of the curable silicone composition.

[0093] The cured silicone imide material formed from this composition may undergo thermal degradation from 300°C to 600°C, from approximately 350°C to approximately 550°C, or from approximately 400°C to approximately 500°C. This thermal degradation may also be referred to as pyrolysis and can be measured by thermogravimetric analysis (TGA). In one embodiment, thermal degradation can be measured using a TGA Q5000 from TA Instruments. Thermal degradation can be evaluated using a heating rate of 10°C / min up to 1000°C in a nitrogen or air atmosphere.

[0094] The curable composition may be cured by preparing a mixture of each component and exposing this mixture to a sufficient temperature for a sufficient amount of time to cure the mixture. Each component may be added separately, or as two or more material packages if the package contains two or more of the components required for the final composition. Curing may be achieved under exposure to rising temperature over a period of time from about 15 minutes to about 120 minutes. In some embodiments, curing can be achieved at 100°C for 60 minutes.

[0095] In one embodiment, the silicone-imide composition can be coated or adhered to a substrate. The composition can be applied in any suitable manner, including, but not limited to, brush application, spraying, curtain coating, dipping, spin coating, and others.

[0096] The substrate can be selected from plastic materials, ceramics, glass, rubber materials, filled metals, metal alloys, metallized plastics, and / or coated or painted metals. Suitable plastics include, but are not limited to, synthetic organic polymer materials, such as poly(methyl methacrylate) and other acrylic polymers; polyesters such as poly(ethylene terephthalate), poly(butylene terephthalate), and other polyesters; polyamides, polyimides, acrylonitrile-styrene copolymers, styrene-acrylonitrile-butadiene copolymers, polyvinyl chloride, polyethylene, and others; polycarbonates; and copolycarbonates such as EXL and high-heat polycarbonates. In one embodiment, the substrate is formed from polycarbonate or acrylic resin. Polycarbonate is a particularly suitable material for transparent substrates due to its excellent physical, mechanical, and chemical properties. Generally, the choice of substrate is ultimately determined by the end application being considered.

[0097] In one embodiment, the cured silicone imide material is formed from a curable composition.

[0098] Curable compositions may be used in a variety of applications. In embodiments, the curable composition is cured and used for properties such as excellent thermal stability, thermal conductivity, dimensional stability, adhesion, mechanical properties, electrical properties, low-temperature flexibility, low dielectric constant, thermal oxidation stability, hydrophobicity, chemical resistance, biocompatibility, flame retardancy, and gas permeability, and is mainly used in applications such as aerospace, electronics, automotive, insulation, coatings, solvent-resistant films, and others.

[0099] The following examples are intended to illustrate embodiments and representations of the present technology. Unless otherwise specified, all parts and percentages are by weight, and all temperatures are in Celsius. All patents, other documents, and U.S. patent applications referenced herein are incorporated in their entirety by reference.

[0100] Examples

[0101] Synthesis of N-allylamide of pyromellitic dianhydride (1): Pyromellitic dianhydride (50 g, 0.2292 mol) and acetic acid (250 ml) were placed in a three-necked round-bottom flask (condenser / overhead stirrer / dropping funnel), and then allylamide (28 g, 0.504 mol) was added dropwise under ice-cold conditions. Once the addition was complete, heating was started from 40°C to 130°C until the reaction mixture became a clear solution. A color change occurred over time. Once the solution became clear, it was heated at 130°C for 4 hours to form a ring. 250 ml of water was placed in another round-bottom flask and heated to ~100°C. The reaction mixture was then slowly poured into this water, and a solid substance was formed. This solid substance was filtered off using filter paper and a funnel. This solid substance was washed with water and methanol and dried using a high-vacuum pump. The yield was 65 g (95%). When this material was analyzed using 1H-NMR, it perfectly matched the desired structure.

[0102] Synthesis of ABn siloxane-polyimide copolymer: Solid N-allyl pyromellitic diimide material (1) (15 g, 0.050 mol) was dissolved in 350 ml of toluene and heated to 75°C. When the temperature reached 75°C, a platinum catalyst (10 ppm) was added, followed by the dropwise addition of silicone hydride (76.53 g). A slight exothermic reaction (~3°C) was observed. After the addition was complete, the reaction was allowed to continue for another 4 hours, and the completion of product formation was monitored by 1H-NMR. Upon completion of the reaction, a mixture of activated carbon and silica gel was added to rapidly cool the reaction. The solute was collected by filtration, and the solvent was removed by distillation to obtain a viscous material (viscosity = 79 Pas). Analysis was performed by 1H-NMR and GPC.

[0103] Preparation of cured samples and measurement of thermal stability by TGA: Alkene-terminated base polymer material was placed in a container and subsequently mixed with an inhibitor and a platinum catalyst. A Si-H crosslinking agent was then added to the mixture and thoroughly mixed by hand and using a speed mixer. The entire mixture was then poured into a Teflon mold of the specified dimensions and thickness. After degassing, the mold was placed in an oven (100°C) for 1 hour to allow it to fully cure.

[0104] Thermal degradation was investigated using TA Instruments' TGA Q5000 in a nitrogen or air atmosphere, with a heating rate of 10°C / min until the temperature reached 1000°C.

[0105] The compositions were prepared according to the examples listed in Tables 1 and 2. These compositions were prepared in a container by mixing alkenyl-functionalized siloxane-imide copolymer materials with inhibitors and catalysts. A crosslinking agent was then added to the mixture and thoroughly mixed by hand and using a speed mixer.

[0106] Alkenyl-functionalized siloxane-imide copolymers include N-allyl pyromellitic acid imide and M H D m M HIt is an allyl-terminated ABn siloxane-polyimide copolymer contained in formula (I), synthesized from a chain extender. [ka] In the siloxane-imide copolymer used in the examples, m is 1 to 200 and n is 1 to 30.

[0107] The composition is 145 mm 2 The material was poured into a Teflon mold with dimensions of ×0.15 mm. After degassing, the mold was placed in an oven and heated to 100°C for 1 hour to allow it to fully cure.

[0108] Thermal Stability: Thermal degradation was investigated by using TA Instruments' TGA Q5000 in a nitrogen or air atmosphere at a heating rate of 10°C / min until the temperature reached 1000°C. T0 represents the start of degradation, and T d This represents the peak of decomposition. [Table 1] [Table 2]

[0109] As illustrated in Tables 1 and 2, the composition containing the siloxane-imide copolymer provides better thermal stability compared to using either the vinyl PDMS-containing composition or the phenyl PDMS-containing composition alone.

[0110] The above descriptions include examples provided herein. Naturally, it is impossible to describe all recognizable combinations of components or methods for the purposes of this specification, but those skilled in the art will recognize that many other combinations and substitutions are possible herein. Thus, this specification is intended to encompass all changes, modifications, and variations that fall within the idea and scope of the claims. Furthermore, where the term “includes” is used in the detailed description of the invention or in the claims, the term is intended to be inclusive in a similar manner to how the term “includes” is interpreted when it is used as a substitute in the claims.

[0111] The above description identifies various, non-limiting embodiments of aromatic-containing silicone compositions and curable compositions containing such compositions. Modifications may be recalled by those skilled in the art and those who can create and use the present invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or the subject matter described in the claims.

Claims

1. An addition-curable silicone-imide composition, which includes: (A) Alkenyl-functionalized siloxane-imide copolymer of formula (I) 【Transformation 6】 R1 is independently selected from C5-C20 aryl groups, polycyclic aryl groups containing two or more C5-C20 aryl groups, where R1 can be unsubstituted or substituted with C1-C6 alkyl groups, halogen groups, haloalkyl groups, hydroxyl groups, and / or C1-C5 alkoxy groups; R2 is independently selected from a divalent C1-C20 hydrocarbon group, a divalent C4-C20 branched-chain hydrocarbon group, or a C4-C30 cyclic hydrocarbon group; R3, R4, R5, and R6 are each independently selected from C1-C10 alkyl groups and C6-C20 aryl groups; m is an integer from 1 to 200; and n is an integer from 1 to 30; Alkenyl-functionalized siloxane-imide copolymer present in an amount of 20 to 50 parts by mass based on the total weight of the addition-curable silicone-imide composition; (B) 20 to 50 parts by mass of an alkenyl-functional organosiloxane based on the total weight of the addition-curable silicone-imide composition; (C) Polyorganohydrogensiloxane having at least two hydrogen atoms bonded to a silicon atom; (D) catalyst; (E) Additives; and (F) An addition-curable silicone-imide composition comprising 0 to 3000 parts by mass of filler based on the total weight of the addition-curable silicone-imide composition.

2. R １ The addition-curable silicone-imide composition of claim 1, wherein is independently selected from benzene, naphthalene, benzophenone, biphenyl, biphenylalkane, biphenyl ether, isopropylidenephenylphenoxy, biphenyl sulfone, biphenyl sulfide, norbornyl, or hexafluoromethylbiphenyl.

3. R １ The addition-curable silicone-imide composition according to claim 1, wherein is benzene.

4. The alkenyl-functional organosiloxane (B) is of the formula M １ ａ M ２ ｂ D １ ｃ D ２ ｄ T １ ｅ T ２ ｆ Q ｇ selected from the compounds of the formula: M １ =R ７ R ８ R ９ SiO １／２ M ２ =R １０ R １１ R １２ SiO １／２ D １ =R １３ R １４ SiO ２／２ D ２ =R １５ R １６ SiO ２／２ T １ =R １７ SiO ３／２ T ２ =R １８ SiO ３／２ Q=SiO ４／２ And here R ７ , R ８ , R ９ , R １１ , R １２、 R １３ , R １４ , R １６ , and R １７ is independently selected from C1-C30 hydrocarbon groups or C6-C30 aromatic groups; R １０ , R １５ , and R １８ R is independently selected from C1-C30 hydrocarbon groups, C6-C30 aromatic groups, C1-C30 alkoxy groups, or C2-C30 alkenyl groups, however R １０ , R １５ , and / or R １８ One or more of these are selected from C2-C30 alkenyl groups; An addition-curable silicone-imide composition according to any one of claims 1 to 3, wherein the subscripts a, b, c, d, e, f, and g are zero or positive numbers under the following constraints: 2 < a + b + c + d + e + f + g < 2000, and b + d + f > 0.

5. R ７ , R ８ , R ９ , R １１ , R １２、 R １３ , R １４ , R １６ , and R １７ R is independently selected from C1-C30 hydrocarbon groups or C6-C30 aromatic groups, where R ７ , R ８ , R ９ , R １１ , R １２、 R １３ , R １４ , R １６ , and R １７ The addition-curable silicone-imide composition of claim 4, wherein at least one of the groups is selected from C6 to C30 aromatic groups.

6. R １３ and / or R １４ The addition-curable silicone-imide composition of claim 5, wherein at least one of the groups is a C6-C30 aromatic group.

7. R １３ and / or R １４ The addition-curable silicone-imide composition of claim 6, wherein is a phenyl group.

8. The curable composition according to claim 6, wherein an alkenyl-functionalized siloxane-imide copolymer (A) is present in an amount of 20 to 50 parts by mass based on the total weight of the addition-curable silicone-imide composition, and an alkenyl-functionalized organosiloxane (B) is present in an amount of 20 to 50 parts by mass based on the total weight of the addition-curable silicone-imide composition.

9. The addition-curable silicone-imide composition according to claim 1, wherein an alkenyl-functionalized siloxane-imide copolymer (A) is present in an amount of 30 to 40 parts by mass based on the total weight of the addition-curable silicone-imide composition, and an alkenyl-functionalized organosiloxane (B) is present in an amount of 30 to 40 parts by mass based on the total weight of the addition-curable silicone-imide composition.

10. The polyorganohydrogensiloxane (C) is of the formula M ３ ｈ M ４ ｉ D ３ ｊ D ４ ｋ T ３ ｍ T ４ ｎ Q ｏ selected from the compounds of the formula: M ３ =R １９ R ２０ R ２１ SiO １／２ M ４ =R ２２ R ２３ R ２４ SiO １／２ D ３ =R ２５ R ２６ SiO ２／２ D ４ =R ２７ R ２８ SiO ２／２ T ３ =R ２９ SiO ３／２ T ４ =R ３０ SiO ３／２ Q=SiO ４／２ And here R １９ , R ２０ , R ２１ , R ２５ , R ２６ , and R ２９ is independently selected from C1-C30 hydrocarbon groups, C6-C30 aromatic groups, or C1-C30 alkoxy groups; R ２２ , R ２３ , R ２４ , R ２７ , R ２８ , and R ３０ R is independently selected from hydrogen, C1-C30 hydrocarbon groups, C6-C30 aromatic groups, C1-C30 alkoxy groups, or C2-C30 alkenyl groups, provided that R ２２ , R ２３ , R ２４ , R ２７ , R ２８ , and / or R ３０ One or more of them are hydrogen; An addition-curable silicone-imide composition according to any one of claims 1 to 9, wherein the subscripts h, i, j, k, m, n, and o are zero or positive numbers under the following constraints: 1 < h + i + j + k + m + n + o < 100, i + k + n > 0.

11. An addition-curable silicone-imide composition according to any one of claims 1 to 10, comprising polyorganohydrogensiloxane (C) in an amount from 0.05 parts by mass to 10 parts by mass based on the total weight of the addition-curable silicone-imide composition.

12. Catalyst (D) is selected from noble metal catalysts, which include ruthenium, rhodium, palladium, osmium, iridium, and platinum, as well as complexes containing one or more of these metals. An addition-curable silicone-imide composition according to any one of claims 1 to 11.

13. The addition-curable silicone-imide composition according to any one of claims 1 to 12, wherein catalyst (D) is present in an amount of 1 to 10 parts by mass based on the total weight of the addition-curable silicone-imide composition.

14. Additive (E) is selected from at least one of a pigment, lubricant, viscosity modifier, heat stabilizer, light stabilizer, flame retardant, inhibitor, adhesion promoter, or a combination of two or more thereof, according to any addition-curable silicone-imide composition of any one of claims 1 to 13.

15. A curable composition according to any one of claims 1 to 14, comprising additive (E) in an amount from 0.05 parts by mass to 3000 parts by mass based on the total weight of the addition-curable silicone-imide composition.

16. The addition-curable silicone-imide composition according to claim 14 or 15, wherein the additive is an inhibitor.

17. The addition-curable silicone-imide composition of claim 16, wherein the inhibitor is selected from ethylenically unsaturated amides, aromatic unsaturated amides, acetylene compounds, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon diesters, unsaturated hydrocarbon monoesters of unsaturated acids, conjugated or unconjugated enynes, hydroperoxides, ketones, sulfoxides, amines, phosphines, phosphates, nitrites, diaziridines, or two or more combinations thereof.

18. The addition-curable silicone-imide composition of claim 16, wherein the inhibitor is selected from alkynyl alcohols, maleates, or combinations thereof.

19. The addition-curable silicone-imide composition of claim 16, wherein the inhibitor is selected from diallyl maleate, hydroquinone, p-methoxyphenol, t-butylcatechol, phenothiazine, or two or more combinations thereof.

20. The curable composition according to claim 16, comprising an inhibitor in an amount of 0.05 to 10 parts by mass based on the total weight of the addition-curable silicone-imide composition.

21. The addition-curable silicone-imide composition according to claim 16, comprising an inhibitor in an amount of 0.05 parts by mass to 2 parts by mass based on the total weight of the addition-curable silicone-imide composition.

22. Filler (F) is SiO ２ , TiO ２ , MgO, ZnO, CaCO ３ , CEO ２ Fe ２ O ３ SiC, clay materials, graphene oxide, boron oxide, boron nitride, carbon nanotubes, zirconium oxide, fly ash, Zr(OEt) ４ , Ti(OEt) ４ An addition-curable silicone-imide composition according to any of claims 1 to 21, selected from any polyimide, polybenzimidazole, polyamideimide, polyBPA sulfone, siloxane-polyimide, siloxane-benzimidazole, siloxane-polysulfone, or two or more combinations thereof, in powder form.

23. Filler (F) is Fe ２ O ３ The addition-curable silicone-imide composition according to claim 21.

24. The addition-curable silicone-imide composition according to any one of claims 1 to 23, wherein the filler (F) is present in an amount from 0 to 100 parts by mass based on the total weight of the addition-curable silicone-imide composition.

25. The addition-curable silicone-imide composition according to claim 22 or 23, wherein the filler (F) is present in an amount of 20 to 30 parts by mass based on the total weight of the addition-curable silicone-imide composition.

26. A process for preparing a cured silicone-imide material, comprising contacting an addition-curable silicone-imide composition according to any one of claims 1 to 25 with curing conditions.

27. The process of claim 25, wherein the curing condition is a curing catalyst.

28. A cured silicone-imide material formed from an addition-curable silicone-imide composition according to any one of claims 1 to 25.

29. The curable silicone-imide material of claim 28, which has thermal decomposition from 300°C to 600°C as measured by thermogravimetric analysis at a heating rate of 10°C / min up to a temperature of 1000°C.

30. The cured silicone-imide material according to claim 28 or 29, which is used in or as part of aerospace equipment, electronic equipment, electronic components, automobiles, insulators, paints, solvent-resistant films.

31. An article comprising a substrate, wherein the substrate is disposed on its surface, and the article comprises an addition-curable silicone-imide composition according to any one of claims 1 to 25.

32. The article of claim 31, wherein the base material comprises a material selected from plastic materials, ceramics, glass, rubber materials, filled metals, metal alloys, metallized plastics, coated or painted metals, or two or more combinations thereof.

33. The article of claim 31 or 32, wherein the base material is selected from acrylic polymer, polyester, polyamide, polyimide, acrylonitrile-styrene copolymer, styrene-acrylonitrile-butadiene polymer, polyvinyl chloride, polyethylene, polycarbonate, copolycarbonate, or two or more combinations thereof.

Images